Anodic oxidation dye, anodic oxidation process and application

Abstract

The invention relates to an anodic oxidation dye, an anodic oxidation process and application. The anodic oxidation dye comprises a combination of dye, sodium sulfate, a pH stabilizer and water. According to the anodic oxidation dye provided by the invention, through the design of all the components and the synergistic compounding of the components, a weight loss test of a metal workpiece subjected to anodic oxidation treatment is qualified on the premise that color difference drop points, gloss drop points and film thickness drop points are relatively small, and the metal workpiece has excellent chemical resistance, ageing resistance and corrosion resistance.

Description

Technical Field

[0001] The present invention belongs to the technical field of anodic surface treatment, and particularly relates to an anodic oxidation dye, an anodic oxidation process and applications thereof. Background Art

[0002] At present, metal workpieces such as proofing machines are subjected to surface sealing treatment using a nickel-free sealing process. After this process is completed, the surface of the product can achieve a normal gloss and color difference effect, and it can ensure that the color difference and gloss loss points of the original product do not exceed the specified range. After the metal workpiece is subjected to surface sealing treatment, a weight loss test needs to be carried out. Through the weight loss test, the thickness and uniformity of the oxide film can be accurately judged, so as to evaluate its corrosion resistance and wear resistance. The smaller the mass loss, the better the sealing effect and the denser the oxide film; and the weight loss test can monitor the sealing effect in real time, ensure the processing quality, and avoid quality problems caused by poor sealing. According to the results of the weight loss test, the process parameters of anodic oxidation and sealing treatment can be adjusted specifically to improve the product quality and production efficiency, which is of great significance for optimizing the production process and reducing costs.

[0003] The dyes used in the existing dyeing process contain E-110 additives, and its components include 0.2 - 0.3 wt% sodium hypophosphite monohydrate, 7.8 - 8 wt% ammonium acetate, 2 - 2.2 wt% polyacrylamide, and 89.5 - 90 wt% water. The structural unit of polyacrylamide in the E-110 additive contains amide groups, which are easy to form hydrogen bonds, making it have good water solubility and high chemical activity. It is easy to obtain various modified products with branched or network structures through grafting or crosslinking, so as to play a certain role in fixing color and sealing. However, the existing dyes generally have the problem that the dyeing quality is good, but the weight loss test is unqualified. Therefore, there is an urgent need to provide an anodic oxidation dye with good dyeing effect and which can ensure the qualified weight loss test of the product. Summary of the Invention

[0004] Aiming at the deficiencies of the prior art, the purpose of the present invention is to provide an anodic oxidation dye, an anodic oxidation process and applications thereof. The anodic oxidation dye provided by the present invention can ensure the qualified weight loss test of the metal workpiece without affecting the color difference, gloss and film thickness of the metal workpiece, and has excellent chemical resistance, aging resistance and corrosion resistance.

[0005] To achieve this purpose, the present invention adopts the following technical solutions:

[0006] In the first aspect, the present invention provides an anodic oxidation dye, and the components of the anodic oxidation dye include a combination of a dye, sodium sulfate, a pH stabilizer and water.

[0007] The anodic oxidation dyes used in the existing dyeing process contain E-110 auxiliaries. The components of the E-110 auxiliaries include 0.2-0.3 wt% sodium hypophosphite monohydrate, 7.8-8 wt% ammonium acetate, 2-2.2 wt% polyacrylamide, and 89.5-90 wt% water. Although the E-110 auxiliaries have a certain color-fixing and sealing effect, the structural unit of polyacrylamide in E-110 contains amide groups and is prone to form hydrogen bonds. In the phosphoric acid weight loss method, the phosphate group has a certain acidity and can react with amino groups and hydrogen bonds in other active molecular forms, resulting in an increase in weight loss and making the weight loss test unqualified. Therefore, the anodic oxidation dyes provided by the present invention do not contain E-110 auxiliaries, and through the design and mutual cooperation of other components, the color difference drop, gloss drop, and film thickness drop of the metal workpiece after anodic oxidation treatment are all small, and the weight loss test is qualified.

[0008] The following are the preferred technical solutions of the present invention, but do not limit the technical solutions provided by the present invention. Through the following preferred technical solutions, the purpose and beneficial effects of the present invention can be better achieved and realized.

[0009] As a preferred technical solution, the dye includes any one of a gray dye, a pink dye, a blue dye, or a first yellow dye.

[0010] Preferably, the components of the gray dye include a combination of a black dye and a first red dye.

[0011] Preferably, the L value of the gray dye is 50.5, the a value is 0.6, and the b value is 0.2.

[0012] Preferably, the components of the pink dye include a combination of a first pink dye and a second yellow dye.

[0013] Preferably, the L value of the pink dye is 66.55, the a value is 48.75, and the b value is 2.25.

[0014] Preferably, the components of the blue dye include a combination of a second pink dye, a dark green dye, and a green dye.

[0015] Preferably, the L value of the blue dye is 55.5, the a value is 3.0, and the b value is -34.2.

[0016] Preferably, the components of the first yellow dye include a combination of a third yellow dye and a second red dye.

[0017] Preferably, the L value of the first yellow dye is 86.3, the a value is -7.0, and the b value is 50.0.

[0018] Preferably, the pH stabilizer includes Okuno pH-5 auxiliaries.

[0019] Preferably, when the dye is the grey dye, the concentration of the pH stabilizer in the anodic oxidation dye is 4.75 - 5.25 mL / L, and can be, for example, 4.8 mL / L, 4.85 mL / L, 4.9 mL / L, 4.95 mL / L, 5 mL / L, 5.05 mL / L, 5.1 mL / L, 5.15 mL / L, 5.2 mL / L, etc.

[0020] Preferably, when the dye is the grey dye, the concentration of sodium sulfate in the anodic oxidation dye is 1.3 - 1.5 g / L, and can be, for example, 1.32 g / L, 1.34 g / L, 1.36 g / L, 1.38 g / L, 1.4 g / L, 1.42 g / L, 1.44 g / L, 1.46 g / L, 1.48 g / L, etc.

