EP3088565A1 - Substrat traité avec développement de couleur et procédé de traitement de substrat avec développement de couleur pour ce dernier - Google Patents

Substrat traité avec développement de couleur et procédé de traitement de substrat avec développement de couleur pour ce dernier Download PDF

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EP3088565A1
EP3088565A1 EP14875156.3A EP14875156A EP3088565A1 EP 3088565 A1 EP3088565 A1 EP 3088565A1 EP 14875156 A EP14875156 A EP 14875156A EP 3088565 A1 EP3088565 A1 EP 3088565A1
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Prior art keywords
color
film
matrix
hydroxide solution
treated substrate
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EP14875156.3A
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German (de)
English (en)
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EP3088565B1 (fr
EP3088565A4 (fr
EP3088565B9 (fr
Inventor
Hyunju JEONG
Yon-Kyun Song
Min Hong Seo
Kanghwan AHN
Yeong-Woo Jeon
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Posco Holdings Inc
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Posco Co Ltd
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Priority claimed from KR1020130164047A external-priority patent/KR101584413B1/ko
Priority claimed from KR1020130164046A external-priority patent/KR101543926B1/ko
Priority claimed from KR1020130164045A external-priority patent/KR101543925B1/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/KR2014/012931 external-priority patent/WO2015099505A1/fr
Publication of EP3088565A1 publication Critical patent/EP3088565A1/fr
Publication of EP3088565A4 publication Critical patent/EP3088565A4/fr
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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 including magnesium and a substrate color treatment method therefor, and specifically, to a color-treated substrate including magnesium which maintains a texture and gloss of metals and uniformly develops a variety of colors, 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 color-treated substrate including magnesium, which maintains the texture and gloss of metals and uniformly develops a variety of colors.
  • Another objective of the present invention is to provide a method of color-treating the substrate.
  • an 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, wherein the film has a structure in which crystals having a plate-shaped structure and an average size in the range of 50 to 100 nm, and containing a compound represented by the following Chemical Formula 1 are stacked such that an average tilt angle formed by a surface of the matrix or a plane which is parallel with the surface of the matrix, and any axis existing on a major axis plane of the crystal is 30° or less: [Chemical Formula 1] M(OH) m where M includes one or more selected from the group consisting of Na, K, Mg, Ca and Ba, and m is 1 or 2.
  • the color-treated substrate according to the present invention can maintain an intrinsic texture and glossiness of metals and uniformly develop a variety of colors by controlling an average thickness of a film according to the degree of stacking of crystals, 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 green color
  • a b* value represents whether a color at a corresponding color coordinate leans toward a pure yellow color or a pure 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 green color.
  • a* value when an a* value is negative, a color leans toward a pure green color, and when an a* value is positive, a color leans toward pure magenta color.
  • 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 blue color.
  • b* max represents a pure yellow color
  • b* min represents a pure blue color.
  • a unit “T”, as used herein, represents a thickness of a substrate including magnesium, and is the same as a unit “mm”.
  • tilt angle ⁇ refers to the largest angle among angles formed by a surface of the matrix or a plane which is parallel with the surface of the matrix, and any axis existing on a major axis plane of the crystal.
  • the present invention provides a color-treated substrate including magnesium 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.
  • the intrinsic texture of metals is not realized in these methods, and thus they are difficult to be applied 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 present invention suggests a color-treated substrate including magnesium and a substrate color treatment method therefor according to the present invention.
  • the color-treated substrate according to the present invention includes a film which has a structure in which crystals having a plate-shaped structure are horizontally uniform and densely stacked on a matrix containing magnesium, and thus may maintain the intrinsic texture and glossiness of metals and uniformly develop a variety of colors on a surface by controlling an average thickness of a film according to the degree of stacking of the crystals.
  • An embodiment of the present invention provides color-treated substrate, including:
  • the color-treated substrate may satisfy the condition of Expression 1 as follows: 30° or less, 29° or less, 28° or less, 27° or less or 26° or less.
  • the color-treated substrate according to the present invention includes a matrix containing magnesium and a film, and develops a color on a surface by scattering and refracting light incident to the surface through the film disposed on the matrix.
  • the film may have a structure in which crystals having a plate-shaped structure and containing a compound represented by Chemical Formula 1 are stacked, and the compound represented by Chemical Formula 1 may be 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 be magnesium hydroxide (Mg(OH) 2 ).
  • NaOH sodium hydroxide
  • KOH potassium hydroxide
  • Mg(OH) 2 magnesium hydroxide
  • Ca(OH) 2 calcium hydroxide
  • Ba(OH) 2 barium hydroxide
  • the color-treated substrate may have 2 ⁇ diffraction peak values of 18.5 ⁇ 1.0°, 38.0 ⁇ 1.0°, 50.5 ⁇ 1.0°, 58.5 ⁇ 1.0°, 62.0 ⁇ 1.0° and 68.5 ⁇ 1.0° when an X-ray diffraction measurement is performed on the surface provided with the film, and the diffraction peak values may satisfy a condition of the following Expression 2: P 1 / P 2 ⁇ 0.9 where P 1 is an intensity of a diffraction peak of 18.5 ⁇ 1.0° at 2 ⁇ , and P 2 is an intensity of a diffraction peak of 38.0 ⁇ 1.0° at 2 ⁇ .
  • the substrate has a ratio between P 1 and P 2 of 0.9 or more, 1.0 or more, 1.1 or more, 1.2 or more or 1.5 or more to satisfy the condition of Expression 2.
  • the size of crystals of the film is not particularly limited, but the average size of the crystals may be in the range of 50 to 100 nm.
