EP0555244A1 - Additif de l'electrolyte d'un bain colorant pour l'aluminium et procede de teinture de l'aluminium. - Google Patents

Additif de l'electrolyte d'un bain colorant pour l'aluminium et procede de teinture de l'aluminium.

Info

Publication number
EP0555244A1
EP0555244A1 EP91918011A EP91918011A EP0555244A1 EP 0555244 A1 EP0555244 A1 EP 0555244A1 EP 91918011 A EP91918011 A EP 91918011A EP 91918011 A EP91918011 A EP 91918011A EP 0555244 A1 EP0555244 A1 EP 0555244A1
Authority
EP
European Patent Office
Prior art keywords
acid
amount
coloring
antioxidant
improver
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP91918011A
Other languages
German (de)
English (en)
Other versions
EP0555244B1 (fr
Inventor
Riese-Meyer Loert De
Volker Sander
Juergen Lindener
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of EP0555244A1 publication Critical patent/EP0555244A1/fr
Application granted granted Critical
Publication of EP0555244B1 publication Critical patent/EP0555244B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

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
    • C25D11/12—Anodising more than once, e.g. in different baths
    • 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
    • C25D11/20—Electrolytic after-treatment
    • C25D11/22—Electrolytic after-treatment for colouring layers

Definitions

  • the invention describes a new electrolyte additive for a sulfuric, tin (II) -containing dye bath for alternating current coloring of anodized aluminum surfaces, which consists of a synergistic mixture of at least one antioxidant of one of the general formulas I to IV and at least one scattering improver of the general formula V and there is a method for alternating current coloring of anodized aluminum surfaces using the electrolyte additives according to the invention.
  • a sulfuric, tin (II) -containing dye bath for alternating current coloring of anodized aluminum surfaces which consists of a synergistic mixture of at least one antioxidant of one of the general formulas I to IV and at least one scattering improver of the general formula V and there is a method for alternating current coloring of anodized aluminum surfaces using the electrolyte additives according to the invention.
  • aluminum is known to be coated with a natural oxide layer, the layer thickness of which is generally less than 0.1 ⁇ m (Wemick, Pinner, Zurbrügg, Weiner;
  • Electrolyte is preferably used as sulfuric acid, chromic acid or phosphoric acid.
  • Organic acids such as oxalic, maleic, phthalic, salicylic, sulfosalicylic, sulfophthalic, tartaric or citric acid are also used in some processes.
  • the anodization is generally carried out in 10 to 20% sulfuric acid with a current density of 1.5 A / mm and a temperature of 18 to 22 ° C. within 15 to 60 minutes, depending on the desired layer thickness and intended use.
  • the oxide layers produced in this way have a high absorption capacity for a large number of organic and inorganic substances or dyes.
  • Electrolytic dyeing processes have been known since the mid-1930s, in which anodized aluminum can be colored in heavy metal salt solutions by treatment with alternating current.
  • the elements of the first transition row such as Cr, Mn, Fe, Co, Ni, Cu and in particular Sn, are used above all.
  • the heavy eta11salze are mostly used as sulfates, whereby a pH of 0.1 to 2.0 is adjusted with sulfuric acid.
  • the counter electrode can either consist of graphite or stainless steel or of the same material which is dissolved in the electrolyte.
  • the heavy metal pigment is deposited in the pores of the anodic oxide layer in the half period of the alternating current, in which aluminum is the cathode, while in the second half period the aluminum oxide layer is further strengthened by anodic oxidation.
  • the heavy metal is deposited on the bottom of the pores, causing the oxide layer to color.
  • a problem with the coloring in tin electrolytes is the easy oxidizability of the tin, which leads to precipitations of basic tin (-IV) oxide hydrates (tin acid) when used and in some cases even when the Sn solutions are stored.
  • Aqueous tin (II) sulfate solutions are known to be oxidized to tin (IV) compounds by the action of atmospheric oxygen or by reaction at the electrodes under current load. This is when staining in anodized tin electrolytes.
  • phenol-like compounds such as phenolsulfonic acid, cresolsulfonic acid or sulfosalicylic acid (see for example in SA Pozzoli, F. Tegiacchi; Korros. Korro ⁇ sionstik Alum., Event. Eur. Foed. Korros., Vortr. 88th 1976. 139 -45 or in Japanese Patent Laid-Open JP-A-7813583, 78 18483, 77 135841, 76 147436, 7431614, 73 101331, 7120568, 75 26066, 76 122637, 54 097545, 56 081598 and in GB-C-1482390).
  • polyfunctional phenols such as the diphenols hydroquinone, pyrocatechol and resorcinol (see in Japanese laid-open documents JP-A-58 113391, 57 200221 and in FR-C-23 84 037) and the triphenols phloroglucin (JP-A-58113391 ), Pyrogallol (SA Pozzoli, F. Tegiacchi; Corros. Corrosion Protection Alum., Veranstst. Eur. Foed. Korros., Vortr. 88th 1976. 139-45 or in Japanese published documents JP-A-58 113391 and 57200221) or gallic acid (JP-A-53 13583) have already been described in this connection.
  • Another important problem with electrolytic coloring is the so-called scattering ability (deep scattering), which is the product property of coloring anodized aluminum parts that are at different distances from the counterelectrode with a uniform color.