[0021] Preferably, when the dye is any one of the pink dye, the blue dye or the first yellow dye, the concentration of the pH stabilizer in the anodic oxidation dye is 1 - 3 mL / L, and can be, for example, 1.2 mL / L, 1.4 mL / L, 1.6 mL / L, 1.8 mL / L, 2 mL / L, 2.2 mL / L, 2.4 mL / L, 2.6 mL / L, 2.8 mL / L, etc.

[0022] Preferably, when the dye is any one of the pink dye, the blue dye or the first yellow dye, the concentration of sodium sulfate in the anodic oxidation dye is 0.3 - 1 g / L, and can be, for example, 0.35 g / L, 0.4 g / L, 0.45 g / L, 0.5 g / L, 0.55 g / L, 0.6 g / L, 0.65 g / L, 0.7 g / L, 0.75 g / L, 0.8 g / L, 0.85 g / L, 0.9 g / L, 0.95 g / L, etc.

[0023] Preferably, the concentration of the black dye in the anodic oxidation dye is 1.4 - 1.8 g / L, and can be, for example, 1.42 g / L, 1.45 g / L, 1.48 g / L, 1.5 g / L, 1.52 g / L, 1.55 g / L, 1.58 g / L, 1.6 g / L, 1.62 g / L, 1.65 g / L, 1.68 g / L, 1.7 g / L, 1.72 g / L, 1.75 g / L, 1.78 g / L, etc.

[0024] Preferably, the concentration of the first red dye in the anodic oxidation dye is 0.03 - 0.05 g / L, and can be, for example, 0.032 g / L, 0.034 g / L, 0.036 g / L, 0.038 g / L, 0.04 g / L, 0.042 g / L, 0.044 g / L, 0.046 g / L, 0.048 g / L, etc.

[0025] Preferably, the black dye includes any one or a combination of at least two of Okuno Black Dye 420, Okuno Black Dye 411, Okuno Black Dye 419, or Okuno Black Dye 415, and further preferably a combination of Okuno Black Dye 420 and Okuno Black Dye 411.

[0026] Preferably, the concentration of Okuno Black Dye 420 in the anodizing dye is 0.5 - 0.7 g / L (for example, it can be 0.52 g / L, 0.54 g / L, 0.56 g / L, 0.58 g / L, 0.6 g / L, 0.62 g / L, 0.64 g / L, 0.66 g / L, 0.68 g / L, etc.), and the concentration of Okuno Black Dye 411 is 0.9 - 1.1 g / L (for example, it can be 0.92 g / L, 0.94 g / L, 0.96 g / L, 0.98 g / L, 1 g / L, 1.02 g / L, 1.04 g / L, 1.06 g / L, 1.08 g / L, etc.).

[0027] Preferably, the first red dye includes Okuno Red Dye 102 and / or Okuno Red Dye 106.

[0028] Preferably, the first pink dye includes any one or a combination of at least two of Okuno Pink Dye 144, Okuno Pink Dye 131, or Okuno Pink Dye 139.

[0029] Preferably, the second yellow dye includes Okuno Yellow Dye 203 and / or Okuno Yellow Dye 201.

[0030] Preferably, the concentration of the first pink dye in the anodizing dye is 0.6 - 0.8 g / L, for example, it can be 0.62 g / L, 0.64 g / L, 0.66 g / L, 0.68 g / L, 0.7 g / L, 0.72 g / L, 0.74 g / L, 0.76 g / L, 0.78 g / L, etc.

[0031] Preferably, the concentration of the second yellow dye in the anodizing dye is 0.2 - 0.4 g / L, for example, it can be 0.22 g / L, 0.24 g / L, 0.26 g / L, 0.28 g / L, 0.3 g / L, 0.32 g / L, 0.34 g / L, 0.36 g / L, 0.38 g / L, etc.

[0032] Preferably, the second pink dye includes any one or a combination of at least two of Okuno Pink Dye 144, Okuno Pink Dye 131, or Okuno Pink Dye 139.

[0033] Preferably, the dark green dye includes Clariant dark green dye SANODYE BLUE 2LW and / or Okuno dark green dye TAC Green GM.

[0034] Preferably, the green dye includes Clariant green dye GLW.

[0035] Preferably, the concentration of the second pink dye in the anodizing dye is 0.4 - 0.6 g / L, and can be, for example, 0.42 g / L, 0.44 g / L, 0.46 g / L, 0.48 g / L, 0.5 g / L, 0.52 g / L, 0.54 g / L, 0.56 g / L, 0.58 g / L, etc.

[0036] Preferably, the concentration of the dark green dye in the anodizing dye is 0.3 - 0.5 g / L, and can be, for example, 0.32 g / L, 0.34 g / L, 0.36 g / L, 0.38 g / L, 0.4 g / L, 0.42 g / L, 0.44 g / L, 0.46 g / L, 0.48 g / L, etc.

[0037] Preferably, the concentration of the green dye in the anodizing dye is 0.01 - 0.03 g / L, and can be, for example, 0.012 g / L, 0.014 g / L, 0.016 g / L, 0.018 g / L, 0.02 g / L, 0.022 g / L, 0.024 g / L, 0.026 g / L, 0.028 g / L, etc.

[0038] Preferably, the third yellow dye includes Okuno yellow dye 203 and / or Okuno yellow dye 201.

[0039] Preferably, the second red dye includes Clariant red dye RLW and / or Okuno red dye 102.

[0040] Preferably, the concentration of the third yellow dye in the anodizing dye is 0.2 - 0.5 g / L, and can be, for example, 0.22 g / L, 0.24 g / L, 0.26 g / L, 0.28 g / L, 0.3 g / L, 0.32 g / L, 0.34 g / L, 0.36 g / L, 0.38 g / L, 0.4 g / L, 0.42 g / L, 0.44 g / L, 0.46 g / L, 0.48 g / L, etc.

[0041] Preferably, the concentration of the second red dye in the anodizing dye is 0.05 - 0.1 g / L, and can be, for example, 0.055 g / L, 0.06 g / L, 0.065 g / L, 0.07 g / L, 0.075 g / L, 0.08 g / L, 0.085 g / L, 0.09 g / L, 0.095 g / L, etc.

