CN114369855B - Anodic oxide film dyeing stabilizer and anodic oxide film dyeing method - Google Patents
Anodic oxide film dyeing stabilizer and anodic oxide film dyeing method Download PDFInfo
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- CN114369855B CN114369855B CN202111629079.0A CN202111629079A CN114369855B CN 114369855 B CN114369855 B CN 114369855B CN 202111629079 A CN202111629079 A CN 202111629079A CN 114369855 B CN114369855 B CN 114369855B
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- 238000004043 dyeing Methods 0.000 title claims abstract description 152
- 239000003381 stabilizer Substances 0.000 title claims abstract description 68
- 239000010407 anodic oxide Substances 0.000 title claims abstract description 29
- 238000000034 method Methods 0.000 title claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000000872 buffer Substances 0.000 claims abstract description 19
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Natural products CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 115
- 239000001632 sodium acetate Substances 0.000 claims description 60
- 230000003647 oxidation Effects 0.000 claims description 55
- 238000007254 oxidation reaction Methods 0.000 claims description 55
- 229910000838 Al alloy Inorganic materials 0.000 claims description 45
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 37
- 235000017281 sodium acetate Nutrition 0.000 claims description 37
- 239000007788 liquid Substances 0.000 claims description 35
- 229920000191 poly(N-vinyl pyrrolidone) Polymers 0.000 claims description 24
- OPGYRRGJRBEUFK-UHFFFAOYSA-L disodium;diacetate Chemical compound [Na+].[Na+].CC([O-])=O.CC([O-])=O OPGYRRGJRBEUFK-UHFFFAOYSA-L 0.000 claims description 23
- 235000017454 sodium diacetate Nutrition 0.000 claims description 23
- 239000002904 solvent Substances 0.000 claims description 19
- 239000006174 pH buffer Substances 0.000 claims description 14
- 238000007789 sealing Methods 0.000 claims description 12
- DAJSVUQLFFJUSX-UHFFFAOYSA-M sodium;dodecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCS([O-])(=O)=O DAJSVUQLFFJUSX-UHFFFAOYSA-M 0.000 claims description 7
- 238000005498 polishing Methods 0.000 claims description 4
- 239000003086 colorant Substances 0.000 claims description 3
- 238000002791 soaking Methods 0.000 claims description 3
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 claims 2
- 239000006179 pH buffering agent Substances 0.000 claims 2
- 238000005422 blasting Methods 0.000 claims 1
- 238000003486 chemical etching Methods 0.000 claims 1
- 238000004140 cleaning Methods 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 abstract description 22
- 230000003449 preventive effect Effects 0.000 abstract description 9
- 230000000087 stabilizing effect Effects 0.000 abstract description 6
- 238000013329 compounding Methods 0.000 abstract description 2
- 230000002950 deficient Effects 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 239000000975 dye Substances 0.000 description 28
- 239000000243 solution Substances 0.000 description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 16
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 15
- 230000000694 effects Effects 0.000 description 14
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- 239000000654 additive Substances 0.000 description 9
- 239000012192 staining solution Substances 0.000 description 8
- 230000000996 additive effect Effects 0.000 description 7
- WXMKPNITSTVMEF-UHFFFAOYSA-M sodium benzoate Chemical compound [Na+].[O-]C(=O)C1=CC=CC=C1 WXMKPNITSTVMEF-UHFFFAOYSA-M 0.000 description 7
- 239000004299 sodium benzoate Substances 0.000 description 7
- 235000010234 sodium benzoate Nutrition 0.000 description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 239000005711 Benzoic acid Substances 0.000 description 5
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 5
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 5
- 235000010233 benzoic acid Nutrition 0.000 description 5
- 229910021538 borax Inorganic materials 0.000 description 5
- 239000007853 buffer solution Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 229940078494 nickel acetate Drugs 0.000 description 5
- 239000001044 red dye Substances 0.000 description 5
- HELHAJAZNSDZJO-OLXYHTOASA-L sodium L-tartrate Chemical compound [Na+].[Na+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O HELHAJAZNSDZJO-OLXYHTOASA-L 0.000 description 5
- 239000001433 sodium tartrate Substances 0.000 description 5
- 229960002167 sodium tartrate Drugs 0.000 description 5
- 235000011004 sodium tartrates Nutrition 0.000 description 5
- 235000010339 sodium tetraborate Nutrition 0.000 description 5
- 235000002906 tartaric acid Nutrition 0.000 description 5
- 239000011975 tartaric acid Substances 0.000 description 5
- 230000003139 buffering effect Effects 0.000 description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 3
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 3
