EP0960220A1 - Stabilisatoren für hydroxylamin in kupfer-haltigen phosphatierlösungen - Google Patents
Stabilisatoren für hydroxylamin in kupfer-haltigen phosphatierlösungenInfo
- Publication number
- EP0960220A1 EP0960220A1 EP97954444A EP97954444A EP0960220A1 EP 0960220 A1 EP0960220 A1 EP 0960220A1 EP 97954444 A EP97954444 A EP 97954444A EP 97954444 A EP97954444 A EP 97954444A EP 0960220 A1 EP0960220 A1 EP 0960220A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- phosphating solution
- solution according
- stabilizer
- hydroxylamine
- phosphating
- 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.)
- Withdrawn
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/07—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing phosphates
- C23C22/08—Orthophosphates
- C23C22/12—Orthophosphates containing zinc cations
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/34—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides
- C23C22/36—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides containing also phosphates
- C23C22/364—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides containing also phosphates containing also manganese cations
Definitions
- the invention relates to phosphating solutions which are suitable for producing crystalline zinc phosphate layers on steel, galvanized or alloy-galvanized steel and on aluminum and its alloys.
- these phosphating solutions contain copper ions and, as accelerators, hydroxylamine in free, salt-like or bound form.
- EP-A-0 315 059 discloses a process for zinc phosphating iron-containing surfaces.
- the desired morphology of the zinc phosphate crystals is set by using hydroxylammonium salts, hydroxylamine complexes and / or hydroxylamine.
- EP-B-633 950 teaches a process for producing copper-containing nickel-free phosphate layers with a copper content in the range from 0.1 to 5% by weight and an edge length of the phosphate crystals in the range from 0.5 to 10 ⁇ m on metal surfaces, selected from Steel, galvanized steel, alloy galvanized steel, aluminum and their alloys, by treating them in the spray, dip or spray / dip process with a phosphating solution which contains the following components:
- hydroxylamine salts, hydroxylamine complexes and / or hydroxylamine in an amount of 500 to 5000 ppm hydroxylamine, based on the phosphating solution.
- Phosphating baths which contain copper ions and hydroxylamine as accelerators have the following disadvantage:
- the catalytic influence of copper ions leads to accelerated decomposition of the hydroxylamine. This effect is particularly pronounced in spray processes in which the phosphating solution comes into intimate contact with air.
- This catalytic decomposition increases the consumption of hydroxylamine considerably and increases the cost of the phosphating process.
- the object of the invention is therefore to provide phosphating solutions in which the decomposition of hydroxylamine by copper is slowed down by the fact that they contain suitable stabilizers.
- the invention accordingly relates to an acidic, aqueous phosphating solution which
- hydroxylamine-releasing compound in free form, as a salt or as a hydroxylamine-releasing compound, characterized in that it additionally contains one or more stabilizers for hydroxylamine, selected from organic molecules containing at least two heteroatoms per molecule or, in the case of polymers, at least one heteroatom per 4 carbon atoms have, wherein at least one of the heteroatoms is a nitrogen or an oxygen atom and heteroatoms bonded to the same carbon atom are only counted once, in the case of carboxyl group-containing molecules or polymers at least three carbon atoms must lie between two adjacent carboxyl groups.
- stabilizers for hydroxylamine selected from organic molecules containing at least two heteroatoms per molecule or, in the case of polymers, at least one heteroatom per 4 carbon atoms have, wherein at least one of the heteroatoms is a nitrogen or an oxygen atom and heteroatoms bonded to the same carbon atom are only counted once, in the case of carboxyl group-containing molecules or polymers at least three
- heteroatoms bound to the same atom simply means that the two oxygen atoms of a carboxyl group are only counted as a single heteroatom.
- sulfonic acid or phosphonic acid groups are also regarded as only one heteroatom.
- the reason for this method of counting is the assumption that the stabilizing effect of heteroatom-containing organic molecules is related to a complexing effect against copper.
- acid groups such as carboxyl groups generally only act as monodentate ligands, ie only a single oxygen atom is available for coordination to the copper.