[0042] Preferably, the pH value of the anodic oxidation dye is 5.5 - 5.9, and can be, for example, 5.52, 5.55, 5.58, 5.6, 5.62, 5.65, 5.68, 5.7, 5.72, 5.75, 5.78, 5.8, 5.82, 5.85, 5.88, etc.

[0043] By limiting the pH value of the anodic oxidation dye within a suitable range, the present invention can ensure the color stability of the metal workpiece. If the pH value of the anodic oxidation dye is too small, the coloring rate during the dyeing process is too fast, resulting in abnormal colors, white spots, etc.; if the pH value is too large, it will cause phenomena such as differences in the size of the edges, abnormal color difference uniformity, and slow coloring rate during the dyeing process.

[0044] Preferably, the components of the anodic oxidation dye further include a color stabilizer.

[0045] Preferably, the color stabilizer includes Okuno TAC.

[0046] Preferably, the concentration of the color stabilizer in the anodic oxidation dye is 1 - 5 mL / L, and can be, for example, 1.2 mL / L, 1.5 mL / L, 1.8 mL / L, 2 mL / L, 2.2 mL / L, 2.5 mL / L, 2.8 mL / L, 3 mL / L, 3.2 mL / L, 3.5 mL / L, 3.8 mL / L, 4 mL / L, 4.2 mL / L, 4.5 mL / L, 4.8 mL / L, etc.

[0047] The preparation method of the anodic oxidation dye provided by the present invention includes:

[0048] Mix the dye, water, sodium sulfate, pH stabilizer, and optionally the color stabilizer, and then cook at 60 - 80 °C for 1 - 4 h to obtain the anodic oxidation dye.

[0049] In a second aspect, the present invention provides an anodic oxidation process, which includes the steps of anodic oxidation, surface conditioning, and dyeing in sequence; the dye used for the dyeing is the anodic oxidation dye as described in the first aspect.

[0050] Preferably, the anodic oxidation solution used for the anodic oxidation includes a combination of sulfuric acid, oxalic acid, aluminum ions, and water.

[0051] Preferably, the concentration of sulfuric acid in the anodic oxidation solution is 95 - 105 g / L, and can be, for example, 95 g / L, 96 g / L, 97 g / L, 98 g / L, 99 g / L, 100 g / L, 101 g / L, 102 g / L, 103 g / L, 104 g / L, 105 g / L, etc.

[0052] Preferably, the concentration of oxalic acid in the anodizing solution is 17-23 g / L, for example, it can be 17.5 g / L, 18 g / L, 18.5 g / L, 19 g / L, 19.5 g / L, 20 g / L, 20.5 g / L, 21 g / L, 21.5 g / L, 22 g / L, 22.5 g / L, etc.

[0053] Preferably, the concentration of aluminum ions in the anodizing solution is 0.1-15 g / L, for example, it can be 0.5 g / L, 1 g / L, 2 g / L, 3 g / L, 4 g / L, 5 g / L, 6 g / L, 7 g / L, 8 g / L, 9 g / L, 10 g / L, 11 g / L, 12 g / L, 13 g / L, 14 g / L, etc.

[0054] Preferably, the temperature of the anodizing is 26-28 °C, for example, it can be 26.2 °C, 26.4 °C, 26.6 °C, 26.8 °C, 27 °C, 27.2 °C, 27.4 °C, 27.4 °C, 27.6 °C, 27.8 °C, etc.

[0055] Preferably, the time of the anodizing is 3200-3800 s, for example, it can be 3200 s, 3300 s, 3400 s, 3500 s, 3600 s, 3700 s, 3800 s, etc.

[0056] Preferably, the anodizing is carried out in a constant voltage mode.

[0057] Preferably, the current density of the constant voltage mode is 0.9-1.1 ASD, for example, it can be 0.92 ASD, 0.94 ASD, 0.96 ASD, 0.98 ASD, 1.0 ASD, 1.02 ASD, 1.04 ASD, 1.06 ASD, 1.08 ASD, etc.

[0058] Preferably, the surface conditioner used for surface conditioning includes an aqueous solution of Okuno surface conditioner 121.

[0059] Preferably, the concentration of the aqueous solution of Okuno surface conditioner 121 is 50-70 g / L, for example, it can be 52 g / L, 54 g / L, 56 g / L, 58 g / L, 60 g / L, 62 g / L, 64 g / L, 66 g / L, 68 g / L, etc.

[0060] Preferably, the number of times of surface conditioning is four times.

[0061] In the present invention, the number of times of surface conditioning is set to four times, which can improve the corrosion resistance and weather resistance of the aluminum alloy surface. If the number of treatment times is too small, the weather resistance of the aluminum alloy surface will be weakened; if the number of treatment times is too large, the color difference stability and gloss stability of the aluminum alloy surface will become poor.

[0062] Preferably, the temperatures of the surface conditioning are each independently 16 - 22°C, and can be, for example, 16.5°C, 17°C, 17.5°C, 18°C, 18.5°C, 19°C, 19.5°C, 20°C, 20.5°C, 21°C, 21.5°C, etc.

[0063] Preferably, the times of the surface conditioning are each independently 300 - 420 s, and can be, for example, 310 s, 320 s, 330 s, 340 s, 350 s, 360 s, 370 s, 380 s, 390 s, 400 s, 410 s, etc.

[0064] Preferably, the temperature of the dyeing is 39 - 41°C, and can be, for example, 39.2°C, 39.4°C, 39.6°C, 39.8°C, 40°C, 40.2°C, 40.4°C, 40.6°C, 40.8°C, etc.

[0065] In the present invention, controlling the temperature of the dyeing within a suitable range can improve the color stability of the metal workpiece. If the dyeing temperature is too low, the coloring rate of the aluminum alloy will be too slow and abnormal color difference will occur; if the temperature is too high, a seven-color phenomenon will appear on the surface of the aluminum alloy.

[0066] Preferably, the time of the dyeing is 200 - 600 s, and can be, for example, 220 s, 240 s, 260 s, 280 s, 300 s, 320 s, 340 s, 360 s, 380 s, 400 s, 420 s, 440 s, 460 s, 480 s, 500 s, 520 s, 540 s, 560 s, 580 s, etc.

[0067] Preferably, before the anodic oxidation, a pretreatment step is further included; the pretreatment includes successively performing degreasing, first nitrogen-free neutralization, chemical polishing, ash removal, alkali washing, and second nitrogen-free neutralization steps.