  • fine and uniform particles in a tissue reduce defect size and residual stress which may become the cause of a decrease in strength occurring in the tissue, and thus may increase the strength of the tissue. That is, when the crystals have an average size in the range of 50 to 100 nm, crystals may be horizontally uniform and densely stacked on a matrix without forming empty spaces between the crystals, and thus not only may prevent diffusion of light incident to a substrate surface to maintain the intrinsic texture and gloss of metals, but also may improve durability of the substrate.
  • the surface of the color-treated substrate was observed with the naked eye and using a scanning electron microscope (SEM). As a result, it can be confirmed with the naked eye that the color-treated substrate maintains the intrinsic gloss of metals and has a uniformly developed color. Furthermore, from the results of observation by scanning electron microscopy, it can be determined that the surface of the substrate has a structure in which crystals having a size in the range of about 50 to 100 nm are horizontally and densely stacked on a surface of a matrix such that an average tilt angle ⁇ formed by the surface of the matrix and any axis existing on a major axis plane of the crystal is 30° or less.
  • the color-treated substrate according to the present invention includes a film in which crystals having a plate-shaped structure are uniformly and densely stacked on a matrix containing magnesium, and satisfies the condition of Expression 1 (refer to Experimental Example 3).
  • the color-treated substrate according to the present invention may realize a variety of colors by controlling an average thickness of a film formed on a matrix.
  • the film may adjust a developed color by controlling properties of incident light transmitted to a matrix surface and light reflected from the matrix surface according to the average thickness of the film.
  • the average thickness of the film is not particularly limited, but may be in the range of 1 to 900 nm, specifically, in the range of 1 to 800 nm; 1 to 700 nm; or 1 to 600 nm.
  • the color-treated substrate according to the present invention may further include a wavelength conversion layer and a top coat formed on the film.
  • the top coat may be further included in order to improve scratch resistance and durability of the surface of the substrate including magnesium.
  • 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 coatings of metals, metal oxides or metal hydroxides. 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.
  • 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, a peel rate of the top coat may be 5% or less.
  • 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, wherein the film has a structure in which a crystal having a plate-shaped structure and an average size in the range of 50 to 100 nm, and containing a compound represented by the following Chemical Formula 1 is stacked such that an average tilt angle formed by a surface of the matrix or a plane which is parallel with the surface of the matrix, and any axis existing on a major axis plane of the crystal is 30° or less: [Chemical Formula 1] M(OH) m where M includes one or more selected from the group consisting of Na, K, Mg, Ca and Ba, and m is 1 or 2,
  • the method of color-treating the substrate according to the present invention includes a step of forming a film on a matrix containing magnesium, and the method for performing the step of forming the film is not particularly limited as long as the method is a generally used to form a film on a metal substrate in the related field.
  • the film may be formed by immersing the substrate including magnesium in a hydroxide solution.
  • the hydroxide solution is not particularly limited as long as the solution includes a hydroxyl group (-OH group).
  • the 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 present invention has an advantage in that the film is uniformly formed on the matrix surface in a short time and the intrinsic gloss and texture of metals are maintained by using the hydroxide solution as an immersion solution.
  • 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 concentration of the hydroxide solution may range from 1 to 20 wt%, and more specifically, from 1 to 15 wt%.
  • the temperature of the hydroxide solution may range from 90 to 200 °C, more specifically, from 100 to 150 °C, and even more specifically, from 95 to 110 °C.
  • the immersion time may be in the range of 1 to 180 minutes, and specifically, in the range of 5 to 90 minutes.
  • various colors may be economically realized on the surface of the substrate and the growth rate of crystals is easily controlled, and thus an excess increase in the average thickness of the film due to the overgrowth of crystals is prevented, and the intrinsic texture and gloss of metals may be maintained.
  • the step of forming the film may include: a first immersion step of immersing the matrix containing magnesium in a hydroxide solution with a concentration of N 1 ; and an n th immersion step of immersing the matrix in a hydroxide solution with a concentration of N n , and the first immersion step and the n th immersion step may be carried out using a method in which the concentration of the hydroxide solution satisfies the following Expressions 4 and 5 independently of each other, and n is an integer of 2 or more and 6 or less: 8 ⁇ N 1 ⁇ 25 N n ⁇ 1 ⁇ N n > 3 where N 1 and N n represent a concentration of a hydroxide solution in each step, and have units of wt%.
  • the step of immersing in the hydroxide solution is a step of realizing a color by forming a film on the surface of the substrate including magnesium, and the developed color may be controlled by adjusting the thickness of the formed film.
  • the thickness of the film may be controlled according to the concentration of the hydroxide solution, when the concentration of the hydroxide solution for immersing the matrix is divided into N 1 to N n , and specifically, N 1 to N 6 ; N 1 to N 5 ; N 1 to N 4 ; N 1 to N 3 ; or N 1 to N 2 ; and the matrix is sequentially immersed therein, minute differences in the color realized on the surface may be controlled.
  • the method of color-treating the substrate according to the present invention substrate may further include one or more steps of: pretreating a surface 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. That is, 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 forming the film on the matrix, specifically 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.
  • a magnesium-containing sample with a size of 1 cm ⁇ 1 cm ⁇ 0.4 T was degreased by immersing in an alkaline cleaning solution, and the degreased sample was immersed in a 10 wt% NaOH solution at 100 °C for the time shown in Table 1. Thereafter, the sample was rinsed using distilled water and dried in a drying oven to prepare a color-treated sample.
  • Example 1 Immersion time Example 1 30 minutes
  • Example 2 80 minutes
