EP3088562A1 - Farbbehandeltes basismaterial und basismaterialfarbbehandlungsverfahren dafür - Google Patents

Farbbehandeltes basismaterial und basismaterialfarbbehandlungsverfahren dafür Download PDF

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Publication number
EP3088562A1
EP3088562A1 EP14873790.1A EP14873790A EP3088562A1 EP 3088562 A1 EP3088562 A1 EP 3088562A1 EP 14873790 A EP14873790 A EP 14873790A EP 3088562 A1 EP3088562 A1 EP 3088562A1
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EP
European Patent Office
Prior art keywords
color
film
wavelength conversion
conversion layer
average thickness
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Granted
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EP14873790.1A
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English (en)
French (fr)
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EP3088562B1 (de
EP3088562A4 (de
Inventor
Hyunju JEONG
Kyoung-Bo Kim
Yon-Kyun Song
Jeong-Hee Lee
Yun Ha Yoo
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Posco Holdings Inc
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Posco Co Ltd
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Priority claimed from KR1020130164045A external-priority patent/KR101543925B1/ko
Priority claimed from KR1020130164046A external-priority patent/KR101543926B1/ko
Priority claimed from KR1020130164047A external-priority patent/KR101584413B1/ko
Priority claimed from KR1020130164044A external-priority patent/KR101543924B1/ko
Application filed by Posco Co Ltd filed Critical Posco Co Ltd
Priority claimed from PCT/KR2014/012926 external-priority patent/WO2015099503A1/ko
Publication of EP3088562A1 publication Critical patent/EP3088562A1/de
Publication of EP3088562A4 publication Critical patent/EP3088562A4/de
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C30/00—Coating with metallic material characterised only by the composition of the metallic material, i.e. not characterised by the coating process
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/60—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using alkaline aqueous solutions with pH greater than 8
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/60—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using alkaline aqueous solutions with pH greater than 8
    • C23C22/62—Treatment of iron or alloys based thereon
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/60—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using alkaline aqueous solutions with pH greater than 8
    • C23C22/64—Treatment of refractory metals or alloys based thereon
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/73—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals characterised by the process
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/82—After-treatment
    • C23C22/83—Chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/32—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
    • C23C28/324—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer with at least one metal matrix material layer comprising a mixture of at least two metals or metal phases or a metal-matrix material with hard embedded particles, e.g. WC-Me
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates

Definitions

  • the present invention relates to a color-treated substrate and a substrate color treatment method therefor.
  • Magnesium is a metal which belongs to lightweight metals among practical metals, has excellent wear resistance, and is very resistant to sunlight and eco-friendly, but has a difficulty in realizing a metal texture and various colors. Further, since it is a metal having the lowest electrochemical performance and is highly active, when a color treatment is not performed thereon, it may be quickly corroded in air or in a solution, and thus has a difficulty in industrial application.
  • Korean Patent Laid-open Publication No. 2011-0016750 disclosed a PVD-sol gel method of performing sol-gel coating after dry coating a surface of a substrate formed of a magnesium alloy with a metal-containing material in order to realize a metal texture and ensure corrosion resistance
  • Korean Patent Laid-open Publication No. 2011-0134769 disclosed an anodic oxidation method of imparting gloss to a surface of a substrate including magnesium using chemical polishing and coloring a surface by anodic oxidation of the substrate in an alkaline electrolyte including a pigment dissolved therein.
  • the PVD-sol gel method has a problem in that a texture realized on the surface of the substrate is not the intrinsic texture of magnesium although a metal texture may be realized on the surface of the substrate, and the realization of a variety of colors is difficult. Furthermore, when a color treatment is performed using the anodic oxidation method, there is a problem in that an opaque oxide film is formed on the surface of the substrate, and the realization of the intrinsic texture of metals is not easy.
  • An objective of the present invention is to provide a substrate which maintains a texture and gloss of metals and has a surface color-treated to have a variety of colors including a black color.
  • Another objective of the present invention is to provide a method of color-treating the substrate.
  • one embodiment of the present invention provides a color-treated substrate, including:
  • another embodiment of the present invention provides a method of color-treating a substrate, including: a step of forming a film on a matrix containing magnesium; and a step of forming a wavelength conversion layer on the film, wherein a condition of the following Expression 1 is satisfied with respect to an arbitrary point A existing on the wavelength conversion layer: 0.1 ⁇ T film / T ML ⁇ 10 where T film represents an average thickness of the film at the point A, T ML represents an average thickness of the wavelength conversion layer at the point A.
  • the color-treated substrate according to the present invention can maintain a texture and gloss of metals, improve durability of a substrate and uniformly realize a variety of colors including a blue color, a green color, an achromatic color such as a gray color, a black color or the like on a surface of the substrate, and thus can be usefully used in the fields of building exterior materials, automobile interiors, and particularly electrical and electronic component materials, such as mobile product frames, in which a metal material is used.
  • Color coordinates refer to coordinates in a CIE color space, including color values defined by the Commission International de l'Eclairage (CIE), and any position in the CIE color space may be expressed as three coordinate values of L*, a* and b*.
  • CIE Commission International de l'Eclairage
  • an L* value represents brightness.
  • an a* value represents whether a color at a corresponding color coordinate leans toward a pure magenta color or a pure a green color
  • a b* value represents whether a color at a corresponding color coordinate leans toward a pure yellow color or a pure a blue color.
  • the a* value ranges from -a to +a
  • the maximum a* value (a* max) represents a pure magenta color
  • the minimum a* value (a* min) represents a pure a green color.
  • a* value is negative
  • an a* value is positive
  • the b* value ranges from -b to +b.
  • the maximum b* value (b* max) represents a pure yellow color
  • the minimum b* value (b* min) represents a pure a blue color.
  • b* max represents a pure yellow color
  • b* min represents a pure a blue color.
  • a "black” color refers to a color of which an average color coordinate (L*) with respect to brightness based on CIE color coordinates is 60 or less.
  • the black color may include an achromatic color such as a black color, a grey color or the like, and a black rust color or a black navy color or the like mixed with a green-based color or a blue-based color.
  • a "blue" color refers to a color in which L* is more than 60 and b* is less than 5 in average color coordinates (L*, a*, b*) based on CIE color coordinates.
  • the blue color refers to a color having a low b* value, and specifically, a color having a b* value of less than 5 in the present invention.
  • color coordinates of a* is not particularly limited, the a* may be 20 or less, 15 or less, 10 or less, or 5 or less.
  • Examples of the blue color according to the present invention may include a navy color; a blue color; a light blue color; or a cyan color mixed with a green-based color and the like, which are included in the range of the color coordinates.