- 239000004327 boric acid Substances 0.000 description 3
- 239000003112 inhibitor Substances 0.000 description 3
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 description 3
- QDWYPRSFEZRKDK-UHFFFAOYSA-M sodium;sulfamate Chemical compound [Na+].NS([O-])(=O)=O QDWYPRSFEZRKDK-UHFFFAOYSA-M 0.000 description 3
- BSVBQGMMJUBVOD-UHFFFAOYSA-N trisodium borate Chemical compound [Na+].[Na+].[Na+].[O-]B([O-])[O-] BSVBQGMMJUBVOD-UHFFFAOYSA-N 0.000 description 3
- UMPSXRYVXUPCOS-UHFFFAOYSA-N 2,3-dichlorophenol Chemical compound OC1=CC=CC(Cl)=C1Cl UMPSXRYVXUPCOS-UHFFFAOYSA-N 0.000 description 2
- 239000004288 Sodium dehydroacetate Substances 0.000 description 2
- 239000003945 anionic surfactant Substances 0.000 description 2
- 238000007743 anodising Methods 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- FCPVYOBCFFNJFS-LQDWTQKMSA-M benzylpenicillin sodium Chemical compound [Na+].N([C@H]1[C@H]2SC([C@@H](N2C1=O)C([O-])=O)(C)C)C(=O)CC1=CC=CC=C1 FCPVYOBCFFNJFS-LQDWTQKMSA-M 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- UQGFMSUEHSUPRD-UHFFFAOYSA-N disodium;3,7-dioxido-2,4,6,8,9-pentaoxa-1,3,5,7-tetraborabicyclo[3.3.1]nonane Chemical compound [Na+].[Na+].O1B([O-])OB2OB([O-])OB1O2 UQGFMSUEHSUPRD-UHFFFAOYSA-N 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000002736 nonionic surfactant Substances 0.000 description 2
- 230000002265 prevention Effects 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 238000005488 sandblasting Methods 0.000 description 2
- 239000007974 sodium acetate buffer Substances 0.000 description 2
- 235000019259 sodium dehydroacetate Nutrition 0.000 description 2
- 229940079839 sodium dehydroacetate Drugs 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- 239000004328 sodium tetraborate Substances 0.000 description 2
- DSOWAKKSGYUMTF-GZOLSCHFSA-M sodium;(1e)-1-(6-methyl-2,4-dioxopyran-3-ylidene)ethanolate Chemical compound [Na+].C\C([O-])=C1/C(=O)OC(C)=CC1=O DSOWAKKSGYUMTF-GZOLSCHFSA-M 0.000 description 2
- 230000001954 sterilising effect Effects 0.000 description 2
- 238000004659 sterilization and disinfection Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- QXNVGIXVLWOKEQ-UHFFFAOYSA-N Disodium Chemical compound [Na][Na] QXNVGIXVLWOKEQ-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 1
- 230000005856 abnormality Effects 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000000987 azo dye Substances 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 230000000740 bleeding effect Effects 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910001453 nickel ion Inorganic materials 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000010186 staining Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
Classifications
-
- 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
- C25D11/14—Producing integrally coloured layers
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Coloring (AREA)
Abstract
The invention discloses an anodic oxide film dyeing stabilizer and an anodic oxide film dyeing method, wherein the anodic oxide film dyeing stabilizer comprises the following components: the pH value buffer agent 80-150 g/L, the mildew preventive 0.1-80 g/L, the leveling agent 10-200 g/L and the balance water are used by compounding the pH value buffer agent, the mildew preventive and the leveling agent, and under the specific proportion and the specific consumption, the pH value stabilizing agent and the leveling agent cooperate to ensure that the anodic oxide film dyeing stabilizer has the functions of leveling, stabilizing the pH value and preventing mildew, so that the market blank is filled, the anodic oxide film dyeing stabilizer is convenient to use, the management difficulty of the production line dye liquor is reduced, the anodic oxide film dyeing efficiency is improved, and the defective rate of uneven dyeing on the surface of a workpiece is reduced.
Description
Technical Field
The invention relates to the technical field of metal surface treatment, in particular to an anodic oxidation film dyeing stabilizer and an anodic oxidation film dyeing method.
Background
The aluminum alloy anodic oxidation process is one of the common surface treatment modes of aluminum alloy products. Anodic electrolytic treatment of an aluminum alloy workpiece in a dilute sulfuric acid solution is utilized to generate an oxide film layer on the surface of the aluminum product, the thickness of the film layer is from a few micrometers to hundreds of micrometers, the aperture of the film layer is about 30-70 nanometers, and the film layer is subjected to sealing treatment to endow the workpiece with high hardness, high wear resistance, insulation and other protection functions; meanwhile, the film layer has relatively strong activity, can adsorb dye to obtain colorful decorative appearance, and is widely applied to the fields of cosmetic outer packages, electronics, digital product shells, automobile ornaments and the like.
