WO2018126789A1 - 铝合金染色用黑色染料的制备方法、铝合金的染色方法 - Google Patents

铝合金染色用黑色染料的制备方法、铝合金的染色方法 Download PDF

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WO2018126789A1
WO2018126789A1 PCT/CN2017/110666 CN2017110666W WO2018126789A1 WO 2018126789 A1 WO2018126789 A1 WO 2018126789A1 CN 2017110666 W CN2017110666 W CN 2017110666W WO 2018126789 A1 WO2018126789 A1 WO 2018126789A1
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dye
aluminum alloy
dyeing
black
black dye
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PCT/CN2017/110666
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English (en)
French (fr)
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王天宇
周尤尚
张波
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广东长盈精密技术有限公司
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
    • C09B67/0033—Blends of pigments; Mixtured crystals; Solid solutions
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
    • C09B67/0071—Process features in the making of dyestuff preparations; Dehydrating agents; Dispersing agents; Dustfree compositions
    • C09B67/0083—Solutions of dyes
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/04—Anodisation of aluminium or alloys based thereon
    • C25D11/06—Anodisation of aluminium or alloys based thereon characterised by the electrolytes used
    • C25D11/08—Anodisation of aluminium or alloys based thereon characterised by the electrolytes used containing inorganic acids
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/04—Anodisation of aluminium or alloys based thereon
    • C25D11/06—Anodisation of aluminium or alloys based thereon characterised by the electrolytes used
    • C25D11/10—Anodisation of aluminium or alloys based thereon characterised by the electrolytes used containing organic acids
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/04—Anodisation of aluminium or alloys based thereon
    • C25D11/18—After-treatment, e.g. pore-sealing
    • C25D11/24—Chemical after-treatment
    • C25D11/243—Chemical after-treatment using organic dyestuffs

Definitions

  • the invention relates to the technical field of dyes, in particular to a method for preparing a black dye for dyeing aluminum alloys and a method for dyeing aluminum alloys.
  • a method for preparing a black dye for dyeing aluminum alloy comprising the following steps:
  • a red black dye, a cyan dye, and a red dye in a solvent to obtain a mixed solution having a concentration of 1.0 g/L to 2.0 g/L in the mixed solution, wherein the blue-green dye is in the
  • the concentration in the mixed solution is 1.0g / L ⁇ 1.5g / L
  • the concentration of the red dye in the mixed liquid is 0.5g / L ⁇ 1.0g / L;
  • a pH stabilizer is added to the mixed solution, and the concentration of the pH stabilizer in the mixed solution is 10 g/L to 15 g/L to obtain a black dye for dyeing the aluminum alloy.
  • the concentration of the red-black dye in the mixed solution is 1.5 g/L, and the concentration of the blue-green dye in the mixed solution is 1.25 g/L, and the red dye is in the In the mixture The concentration was 0.75 g/L.
  • the red-black dye is Okuno dye 402
  • the cyan dye is Okuno dye 411
  • the red dye is Okuno dye 102.
  • the solvent is water.
  • the pH of the mixed solution in the operation of adjusting the pH of the mixed solution to 5.0 to 5.5, is adjusted to 5.0 to 5.5 by the addition of sodium hydroxide.
  • the pH stabilizer is selected from at least one of ammonium chloride and sodium acetate.
  • the concentration of the pH stabilizer in the mixture is 12.5 g/L.
  • a method for dyeing an aluminum alloy comprising the following steps:
  • the anodized aluminum alloy was immediately immersed in the black dye for dyeing.
  • the anodizing aluminum alloy is immediately immersed in the black dye before the operation of dyeing, further comprising immersing the aluminum alloy in the electrolyte, using the aluminum alloy as an anode,
  • the electrolytic solution is electrolyzed under the conditions of a voltage of 15 V to 22 V and a temperature of 14 ° C to 22 ° C to form an oxide film on the surface of the aluminum alloy to obtain the anodized aluminum alloy.
  • the anodized aluminum alloy is immediately immersed in the dyeing operation in the black dye, the dyeing time is 2 min to 10 min, and the temperature of the black dye is controlled to be constant during the dyeing process.
  • the black dye prepared by the method for preparing the black dye for aluminum alloy dyeing includes 1.0 g/L to 2.0 g/L of red-black dye, 1.0 g/L to 1.5 g/L of cyan dye, and 0.5 g/L to 1.0 g. /L red dye.
  • the inventors have unexpectedly found that the above ratio of red-black dye, blue-green dye, and red dye are mixed to adjust the pH to 5.0-5.5, and the black dye formed by adding 10g/L to 15g/L of pH stabilizer is more than the conventional black dye. Suitable for dyeing aluminum alloys, it is easy to dye aluminum alloys in black.
  • the mixed black dye is colored in the pores of the oxide film formed after the anodization, and the black dye and the oxide film are integrated in a stable state due to the sealing treatment.
  • the adsorption speed of each dye is different.
  • the black dye dyed by the above method can maintain the stability and timeliness of the aluminum alloy color, and it is easy to dye the aluminum alloy into color stability and coloring. Durable black.