  • a "green” color refers to a color in which L* is more than 60, a* is -5 or less and b* is 5 or more in average color coordinates (L*, a*, b*) based on CIE color coordinates. Since a* represents pure magenta and a green colors in a CIE color space, the green color refers to a color having a negative a* value, specifically, a color having an a* value of -5 or less, and more specifically, a color having an a* value of -6 or less, or -7 or less in the present invention. Further, coordinates of b* of the green color may be 5 or more, and specifically, 6 or more or 7 or more. Examples of the green color according to the present invention may include a yellow-green color; a pale blue-green color, an iron blue color, a green color or the like, which are included in the range of the color coordinates.
  • a “wavelength conversion layer”, as used herein, refers to a layer, including intercalation interface on the surface of the film, for controlling a wavelength of incident light by adjusting reflection, refraction, scattering, diffraction or the like of light, which may serve to minimize additional refraction and/or scattering, in a top coat, of light refracted and/or scattered in a film, and maintain a color developed by the layer by inducing light reflection.
  • a unit “T”, as used herein, represents a thickness of a substrate including magnesium, and is the same as a unit “mm”.
  • the present invention provides a color-treated substrate and a substrate color treatment method therefor.
  • a PVD-sol gel method, an anodic oxidation method or the like which is a method of coating a surface of a material with a metal-containing material, a pigment or the like, has been conventionally known as a method for realizing a color on the material including magnesium.
  • these methods may cause a reduction in durability of the substrate.
  • it is difficult to realize a uniform color on the surface of the material and there is a problem of unmet reliability because a coated film layer is easily detached.
  • products formed of a metal material which is color-treated to have a black color have become popular according to various needs of the recent consumer and the trend of high-quality fashion. To this end, there is an increasing need for a technique to realize a black color on the surface of the material.
  • the present invention suggests a substrate which maintains a texture and gloss of metals and is color-treated to have a variety of colors including a black color, and a method of color-treating the substrate.
  • the color-treated substrate according to the present invention may maintain a texture and gloss of metals, improve durability of a substrate and uniformly realize a variety of colors including an achromatic color such as a gray color, a black color or the like on a surface of the substrate by including a nanometer scale film and a wavelength conversion layer which have a specific ratio on the substrate, and thus may be usefully used in the fields of building exterior materials, automobile interiors, and particularly electrical and electronic component materials, such as mobile product frames, in which a metal material is used.
  • An embodiment of the present invention provides a color-treated substrate, including:
  • the substrate satisfies the condition of the following Expression 1 as follows: 0.1 to 10; 0.1 to 9; 0.1 to 8.5; 0.5 to 6; 0.5 to 4; or 1 to 8.5.
  • the color-treated substrate according to the present invention may have a structure in which the film and the wavelength conversion layer are sequentially stacked on the matrix containing magnesium, and this stacked structure may be formed on one or both surfaces of a metal matrix. Further, the substrate may prevent a decrease in the light transmittance of the wavelength conversion layer as well as uniformly develop a color on the surface by satisfying the condition of Expression 1.
  • examples of the developed color may include an achromatic color such as a grey color, a black color or the like as well as a blue color, a green color, etc.
  • an average thickness ratio T film /T ML of the film to the wavelength conversion layer at an arbitrary point A existing on the wavelength conversion layer is in the range of 0.1 to 6.0
  • an achromatic color such as a black color, a grey color or the like may be developed.
  • L* of average color coordinates of any three points included in an arbitrary area with a width of 1 cm and length of 1cm existing on the wavelength conversion layer may be 60 or less.
  • the average thickness of the film may be less than 80 nm, and specifically, may be 75 nm or less, 70 nm or less, 65 nm or less, 60 nm or less; 50 nm or less, 10 to 55 nm or 25 to 55 nm (refer to Experimental Example 2).
  • an average thickness ratio T film /T ML of the film to the wavelength conversion layer with respect to an arbitrary point A existing on the wavelength conversion layer is in the range of 0.2 to 4.0
  • a blue-based color such as a blue color, a cyan color, a sky blue color or the like may be developed.
  • L* is more than 60 and b* is less than 5 in average color coordinates of any three points included in an arbitrary area with a width of 1 cm and length of 1cm existing on the wavelength conversion layer.
  • the average thickness of the film may be in the range of 80 to 140 nm, and specifically, may be 80 to 100 nm, 120 to 140 nm, 110 to 130 nm, 100 to 135 nm or 85 to 135 nm (refer to Experimental Example 2).