[0068] Preferably, the degreasing agent used for degreasing includes an aqueous solution of Okuno degreasing agent 161.

[0069] Preferably, the concentration of the aqueous solution of Okuno degreasing agent 161 is 50 - 70 g / L, and can be, for example, 52 g / L, 54 g / L, 56 g / L, 58 g / L, 60 g / L, 62 g / L, 64 g / L, 66 g / L, 68 g / L, etc.

[0070] Preferably, the temperature of the degreasing is 58 - 62°C, and can be, for example, 58.2°C, 58.5°C, 58.8°C, 59°C, 59.2°C, 59.5°C, 59.8°C, 60°C, 60.2°C, 60.5°C, 60.8°C, 61°C, 61.2°C, 61.5°C, 61.8°C, etc.

[0071] Preferably, the defatting time is 120 - 180 s, for example, it can be 125 s, 130 s, 135 s, 140 s, 145 s, 150 s, 155 s, 160 s, 165 s, 170 s, 175 s, etc.

[0072] Preferably, the neutralizing agents used in the first nitrogen - free neutralization and the second nitrogen - free neutralization are both Okuno nitrogen - free neutralizing agents.

[0073] Preferably, both the first nitrogen - free neutralization and the second nitrogen - free neutralization are carried out at room temperature.

[0074] Preferably, the times of the first nitrogen - free neutralization and the second nitrogen - free neutralization are independently 120 - 180 s, for example, it can be 125 s, 130 s, 135 s, 140 s, 145 s, 150 s, 155 s, 160 s, 165 s, 170 s, 175 s, etc.

[0075] Preferably, the chemical polishing solution used for chemical polishing comprises a combination of phosphoric acid, sulfuric acid, aluminum ions and water.

[0076] Preferably, the concentration of phosphoric acid in the chemical polishing solution is 1200 - 1450 g / L, for example, it can be 1220 g / L, 1250 g / L, 1280 g / L, 1300 g / L, 1320 g / L, 1350 g / L, 1380 g / L, 1400 g / L, 1420 g / L, etc.

[0077] Preferably, the concentration of sulfuric acid in the chemical polishing solution is 140 - 220 g / L, for example, it can be 150 g / L, 160 g / L, 170 g / L, 180 g / L, 190 g / L, 200 g / L, 210 g / L, etc.

[0078] Preferably, the concentration of aluminum ions in the chemical polishing solution is 10 - 40 g / L, for example, it can be 12 g / L, 14 g / L, 16 g / L, 18 g / L, 20 g / L, 22 g / L, 24 g / L, 26 g / L, 28 g / L, 30 g / L, 32 g / L, 34 g / L, 36 g / L, 38 g / L, etc.

[0079] Preferably, the temperature of chemical polishing is 70 - 80 °C, for example, it can be 71 °C, 72 °C, 73 °C, 74 °C, 75 °C, 76 °C, 77 °C, 78 °C, 79 °C, etc.

[0080] Preferably, the time of chemical polishing is 150 - 300 s, for example, it can be 160 s, 170 s, 180 s, 190 s, 200 s, 210 s, 220 s, 230 s, 240 s, 250 s, 260 s, 270 s, 280 s, 290 s, etc.

[0081] Preferably, the ash removing agent used for ash removal comprises a combination of sulfuric acid, ferric sulfate and water.

[0082] Preferably, the concentration of sulfuric acid in the ash removing agent is 130 - 220 g / L, for example, it can be 140 g / L, 150 g / L, 160 g / L, 170 g / L, 180 g / L, 190 g / L, 200 g / L, 210 g / L, etc.

[0083] Preferably, the concentration of ferrous ions in the ash removing agent is 1.5 - 3.5 g / L, for example, it can be 1.6 g / L, 1.8 g / L, 2 g / L, 2.2 g / L, 2.4 g / L, 2.6 g / L, 2.8 g / L, 3 g / L, 3.2 g / L, 3.4 g / L, etc.

[0084] Preferably, the temperature for ash removal is 30 - 35 °C, for example, it can be 30.5 °C, 31 °C, 31.5 °C, 32 °C, 32.5 °C, 33 °C, 33.5 °C, 34 °C, 34.5 °C, etc.

[0085] Preferably, the time for ash removal is 180 - 300 s, for example, it can be 190 s, 200 s, 210 s, 220 s, 230 s, 240 s, 250 s, 260 s, 270 s, 280 s, 290 s, etc.

[0086] Preferably, the reagent used for alkali washing is sodium hydroxide solution.

[0087] Preferably, the concentration of the sodium hydroxide solution is 30 - 50 g / L, for example, it can be 32 g / L, 34 g / L, 36 g / L, 38 g / L, 40 g / L, 42 g / L, 44 g / L, 46 g / L, 48 g / L, etc.

[0088] Preferably, the temperature for alkali washing is 30 - 35 °C, for example, it can be 30.5 °C, 31 °C, 31.5 °C, 32 °C, 32.5 °C, 33 °C, 33.5 °C, 34 °C, 34.5 °C, etc.

[0089] Preferably, the time for alkali washing is 30 - 70 s, for example, it can be 32 s, 35 s, 38 s, 40 s, 42 s, 45 s, 48 s, 50 s, 52 s, 55 s, 58 s, 60 s, 62 s, 65 s, 68 s, etc.

[0090] Preferably, after the dyeing is completed, it further includes a post-treatment step; the post-treatment includes sequentially performing a sealing hole and a drying step.

[0091] Preferably, the sealing hole includes sequentially performing a first sealing hole treatment and a second sealing hole treatment.

[0092] Preferably, the first sealing agent used for the first sealing treatment comprises a combination of Okuno sealing agent 602, Okuno sealing agent FSO2-R, and water.

[0093] Preferably, the concentration of Okuno sealing agent 602 in the first sealing agent is 45 - 55 g / L, and can be, for example, 45 g / L, 46 g / L, 47 g / L, 48 g / L, 49 g / L, 50 g / L, 51 g / L, 52 g / L, 53 g / L, 54 g / L, 55 g / L, etc.