  • Good spreadability is particularly important if the aluminum parts used have a complicated shape (coloring of the depressions), if the aluminum parts are very large and if, for economic reasons, many aluminum parts are to be colored at the same time and medium shades are to be achieved. In application, therefore, a high spreadability is very desirable, since incorrect production is avoided and the optical quality of the colored aluminum parts is generally better.
  • the process is more economical due to its good spreadability, since more parts can be colored in one operation.
  • the term spreadability is not identical to the term uniformity and must be strictly differentiated from this.
  • the uniformity concerns a coloring with the least possible local disturbances in the color (spotty coloring). Poor uniformity is mostly due to impurities such as nitrate or process errors in the anodization. A good color Under no circumstances should beelectrolyte impair the uniformity of the coloring.
  • a dyeing process can achieve good uniformity and still have poor spreading power; the reverse is also possible.
  • the uniformity is generally only influenced by the chemical composition of the electrolyte, while the scattering ability also depends on electrical and geometric parameters, such as the shape of the workpiece or its position and size.
  • DE-A-26 09 146 describes a process for coloring in tin electrolytes, in which the scatterability is set by the special circuit and voltage arrangement.
  • DE-A-2428635 describes the use of a combination of tin (II) and zinc salts with the addition of sulfuric acid and additional boric acid as well as aromatic carboxylic and sulfonic acids (sulfophthalic acid or sulfosalicylic acid) in the electrolytic gray coloring of anodically oxidized Objects made of aluminum.
  • excellent scattering of the dyeing effect should be achieved when the pH is between 1 and 1.5.
  • the setting of the pH to 1 to 1.5 is a basic prerequisite for good electrolytic coloring. It is not described whether the added organic acids have an effect on the spreadability. The spreadability achieved is also not quantified.
  • DE-C-32 46 704 describes a process for electrolytic coloring in which good scattering capacity is ensured by using a special geometry in the dye bath.
  • cresol and phenol sulfonic acid, organic substances such as dextran trin and / or thiourea and / or gelatin ensure an even coloration.
  • the disadvantage of this method is the high investment that is required for the creation of the mechanical devices.
  • deposition inhibitors such as dextrin, thiourea and gelatin has only a slight influence on the scatterability, since the deposition process in electrolytic dyeing differs significantly from that in galvanic tinning. A possibility of measuring the improvements in the spreadability is also not given here.
  • the object of the present invention was to provide a new electrolyte additive for a sulfuric acid, tin (II) -containing dye bath for AC coloring of anodized aluminum surfaces, which provides the problems known from the above-mentioned prior art, how to ensure lasting dye bath stability, avoidance of Sn (II) oxidation and at the same time guarantee good spreading power.
  • the present invention accordingly relates to an electrolyte additive for a sulfuric acid, tin (II) -containing dye bath for AC coloring of anodized aluminum surfaces.
  • Chen containing at least one antioxidant and at least one litter improver, characterized in that the electrolyte additive a) as antioxidant, at least one compound of one of the general formulas I to IV,
  • Rl and R2 represent hydrogen, alkyl, aryl, alkylaryl, alkylarylsulfonic acid, alkylsulfonic acid each having 1 to 22 carbon atoms and their alkali metal salts
  • R3 represents one or more hydrogen and / or alkyl, aryl, Alkylaryl radicals having 1 to 22 carbon atoms are at least one of the radicals R, R2 and R3 being a radical not equal to hydrogen, and b) at least one aromatic carboxylic acid of the general formula V as a scattering improver
  • R * to R5 represent hydrogen, hydroxyl, carboxyl and / or sulfonic acid residues.
  • Another object of the present invention is a process for AC coloring of anodized aluminum surfaces in a sulfuric acid, tin (II) -containing dye bath, characterized in that an electrolyte additive according to the above definition is used at a pH of 0. 1 to 2.0, at a temperature of 10 to 30 ° C and at an alternating voltage with a frequency of 50 to 60 Hz and a terminal voltage of 10 to 25 V for electrolytic coloring in the sulfuric acid, tin (II) containing dye bath.
  • An essential advantage of the electrolyte additive according to the invention is the use of oxidation-stable, water-soluble scatter improvers.
  • p-toluenesulfonic acid known from the teaching of EP-A-354365, develops malodorous vapors by oxidizing the methyl group, which makes long dyebath use intolerable.
  • it is therefore particularly important to equip the scatter improver with oxidation-stable, functional groups, such as carboxyl, hydroxyl and / or sulfonic acid groups.
  • the functional groups mentioned also ensure the required water solubility.
  • the electrolyte additive contains at least one of the compounds of the general formulas I to IV in an amount of 0.01 to 2 g / l as an antioxidant and at least one of the compounds of the general formula V in an amount of 0.1 to 30 g / 1 - each based on the dye bath - as a litter improver.
  • the antioxidants of the general formulas I to IV in the above concentrations are in particular 2-tert-butyl-1,4-dihydroxybenzene (tert-butylhydroquinone), methylhydroquinone, trimethylhydroquinone, 4-hydroxy-2, 7-naphthalene disulfonic acid and / or p-hydroxyanisole used.