  • an average thickness ratio T film /T ML of the film to the wavelength conversion layer with respect to an arbitrary point A existing on the wavelength conversion layer is in the range of 0.7 to 8.5
  • a green-based color such as a yellow-green color; a pale blue-green color, an iron blue color, a green color or the like
  • L* is more than 60
  • a* is -5 or less
  • b* is 5 or more in average color coordinates of any three points included in an arbitrary area with a width of 1 cm and length of 1cm existing on the wavelength conversion layer.
  • the average thickness of the film may be more than 140 nm and 300 nm or less, and specifically, may be 145 nm to 300 nm, 146 nm to 290 nm, 147 nm or more to 260 nm, 145 nm to 200 nm or 145 nm to 170 nm (refer to Experimental Example 2).
  • the matrix containing magnesium serves to define a basic framework and physical properties of a substrate, and may be regarded as a form before the color-treated substrate according to the present invention is subject to a color treatment.
  • the type or form of the matrix containing magnesium is not particularly limited as long as it is usable as a frame in the fields of electrical and electronic component materials.
  • a magnesium substrate formed of magnesium; a stainless steel or titanium (Ti) substrate of which a surface has magnesium dispersed therein or the like may be used as the matrix.
  • the film is formed on the surface of the matrix and functions to scatter or refract light incident to the surface.
  • the film is not particularly limited as long as it is a transparent film which allows light to be transmitted and may refract or scatter incident light.
  • the film may include one or more of sodium hydroxide (NaOH), potassium hydroxide (KOH), magnesium hydroxide (Mg(OH) 2 ), calcium hydroxide (Ca(OH) 2 ) and barium hydroxide (Ba(OH) 2 ), and more specifically, may include magnesium hydroxide (Mg(OH) 2 ).
  • the film develops a variety of colors such as an achromatic color such as a black color, a grey color, and a blue color, a green color or the like on the substrate by having a specific average thickness ratio with the wavelength conversion layer formed on the film, and here, the film may serves as a color-developing layer which defines a developed color.
  • the average thickness ratio of the film and the wavelength conversion layer is the same while the average thickness of the film formed on the matrix is different, a color developed on the surface may be different.
  • the average thickness of the film is not particularly limited as long as it is a nanometer scale thickness.
  • the average thickness of the film may be in the range of 500 nm or less, 400 nm or less, 300 or less, 100 nm to 250 nm, 10 to 75 nm, 50 to 140 nm, 140 to 200 nm, or 1 to 300 nm.
  • the wavelength conversion layer is formed on the film and includes an intercalation interface on the surface of the film, and thus scatters and/or refracts light which is refracted and/or scattered in the film; and light reflected on the surface of the matrix again to develop a color on the surface of the matrix.
  • the wavelength conversion layer has to have an average thickness ratio with the film, which satisfies the condition of Expression 1, and have a nanometer scale average thickness in order to develop a color on the surface of the matrix.
  • the average thickness of the wavelength conversion layer may be 200 nm or less. More specifically, the average thickness may be 190 nm or less; 180 nm or less; 170 nm or less; 160 nm or less; or 150 nm or less.
  • the failure of coloring due to a decrease in the light transmittance of the wavelength conversion layer may be prevented by adjusting the average thickness of the wavelength conversion layer to within the above-described range in the present invention.
  • the component or form of the wavelength conversion layer is not particularly limited.
  • the wavelength conversion layer may include one or more selected from the group consisting of metals including aluminum (Al), chromium (Cr), titanium (Ti), gold (Au), molybdenum (Mo), silver (Ag), manganese (Mn), zirconium (Zr), palladium (Pd), platinum (Pt), cobalt (Co), cadmium (Cd) or copper (Cu) and ions thereof, and specifically, may include chromium (Cr).
  • metals including aluminum (Al), chromium (Cr), titanium (Ti), gold (Au), molybdenum (Mo), silver (Ag), manganese (Mn), zirconium (Zr), palladium (Pd), platinum (Pt), cobalt (Co), cadmium (Cd) or copper (Cu) and ions thereof, and specifically, may include chromium (Cr).
  • the metals may be in the form of metal particles, and may include various types such as a metal nitride, a metal oxide, a metal carbide or the like by reacting with a nitrogen gas, an ethane gas, an oxygen gas and the like in the process of forming the wavelength conversion layer.
  • the wavelength conversion layer may be a continuous layer in which the metals are densely stacked on the film and fully cover the surface of the film, or a discontinuous layer in which the metals are dispersed on the film, but is not limited thereto.
  • the color-treated substrate according to the present invention may further include a top coat formed on the wavelength conversion layer in order to improve scratch resistance and durability of the surface of the substrate.