  • FIG. 1 is a flow chart showing a method of preparing a black dye for dyeing an aluminum alloy according to an embodiment
  • Fig. 2 is a flow chart showing a method of dyeing an aluminum alloy according to an embodiment.
  • a method for preparing a black dye for dyeing aluminum alloy includes the following steps S110 to S130.
  • a red black dye, a cyan dye, and a red dye may be added depending on the total volume of the black dye for the aluminum alloy dyeing to be configured to obtain a mixed liquid.
  • the solvent for the black dye for aluminum alloy dyeing may be water.
  • a red black dye, a blue-green dye, and a red dye are dissolved in water to obtain a mixed solution, wherein the concentration of the red-black dye in the mixed solution is 1.5 g/L, and the concentration of the blue-green dye in the mixed solution is At 1.25 g/L, the concentration of the red dye in the mixture was 0.75 g/L.
  • the red-black dye is Okuno dye 402
  • the cyan dye is Okuno dye 411
  • the red dye is Okuno dye 102.
  • Okuno dye is supplied by Okuno Corporation of Japan
  • 402, 411, and 102 are product numbers, respectively.
  • Okuno dye 402 is generally reddish black
  • Okuno dye 411 is generally blue-green
  • Okuno dye 102 is generally red. It can be understood that in other embodiments, the dyes provided by other manufacturers may also be used to ensure the ratio of the red black dye, the blue green dye and the red dye.
  • the difference in dye ratio and pH of each color will affect the stability of the final mixed black dye color system and the durability of coloring, especially for black.
  • the inventors have found that by setting the pH of the mixed solution to 5.0 to 5.5, the black dye is weakly acidic, and the aluminum alloy can be uniformly colored to form a black aluminum alloy.
  • the red black dye, the blue-green dye, and the red dye are dissolved in a solvent to obtain an acidic mixture, and the pH of the mixed solution can be adjusted to 5.0 to 5.5 by adding sodium hydroxide.
  • the pH of the mixed solution can be adjusted to 5.25 by adding sodium hydroxide.
  • a pH stabilizer is added to the mixed solution obtained in S120, and the concentration of the pH stabilizer in the mixed solution is 10 g/L to 15 g/L to obtain a black dye for dyeing an aluminum alloy.
  • a pH stabilizer stabilizes the pH of the mixture of the red-black dye, the cyan dye, and the red dye to ensure uniformity of coloration.
  • the concentration of the pH stabilizer in the mixed solution is 12.5 g/L.
  • the pH stabilizer is selected from at least one of ammonium chloride and sodium acetate. After the red black dye, the blue-green dye and the red dye are mixed, it is difficult to form a stable dye due to the difference in acidity and alkalinity of the three, and the addition of the pH stabilizer can stabilize the mixed dye, uniformly dye, and dye the aluminum alloy after black. The color is stable and the coloring is durable.
  • the black dye prepared by the method for preparing the black dye for aluminum alloy dyeing includes 1.0 g/L to 2.0 g/L of red-black dye, 1.0 g/L to 1.5 g/L of cyan dye, and 0.5 g/L to 1.0 g. /L red dye.
  • the above-mentioned ratio of red black dye, blue green dye and red dye is mixed to adjust the pH value to 5.0-5.5, and the black dye formed by adding 10 g/L to 15 g/L of pH stabilizer is more suitable for the aluminum alloy than the conventional black dye.
  • Dyeing, the aluminum alloy can be easily dyed black.
  • the present invention further provides a method for dyeing an aluminum alloy according to an embodiment, comprising the following steps S210 to S220.
  • the black dye for aluminum alloy dyeing is prepared by a method for preparing a black dye for dyeing aluminum alloy according to any one of the above methods.
  • the black dye for dyeing aluminum alloy includes a red black dye of 1.0 g/L to 2.0 g/L, A blue-green dye of 1.0 g/L to 1.5 g/L, a red dye of 0.5 g/L to 1.0 g/L, and a pH stabilizer of 10 g/L to 15 g/L, and the pH of the black dye is 5.0 to 5.5.
  • the black dye for aluminum alloy dyeing comprises 1.5 g/L of red-black dye, 1.25 g/L of cyan dye, 0.75 g/L of red dye, and 12.5 g/L of pH stabilizer and balance.
  • the pH of the water, black dye to 5.25.
  • the red-black dye is Okuno dye 402
  • the cyan dye is Okuno dye 411
  • the red dye is Okuno dye 102.
  • the anodized aluminum alloy is immediately immersed in the black dye obtained in S210 for dyeing.
  • An oxidized film is formed on the surface of the anodized aluminum alloy, and is immediately immersed in the black dye.
  • the surface of the oxide film is also charged, and the sulfonic acid group [D(-SO 3 Na) - ] of the dye is It has a negative charge and is adsorbed into the pores of the positively charged anodized film ⁇ Al(H 2 O) 4 (OH) 2+ ⁇ AlO n+ >.
  • the adsorption of the dye generally only enters 1/2 to 1/3 of the thickness of the oxide film because of the action of static electricity, and the entered dye is adsorbed in the pore by ion binding and acid precipitation.