  • a magnesium-containing sample with a size of 1 cm ⁇ 1 cm ⁇ 0.4 T was degreased by immersing in an alkaline cleaning solution, and the degreased sample was immersed in an immersion solution at 100 °C as shown in the following Table 2. Thereafter, the sample was rinsed using distilled water and dried in a drying oven to prepare a color-treated sample.
  • Table 2 Immersion solution Immersion time Comparative Example 1 10 wt% NaOH solution 240 minutes Comparative Example 2 Distilled water 40 minutes Comparative Example 3 Distilled water 60 minutes Comparative Example 4 Distilled water 120 minutes
  • X-ray diffraction of samples obtained in Examples 1 to 3, and Comparative Example 2 was measured.
  • Rigaku ultra-X CuKa radiation, 40 kV, 120 mA was used as a measuring device.
  • an X-ray diffraction pattern in the range of 10 to 80° at 2 ⁇ was obtained by radiation at a wavelength of 1.5406 ⁇ with a scanning speed of 0.02°/sec.
  • Example 1 10 wt% NaOH solution 30 200 ⁇ 50
  • Example 2 10 wt% NaOH solution 80 600 ⁇ 50
  • Example 3 10 wt% NaOH solution 170 800 ⁇ 50
  • the samples obtained in Examples 1 to 3 were determined to have 2 ⁇ diffraction peaks values of 18.5 ⁇ 1.0°, 38.0 ⁇ 1.0°, 50.5 ⁇ 1.0°, 58.5 ⁇ 1.0°, 62.0 ⁇ 1.0° and 68.5 ⁇ 1.0° of magnesium as a matrix. Further, it was determined that, in the diffraction peak values, intensities of peaks at 18.5 ⁇ 1.0° at 2 ⁇ were the highest, and had a ratio of about 1.66 to 4.8 with peaks at 38.0 ⁇ 1.0°at 2 ⁇ .
  • the diffraction peak values and patterns are the same as those of a brucite crystalline form, that is, magnesium hydroxide having a hexagonal shape, and thus indicates that the film formed on the matrix has a structure in which magnesium hydroxide (Mg(OH) 2 ) having hexagonal crystals and a plate-shaped structure are stacked.
  • Mg(OH) 2 magnesium hydroxide
  • 2 ⁇ diffraction peaks values of the sample obtained in Comparative Example 2 were similar to those of the samples of the examples, but intensities of peaks at 18.5 ⁇ 1.0° at 2 ⁇ were low, and had a ratio of about 0.4 with peaks at 38.0 ⁇ 1.0° at 2 ⁇ . This indicates that the film formed on the sample of Comparative Example 2 has a structure in which crystals of magnesium hydroxide are stacked, but the structure in which these crystals are stacked on the matrix is different from that of the examples.
  • the thickness of the film was determined to increase as immersion time increases. Specifically, in the case of the samples of Examples 1 to 3 of which the immersion time was respectively 30 minutes, 80 minutes and 170 minutes, it was determined that the average thickness of the film was 200 ⁇ 50 nm, 600 ⁇ 50 nm and 800 ⁇ 50 nm, respectively.
  • the color-treated substrate according to the present invention includes a film in which crystals having a plate-shaped structure and containing a compound represented by the following Chemical Formula 1 are stacked, and the average thickness of the film is in the range of 1 to 900 nm, which increases as the time of immersing the substrate increases.
  • a magnesium-containing sample with a size of 1 cm ⁇ 1 cm ⁇ 0.4 T was degreased by immersing in an alkaline cleaning solution, and the degreased sample was immersed in a 10 wt% NaOH solution at 100 °C for 170 minutes.
  • the color of the surface of the sample was observed with the naked eye at intervals of 5 to 10 minutes immediately after the sample was immersed in the NaOH solution to determine a developed color.
  • any three points A to C which are present on each surface of the samples which were color-treated in Examples 2 and 3 were selected, and measurement of color coordinates in a CIE color space of the selected points were repeated 4 times to calculate average color coordinates (L*, a*, b*) and color coordinate deviations.
  • the color-treated substrate according to the present invention may develop a variety of colors on the surface according to immersion time.
  • a silver color which is an intrinsic color of magnesium is maintained for 30 minutes, and then yellow, magenta, purple, navy and green colors were sequentially and uniformly developed. This indicates that a color developed on the matrix surface may be adjusted by controlling the immersion time of the matrix.
  • the color uniformity of the color developed on the color-treated substrate is excellent.
  • the color coordinate deviations of the sample of Example 2 were determined as 0.25 ⁇ L* ⁇ 0.30, 0.15 ⁇ a* ⁇ 0.20, 0.15 ⁇ b* ⁇ 0.20 and ⁇ E* ⁇ 0.400.
  • the color coordinate deviations of the sample of Example 3 were determined as 0.20 ⁇ L* ⁇ 0.25, 0.15 ⁇ a* ⁇ 0.20, 0.35 ⁇ b* ⁇ 0.40 and 0.45 ⁇ E* ⁇ 0.500, that is, deviations were small.
  • a variety of colors may be uniformly developed on the surface of the substrate by controlling a time of immersing the matrix containing magnesium in a hydroxide solution with a concentration of 1 to 20 wt% and a temperature of 50 to 200 °C, such as a NaOH, KOH, Mg(OH) 2 , Ca(OH) 2 and Ba(OH) 2 solution.
  • the samples of Examples 1 and 2 includes a film in which crystals having an average size in the range of 50 to 100 nm and having a plate-shaped structure are stacked. Further, it can be determined that almost no gap is present between the crystals forming the film. This indicates that an average tilt angle formed by the surface of the matrix, and any axis existing on the major axis plane of the crystal is 30° or less, that is, the average tilt angle is low.
  • the average size of the crystals forming the film is more than 100 nm and the surface is not uniform. Further, it can be determined that the samples according to Comparative Examples 2 and 4 include a film having a structure in which an average tilt angle formed by the surface of the matrix, and any axis existing on the major axis plane of the crystal is in the range of about 75 to 105°, and crystals form an irregular network.
  • crystals having a plate-shaped structure are horizontally and densely stacked on a matrix by immersing the matrix containing magnesium in a hydroxide solution with a concentration of 1 to 20 wt% and a temperature of 50 to 200 °C, such as a NaOH, KOH, Mg(OH) 2 , Ca(OH) 2 and Ba(OH) 2 solution. Further, it can be determined that a substrate on which a color is uniformly developed may be obtained by this stacked structure, without a decrease in the intrinsic glow of metals.
  • the color-treated substrate according to the present invention can maintain an intrinsic texture of metals and glossiness and uniformly develop a variety of colors by controlling an average thickness of a film according to the degree of stacking of crystals, 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)
EP14875156.3A 2013-12-26 2014-12-26 Substrat traité avec développement de couleur et procédé de traitement de substrat avec développement de couleur pour ce dernier Active EP3088565B9 (fr)