  • a clear coating agent for forming the top coat is not particularly limited as long as it is a clear coating agent which is applicable to metal coatings. More specifically, a matte clear coating agent or a glossy/matte clear coating agent which is applicable to metal coatings or the like may be exemplified. Further, the top coat may have an excellent adhesiveness with the wavelength conversion layer. Specifically, when the color-treated substrate including the top coat was sprayed with 5 wt% salt water at 35 °C and the adhesiveness thereof was evaluated after 72 hours, the top coat may have a peel rate of 5% or less.
  • the color-treated substrate having a matte or glossy/matte top coat formed thereon was sprayed with 5 wt% salt water at 35 °C and was tested by a cross-cut tape test method after 72 hours. As a result, it was determined that the area of the peeled top coat was 5% or less with respect to the total area of the sample. As can be seen from the results, the substrate having the top coat formed thereon according to the present invention has excellent adhesiveness between the color-treated substrate and the top coat (refer to Experimental Example 3).
  • an embodiment of the present invention provides a method of color-treating a substrate, including: a step of forming a film on a matrix containing magnesium; and a step of forming a wavelength conversion layer on the film, wherein the condition of the following Expression 1 is satisfied with respect to an arbitrary point A existing on the wavelength conversion layer: 0.1 ⁇ T film / T ML ⁇ 10 where T film represents an average thickness of the film at the point A, T ML represents an average thickness of the wavelength conversion layer at the point A.
  • a diversity of colors such as an achromatic color such as a black color, a grey color or the like as well as a blue color, a green color or the like may be uniformly developed on a surface of a substrate by forming a nanometer scale film and wavelength conversion layer having a specific ratio in the range of 0.1 to 10.
  • the step of forming the film may be performed by immersing the matrix containing magnesium in a hydroxide solution in the color treatment method.
  • any solution including a hydroxyl group may be used as the hydroxide solution, without particular limitation.
  • a solution having one or more selected from the group consisting of NaOH, KOH, Mg(OH) 2 , Ca(OH) 2 and Ba(OH) 2 dissolved therein may be used.
  • the hydroxide solution has an advantage in that the film is uniformly formed on the surface of the substrate in a short time and a developed color has excellent coloring power and clarity (refer to Experimental Example 1).
  • the preparation method according to the present invention may control the thickness of the film formed on the surface of the matrix according to immersion conditions.
  • the thickness of the films formed on matrices may be different even though the matrices were immersed under the same conditions. Accordingly, it is preferable to control the thickness of the film by adjusting immersion conditions according to the thickness of the matrix containing magnesium.
  • the temperature of the hydroxide solution may be in the range of 15 to 200 °C, and specifically, 15 to 50 °C, 15 to 30 °C, 90 to 150 °C, or 95 to 110 °C.
  • the immersion time of the matrix may be 60 minutes or less, and specifically, may be 50 minutes or less, 40 minutes or less, 30 minutes or less, 20 minutes or less, or 15 minutes or less.
  • the concentration of the hydroxide solution may be in the range of 1 to 80 wt%, and specifically, may be in the range of 1 to 70 wt%; 5 to 50 wt%; 10 to 20 wt%; 1 to 40 wt%; 30 to 60 wt%; 15 to 45 wt% or 5 to 20 wt%.
  • the film may be uniformly formed in a short time and a decrease in the intrinsic glossiness of metals due to an excessively increased thickness of the film may be prevented by immersing the matrix in the above-described condition ranges.
  • the step of forming the wavelength conversion layer in the color treatment method may be performed using a method which is generally used in the related field without particular limitation. As a specific example, it may be performed by a method such as vacuum deposition, sputtering, ion plating, ion beam deposition or the like.
  • the method of color treating the substrate according to the present invention substrate may further include one or more steps of: pretreating the surface of the matrix before the step of forming the film; and rinsing after the step of forming the film.
  • the step of pretreating the surface is a step of eliminating contaminants remaining on the surface by treating the surface using an alkaline cleaning solution or grinding the surface before forming the film on the matrix.
  • the alkaline cleaning solution is not particularly limited as long as the solution is generally used to clean a surface of metals, metal oxides or metal hydroxides in the related field.
  • the grinding may be performed by buffing, polishing, blasting, electrolytic polishing or the like, but is not limited thereto.
  • the speed of forming the film may be controlled by surface energy of the surface and/or surface conditions, specifically, microstructural changes of the surface.
  • the thickness of the film formed on the polished matrix may be different from that of the film formed on the unpolished matrix even though the film is formed on the polished matrix under the same conditions as the film of the unpolished matrix, and each color developed on the surface may be different accordingly.