  • the black dye prepared by the method of the invention has different adsorption speeds of each dye in the process of coloring, and the dyes of the plurality of color systems are mixed to form a mixed dye into the micropores of the anodized film for coloring, and then, due to the sealing treatment, It is in a stable state with the anodized film, and the color system changes uniformly, so that the aluminum alloy is dyed into a stable and durable black.
  • the anodized aluminum alloy is immediately immersed in the dyeing operation of the black dye, and further includes immersing the aluminum alloy in the electrolyte, using the aluminum alloy as the anode, at a voltage of 15V to 22V, and a temperature.
  • the electrolytic solution is electrolyzed under the conditions of 14 ° C to 22 ° C to form an oxide film on the surface of the aluminum alloy to obtain an anodized aluminum alloy.
  • the electrolytic solution may be, for example, concentrated sulfuric acid of 80 g/L to 140 g/L and oxalic acid of 10 g/L to 50 g/L.
  • the electrolyte mixed with concentrated sulfuric acid and oxalic acid makes the prepared oxide film uniform and not easy to fall off.
  • the aluminum alloy on which the oxide film is formed is immersed in the black dye, and the black dye can enter the micropores of the oxide film to form a stable black color.
  • the anodized aluminum alloy is immediately immersed in the dyeing operation of the black dye, the dyeing time is 2 min to 10 min, and the temperature of the black dye is controlled to be constant during the dyeing process.
  • the temperature range of dyeing may be, for example, 20 ° C to 25 ° C. Constant temperature ensures uniformity of dyeing, and the mixed black dye enters the micropores of the oxide film formed after anodization, and then the black dye and oxide film become sealed due to the sealing treatment. The whole is in a stable state. In the process of coloring, the adsorption speed of each dye is different.
  • the black dye dyed by the above method can maintain the stability and timeliness of the color of the aluminum alloy, and is easy to dye the aluminum alloy into color stable and durable. black.
  • the anodized aluminum alloy is immediately immersed in a black dye, and the black dye is colored at the same time, and the dyes of the various dyes are mixed to form a mixed dye.
  • the anodized film is colored in the micropores, and after the sealing treatment, it can be integrated with the anodized film in a stable state, and the color system changes uniformly, thereby dyeing the aluminum alloy into a stable and durable black.
  • the process is simple and can be widely applied to dyeing the outer casing of electronic products such as mobile phones and computers made of aluminum alloy.
  • the mixture of Okuno Dye 402, Okuno Dye 411, and Okuno Dye 102 was dissolved in water to obtain a mixed solution, wherein the amount of Okuno Dye 402 added was 1.5 g/L, and the amount of Okuno Dye 411 was 1.25 g/L, and the addition of Okuno Dye 102 was carried out. The amount is 0.75 g/L.
  • the pH of the mixture was adjusted to 5.25 by the addition of NaOH. And adding 12.5 g/L of ammonium chloride to the mixture, and mixing to obtain a black dye for dyeing the aluminum alloy.
  • the mixture of Okuno dye 402, Okuno dye 411, and Okuno dye 102 was dissolved in water to obtain a mixed solution.
  • the amount of Okuno dye 402 was 1.0 g/L
  • the amount of Okuno dye 411 was 1.0 g/L
  • the amount of Okuno dye 102 was 1.0g/L.
  • the pH of the mixture was adjusted to 5.0 by the addition of NaOH. 10 g/L of sodium acetate was added to the mixed solution to obtain a black dye for dyeing an aluminum alloy.
  • the mixture of Okuno dye 402, Okuno dye 411, and Okuno dye 102 was dissolved in water to obtain a mixed solution.
  • the amount of Okuno dye 402 was 2.0 g/L
  • the amount of Okuno dye 411 was 1.5 g/L
  • the amount of Okuno dye 102 was 0.5g/L.
  • the pH of the mixture was adjusted to 5.5 by the addition of NaOH.
  • 15 g/L of ammonium chloride was added to obtain a black dye for dyeing an aluminum alloy.
  • the aluminum alloy was immersed in an electrolytic solution, and an aluminum alloy was used as an anode.
  • the electrolytic solution was electrolyzed under the conditions of a voltage of 18 V and a temperature of 18 ° C to form an oxide film on the surface of the aluminum alloy to obtain an anodized aluminum alloy.
  • the anodized aluminum alloy was immediately immersed in the obtained black dye prepared by the method of Example 1, and immersed and dyed at 23 ° C for 5 minutes.
  • the aluminum alloy was immersed in an electrolytic solution, and an aluminum alloy was used as an anode.
  • the electrolytic solution was electrolyzed under the conditions of a voltage of 15 V and a temperature of 22 ° C to form an oxide film on the surface of the aluminum alloy to obtain an anodized aluminum alloy.
  • the anodized aluminum alloy was immediately immersed in the obtained black dye prepared by the method of Example 2, and immersed and dyed at 20 ° C for 10 minutes.
  • the aluminum alloy was immersed in an electrolytic solution, and an aluminum alloy was used as an anode.
  • the electrolytic solution was electrolyzed under the conditions of a voltage of 22 V and a temperature of 14 ° C to form an oxide film on the surface of the aluminum alloy to obtain an anodized aluminum alloy.