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KR1020130164046A KR101543926B1 (ko) 2013-12-26 2013-12-26 발색 처리된 마그네슘 및 이를 위한 마그네슘 발색 처리방법
KR1020130164045A KR101543925B1 (ko) 2013-12-26 2013-12-26 패터닝된 발색 마그네슘 및 이를 위한 마그네슘의 패터닝 방법
KR1020130164044A KR101543924B1 (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
PCT/KR2014/012931 WO2015099505A1 (fr) 2013-12-26 2014-12-26 Substrat traité avec développement de couleur et procédé de traitement de substrat avec développement de couleur pour ce dernier

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EP3088565A4 EP3088565A4 (fr) 2017-03-08
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EP14875156.3A Active EP3088565B9 (fr) 2013-12-26 2014-12-26 Substrat traité avec développement de couleur et procédé de traitement de substrat avec développement de couleur pour ce dernier
EP14873790.1A Active EP3088562B1 (fr) 2013-12-26 2014-12-26 Matière de base à traitement de couleur et procédé de traitement de couleur de matière de base correspondant
EP14874603.5A Active EP3088563B1 (fr) 2013-12-26 2014-12-26 Substrat traité en surface et procédé de traitement de surface pour celui-ci
EP14875687.7A Active EP3088566B1 (fr) 2013-12-26 2014-12-26 Substrat traité avec développement de couleur et procédé de traitement de substrat avec développement de couleur pour ce dernier