[0094] Preferably, the concentration of Okuno sealing agent FSO2-R in the first sealing agent is 7.9 - 9.1 mL / L, and can be, for example, 7.9 mL / L, 8.0 mL / L, 8.1 mL / L, 8.2 mL / L, 8.3 mL / L, 8.4 mL / L, 8.5 mL / L, 8.6 mL / L, 8.7 mL / L, 8.8 mL / L, 8.9 mL / L, 9.0 mL / L, 9.1 mL / L, etc.

[0095] Preferably, the weight content of phosphate ions in the first sealing agent is < 0.15 ppm, and can be, for example, 0.02 ppm, 0.04 ppm, 0.06 ppm, 0.08 ppm, 0.1 ppm, 0.12 ppm, 0.14 ppm, etc.

[0096] Preferably, the weight content of phosphorus ions in the first sealing agent is 2.16 - 3.24 ppm, and can be, for example, 2.2 ppm, 2.4 ppm, 2.6 ppm, 2.8 ppm, 3 ppm, 3.2 ppm, etc.

[0097] Preferably, the pH value of the first sealing agent is 4.1 - 4.5, and can be, for example, 4.12, 4.15, 4.18, 4.2, 4.22, 4.25, 4.28, 4.3, 4.32, 4.35, 4.38, 4.4, 4.42, 4.45, 4.48, etc.

[0098] Preferably, the time of the first sealing treatment is 590 - 610 s, and can be, for example, 592 s, 594 s, 596 s, 598 s, 600 s, 602 s, 604 s, 606 s, 608 s, etc.

[0099] Preferably, the temperature of the first sealing treatment is 95 - 99 °C, and can be, for example, 95.2 °C, 95.5 °C, 95.8 °C, 96 °C, 96.2 °C, 96.5 °C, 96.8 °C, 97 °C, 97.2 °C, 97.5 °C, 97.8 °C, 98 °C, 98.2 °C, 98.5 °C, 98.8 °C, etc.

[0100] Preferably, the second sealing agent used for the second sealing treatment comprises an aqueous solution of Okuno Sealing Agent 702.

[0101] Preferably, the concentration of Okuno Sealing Agent 702 in the second sealing agent is 40 - 60 g / L, and can be, for example, 40 g / L, 41 g / L, 42 g / L, 43 g / L, 44 g / L, 45 g / L, 46 g / L, 47 g / L, 48 g / L, 49 g / L, 50 g / L, 51 g / L, 52 g / L, 53 g / L, 54 g / L, 55 g / L, 56 g / L, 57 g / L, 58 g / L, 59 g / L, 60 g / L, etc.

[0102] Preferably, the weight content of phosphate ions in the second sealing agent is < 0.15 ppm, and can be, for example, 0.02 ppm, 0.04 ppm, 0.06 ppm, 0.08 ppm, 0.1 ppm, 0.12 ppm, 0.14 ppm, etc.

[0103] Preferably, the weight content of phosphorus ions in the second sealing agent is 0.56 - 0.84 ppm, and can be, for example, 0.58 ppm, 0.6 ppm, 0.62 ppm, 0.64 ppm, 0.66 ppm, 0.68 ppm, 0.7 ppm, 0.72 ppm, 0.74 ppm, 0.76 ppm, 0.78 ppm, 0.8 ppm, 0.82 ppm, etc.

[0104] Preferably, the pH value of the second sealing agent is 5.3 - 5.7, and can be, for example, 5.32, 5.35, 5.38, 5.4, 5.42, 5.45, 5.48, 5.5, 5.52, 5.55, 5.58, 5.6, 5.62, 5.65, 5.68, etc.

[0105] Preferably, the time for the second sealing treatment is 57 - 60 min, and can be, for example, 57.2 min, 57.4 min, 57.6 min, 57.8 min, 58 min, 58.2 min, 58.4 min, 58.6 min, 58.8 min, 59 min, 59.2 min, 59.4 min, 59.6 min, 59.8 min, etc.

[0106] Preferably, the temperature for the second sealing treatment is 95 - 99 °C, and can be, for example, 95.2 °C, 95.5 °C, 95.8 °C, 96 °C, 96.2 °C, 96.5 °C, 96.8 °C, 97 °C, 97.2 °C, 97.5 °C, 97.8 °C, 98 °C, 98.2 °C, 98.5 °C, 98.8 °C, etc.

[0107] Preferably, the drying temperature is 70 - 80°C, for example, it can be 71°C, 72°C, 73°C, 74°C, 75°C, 76°C, 77°C, 78°C, 79°C, etc.

[0108] Preferably, the drying time is 600 - 1800 s, for example, it can be 650 s, 700 s, 750 s, 800 s, 850 s, 900 s, 950 s, 1000 s, 1100 s, 1200 s, 1300 s, 1400 s, 1500 s, 1600 s, 1700 s, etc.

[0109] In a third aspect, the present invention provides an aluminum alloy obtained by treating with the anodizing process as described in the second aspect.

[0110] Compared with the prior art, the present invention has the following beneficial effects:

[0111] The anodizing dye provided by the present invention has good dyeing effect through the design of each component and the synergistic compounding between components. It can make the metal workpiece after anodizing treatment pass the weight loss test on the premise that the color difference drop point, gloss drop point and film thickness drop point are all small, and has excellent chemical resistance, aging resistance and corrosion resistance.

[0112] For the metal workpiece dyed with the anodizing dye provided by the present invention, the △L value is 0.03 - 0.5, the △a value is 0.01 - 0.09, the △b value is 0.1 - 0.9, the gloss drop point is 0.3 - 0.9, and the film thickness drop point is 0.12 - 0.9. Detailed Embodiments

[0113] To facilitate the understanding of the present invention, the following examples are listed. Those skilled in the art should understand that the examples are only for helping to understand the present invention and should not be regarded as specific limitations to the present invention.