  • the step of rinsing is a step of eliminating any hydroxide solution remaining on the surface by rinsing the surface of the matrix after the step of immersing the matrix in the hydroxide solution. In this step, additional formation of the film due to any remaining hydroxide solution may be prevented by removing the hydroxide solution remaining on the surface of the matrix.
  • TEM transmission electron microscope
  • a thickness of a matte clear coating layer was about 25 ⁇ m.
  • An average thickness of each of the film and the wavelength conversion layer formed on the matrix was about 150 ⁇ 5 nm and 220 nm, respectively.
  • Magnesium-containing samples with a size of 1 cm ⁇ 1 cm ⁇ 0.4 T were degreased by immersing in an alkaline cleaning solution, and the degreased samples were respectively immersed in a 10 wt% NaOH solution at 100 °C for 40 minutes, 1 hour and 2 hours. Thereafter, the sample was rinsed using distilled water and dried in a drying oven, and colors developed on the surface were evaluated with the naked eye.
  • the sample prepared by immersing in a 10 wt% NaOH solution has a faster coloring speed in comparison with that of a sample prepared by immersing in distilled water as a hydroxide solution. More specifically, the sample prepared by immersing in a 10 wt% NaOH solution was colored to have a silver color after 10 minutes of immersion, and changed to a yellow color, and then colored to have an orange color within 40 minutes. However, in the case of the sample in which the immersion time was 40 minutes, it was determined that a color change amount of the surface was slight and a color difference was not so large as compared to a non-color-treated substrate.
  • the color-treated substrate according to the present invention may develop a diversity of colors such as an achromatic color such as a black color, a grey color or the like as well as a blue color, a green color or the like on the surface of the substrate by forming the nanometer scale film and wavelength conversion layer having a specific ratio, and a color may be selectively developed in accordance with the average thickness of the film.
  • an achromatic color such as a black color, a grey color or the like as well as a blue color, a green color or the like
  • a color may be selectively developed in accordance with the average thickness of the film.
  • the color-treated sample of Example 4 having a top coat formed thereon was uniformly sprayed with 5 wt% salt water at 35 °C using a salt spray tester (SST), and surface corrosion resistance of the sample; and adhesiveness between the color-treated substrate and the top coat formed on the surface were evaluated after 72 hours of spraying salt water had passed.
  • the adhesiveness was evaluated using a cross-cut tape test method.
  • the adhesiveness was evaluated using a method, in which a coated top coat was cut to have 6 vertical cuts and 6 horizontal cuts intersecting one another and formed at 1 mm intervals using a knife, the tape was firmly attached to the intersection points of the vertical cuts and horizontal cuts, and the area of the top coat which is detached when the tape was quickly detached with respect to the total area of the sample was measured.
  • the color-treated substrate having the top coat formed thereon according to the present invention has excellent corrosion resistance, and outstanding adhesiveness between the color-treated substrate and the top coat. More specifically, it was determined that no deformation of the surface due to corrosion occurred in the case of the sample having a matte top coat formed thereon in Example 4. Further, as a result of evaluating the adhesiveness of the sample on which a corrosion resistance test was performed, it was determined that the area of the top coat which is detached due to the tape is 5% or less based on the total area of the top coat.
  • the color-treated substrate having a top coat formed thereon according to the present invention has excellent corrosion resistance as well as outstanding adhesiveness between a color-treated substrate and a top coat.
  • the color-treated substrate according to the present invention can maintain the intrinsic texture and gloss of metals of a substrate, improve the durability of the substrate and uniformly realize a variety of colors including a blue color, a green color, an achromatic color such as a black color on the surface of the substrate by including a nanometer-scale film and wavelength conversion layer which have a specific ratio on the substrate, and thus can be usefully used in the fields of building exterior materials, automobile interiors, and particularly electrical and electronic component materials, such as mobile product frames, in which a metal material is used.
  • the color-treated substrate according to the present invention can maintain a texture of metals and gloss of a substrate, improve durability of the substrate and uniformly realize a variety of colors including a blue color, a green color, an achromatic color such as a black color on the surface of the substrate, and thus can be usefully used in the fields of building exterior materials, automobile interiors, and particularly electrical and electronic component materials, such as mobile product frames, in which a metal material is used.