  • the anodized aluminum alloy was immediately immersed in the obtained black dye prepared by the method of Example 3, and immersed and dyed at 25 ° C for 2 minutes.
  • the parameter conditions for dyeing the aluminum alloy in this embodiment are the same as those in the embodiment 4.
  • the different anodized aluminum alloys are immersed in a black dye of a common black color.
  • the Okuno used in the present embodiment is used.
  • 420 dye pure black dye.
  • the parameter conditions for dyeing the aluminum alloy in this example were the same as in Example 4 except that the aluminum alloy was not anodized and directly immersed in the dye for dyeing.
  • the aluminum alloy was dyed by the methods of Example 4 and Example 7, respectively, with 305 pieces of each method. After dyeing, the aluminum alloy is compared with the standard color plate. The color of the aluminum alloy is qualified in the standard color plate, and the black color is unqualified. The results are shown in Table 1 below:
  • the method of dyeing the aluminum alloy of Example 4 (using the black dye for dyeing aluminum alloy of the present invention) can be seen from Table 1, and the total defective ratio is 0%.
  • the dyeing is stable and can form a durable black on the surface of the aluminum alloy.
  • the aluminum alloy was dyed by the methods of Example 4 and Example 8, respectively, and the aluminum alloy was compared with the standard color plate after dyeing.
  • the color of the aluminum alloy was qualified in the standard color plate, and the deviation was black. qualified.
  • the results are shown in Table 2 below.
  • the method of dyeing the aluminum alloy of Example 4 (the aluminum alloy after the anodization was immediately immersed in the black dye for dyeing the aluminum alloy of the present invention) was dyed, and the total defective ratio was 0%.
  • the dyeing is stable and can form a durable black on the surface of the aluminum alloy.
  • the aluminum alloy was dyed by the methods of Examples 4 to 6, respectively, and 20 pieces were tested for each method. After dyeing, the aluminum alloy was compared with the standard color plate, and the color of the aluminum alloy was qualified in the standard color plate. Deviation from black is unqualified. The results show that after the methods of Examples 4 to 6 were applied to the aluminum alloy, the results of the 60 aluminum alloys were all black.