  • 5-sulfosalicylic acid 4-sulfophthalic acid, 2-sulfobenzoic acid, benzoic acid and / or benzene hexacarboxylic acid are used in particular as a scatter improver of the general formula V.
  • the combination of 5-sulfosalicylic acid and 4-sulfophthalic acid has proven to be particularly effective in the sense of a synergistic effect.
  • the electrolyte additive according to the invention accordingly contains, in each case based on the total volume of the dyebath:
  • the electrolyte additive according to the invention - in each case based on the total volume of the dyebath - contains in particular: a) as an antioxidant t-butylhydroquinone in an amount of 0.1 to 0.5, preferably 0.2 to 0, 3 g / 1 and b) as a scattering improver 5-sulfosalicylic acid in an amount of 1 to 3 g / 1, preferably 1.5 to 2.5 g / 1 and 4-sulfophthalic acid in an amount of 8 to 12 g / 1, preferably 10 g / 1.
  • the dyeing is usually carried out with the aid of a tin (II) sulfate solution which contains about 3 to 20 g, preferably 7 to 16 g, of tin (II) per liter.
  • Coloring is preferably carried out at a pH of 0.1 to 2.0, corresponding to 16 to 22 g of sulfuric acid per liter, at a temperature of about 14 to 30 ° C.
  • the alternating voltage or alternating current superimposed on the direct current (50 to 60 Hz) is preferably set at 10 to 25 V, preferably 15 to 18 V, with an optimum of approximately 17 V + 3 V.
  • alternating current coloring means either the coloring with pure alternating current or the coloring with "direct current superimposed alternating current” or "alternating current superimposed direct current”.
  • the value of the terminal voltage is given in each case.
  • the coloring begins at a current density of usually about 1 A / dm 2 , which then drops to a constant value of 0.2 to 0.5 A / dm 2 .
  • the metal concentration in the dyebath and the dipping times different tones are obtained, which can vary between champagne-colored and various bronze tones to black.
  • the method of the present invention is characterized in that the electrolyte contains further heavy metal salts in addition to tin, for example nickel, cobalt, copper and / or zinc (see Wernick et al, loc. Cit.).
  • test 1 a) Quick test to assess the storage stability of the baths (test 1)
  • An aqueous electrolyte was prepared, each containing 20 g / 1 sulfuric acid and 10 g / 1 Sn (II) ions, as well as corresponding amounts of an electrolyte additive.
  • 1-1- solutions were stirred vigorously at room temperature with a magnetic stirrer and gassed with 12 l / h of pure oxygen over a glass frit.
  • the content of Sn (II) ions after 4 hours was recorded iodometrically.
  • the percentage decrease in Sn (II) concentration was recorded.
  • an aqueous electrolyte which contained 20 g / 1 sulfuric acid, 10 g / 1 Sn (II) ions and corresponding amounts of an electrolyte additive.
  • the permanent electrolysis (alternating current 50 Hz, voltage: 12 V) was carried out with stainless steel electrodes.
  • the flowing amount of electricity was registered with an Ah counter.
  • the characteristic behavior of the oxide layer to be colored was simulated by corresponding sinusoidal distortion of the alternating current at high capacitive loads.
  • the amount of Sn (II) ions oxidized by electrode reactions was determined by continuous iodometric titration of the electrolyte and by gravi etric determination of the reductively deposited Sn and the difference from the suirane of these two values to the initial amount of dissolved Sn (II).
  • the Ah value was chosen to have an antioxidant effect, at which a reduction in the Sn (II) concentration by 5 g / l can no longer be prevented.
  • Test sheets measuring 50 mm x 460 mm x 1 mm made of the DIN material AI 99.5 were conventionally pretreated and then electrolytically colored in a dye bath with a suitable geometry (electrode at a distance of 1 to 5 cm from the counter electrodes).
  • the dyebath also contained different amounts of the test substances (see examples and comparative examples).
  • the standard dyeing was 16 V (alternating current 50 Hz) for 5 minutes.
  • the "mean coloring" results from the individual measured values.
  • the scatterability is determined from this as a measure of the correspondence of each measuring point with the mean value and is given as a process value.
  • the Streuauch ⁇ mean speed of 100% r is that the test sheet over the entire length ein ⁇ uniformly colored. The closer the values come to 0%, the more differently the sheet ends are colored.
  • Test sheets made of the DIN material AI 99.5 were conventionally pretreated (degreased, pickled, decapitated) and after the GS process (200 g / 1 sulfuric acid, 10 g / 1 Al (III), air flow rate, 1 , 5 A / dm 2 , 18 ° C) anodized for 60 minutes. This resulted in a layer structure of approximately 20 ⁇ m.
  • the one so pretreated As described in the following examples, sheets were electrolytically colored with alternating current (50 Hz). The results are summarized in Table 1.
  • Electrolyte 10.0 g / 1 Sn (II)
  • Electrolyte 10.0 g / 1 Sn (II)
  • Electrolyte 10.0 g / 1 Sn (II)
  • Electrolyte 10.0 g / 1 Sn (lT)
  • Electrolyte 10.0 g / 1 Sn (II)
  • Electrolyte 10.0 g / 1 Sn (II)
  • Tin (II) salt electrolytes such as storage stability, antioxidant activity and scatterability, were significantly improved compared to Comparative Examples 1 to 4.
  • Comparative Example 5 an intensifying, malodorous odor occurs after only 15 minutes.