However, the appearance and color of the aluminum alloy product are difficult to be consistent due to the process characteristic, and certain trouble is brought to industrialized and batch production, so that the problem of uneven special needle dyeing is required to be researched and solved in a targeted manner.
Factors affecting the instability of the anodic staining of aluminum alloys mainly include the following: (1) Because the current density of the edge of the aluminum alloy workpiece is higher during electrolytic treatment, the thickness of an oxide film generated at the edge position of the same technological parameter is about 1-2 microns thicker than the middle part of a product, the porosity of the generated film is large, the capability of absorbing dye in the subsequent dyeing is different, the color is uneven finally, and the color is more obvious when the color is dyed light; (2) influence of pH instability of the staining solution. The aluminium alloy anodic oxidation uses weak acid azo dye, and the pH value of the conventional dyeing liquid ranges from 5 to 6. The slight fluctuation of the pH value can lead to larger deviation of the coloring speed and the hue of the color of the oxidized aluminum alloy workpiece. The phenomena of residual polishing bath liquid, anode bath liquid and other foreign impurities in the blind holes of the workpiece, the gaps of the clamp and the like cannot be avoided. Finally, the PH value of the dyeing liquid is fluctuated, and the stability of the dyeing process is affected; (3) influence of mildew and deterioration of the staining solution. As the coloring agent is organic matter, the pH range of the process is 5-6 in weak acidic working environment. Is easy to mildew under certain temperature and humidity conditions. Slight mildew and bacterial plaque are adsorbed on the surface of an aluminum alloy workpiece to form dirt abnormality, and severe mildew directly leads to scrapping of the dyeing liquid and loss of dyeing function.
The traditional method adopts to add corresponding additive to overcome the three risk items, but because the market products are complex in type and the additive functions are single, the three risks can not be overcome at the same time, multiple additives are generally required to be added at the same time, and the using functions and effects of the different additives can be influenced mutually. Therefore, in order to meet the market demand, it is necessary to develop a novel dyeing additive which can simultaneously meet the improvement of the three risk items, complement functions and is convenient to use.
Disclosure of Invention
In order to overcome the defects and shortcomings of the prior art, the primary purpose of the invention is to provide an anodic oxidation film dyeing stabilizer with a leveling function, stable pH value and mildew resistance.
Another object of the present invention is to provide a dyeing method using the above anodic oxide film dyeing stabilizer.
In order to achieve the aim of the invention, the invention adopts the following technical scheme:
An anodic oxidation film dyeing stabilizer comprises the following components: 80-150 g/L of pH buffer, 10-80 g/L of mildew inhibitor, 10-200 g/L of leveling agent and the balance of water.
Further, the pH buffer is at least one of benzoic acid/sodium benzoate, acetic acid/sodium acetate, sulfamic acid/sodium sulfamate, tartaric acid/sodium tartrate, boric acid/sodium borate buffer system and the like; preferably an acetic acid/sodium acetate buffer system is used.
Further, when the pH buffer adopts one of the above buffer systems, the mass ratio of the benzoic acid to the sodium benzoate in the benzoic acid/sodium benzoate buffer system is 1:10; the mass ratio of the acetic acid to the sodium acetate in the acetic acid/sodium acetate buffer system is 1.8:10; the mass ratio of the tartaric acid to the sodium tartrate in the tartaric acid/sodium tartrate buffer system is 3.2:6; the mass ratio of the sulfamic acid to the sodium sulfamate in the sulfamic acid/sodium sulfamate buffer system is 0.2:6; the mass ratio of the boric acid to the sodium borate in the boric acid/sodium borate buffer system is 4:6.
Further, the leveling agent is at least one of anhydrous sodium sulfate, sodium tetraborate, sodium dodecyl sulfonate, disodium dinaphthyl sulfonate, nickel acetate, peregal O-15, peregal O-25 and the like.
Further, when the leveling agent adopts one of the leveling agents, the content of the sodium sulfate in the anodic oxidation film dyeing stabilizer is 120-200g/L; the content of the sodium tetraborate in the anodic oxidation film dyeing stabilizer is 60-120g/L; the content of the sodium dodecyl sulfate in the anodic oxidation film dyeing stabilizer is 20-30g/L; the content of the dinaphthyl sodium sulfonate in the anodic oxide film dyeing stabilizer is 10-30g/L; the content of the nickel acetate in the anodic oxidation film dyeing stabilizer is 120-200g/L; the content of peregal O-15 or peregal O-25 in the anodic oxidation film dyeing stabilizer is 20-30g/L.