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Abstract

公开了一种铝合金染色用黑色染料的制备方法及一种采用该黑色染料的铝合金的染色方法。制备的黑色染料包括1.0g/L～2.0g/L的红黑色染料、1.0g/L～1.5g/L的蓝绿色染料以及0.5g/L～1.0g/L红色染料。上述配比的红黑色染料、蓝绿色染料、红色染料混合调节pH值至5.0～5.5，并加入10g/L～15g/L的pH稳定剂形成的黑色染料比传统的黑色染料更适宜对铝合金染色，能够容易的将铝合金染成黑色。特别是对经过阳极氧化后的铝合金进行染色时，这种混合黑色染料容易将铝合金染成颜色稳定、着色耐久的黑色。

Description

铝合金染色用黑色染料的制备方法、铝合金的染色方法 技术领域
本发明涉及染料技术领域，尤其是涉及一种铝合金染色用黑色染料的制备方法及一种铝合金的染色方法。
背景技术
大部分金属都是具有金属光泽的物质，但除去金和铜以外，其它金属都只有原色，使得金属形成的合金的颜色有限，难以实现手机外壳、电脑外壳及边框等电子产品颜色的多样化要求。其中黑色是区分染色方法的重要指标之一，目前我国制造业中最主要的黑色着色方法主要有有机染色法。有机染料一般有水溶性染料和油溶性染料之分，现在使用的大部分染料为水溶性有机染料。
然而，传统的染料很难将铝合金染成黑色。
发明内容
基于此，有必要提供一种容易将铝合金染成黑色的黑色染料的制备方法及一种铝合金的染色方法。
一种铝合金染色用黑色染料的制备方法，包括如下步骤：
将红黑色染料、蓝绿色染料以及红色染料溶于溶剂中得到混合液，所述红黑色染料在所述混合液中的浓度为1.0g/L～2.0g/L，所述蓝绿色染料在所述混合液中的浓度为1.0g/L～1.5g/L，所述红色染料在所述混合液中的浓度为0.5g/L～1.0g/L；
调节所述混合液的pH值至5.0～5.5；以及
向所述混合液中加入pH稳定剂，所述pH稳定剂在所述混合液中的浓度为10g/L～15g/L，得到所述铝合金染色用黑色染料。
在一个实施方式中，所述红黑色染料在所述混合液中的浓度为1.5g/L，所述蓝绿色染料在所述混合液中的浓度为1.25g/L，所述红色染料在所述混合液中的 浓度为0.75g/L。
在一个实施方式中，所述红黑色染料为奥野染料402，所述蓝绿色染料为奥野染料411，所述红色染料为奥野染料102。
在一个实施方式中，所述溶剂为水。
在一个实施方式中，调节所述混合液的pH值至5.0～5.5的操作中，通过加入氢氧化钠调节所述混合液的pH值至5.0～5.5。
在一个实施方式中，所述pH稳定剂选自氯化铵和醋酸钠中的至少一种。
在一个实施方式中，所述pH稳定剂在所述混合液中的浓度为12.5g/L。
一种铝合金的染色方法，包括如下步骤：
提供如权利要求1～7任一项所述的方法制备的铝合金染色用黑色染料；以及
将经过阳极氧化后的铝合金立刻浸泡在所述黑色染料中染色。
在一个实施方式中，所述将经过阳极氧化后的铝合金立刻浸泡在所述黑色染料中染色的操作之前，还包括将铝合金浸泡在在电解液中，以所述铝合金作为阳极，在电压为15V～22V，温度为14℃～22℃的条件下电解所述电解液，从而在所述铝合金表面形成氧化膜，得到经过阳极氧化后的所述铝合金。
在一个实施方式中，所述将经过阳极氧化后的铝合金立刻浸泡在所述黑色染料中染色的操作中，染色时间为2min～10min，染色过程中控制所述黑色染料的温度恒定。
上述铝合金染色用黑色染料的制备方法制备的黑色染料包括1.0g/L～2.0g/L的红黑色染料、1.0g/L～1.5g/L的蓝绿色染料以及0.5g/L～1.0g/L红色染料。发明人意外发现上述配比的红黑色染料、蓝绿色染料、红色染料混合调节pH值至5.0～5.5，并加入10g/L～15g/L的pH稳定剂形成的黑色染料比传统的黑色染料更适宜对铝合金染色，能够容易的将铝合金染成黑色。特别是对经过阳极氧化后的铝合金进行染色时，这种混合黑色染料进入阳极氧化后形成的氧化膜的微孔内着色，再由于封孔处理，黑色染料与氧化膜成为一体处于稳定状态。而在着色的过程中，每种染料的吸附速度不同，上述方法制备的铝合金染色用黑色染料能够保持铝合金色系的稳定性和时效性，容易将铝合金染成颜色稳定、着色 耐久的黑色。
附图说明
图1为一实施方式的铝合金染色用黑色染料的制备方法的流程图；
图2一实施方式的铝合金的染色方法的流程图。
具体实施方式
为使本发明的上述目的、特征和优点能够更加明显易懂，下面结合附图对本发明的具体实施方式做详细的说明。在下面的描述中阐述了很多具体细节以便于充分理解本发明。但是本发明能够以很多不同于在此描述的其它方式来实施，本领域技术人员可以在不违背本发明内涵的情况下做类似改进，因此本发明不受下面公开的具体实施的限制。
请参阅图1，一实施方式的铝合金染色用黑色染料的制备方法包括以下步骤S110～S130。
S110、将红黑色染料、蓝绿色染料以及红色染料溶于溶剂中得到混合液，其中，红黑色染料在混合液中的浓度为1.0g/L～2.0g/L，蓝绿色染料在混合液中的浓度为1.0g/L～1.5g/L，红色染料在混合液中的浓度为0.5g/L～1.0g/L。
可根据要配置的铝合金染色用黑色染料的总体积加入红黑色染料、蓝绿色染料以及红色染料从而得到混合液。具体的，铝合金染色用黑色染料的溶剂可以为水。
本实施方式中，将红黑色染料、蓝绿色染料以及红色染料溶于水中得到混合液，其中，红黑色染料在混合液中的浓度为1.5g/L，蓝绿色染料在混合液中的浓度为1.25g/L，红色染料在混合液中的浓度为0.75g/L。