Abstract

Un nouvel additif de l'électrolyte d'un bain colorant d'acide sulfurique contenant de l'étain et servant à colorer, sous un courant alternatif, des surfaces anodisées en aluminium se compose d'un mélange synergique d'au moins un anti-oxydant défini par une des formules générales (I à IV) et au moins un agent améliorateur de la dispersion de la formule générale (V). L'invention concerne également un procédé de teinture sous un courant alternatif de surfaces anodisées en aluminium avec l'additif d'électrolyte décrit.
EP91918011A 1990-10-29 1991-10-21 Additif de l'electrolyte d'un bain colorant pour l'aluminium et procede de teinture de l'aluminium Expired - Lifetime EP0555244B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE4034304A DE4034304A1 (de) 1990-10-29 1990-10-29 Elektrolytzusatzmittel fuer ein faerbebad zur aluminiumeinfaerbung und verfahren zur einfaerbung von aluminium
DE4034304 1990-10-29
PCT/EP1991/001994 WO1992007976A1 (fr) 1990-10-29 1991-10-21 Additif de l'electrolyte d'un bain colorant pour l'aluminium et procede de teinture de l'aluminium

Publications (2)

Publication Number Publication Date
EP0555244A1 true EP0555244A1 (fr) 1993-08-18
EP0555244B1 EP0555244B1 (fr) 1995-04-12

Family

ID=6417215

Family Applications (1)

Application Number Title Priority Date Filing Date
EP91918011A Expired - Lifetime EP0555244B1 (fr) 1990-10-29 1991-10-21 Additif de l'electrolyte d'un bain colorant pour l'aluminium et procede de teinture de l'aluminium

Country Status (17)