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EP14875687.7A Active EP3088566B1 (fr) 2013-12-26 2014-12-26 Substrat traité avec développement de couleur et procédé de traitement de substrat avec développement de couleur pour ce dernier

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107849701A (zh) * 2015-07-10 2018-03-27 Posco公司 经显色处理的基板及用于其的显色处理方法
CN112020248B (zh) * 2019-05-28 2021-12-10 苹果公司 具有糙面黑色外观的阳极化部件
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

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB532878A (en) * 1938-08-12 1941-02-03 Dow Chemical Co Improved method of producing coloured corrosion-resistant coatings upon articles of magnesium or its alloys
US2250473A (en) * 1940-05-24 1941-07-29 Dow Chemical Co Coating magnesium articles
JP2002047597A (ja) * 2000-08-01 2002-02-15 Boshin Ro マグネシウム又はその合金用電解発色剤及び電解発色法
KR20090088199A (ko) * 2008-02-14 2009-08-19 주식회사 미래 엠. 텍. 마그네슘계 금속의 아노다이징 표면처리 방법
KR100998029B1 (ko) * 2008-02-27 2010-12-03 (주) 유원컴텍 마그네슘재의 착색 방법 및 이에 의하여 착색된 마그네슘재
JP2010030191A (ja) * 2008-07-30 2010-02-12 Chiba Inst Of Technology 耐食性、耐熱性マグネシウム複合材料及びその製造方法
JP5334499B2 (ja) * 2008-08-29 2013-11-06 新日鐵住金株式会社 塗装密着性に優れた表面処理金属板およびその製造方法
JP2010265522A (ja) * 2009-05-15 2010-11-25 Kansai Paint Co Ltd 発色金属の保護方法
KR101765906B1 (ko) * 2010-08-19 2017-08-07 엘지이노텍 주식회사 아노다이징을 이용한 회로기판 및 그 제조 방법
KR101238895B1 (ko) * 2010-12-28 2013-03-04 재단법인 포항산업과학연구원 표면 조직이 치밀한 마그네슘 합금 및 그 표면 처리 방법
JP5705054B2 (ja) * 2011-07-26 2015-04-22 独立行政法人産業技術総合研究所 マグネシウム合金材、およびマグネシウム合金の表面処理方法

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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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EP3088562A4 (fr) 2017-03-08
CN105849313A (zh) 2016-08-10
CN105849314A (zh) 2016-08-10
EP3088564B1 (fr) 2019-05-22
CN105849315B (zh) 2018-09-21
EP3088564A1 (fr) 2016-11-02
EP3088566B1 (fr) 2018-08-15
EP3088566A4 (fr) 2017-03-08
EP3088563A1 (fr) 2016-11-02
EP3088562A1 (fr) 2016-11-02
EP3088564A4 (fr) 2017-03-08
EP3088565B1 (fr) 2019-06-12
CN105849313B (zh) 2018-03-09
EP3088563A4 (fr) 2017-03-08
EP3088566A1 (fr) 2016-11-02
EP3088565A4 (fr) 2017-03-08
EP3088562B1 (fr) 2019-05-08
EP3088563B1 (fr) 2019-05-15
EP3088565B9 (fr) 2019-10-23
CN105849314B (zh) 2018-06-26
CN105849315A (zh) 2016-08-10

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