具体的，红黑色染料为奥野染料402，蓝绿色染料为奥野染料411，红色染料为奥野染料102。本实施方式中，奥野染料为日本奥野公司提供，402、411、102分别为产品编号。奥野染料402一般呈红黑色，奥野染料411一般呈蓝绿色，奥野染料102一般呈红色。可以理解，在其他实施方式中，也可以是其他厂家提供的染料，保证红黑色染料、蓝绿色染料以及红色染料的配比即可。
S120、调节S110中得到的混合液的pH值至5.0～5.5。
各色染料配比和pH值的不同将影响着最终的混合黑色染料色系的稳定性和着色的耐久性，尤其是黑色的要求更高。发明人发现，通过将混合液的pH值至5.0～5.5，使得黑色染料呈弱酸性，能够使得铝合金着色均匀，形成黑色的铝合金。
具体的，红黑色染料、蓝绿色染料以及红色染料溶于溶剂中得到混合液呈酸性，可通过加入氢氧化钠调节混合液的pH值至5.0～5.5。
本实施方式中，可通过加入氢氧化钠调节混合液的pH值至5.25。
S130、向S120中得到的混合液中加入pH稳定剂，pH稳定剂在混合液中的浓度为10g/L～15g/L，得到铝合金染色用黑色染料。
加入pH稳定剂能够使得红黑色染料、蓝绿色染料以及红色染料形成的混合液pH值稳定，从而保证着色的均匀性。
本实施方式中，pH稳定剂在混合液中的浓度为12.5g/L。
具体的，pH稳定剂选自氯化铵和醋酸钠中的至少一种。红黑色染料、蓝绿色染料、红色染料混合后，由于三者的酸碱性不同，很难形成稳定的染料，加入pH稳定剂能够使得混合染料稳定，染色均匀，且将铝合金染成黑色后颜色稳定、着色耐久。
上述铝合金染色用黑色染料的制备方法制备的黑色染料包括1.0g/L～2.0g/L的红黑色染料、1.0g/L～1.5g/L的蓝绿色染料以及0.5g/L～1.0g/L红色染料。上述配比的红黑色染料、蓝绿色染料、红色染料混合调节pH值至5.0～5.5，并加入10g/L～15g/L的pH稳定剂形成的黑色染料比传统的黑色染料更适宜对铝合金染色，能够容易的将铝合金染成黑色。
请参阅图2，本发明还提供一实施方式的铝合金的染色方法，包括以下步骤S210～S220。
S210、提供铝合金染色用黑色染料。
具体的，该铝合金染色用黑色染料通过上述方法任一实施方式的铝合金染色用黑色染料的制备方法制备得到。
具体的，该铝合金染色用黑色染料包括1.0g/L～2.0g/L的红黑色染料、 1.0g/L～1.5g/L的蓝绿色染料、0.5g/L～1.0g/L的红色染料以及10g/L～15g/L的pH稳定剂，黑色染料的pH值至5.0～5.5。
本实施方式中，该铝合金染色用黑色染料包括1.5g/L的红黑色染料、1.25g/L的蓝绿色染料、0.75g/L的红色染料以及12.5g/L的pH稳定剂以及余量的水，黑色染料的pH值至5.25。红黑色染料为奥野染料402，蓝绿色染料为奥野染料411，红色染料为奥野染料102。
S220、将经过阳极氧化后的铝合金立刻浸泡在S210中得到的黑色染料中染色。
经过阳极氧化后的铝合金的表面上形成一层氧化膜，立刻浸泡在黑色染料中，氧化膜的表面还带有电荷，而染料的磺酸基[D(-SO3Na)-]因为带有负电荷，被吸附到带有正电荷的阳极氧化膜＜Al(H2O)4(OH)2+·AlOn+＞的孔内。染料的吸附因为依靠静电作用，一般只能进入到氧化膜厚度的的1/2～1/3，进入的染料通过与离子结合和酸析现象吸附在孔内。本发明的方法制备的黑色染料，在着色的过程中，每种染料的吸附速度不同，多种色系的染料混合形成混合染料进入阳极氧化膜的微孔内着色，再由于封孔处理，能够与阳极氧化膜成为一体处于稳定状态，色系变化均匀，从而将铝合金染成稳定而耐久的黑色。
具体的，将经过阳极氧化后的铝合金立刻浸泡在所述黑色染料中染色的操作之前，还包括将铝合金浸泡在在电解液中，以铝合金作为阳极，在电压为15V～22V，温度为14℃～22℃的条件下电解电解液，从而在铝合金表面形成氧化膜，得到经过阳极氧化后的铝合金。
电解液例如可以为含有80g/L～140g/L的浓硫酸和10g/L～50g/L的草酸。浓硫酸与草酸的混合的电解液使得制备的氧化膜均匀，不易脱落。表面形成有氧化膜的铝合金浸泡在黑色染料中，黑色染料能够进入氧化膜的微孔中，从而形成将铝合金染成稳定的黑色。
具体的，将经过阳极氧化后的铝合金立刻浸泡在黑色染料中染色的操作中，染色时间为2min～10min，染色过程中控制黑色染料的温度恒定。染色的温度范围例如可以为20℃～25℃。温度恒定保证染色的均匀性，混合黑色染料进入阳极氧化后形成的氧化膜的微孔内着色，再由于封孔处理，黑色染料与氧化膜成为 一体处于稳定状态。而在着色的过程中，每种染料的吸附速度不同，上述方法制备的铝合金染色用黑色染料能够保持铝合金色系的稳定性和时效性，容易将铝合金染成颜色稳定、着色耐久的黑色。
上述铝合金的染色方法，将经过阳极氧化后的铝合金立刻浸泡在黑色染料中染色，黑色染料在着色的过程中，每种染料的吸附速度不同，多种色系的染料混合形成混合染料进入阳极氧化膜的微孔内着色，再由于封孔处理，能够与阳极氧化膜成为一体处于稳定状态，色系变化均匀，从而将铝合金染成稳定而耐久的黑色。工艺操作简单，可广泛应用于对铝合金的材质的手机、电脑等电子产品的外壳进行染色。
以下为具体的实施例。
以下实施例如无特别说明，未注明具体条件的实验方法，通常按照常规条件，奥野染料由日本奥野公司提供。
实施例1
制备铝合金染色用黑色染料
将奥野染料402、奥野染料411、奥野染料102溶于水中得到混合液，其中，奥野染料402的加入量为1.5g/L，奥野染料411的加入量为1.25g/L，奥野染料102的加入量为0.75g/L。加入NaOH调节混合液的pH值至5.25。并向混合液中加入12.5g/L的氯化铵，混匀后得到铝合金染色用黑色染料。