When nickel acetate is used as the leveling agent, the nickel acetate has the functions of sterilization and mildew prevention besides the leveling effect, and the mechanism is that nickel ions containing positive charges can penetrate through the outer surface of microorganisms to enter the space where the inside of nuclei is destroyed or the survival space of bacteria is simulated, so that the functions of mildew prevention of the staining solution and prolonged service life are achieved.
More preferably, the leveling agent is a compound mixture of the sodium dodecyl sulfate and the peregal 0-25; the mass concentration ratio of the sodium dodecyl sulfate to the peregal O-25 in the anodic oxidation film dyeing stabilizer is (6-15) to (10-20).
The sodium dodecyl sulfate is an anionic surfactant, and the peregal O-25 is a nonionic surfactant, so that the anionic surfactant and the nonionic surfactant are compounded for use, the synergistic effect can be achieved, and the dyeing uniformity effect can be improved.
Further, the mildew preventive is at least one of ethanol, dichlorophenol, sodium benzoate, sodium diacetate, sodium dehydroacetate, sodium penicillin and the like; preferably, the sodium diacetate and/or the ethanol are used.
Further, when the mildew preventive adopts one of the mildew preventive, the content of the ethanol in the anodic oxidation film dyeing stabilizer is 30-60ml/L; the content of the dichlorophenol in the anodic oxidation film dyeing stabilizer is 10-20g/L; the content of the sodium benzoate in the anodic oxidation film dyeing stabilizer is 30-70g/L; the content of the sodium diacetate in the anodic oxidation film dyeing stabilizer is 20-80g/L; the content of the sodium dehydroacetate in the anodic oxidation film dyeing stabilizer is 20-50g/L; the content of the penicillin sodium in the anodic oxidation film dyeing stabilizer is 10-30g/L.
When the ethanol is used as the mildew inhibitor, the ethanol has the capability of dyeing uniformly while being used as the mildew inhibitor, and the principle is that the ethanol can improve the surface tension of a liquid-solid interface, so that the dyeing liquid uniformly reaches the inside of the anode film hole of the aluminum alloy workpiece, and the purpose of dyeing uniformly is achieved.
When the sodium diacetate is used as the mildew preventive, the sodium diacetate has the function of stabilizing the pH value of the staining solution, and the principle is that the sodium diacetate is a molecular complex of sodium acetate and acetic acid and has a certain pH value stabilizing function.
The invention also provides an anodic oxide film dyeing method, which comprises the following steps:
S1: pre-treating an aluminum alloy workpiece;
s2: performing anodic oxidation treatment on the aluminum alloy workpiece to generate an oxide film of 5-15 mu m on the surface of the aluminum alloy workpiece;
S3: dyeing the anodized aluminum alloy workpiece in a dyeing liquid added with the anodic oxidation film dyeing stabilizer;
s4: and carrying out hole sealing treatment on the dyed aluminum alloy workpiece in a sealing liquid lithium.
Further, in the step S3, the addition amount of the anodic oxidation film dyeing stabilizer in the dyeing liquid is 1-10 mL/L.
Further, in the step S3, the pH of the staining solution is 5-6; the dyeing treatment conditions are as follows: soaking at 20-60 deg.c for 30-1200 s.
Furthermore, when the aluminum alloy workpiece is dyed light (the dyeing depth L value is more than 75), the thickness of the oxide film of the aluminum alloy workpiece is required to be controlled to be smaller than 10 mu m, the slotting concentration of the coloring agent is smaller than 2g/L, the dyeing time is longer than 2min, and the aluminum alloy workpiece is simultaneously accompanied by more uniform air stirring, so that a better dyeing effect can be obtained.
Compared with the prior art, the invention has the following advantages:
The anodic oxide film dyeing stabilizer provided by the invention comprises the following components: the pH value buffer agent 80-150 g/L, the mildew preventive 0.1-80 g/L, the leveling agent 10-200 g/L and the balance water are used by compounding the pH value buffer agent, the mildew preventive and the leveling agent, and under the specific proportion and the specific consumption, the pH value stabilizing agent and the leveling agent cooperate to ensure that the anodic oxide film dyeing stabilizer has the functions of leveling, stabilizing the pH value and preventing mildew, so that the market blank is filled, the anodic oxide film dyeing stabilizer is convenient to use, the management difficulty of the production line dye liquor is reduced, the anodic oxide film dyeing efficiency is improved, and the defective rate of uneven dyeing on the surface of a workpiece is reduced. Furthermore, the anodic oxide film dyeing method provided by the invention has the characteristics of simple operation, response, dyeing time period and mild dyeing condition.