Country Link
US (1) US5409592A (fr)
EP (1) EP0555244B1 (fr)
JP (1) JP2941055B2 (fr)
KR (1) KR0185157B1 (fr)
CN (1) CN1066496C (fr)
AR (1) AR245786A1 (fr)
AT (1) ATE121145T1 (fr)
AU (1) AU646508B2 (fr)
CA (1) CA2095247C (fr)
CS (1) CS327291A3 (fr)
DE (2) DE4034304A1 (fr)
ES (1) ES2070514T3 (fr)
MX (1) MX9101817A (fr)
PT (1) PT99342B (fr)
WO (1) WO1992007976A1 (fr)
YU (1) YU170691A (fr)
ZA (1) ZA918569B (fr)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4120415A1 (de) * 1991-06-20 1992-12-24 Henkel Kgaa Konfektioniertes zinn(ii)sulfat-granulat zur elektrolytischen metallsalzeinfaerbung
DE4244021A1 (de) * 1992-12-24 1994-06-30 Henkel Kgaa Verfahren zur elektrolytischen Wechselstromeinfärbung von Aluminiumoberflächen
CN1038856C (zh) * 1993-01-16 1998-06-24 成都科技大学 铝及铝合金的复合着色方法
DE19852219C1 (de) * 1998-11-12 2000-05-11 Schloetter Fa Dr Ing Max Wäßrige Lösung zur elektrolytischen Abscheidung von Zinn-Zink-Legierungen und Verwendung der Lösung
CN104651905B (zh) * 2015-01-28 2017-11-07 永保纳米科技(深圳)有限公司 一种阳极铝匀染缓染助剂及其操作液，和阳极铝匀染缓染处理工艺
CN107815716B (zh) * 2017-09-12 2019-09-20 广东长盈精密技术有限公司 对工件的表面进行处理的方法

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FR752359A (fr) * 1933-09-20
GB1151460A (en) * 1967-10-09 1969-05-07 Motohiko Kanai Improvements in and relating to the Electroplating of Tin-Lead Alloy
JPS4931674A (fr) * 1972-07-25 1974-03-22
JPS5245650B2 (fr) * 1972-04-03 1977-11-17
AT324795B (de) * 1973-07-02 1975-09-25 Piesslinger Ind Baubedarf Verfahren und färbeelektrolyt zum graufärben von anodisch oxydierten gegenständen aus aluminium oder dessen legierungen
JPS5423664B2 (fr) * 1975-03-06 1979-08-15
JPS51122637A (en) * 1975-04-19 1976-10-26 Riyouji Suzuki Process for rapid coloring anodic coating of aluminum
JPS51147436A (en) * 1975-06-13 1976-12-17 Aiden Kk Process for coloring aluminum anodized coating
GB1482390A (en) * 1975-11-24 1977-08-10 Norsk Hydro As Process for colouring of anodised aluminium and aluminium alloys
JPS6012437B2 (ja) * 1976-05-10 1985-04-01 株式会社パイロット アルミニウム又はその合金の電解着色法
JPS5318483A (en) * 1976-08-04 1978-02-20 Hitachi Denkaihaku Kenkyusho Method of manufacturing aluminumminorganic aggregating agents
FR2384037A1 (fr) * 1977-03-17 1978-10-13 Nice Anodisation Sa Perfectionnement au procede de coloration electrolytique de l'aluminium et de ses alliages
JPS5497545A (en) * 1978-01-19 1979-08-01 Sumitomo Light Metal Ind Forming of colored skin of aluminium
JPS6049138B2 (ja) * 1981-06-05 1985-10-31 三菱マテリアル株式会社 錫塩酸性溶液における錫塩の加水分解防止法
JPS6026840B2 (ja) * 1981-12-25 1985-06-26 三菱マテリアル株式会社 Ａｌ又はＡｌ金の電解着色法
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Also Published As

Publication number Publication date
PT99342A (pt) 1992-09-30
WO1992007976A1 (fr) 1992-05-14
US5409592A (en) 1995-04-25
YU170691A (sh) 1994-01-20
MX9101817A (es) 1992-06-05
CA2095247A1 (fr) 1992-04-30
CA2095247C (fr) 2002-01-01
ES2070514T3 (es) 1995-06-01
KR930702556A (ko) 1993-09-09
JPH06502217A (ja) 1994-03-10
DE4034304A1 (de) 1992-04-30
DE59105203D1 (de) 1995-05-18
CN1061056A (zh) 1992-05-13
EP0555244B1 (fr) 1995-04-12
ATE121145T1 (de) 1995-04-15
AU8743991A (en) 1992-05-26
PT99342B (pt) 1999-02-26
KR0185157B1 (ko) 1999-04-01
AU646508B2 (en) 1994-02-24
JP2941055B2 (ja) 1999-08-25
CN1066496C (zh) 2001-05-30
ZA918569B (en) 1992-07-29
AR245786A1 (es) 1994-02-28
CS327291A3 (en) 1992-06-17

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