实施例2
制备铝合金染色用黑色染料
将奥野染料402、奥野染料411、奥野染料102溶于水中得到混合液，奥野染料402的加入量为1.0g/L，奥野染料411的加入量为1.0g/L，奥野染料102的加入量为1.0g/L。加入NaOH调节混合液的pH值至5.0。向混合液中加入10g/L的醋酸钠，得到铝合金染色用黑色染料。
实施例3
制备铝合金染色用黑色染料
将奥野染料402、奥野染料411、奥野染料102溶于水中得到混合液，奥野染料402的加入量为2.0g/L，奥野染料411的加入量为1.5g/L，奥野染料102的加入量为0.5g/L。加入NaOH调节混合液的pH值至5.5。向混合液中加入15g/L的氯化铵，得到铝合金染色用黑色染料。
实施例4
对铝合金的染色
将铝合金浸泡在在电解液中，以铝合金作为阳极，在电压为18V，温度为18℃的条件下电解电解液，从而在铝合金表面形成氧化膜，得到经过阳极氧化后的铝合金。将阳极氧化后的铝合金立刻浸泡在采用实施例1的方法制备的得到的黑色染料，23℃下浸泡染色5min。
实施例5
对铝合金的染色
将铝合金浸泡在在电解液中，以铝合金作为阳极，在电压为15V，温度为22℃的条件下电解电解液，从而在铝合金表面形成氧化膜，得到经过阳极氧化后的铝合金。将阳极氧化后的铝合金立刻浸泡在采用实施例2的方法制备的得到的黑色染料，20℃下浸泡染色10min。
实施例6
对铝合金的染色
将铝合金浸泡在在电解液中，以铝合金作为阳极，在电压为22V，温度为14℃的条件下电解电解液，从而在铝合金表面形成氧化膜，得到经过阳极氧化后的铝合金。将阳极氧化后的铝合金立刻浸泡在采用实施例3的方法制备的得到的黑色染料，25℃下浸泡染色2min。
实施例7
对铝合金的染色
本实施例中对铝合金的染色的参数条件与实施例4相同，不同的阳极氧化后的铝合金浸泡在普通的颜色为黑色的黑色染料中染色，为方便对比，本实施例中采用的奥野420染料(纯黑色染料)。
实施例8
对铝合金的染色
本实施例中对铝合金的染色的参数条件与实施例4相同，不同的是铝合金未经过阳极氧化，直接浸泡在染料中染色。
测试一
分别通过实施例4和实施例7的方法对铝合金的染色，每种方法305块。染色后铝合金与标准色板比对，铝合金的颜色在标准色板比对结果为黑色则为合格，偏离黑色则为不合格。结果如下表1显示：
表1：实施例4和实施例7的方法对铝合金的染色的测试结果
染色方法 投入(块) 不良数(块) 总不良率
实施例7 305 9 2.95％
实施例4 305 0 0％
从表1可以看出实施例4的对铝合金的染色的方法(采用本发明的铝合金染色用黑色染料)染色，总不良率为0％。染色稳定，能够在铝合金表面形成耐久的黑色。
测试二
分别通过实施例4和实施例8的方法对铝合金的染色，染色后铝合金与标准色板比对，铝合金的颜色在标准色板比对结果为黑色则为合格，偏离黑色则为不合格。结果如下表2所示。
表2：实施例4和实施例8的方法对铝合金的染色的测试结果
Figure PCTCN2017110666-appb-000001
从表2可以看出实施例4的对铝合金的染色的方法(阳极氧化后的铝合金立刻浸泡本发明的铝合金染色用黑色染料)染色，总不良率为0％。染色稳定，能够在铝合金表面形成耐久的黑色。
测试三
分别采用实施例4～6的方法对铝合金的染色，每种方法测试20块，染色后铝合金与标准色板比对，铝合金的颜色在标准色板比对结果为黑色则为合格，偏离黑色则为不合格。结果显示实施例4～6的方法对铝合金的染色后，60块铝合金的结果均为黑色。
以上所述实施例仅表达了本发明的几种实施方式，其描述较为具体和详细，但并不能因此而理解为对本发明专利范围的限制。应当指出的是，对于本领域的普通技术人员来说，在不脱离本发明构思的前提下，还可以做出若干变形和改进，这些都属于本发明的保护范围。因此，本发明专利的保护范围应以所附权利要求为准。

Claims (10)

  1. 一种铝合金染色用黑色染料的制备方法，其特征在于，包括如下步骤：
    将红黑色染料、蓝绿色染料以及红色染料溶于溶剂中得到混合液，所述红黑色染料在所述混合液中的浓度为1.0g/L～2.0g/L，所述蓝绿色染料在所述混合液中的浓度为1.0g/L～1.5g/L，所述红色染料在所述混合液中的浓度为0.5g/L～1.0g/L；
    调节所述混合液的pH值至5.0～5.5；以及
    向所述混合液中加入pH稳定剂，所述pH稳定剂在所述混合液中的浓度为10g/L～15g/L，得到所述铝合金染色用黑色染料。
  2. 根据权利要求1所述的铝合金染色用黑色染料的制备方法，其特征在于，所述红黑色染料在所述混合液中的浓度为1.5g/L，所述蓝绿色染料在所述混合液中的浓度为1.25g/L，所述红色染料在所述混合液中的浓度为0.75g/L。
  3. 根据权利要求1所述的铝合金染色用黑色染料的制备方法，其特征在于，所述红黑色染料为奥野染料402，所述蓝绿色染料为奥野染料411，所述红色染料为奥野染料102。
  4. 根据权利要求1所述的铝合金染色用黑色染料的制备方法，其特征在于，所述溶剂为水。
  5. 根据权利要求1所述的铝合金染色用黑色染料的制备方法，其特征在于，调节所述混合液的pH值至5.0～5.5的操作中，通过加入氢氧化钠调节所述混合液的pH值至5.0～5.5。
  6. 根据权利要求1所述的铝合金染色用黑色染料的制备方法，其特征在于，所述pH稳定剂选自氯化铵和醋酸钠中的至少一种。
  7. 根据权利要求1所述的铝合金染色用黑色染料的制备方法，其特征在于，所述pH稳定剂在所述混合液中的浓度为12.5g/L。
  8. 一种铝合金的染色方法，其特征在于，包括如下步骤：