Drawings
FIG. 1 is a process route diagram of the anodic oxide film uniform dyeing method provided by the invention;
FIG. 2 is a graph showing the comparison of pH stability of anodized film stain stabilizers provided by the present invention with commercially available stabilizers;
FIG. 3 is a graph showing the effect of the anodic oxide film dyeing stabilizer leveling test provided by the invention;
Fig. 4 is a graph showing the effect of the anodic oxidation film dyeing stabilizer provided by the invention in the dyeing test.
Detailed Description
The invention will be described in further detail with reference to specific embodiments and examples in the following, but embodiments of the invention are not limited thereto. All materials and reagents used in the present invention are commercially available conventional materials and reagents unless otherwise specified. The dosage of each component in the examples is g and mL in parts by mass and volume.
Example 1
S1: carrying out sand blasting treatment on an aluminum alloy workpiece by adopting glass beads with 220 meshes, and then carrying out chemical polishing on the aluminum alloy workpiece to control the surface glossiness of the aluminum alloy to be 60 Klems;
S2: anodizing the pretreated aluminum alloy workpiece in a 20% sulfuric acid solution to generate an oxide film of 10 mu m on the surface of the aluminum alloy workpiece;
S3: dyeing the anodized aluminum alloy workpiece in a dyeing liquid containing 0.5g/L of an wild 102 dyeing agent and 5mL/L of an anodic oxide film dyeing stabilizer, wherein the dyeing treatment condition is that soaking is carried out for 200s at 33 ℃;
Wherein the anodic oxidation film dyeing stabilizer comprises the following components: 100g/L pH buffer (acetic acid/sodium acetate system, wherein the mass ratio of acetic acid to sodium acetate is 1.8:10), 15g/L peregal O-25, 10g/L sodium dodecyl sulfate, 15g/L sodium diacetate, and water as solvent.
S4: sealing the dyed aluminum alloy workpiece in sealing liquid, wherein the sealing agent is DX-500 high-temperature sealing agent of Australian, the concentration is 10g/L, the temperature is controlled to 93+/-2 ℃, and the sealing time is 30min.
The process flow diagram of example 1 is shown in FIG. 1.
Example 2
The difference from example 1 is that the anodic oxidation film dyeing stabilizer comprises the following components: 120g/LpH of buffer (acetic acid/sodium acetate system, wherein the mass ratio of acetic acid to sodium acetate is 1.8:10), 12g/L peregal O-25, 12g/L sodium dodecyl sulfate, 20g/L sodium diacetate, and water as solvent.
Example 3
The difference from example 1 is that the anodic oxidation film dyeing stabilizer comprises the following components: 130g/LpH buffer (acetic acid/sodium acetate system, wherein the mass ratio of acetic acid to sodium acetate is 1.8:10), 8g/L peregal O-25, 15g/L sodium dodecyl sulfate, 25g/L sodium diacetate, and water as solvent.
Example 4
The difference from example 1 is that the anodic oxidation film dyeing stabilizer comprises the following components: 120g/LpH of buffer (acetic acid/sodium acetate system, wherein the mass ratio of acetic acid to sodium acetate is 2.0:10), 6g/L peregal O-25, 18g/L sodium dodecyl sulfate, 20g/L sodium diacetate, and water as solvent.
Example 5
The difference from example 1 is that the anodic oxidation film dyeing stabilizer comprises the following components: 120g/LpH buffer (acetic acid/sodium acetate system, wherein the mass ratio of acetic acid to sodium acetate is 2.5:10), 4g/L peregal O-25, 20g/L sodium dodecyl sulfate, 30g/L sodium diacetate, and water as solvent.
Example 6
The difference from example 1 is that the anodic oxidation film dyeing stabilizer comprises the following components: 100g/LpH buffer (benzoic acid/sodium benzoate system, wherein the mass ratio of benzoic acid to sodium benzoate is 1:10), 4g/L peregal O-25, 20g/L sodium dodecyl sulfate, 40mL/L ethanol, water as solvent.
Example 7
The difference from example 1 is that the anodic oxidation film dyeing stabilizer comprises the following components: 100g/LpH buffer (acetic acid/sodium acetate system, wherein the mass ratio of acetic acid to sodium acetate is 1.8:10), 15g/L peregal O-25, 10g/L sodium dodecyl sulfate, 15g/L sodium diacetate, and water as solvent.