[0114] Example 1

[0115] An anodizing dye, the components of the anodizing dye include a gray dye (its components include Okuno black dye 420, Okuno black dye 411 and Okuno red dye 102), Na 2 SO 4 , Okuno pH-5 assistant and water; the concentration of Okuno black dye 420 in the anodizing dye is 0.6 g / L, the concentration of Okuno black dye 411 is 1 g / L, the concentration of Okuno red dye 102 is 0.04 g / L, and the concentration of Na 2 SO 4 is 1.4 g / L, and the concentration of Okuno pH-5 assistant is 5 mL / L; the pH value of the anodizing dye is 5.7;

[0116] The preparation method of the anodic oxidation dye includes:

[0117] Mix Orihara Black Dye 420, Orihara Black Dye 411 and Orihara Red Dye 102 evenly to obtain a gray dye; mix the gray dye, water, Orihara pH-5 auxiliary agent, and Na 2 SO 4 Mix them, cook at 80 °C for 2 h, and then cool to 40 °C to obtain the anodic oxidation dye.

[0118] Examples 2 to 12, Comparative Examples 1 to 3

[0119] An anodic oxidation dye, which is different from that in Example 1 in that the types and / or concentrations of the components are different, as shown in Tables 1, 2 and 3 specifically. The preparation method of the anodic oxidation dye is the same as that in Example 1.

[0120] Table 1

[0121]

[0122]

[0123] Table 2

[0124]

[0125] Table 3

[0126]

[0127]

[0128] Application Example 1

[0129] An aluminum alloy obtained by subjecting the aluminum alloy to an anodic oxidation process. The anodic oxidation process includes the following steps:

[0130] (1) Degreasing: Degrease an aluminum product with a length of 20 cm, a width of 10 cm and a thickness of 1 cm in an aqueous solution of Orihara degreasing agent 161 with a concentration of 60 g / L at 60 °C for 180 s;

[0131] (2) First nitrogen-free neutralization: After the degreasing is completed, neutralize the aluminum product in Orihara nitrogen-free neutralizing agent with a concentration of 300 g / L at room temperature for 180 s;

[0132] (3) Chemical polishing: After the nitrogen-free neutralization described in step (2) is completed, chemical polishing is carried out for 200 s at 75 °C using a chemical polishing solution. The chemical polishing solution includes phosphoric acid, sulfuric acid, aluminum ions and water; the concentration of phosphoric acid in the chemical polishing solution is 1350 g / L, the concentration of sulfuric acid is 180 g / L, and the concentration of aluminum ions is 25 g / L;

[0133] (4) Desmutting: After the chemical polishing is completed, the aluminum product is desmutted in a desmutting agent at 35 °C for 240 s; the desmutting agent includes sulfuric acid, ferric sulfate and water; the concentration of sulfuric acid in the desmutting agent is 180 g / L, and the concentration of ferrous ions is 2.5 g / L;

[0134] (5) Alkaline washing: After the desmutting is completed, the aluminum product is alkaline washed in a sodium hydroxide solution with a concentration of 40 g / L. The temperature of the alkaline washing is 30 °C and the time is 50 s;

[0135] (6) Second nitrogen-free neutralization: After the alkaline washing is completed, the aluminum product is subjected to nitrogen-free neutralization in an Okuno nitrogen-free neutralizing agent with a concentration of 300 g / L at room temperature for 180 s;

[0136] (7) Anodic oxidation: After the nitrogen-free neutralization described in step (6) is completed, the aluminum product is anodized in an anodic oxidation solution in a constant voltage mode. The temperature of the anodic oxidation is 27 °C, the time is 3600 s, and the current density is 1.0 ASD; the anodic oxidation solution includes sulfuric acid, oxalic acid, aluminum ions and water; the concentration of sulfuric acid in the anodic oxidation solution is 100 g / L, the concentration of oxalic acid is 20 g / L, and the concentration of aluminum ions is 5 g / L;

[0137] (8) Surface conditioning: After the anodic oxidation is completed, the aluminum product is surface conditioned 4 times in an aqueous solution of Okuno surface conditioner 121 with a concentration of 60 g / L. The time for each surface conditioning is 360 s, and the temperature for each surface conditioning is 20 °C;

[0138] (9) Dyeing: The surface-conditioned aluminum product is dyed using the anodic oxidation dye provided in Example 1. The temperature of the dyeing is 40 °C and the time is 400 s;

[0139] (10) Sealing: The dyed aluminum product is subjected to a first sealing treatment in a first sealing agent with a pH value of 4.3. The time for the first sealing treatment is 600 s and the temperature is 96 °C; the first sealing agent is a mixture of Okuno sealing agent 602, Okuno sealing agent FS02-R and water; the concentration of Okuno 602 sealing agent in the first sealing agent is 50 g / L, the concentration of Okuno sealing agent FS02-R is 8.5 mL / L, the weight content of phosphate ions is 0.12 ppm, and the weight content of phosphorus ions is 2.2 ppm;

[0140] Then, the aluminum product is subjected to a second sealing treatment in an aqueous solution of Okuno sealing agent 702 with a pH value of 5.5. The time of the second sealing treatment is 60 min, and the temperature is 96 °C. The concentration of Okuno sealing agent 702 in the aqueous solution of Okuno sealing agent 702 is 60 g / L, the weight content of phosphate ions is 0.08 ppm, and the weight content of phosphorus ions is 0.6 ppm.

[0141] (11) Drying: After drying the sealed aluminum product at a temperature of 80 °C for 1000 s, the aluminum alloy is obtained.

[0142] Application Example 2 - 12

[0143] An aluminum alloy and an anodizing process for the aluminum alloy, which are different from Application Example 1 only in that the anodizing dyes provided in Example 1 in step (9) are respectively replaced by the anodizing dyes provided in Examples 2 - 12, and the remaining raw materials, process parameters, and steps are the same as those in Application Example 1.

[0144] Application Example 13

[0145] An aluminum alloy and an anodizing process for the aluminum alloy, which are different from Application Example 1 only in that the dyeing temperature in step (9) is 35 °C, and the remaining raw materials, process parameters, and steps are the same as those in Application Example 1.

[0146] Application Example 14

[0147] An aluminum alloy and an anodizing process for the aluminum alloy, which are different from Application Example 1 only in that the dyeing temperature in step (9) is 45 °C, and the remaining raw materials, process parameters, and steps are the same as those in Application Example 1.

[0148] Comparative Application Examples 1 - 3

[0149] An aluminum alloy and an anodizing process for the aluminum alloy, which are different from Application Example 1 only in that the anodizing dyes provided in Example 1 in step (9) are respectively replaced by the anodizing dyes provided in Comparative Examples 1 - 3, and the remaining raw materials, process parameters, and steps are the same as those in Application Example 1.