    提供如权利要求1～7任一项所述的方法制备的铝合金染色用黑色染料；以及
    将经过阳极氧化后的铝合金立刻浸泡在所述黑色染料中染色。
  9. 根据权利要求8所述的铝合金的染色方法，其特征在于，所述将经过阳极氧化后的铝合金立刻浸泡在所述黑色染料中染色的操作之前，还包括将铝合金浸泡在在电解液中，以所述铝合金作为阳极，在电压为15V～22V，温度为14℃～22℃的条件下电解所述电解液，从而在所述铝合金表面形成氧化膜，得到经过阳极氧化后的所述铝合金。
  10. 根据权利要求8所述的铝合金的染色方法，其特征在于，所述将经过阳极氧化后的铝合金立刻浸泡在所述黑色染料中染色的操作中，染色时间为2min～10min，染色过程中控制所述黑色染料的温度恒定。
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114775012A (zh) * 2022-05-05 2022-07-22 湖北蓝华铝业有限公司 一种铝合金加工用表面着色剂
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Families Citing this family (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106867275B (zh) * 2017-01-09 2019-05-17 广东长盈精密技术有限公司 铝合金染色用黑色染料的制备方法、铝合金的染色方法
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CN110016705B (zh) * 2019-04-23 2021-03-05 绍兴市上虞嘉利盛助剂工业有限公司 用于阳极氧化铝染色的染液及黑色染料组合物和染色方法
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1066691A (zh) * 1991-05-11 1992-12-02 程显辉 铝着色方法及制品
CN1110996A (zh) * 1994-04-27 1995-11-01 江南机器厂 单色的有机染料染色方法
JP3335941B2 (ja) * 1999-04-09 2002-10-21 三和メッキ工業株式会社 アルミニウム又はアルミニウム合金の硬質又は超硬質陽極酸化皮膜に対する着色用染料組成物
CN106867275A (zh) * 2017-01-09 2017-06-20 广东长盈精密技术有限公司 铝合金染色用黑色染料的制备方法、铝合金的染色方法

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TW311925B (zh) * 1994-06-02 1997-08-01 Sakura Color Prod Corp
JPH08325792A (ja) * 1995-05-30 1996-12-10 Sakura Color Prod Corp アルミニウム又はアルミニウム合金酸化皮膜の充填着色用顔料分散体組成物
CN101210336B (zh) * 2006-12-31 2011-05-18 比亚迪股份有限公司 一种轻金属材料的表面处理方法
CN101476145B (zh) * 2008-11-21 2010-12-29 上海瑞尔实业有限公司 多盲孔的铝挤压型材产品阳极氧化染色工艺
CN102337572B (zh) * 2011-09-26 2014-07-23 上海瑞尔实业有限公司 一种硅铜铸造铝合金的染色阳极氧化方法
JP6093523B2 (ja) * 2011-09-29 2017-03-08 電化皮膜工業株式会社 着色アルミニウム製品または着色アルミニウム合金製品の製造方法
CN105506640A (zh) * 2015-11-13 2016-04-20 广东长盈精密技术有限公司 铝合金表面处理方法
CN105839161B (zh) * 2016-05-10 2017-10-27 广东长盈精密技术有限公司 金属件的染色方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1066691A (zh) * 1991-05-11 1992-12-02 程显辉 铝着色方法及制品
CN1110996A (zh) * 1994-04-27 1995-11-01 江南机器厂 单色的有机染料染色方法
JP3335941B2 (ja) * 1999-04-09 2002-10-21 三和メッキ工業株式会社 アルミニウム又はアルミニウム合金の硬質又は超硬質陽極酸化皮膜に対する着色用染料組成物
CN106867275A (zh) * 2017-01-09 2017-06-20 广东长盈精密技术有限公司 铝合金染色用黑色染料的制备方法、铝合金的染色方法

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114775012A (zh) * 2022-05-05 2022-07-22 湖北蓝华铝业有限公司 一种铝合金加工用表面着色剂
CN115110129A (zh) * 2022-06-09 2022-09-27 泰州星瑞精密工业有限公司 一种新型铝合金产品的表面氧化加工工艺
CN115110129B (zh) * 2022-06-09 2023-11-17 泰州星瑞精密工业有限公司 一种铝合金产品的表面氧化加工工艺

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