Example 8
The difference from example 1 is that the anodic oxidation film dyeing stabilizer comprises the following components: 120g/LpH of buffer (tartaric acid/sodium tartrate system, wherein the mass ratio of tartaric acid to sodium tartrate is 3.2:6), 180g/L of sodium sulfate, 15g/L of sodium diacetate, and water as solvent.
Example 9
The difference from example 1 is that the anodic oxidation film dyeing stabilizer comprises the following components: 150g/LpH buffer (acetic acid/sodium acetate system, wherein the mass ratio of acetic acid to sodium acetate is 1.8:10), 150g/L nickel acetate, 40mL/L ethanol, and water as solvent.
Comparative example 1
The difference from example 1 is that the anodic oxidation film dyeing stabilizer is not added to the dyeing liquid.
The performance of the staining solutions obtained in examples 1 to 5 and comparative example 1 was tested, and the specific results are shown in Table 1. Wherein the pH value of the staining solution is directly measured by a pH meter; the product yield is calculated by 100 aluminum alloy workpieces, and the surface unevenness such as surface mottle, flow mark, hole edge heterochromatic and the like are all bad; the life test method of the dyeing liquid is that static placement is adopted, and the temperature is 28-33 ℃; humidity is 75-90% RH, and the dyeing liquid is turbid and foamed or has mildew spots.
TABLE 1 results of Performance test of staining solutions of different examples
| Project | PH value of dyeing liquid | Product yield/% | Dye liquor lifetime/d |
| Comparative example 1 | 7.2 | 43％ | 3 |
| Example 1 | 5.68 | 97％ | 9 |
| Example 2 | 5.55 | 98％ | 12 |
| Example 3 | 5.52 | 99％ | 14 |
| Example 4 | 5.30 | 96％ | 12 |
| Example 5 | 5.20 | 92％ | 15 |
As can be seen from the data in Table 1, the pH value of the dyeing liquid after the addition of the anodic oxidation film dyeing stabilizer can be kept between 5 and 6, while the pH value of the comparative example 1 without the addition of the anodic oxidation film dyeing stabilizer is obviously beyond the range, and the product yield is obviously improved compared with the service life of the dyeing liquid and the service life of the comparative example 1, and the comprehensive comparison shows that the embodiment 2 is a preferred embodiment of the invention, can improve the product yield to 98%, the service life of the dyeing liquid to 12d, and the embodiment 3 is a preferred embodiment of the invention, can improve the product yield to 99% and the service life of the dyeing liquid to 14d. The performance of the anodic oxide film dyeing stabilizer of the embodiment 6 to the embodiment 9 is similar to that of the embodiment 1, and the anodic oxide film dyeing stabilizer has the functions of uniform dyeing, stable pH value and mildew resistance through the synergistic effect of the pH value buffer, the mildew preventive and the leveling agent in a specific proportion and a specific dosage, so that the market blank is filled.
In order to further verify the performance of the anodic oxidation film dyeing stabilizer, the pH value buffering capacity and the dyeing uniformity of the dyeing liquid are compared. The following test dyes were each tested using an Aofield TAC-102 red dye at a concentration of 0.5 g/L.
Comparison of pH buffering Capacity
Group A: the TAC-102 red dye is dissolved in water (the dye content is 0.5 g/L) to obtain a dye solution A, the pH value of the dye solution A is measured by adopting a pH agent (the result is shown in the graph 2-A1), then 5mL/L of the Oriental TAC-pH5A is added to the dye solution A, and the pH value of the dye solution A is measured again after uniform mixing (the result is shown in the graph 2-A2).
Group B: dissolving TBC-102 red dye in water (dye content 0.5 g/L) to obtain a dye solution B, measuring the pH value of the dye solution B by using a pH agent (the result is shown in fig. 2-B1), adding 5mL/L anodic oxidation film dye stabilizer (130 g/L pH buffer agent, acetic acid/sodium acetate system, wherein the mass ratio of acetic acid to sodium acetate is 1.8:10, 8g/L peregal O-25, 15g/L sodium dodecyl sulfonate, 25g/L sodium diacetate and taking water as a solvent) into the dye solution B, and measuring the pH value of the dye solution B again after uniform mixing (the result is shown in fig. 2-B2).