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  • Chemical & Material Sciences (AREA)
  • Metallurgy (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Treatment Of Metals (AREA)
  • Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
  • Laminated Bodies (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
EP14873790.1A 2013-12-26 2014-12-26 Farbbehandeltes basismaterial und basismaterialfarbbehandlungsverfahren dafür Active EP3088562B1 (de)

Applications Claiming Priority (5)

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KR1020130164045A KR101543925B1 (ko) 2013-12-26 2013-12-26 패터닝된 발색 마그네슘 및 이를 위한 마그네슘의 패터닝 방법
KR1020130164046A KR101543926B1 (ko) 2013-12-26 2013-12-26 발색 처리된 마그네슘 및 이를 위한 마그네슘 발색 처리방법
KR1020130164047A KR101584413B1 (ko) 2013-12-26 2013-12-26 표면 처리 금속 및 이를 위한 금속재의 표면 처리 방법
KR1020130164044A KR101543924B1 (ko) 2013-12-26 2013-12-26 발색 처리된 마그네슘 및 이를 위한 마그네슘 발색 처리방법
PCT/KR2014/012926 WO2015099503A1 (ko) 2013-12-26 2014-12-26 발색 처리된 기재 및 이를 위한 기재의 발색 처리방법

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EP3088562A1 true EP3088562A1 (de) 2016-11-02
EP3088562A4 EP3088562A4 (de) 2017-03-08
EP3088562B1 EP3088562B1 (de) 2019-05-08

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EP14875156.3A Active EP3088565B9 (de) 2013-12-26 2014-12-26 Mit farbentwicklung behandeltes substrat und substratfarbentwicklungsbehandlungsverfahren dafür
EP14874603.5A Active EP3088563B1 (de) 2013-12-26 2014-12-26 Oberflächenbehandeltes substrat und oberflächenbehandlungsverfahren dafür
EP14874919.5A Active EP3088564B1 (de) 2013-12-26 2014-12-26 Farbbehandeltes basismaterial und basismaterialfarbbehandlungsverfahren dafür
EP14875687.7A Active EP3088566B1 (de) 2013-12-26 2014-12-26 Mit farbentwicklung behandeltes substrat und substratfarbentwicklungsbehandlungsverfahren dafür

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EP14874603.5A Active EP3088563B1 (de) 2013-12-26 2014-12-26 Oberflächenbehandeltes substrat und oberflächenbehandlungsverfahren dafür
EP14874919.5A Active EP3088564B1 (de) 2013-12-26 2014-12-26 Farbbehandeltes basismaterial und basismaterialfarbbehandlungsverfahren dafür
EP14875687.7A Active EP3088566B1 (de) 2013-12-26 2014-12-26 Mit farbentwicklung behandeltes substrat und substratfarbentwicklungsbehandlungsverfahren dafür

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US11751349B2 (en) 2019-05-28 2023-09-05 Apple Inc. Anodized part having a matte black appearance

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CN111962054A (zh) * 2020-08-28 2020-11-20 湖州冠居金属装饰材料股份有限公司 一种适用于仿古建筑的铜装饰品着色方法

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US11751349B2 (en) 2019-05-28 2023-09-05 Apple Inc. Anodized part having a matte black appearance
US11614778B2 (en) 2019-09-26 2023-03-28 Apple Inc. Anodized part having low reflectance of visible and near-infrared light

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Publication number Publication date
EP3088565B1 (de) 2019-06-12
EP3088565B9 (de) 2019-10-23
EP3088563A1 (de) 2016-11-02
CN105849313A (zh) 2016-08-10
EP3088565A4 (de) 2017-03-08
CN105849314A (zh) 2016-08-10
EP3088564B1 (de) 2019-05-22
CN105849315A (zh) 2016-08-10
EP3088562B1 (de) 2019-05-08
EP3088566A4 (de) 2017-03-08
EP3088563A4 (de) 2017-03-08
EP3088566B1 (de) 2018-08-15
EP3088566A1 (de) 2016-11-02
EP3088564A1 (de) 2016-11-02
EP3088564A4 (de) 2017-03-08
CN105849313B (zh) 2018-03-09
EP3088565A1 (de) 2016-11-02
EP3088562A4 (de) 2017-03-08
CN105849314B (zh) 2018-06-26
CN105849315B (zh) 2018-09-21
EP3088563B1 (de) 2019-05-15

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