[0150] Comparative Application Example 4

[0151] An aluminum alloy and an anodizing process for the aluminum alloy, which are different from Application Example 1 only in that steps (8) and (9) are carried out as follows, and the remaining raw materials, process parameters, and steps are the same as those in Application Example 1;

[0152] (8) Surface conditioning: After the anodizing is completed, the aluminum product is surface - conditioned 5 times in an aqueous solution of Okuno surface conditioner 121 with a concentration of 60 g / L. The time of each surface conditioning is 360 s, and the temperature of each surface conditioning is 50 °C.

[0153] (9) Dyeing: The surface-adjusted aluminum product was dyed with the anodic oxidation dye provided in Comparative Example 3. The dyeing temperature was 35 °C and the time was 400 s.

[0154] Performance Test

[0155] (1) Color difference drop: The L value, b value and a value of the aluminum product before and after sealing were measured using a 3700A color difference meter, and the difference in L value △L, a value △a and b value △b of the aluminum product before and after sealing were calculated;

[0156] △L = L 0 - L 1 ; △a = a 0 - a 1 ; △b = b 0 - b 1 ;

[0157] Among them, L 0 represents the L value before sealing, and L 1 represents the L value after sealing; a 0 represents the a value before sealing, and a 1 represents the a value after sealing; b 0 represents the b value before sealing, and b 1 represents the b value after sealing;

[0158] When △L is 0.03 - 0.5, △a is 0 - 0.1, and △b is 0.05 - 1, the smaller the difference, the better the sealing effect;

[0159] (2) Gloss drop: The gloss of the aluminum product before and after sealing was measured using a BYK gloss meter, and the gloss difference before and after sealing was calculated. The difference range was 0.2 - 1 GU. The smaller the difference, the better the sealing effect;

[0160] (3) Film thickness drop: The film thickness of the aluminum product before and after sealing was measured using an F40 film thickness gauge, and the film thickness difference before and after sealing was calculated. The difference range was 0.02 - 1 μm. The smaller the difference, the better the sealing effect;

[0161] (4) Chemical test: A thin layer of Banana Boat sunscreen was applied to the surface of the aluminum alloy provided in the application example and the comparative application example using a one-inch cotton swab in an area with a diameter of 18 - 20 mm; after placing the aluminum alloy coated with sunscreen in an environment of 65 °C / 90% RH for 72 h, the following operations were carried out:

[0162] a. Apply an appropriate amount of dishwashing liquid to the area coated with sunscreen; rub with a wet folded paper for about 1 min, and rinse with deionized water for about 1 min at the same time;

[0163] b. If there is any chemical residue on the product surface after rinsing, repeat step a until the sunscreen is wiped clean. After wiping clean, observe whether there are surface texture spots or potential chemical imprints caused by the sunscreen on the aluminum alloy surface. If not, the test is considered passed.

[0164] Replace the sunscreen with Vaseline intensive care lotion, Purell hand sanitizer, L'Oréal hairspray, Maybelline lip balm, Maybelline blush, Ivory dishwashing liquid, all-purpose cleaner, 409 cleaner, glass cleaner, iPad cleaner, wet wipes, 70% isopropyl alcohol, acetone, artificial sweat, sebum, oleic acid, French mustard, Kraft mayonnaise, Heinz ketchup, extra-virgin olive oil, Coca-Cola, Starbucks coffee, chemical cocktail in sequence, and conduct the test according to the above method. As long as one chemical test fails, the chemical test is unqualified.

[0165] (5) Salt spray test: Use a salt spray chamber device to test the aluminum alloy provided by the application example and the comparative application example. The reagent used is 5% NaCl aqueous solution with a pH value of 6.5. The temperature is 35 °C, and the atomization rate is 1 - 2 mL per 80 cm 2 ; The placement time is 24 h. After the test, make a judgment: Visually check whether the aluminum alloy changes color, corrodes, or is damaged. If there is no corrosion, color change, or damage, the test is considered passed.

[0166] (6) UV test: Place the aluminum alloy provided by the application example and the comparative application example in an ultraviolet aging chamber for ultraviolet irradiation. The ultraviolet energy is 0.8 W / m 2 . After 300 h of irradiation, conduct a color difference test to compare the color difference before and after irradiation.

[0167] Calculation formula: If △E94 is less than 3, the test is considered passed.

[0168] △L = L 0 - L 1 ; △a = a 0 - a 1 ; △b = b 0 - b 1 ;

[0169] Among them, L 0 represents the L value before irradiation, and L 1 represents the L value after irradiation; a 0 represents the a value before irradiation, and a 1 represents the a value after irradiation; b 0 represents the b value before irradiation, and b 1 represents the b value after irradiation.

[0170] (7) Weight loss test: Immerse the aluminum alloys provided in the application example and the comparative application example in a phosphoric acid solution of 38 mL / L for 10 min, measure the mass loss of the aluminum alloy before and after immersion to judge the sealing quality of the oxide film. If the mass loss < 30 mg / dm 2 , the weight loss test is qualified.

[0171] Table 4

[0172]

[0173]

[0174] It can be seen from the data in Table 4 that after dyeing the metal workpiece with the anodic oxidation dye provided by the present invention, the color difference drop points, gloss drop points and film thickness drop points of the metal workpiece are all small, and the weight loss test, chemical test, salt spray test and UV test are all qualified.

[0175] It can be known from Application Examples 5-12 that the concentrations of the components in the anodic oxidation dye need to be limited within a suitable range, otherwise the color difference drop points, gloss drop points or film thickness drop points of the aluminum products will increase.

[0176] It can be known from Application Examples 13-14 that if the dyeing temperature is too low or too high, the color difference drop points and film thickness drop points of the aluminum products will increase.

[0177] It can be known from the comparison between Application Example 1 and Comparative Application Example 1 that if the Okuno E-110 additive is used, the color difference drop points, gloss drop points and film thickness drop points of the metal workpiece before and after sealing are relatively large, and the weight loss test and UV test are unqualified.