As shown by the test result, the pH value of the dyeing liquid A is 6.7 when the pH buffer additive is not added, and the pH value of the dyeing liquid A is 5.4 after the 5mL/L of the Okinawa TAC-PH5S buffer additive is added; the pH value of the dyeing solution B is 6.8 when the anodic oxidation film dyeing stabilizer is not added, and the pH value of the dyeing solution B is 5.5 after the 5mL/L anodic oxidation film dyeing stabilizer is added, namely, the test result shows that the anodic oxidation film dyeing stabilizer provided by the invention has the pH value adjusting and buffering capacity, the dyeing solution can be controlled in the optimal pH value working range, and the buffering or adjusting capacity of the anodic oxidation film dyeing stabilizer is equivalent to that of the commercially available wild TAC-PH 5S.
Mildew-proof effect test
Group A: the TBC-102 red dye is dissolved in water (the dye content is 0.5 g/L) to obtain a dye solution A, the dye solution A is placed in an environment with the temperature of 28-33 ℃ and the humidity of 75-90% RH for observation, and the result shows that the dye solution A has the phenomenon of turbidity after being placed for 3 days, has mould after being placed for 7 days and is suspended in the middle of the dye solution.
And B, dissolving TBC-102 red dye in water (dye content is 0.5 g/L) to obtain a dyeing liquid B, adding 5mL/L anodic oxidation film dyeing stabilizer (120 g/L pH buffer (acetic acid/sodium acetate system, wherein the mass ratio of acetic acid to sodium acetate is 1.8:10), 12g/L peregal O-25, 12g/L sodium dodecyl sulfate, 20g/L sodium diacetate and water as solvents) into the dyeing liquid B, uniformly mixing, placing the dyeing liquid B in an environment with the temperature of 28-33 ℃ and the humidity of 75-90% RH for observation, and finding that the solution is still clear and transparent after the dyeing liquid B is placed for 7 days, slightly turbid after the dyeing liquid is placed for 12 days, and the dyeing is mildewed after the dyeing is performed for 15 days.
The comparison test results prove that the anodic oxidation film dyeing stabilizer has the sterilization and mildew resistance capability, and the service life of the dyeing liquid can be prolonged.
Level dyeing effect contrast test
C1 group
S1: carrying out sand blasting treatment on an aluminum alloy workpiece by adopting glass beads with 220 meshes, and then carrying out chemical polishing on the aluminum alloy workpiece to control the surface glossiness of the aluminum alloy to be 60 Klems;
S2: anodizing the pretreated aluminum alloy workpiece in a 20% sulfuric acid solution to generate an oxide film of 10 mu m on the surface of the aluminum alloy workpiece;
S3: dyeing the anodized aluminum alloy workpiece in a dyeing liquid containing 0.5g/L of an wild 102 dyeing agent, wherein the dyeing treatment condition is that the aluminum alloy workpiece is soaked for 120s at 28 ℃;
S4: and (3) carrying out hole sealing treatment on the dyed aluminum alloy workpiece in a sealing liquid. The average dyeing effect is shown in the figure 3-C1.
Group C2:
The difference with the group C1 is that the step S3 is to dye the anodized aluminum alloy workpiece in a dyeing liquid containing 0.5g/L of the wild 102 dyeing agent and 5mL/L of the anodic oxidation film dyeing stabilizer, wherein the dyeing treatment condition is that the aluminum alloy workpiece is soaked for 120S at 28 ℃;
Wherein the anodic oxidation film dyeing stabilizer comprises the following components: 100g/L pH buffer (acetic acid/sodium acetate system, wherein the mass ratio of acetic acid to sodium acetate is 1.8:10), 15g/L peregal O-25, 10g/L sodium dodecyl sulfate, 15g/L sodium diacetate, and water as solvent. The effect of the average dyeing is shown in the figure 3-C2.
Group D1:
The difference from the group C2 is that the step S3 is to dye the anodized aluminum alloy workpiece in a dyeing liquid containing the wild TAC-413 g/L, the wild 102 dyeing agent 0.3g/L and the anodic oxidation film dyeing stabilizer 5mL/L for dyeing, wherein the dyeing condition is to soak for 3.5min at 28 ℃.
The adopted anodic oxidation film dyeing stabilizer comprises the following components: 100g/L pH buffer (acetic acid/sodium acetate system, wherein the mass ratio of acetic acid to sodium acetate is 1.8:10), 4g/L peregal O-25, 40g/L sodium dodecyl sulfate, 15g/L sodium diacetate, and water as solvent. The effect of the average dyeing is shown in the figure 4-D1.
Group D2:
The difference from the group D1 is that the anodic oxidation film dyeing stabilizer comprises the following components: 100g/L pH buffer (acetic acid/sodium acetate system, wherein the mass ratio of acetic acid to sodium acetate is 1.8:10), 15g/L peregal O-25, 10g/L sodium dodecyl sulfate, 15g/L sodium diacetate, and water as solvent. The effect of the average dyeing is shown in the figure 4-D2.