[0178] It can be known from Comparative Application Example 2 that without using Na 2 SO 4 , the color difference drop points and gloss drop points of the metal workpiece are relatively large, and the chemical test and UV test are unqualified.

[0179] It can be known from Comparative Application Example 3 that on the premise of adding the Okuno E-110 additive, even if the concentrations of Okuno black dye 411, Okuno black dye 420 and Okuno red dye 102 are adjusted, the weight loss test of the metal workpiece is still unqualified.

[0180] It can be known from Comparative Application Example 4 that by increasing the surface conditioning once, the color difference, gloss and film thickness deviation of the metal workpiece are large, the salt spray test is unqualified, and too many surface conditioning times will cause the film holes on the material surface to crack, thereby affecting the corrosion resistance, wear resistance and other properties of the oxide film.

[0181] The applicant declares that the present invention uses the above embodiments to illustrate the anodic oxidation dye, anodic oxidation process and application of the present invention. However, the present invention is not limited to the above embodiments, that is, it does not mean that the present invention must rely on the above embodiments to be implemented. Those skilled in the art should understand that any improvement to the present invention, the equivalent substitution of each raw material of the products of the present invention, the addition of auxiliary components, the selection of specific methods, etc., all fall within the protection scope and the disclosure scope of the present invention.

Claims

1. An anodic oxidation dye, characterized in that: The components of the anodizing dye include a combination of dye, sodium sulfate, a pH stabilizer and water.

2. The anodic oxidation dye according to claim 1, characterized in that: The dye includes any one of a gray dye, a pink dye, a blue dye or a first yellow dye; Preferably, the composition of the gray dye comprises a combination of a black dye and a first red dye; Preferably, the pink dye component comprises a combination of a first pink dye and a second yellow dye; Preferably, the blue dye component includes a combination of a second pink dye, a dark green dye, and a green dye; Preferably, the component of the first yellow dye comprises a combination of a third yellow dye and a second red dye; Preferably, the pH stabilizer includes Ono pH-5 aid; Preferably, when the dye is the gray dye, the concentration of the pH stabilizer in the anodized dye is 4.75-5.25 mL / L; Preferably, when the dye is the gray dye, the concentration of sodium sulfate in the anodized dye is 1.3-1.5 g / L; Preferably, when the dye is any one of the pink dye, the blue dye or the first yellow dye, the concentration of the pH stabilizer in the anodized dye is 1-3 mL / L; Preferably, when the dye is any one of the pink dye, the blue dye or the first yellow dye, the concentration of sodium sulfate in the anodized dye is 0.3-1 g / L.

3. The anodic oxidation dye according to claim 2, characterized in that: The concentration of the black dye in the anodized dye is 1.4-1.8 g / L; Preferably, the concentration of the first red dye in the anodized dye is 0.03-0.05 g / L; Preferably, the black dye includes any one of Oye black dye 420, Oye black dye 411, Oye black dye 419 or Oye black dye 415, or a combination of at least two thereof, and a combination of Oye black dye 420 and Oye black dye 411 is further preferred; Preferably, the concentration of the Aoye black dye 420 in the anodizing dye is 0.5-0.7 g / L, and the concentration of the Aoye black dye 411 is 0.9-1.1 g / L; Preferably, the first red dye includes Ono red dye 102 and / or Ono red dye 106 .

4. The anodic oxidation dye according to claim 2, characterized in that: The first pink dye includes any one of Oono pink dye 144, Oono pink dye 131 or Oono pink dye 139, or a combination of at least two thereof; Preferably, the second yellow dye includes Aoye yellow dye 203 and / or Aoye yellow dye 201; Preferably, the concentration of the first pink dye in the anodized dye is 0.6-0.8 g / L; Preferably, the concentration of the second yellow dye in the anodized dye is 0.2-0.4 g / L.

5. The anodic oxidation dye according to claim 2, characterized in that: The second pink dye includes any one of Oono pink dye 144, Oono pink dye 131 or Oono pink dye 139, or a combination of at least two thereof; Preferably, the dark green dye comprises Clariant dark green dye SANODYE BLUE 2LW and / or Okuno dark green dye TAC Green GM; Preferably, the green dye comprises Clariant Green Dye GLW; Preferably, the concentration of the second pink dye in the anodized dye is 0.4-0.6 g / L; Preferably, the concentration of the dark green dye in the anodized dye is 0.3-0.5 g / L; Preferably, the concentration of the green dye in the anodized dye is 0.01-0.03 g / L.

6. The anodic oxidation dye according to claim 2, characterized in that: The third yellow dye includes Aoye yellow dye 203 and / or Aoye yellow dye 201; Preferably, the second red dye comprises Clariant Red Dye RLW and / or Okuno Red Dye 102; Preferably, the concentration of the third yellow dye in the anodic oxidation dye is 0.2-0.5 g / L; Preferably, the concentration of the second red dye in the anodized dye is 0.05-0.1 g / L.

7. The anodic oxidation dye according to any one of claims 1 to 6, characterized in that The pH value of the anodized dye is 5.5-5.9; Preferably, the components of the anodized dye also include a color stabilizer; Preferably, the color stabilizer is Okuno TAC; Preferably, the concentration of the color stabilizer in the anodic oxidation dye is 1-5 mL / L.

8. An anodizing process, characterized in that: The anodizing process comprises the steps of anodizing, surface conditioning and dyeing in sequence; The dye used for dyeing is the anodic oxidation dye as described in any one of claims 1 to 7.

9. The anodizing process according to claim 8, characterized in that: The table adjustment is processed four times; Preferably, the temperature of the surface adjustment is independently 16-22°C; Preferably, the time of the table adjustment is independently 300-420s; Preferably, the dyeing temperature is 39-41°C; Preferably, the dyeing time is 200-600s; Preferably, the anodizing step further includes a pre-treatment step before the anodizing step; the pre-treatment step includes degreasing, first nitrogen-free neutralization, chemical polishing, ash removal, alkali washing and second nitrogen-free neutralization steps performed in sequence; Preferably, after the dyeing is completed, a post-processing step is also included; the post-processing includes the steps of sealing and drying in sequence.

10. An aluminum alloy, characterized in that: The aluminum alloy is obtained by anodizing as described in claim 8 or 9.

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