As shown in the test results of the above-mentioned leveling effect, the same test conditions were used, and the addition of the anodic oxidation film dyeing stabilizer (C1) was omitted or the addition of the anodic oxidation film dyeing stabilizer was beyond the limit range (D1) of the present invention, and the surface of the workpiece was liable to have bad appearance such as the bleeding end, the hole edge discoloration, the surface mottle, etc. (see FIGS. 3-C1 and 4-D1). The color of the surface of the workpiece is uniform after the workpiece is treated by the dyeing liquid added with the anodic oxidation film dyeing stabilizing additive, which shows that the anodic oxidation film dyeing stabilizing additive has good dyeing uniformity (as shown in figures 3-C2 and 4-D2).
The above examples are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above examples, and any other changes, modifications, substitutions, combinations, and simplifications that do not depart from the spirit and principle of the present invention should be made in the equivalent manner, and the embodiments are included in the scope of the present invention.
Claims (6)
1. An anodic oxidation film dyeing stabilizer is characterized in that,
The anodic oxidation film dyeing stabilizer is one of the following combinations:
(a) 100g/L of pH buffering agent, 15g/L of peregal O-25, 10g/L of sodium dodecyl sulfonate and 15g/L of sodium diacetate, wherein water is taken as a solvent, the pH buffering agent is an acetic acid/sodium acetate system, and the mass ratio of acetic acid to sodium acetate is 1.8:10;
(b) 120g/LpH of buffer, 12g/L peregal O-25, 12g/L sodium dodecyl sulfonate, 20g/L sodium diacetate, water as solvent and pH buffer as acetic acid/sodium acetate system, wherein the mass ratio of acetic acid to sodium acetate is 1.8:10;
(c) 130g/LpH of buffer, 8g/L peregal O-25, 15g/L sodium dodecyl sulfonate and 25g/L sodium diacetate, and taking water as a solvent, wherein the pH buffer is an acetic acid/sodium acetate system, and the mass ratio of acetic acid to sodium acetate is 1.8:10;
(d) 120g/LpH of buffer, 6g/L peregal O-25, 18g/L sodium dodecyl sulfonate and 20g/L sodium diacetate, taking water as a solvent, and taking pH buffer as an acetic acid/sodium acetate system, wherein the mass ratio of acetic acid to sodium acetate is 2.0:10;
(e) 120g/LpH buffer, 4g/L peregal O-25, 20g/L sodium dodecyl sulfonate, 30g/L sodium diacetate, water as solvent, and pH buffer as acetic acid/sodium acetate system, wherein the mass ratio of acetic acid to sodium acetate is 2.5:10.
2. A method for dyeing an anodic oxide film, comprising the steps of:
S1: pre-treating an aluminum alloy workpiece;
s2: performing anodic oxidation treatment on the aluminum alloy workpiece to generate an oxide film of 5-15 mu m on the surface of the aluminum alloy workpiece;
S3: dyeing the anodized aluminum alloy workpiece in a dyeing liquid added with the anodic oxidation film dyeing stabilizer in claim 1;
s4: and carrying out hole sealing treatment on the dyed aluminum alloy workpiece in a sealing liquid.
3. The method for dyeing an anodic oxide film according to claim 2, wherein the addition amount of the anodic oxide film dyeing stabilizer in the step S3 is 1 to 10mL/L.
4. The method for dyeing an anodic oxide film according to claim 2, wherein the pH of the dyeing liquid in step S3 is 5 to 6; the dyeing treatment condition is soaking for 30-1200 s at 20-60 ℃.
5. The method for dyeing an anodic oxide film according to claim 2, wherein when the dyeing depth L value of the aluminum alloy workpiece is more than 75, the thickness of the oxide film of the aluminum alloy workpiece is controlled to be less than 10 μm, the slotting concentration of the coloring agent is controlled to be less than 2g/L, and the dyeing time is controlled to be more than 2min.
6. The method of dyeing an anodic oxide film according to claim 2, wherein the pretreatment in step S1 is to treat the aluminum alloy workpiece by at least one of polishing, blasting, cleaning, and chemical etching.
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| JPH11323597A (en) * | 1998-05-08 | 1999-11-26 | Matsushita Seiko Co Ltd | Aluminum anodized film subjected to antiviral, antibacterial and antimold treatment |
| CN105839161A (en) * | 2016-05-10 | 2016-08-10 | 广东长盈精密技术有限公司 | Dyeing method of metal component |
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