- the result of this counting method is that monocarboxylic acids which, apart from the only carboxyl group, have no further heteroatoms are not covered by the invention.
- the definition of the invention further excludes di-, oligo- or polycarboxylic acids in which there are not at least three carbon atoms between adjacent carboxyl groups. Acids with denser carboxyl groups can directly influence the layer formation due to their complexing effect on iron and can lead, for example, to undesirable layer weights. Only those di-, oligo- or polycarboxylic acids can be recommended as stabilizers, without possibly negative side effects, in which neighboring carboxyl groups are separated by at least three carbon atoms. Therefore, for example, oxalic acid, malic acid, tartaric acid or citric acid and poly (meth) acrylic acids are not covered by the protection request.
- the stabilizer can, for example, be characterized in that it has an atomic sequence X - C ⁇ _3 - Y, where X stands for an oxygen or nitrogen atom and Y for an oxygen, nitrogen, phosphorus or sulfur atom.
- stabilizers are suitable which have an atomic sequence O - C - C - O or O - C - C - C - 0, in which case according to the above restriction at most one of the two O atoms of the atomic sequence mentioned belongs to a carboxyl group may.
- these can be polyethylene glycols, polypropylene glycols or polytetrahydrofuran.
- polyethylene glycols with an average molecular weight of 200 to 10,000, which can be determined by gel permeation chromatography are suitable.
- the stabilizer can also be a diazole or a triazole derivative. Examples of such effective derivatives are carbendiazim and 1H-benzotriazole-5-carboxylic acid.
- the stabilizer can be selected from molecules which have an atomic sequence -N - C - C - Y '- Z, where Z represents an oxygen or a nitrogen atom and Y ' represents a carbon, sulfur or phosphorus atom or else entirely may be missing.
- this sequence of atoms can be - N - C - C - N -.
- Preferred molecules are those in which the two nitrogen atoms are members of two aromatic heterocyclic rings. These include in particular 2,2'-bipyridine, 2,2 ' : 6', 2 "-terpyridine and 1,10-phenanthroline.
- the stabilizer can have the atomic sequence - N - C - C - O.
- These stabilizers can represent alpha-amino acids, for example. Those amino acids which have at least one aromatic residue are preferred. Examples include phenylalanine, thyrosine, tryptophan and histidine.
- Molecules with an atomic sequence - N - C - C - O are also suitable in which the nitrogen atom is a member of a heterocyclic aromatic ring.
- the nitrogen atom can be in a pyridine ring.
- An example of such a compound is picolinic acid.
- the phosphating bath can furthermore contain a stabilizer which has an atomic sequence - N - C - C - Y - 0, in which Y represents a sulfur or a phosphorus atom.
- a stabilizer which has an atomic sequence - N - C - C - Y - 0, in which Y represents a sulfur or a phosphorus atom.
- a molecular structure of the stabilizer is favorable, in which the nitrogen atom is a member of a heterocyclic aromatic ring, in particular a pyridine ring.
- An example of such a heterocyclic sulfonic acid is quinoline-8-sulfonic acid.
- Aromatic hydroxycarboxylic acids are further examples of stabilizers according to the general definition. Hydroxybenzoic acids with one or more hydroxyl groups are particularly suitable. P-Hydroxybenzoic acid is particularly suitable. In general, the type and amount of stabilizer should be chosen so that it
- the molar ratio of stabilizer to copper ions should be in the range from 1: 1 to 20: 1. If a polymer such as polyglycol is used as the stabilizer, the term “mole” refers to the concentration calculation
- the stabilizer is used in particular for copper-containing zinc phosphating solutions that additionally contain up to 2 g / 1 manganese ions.
- Phosphating solutions are usually prepared by diluting an aqueous concentrate with water to the application concentration and, if appropriate, adjusting the desired pH or the value of the "free acid" (a term generally known in the phosphating field) by adding alkalis. Accordingly, the invention also encompasses an aqueous concentrate which, after dilution with water in a ratio of 1:10 to 1: 100 and, if appropriate, adjustment of the pH, gives a phosphating solution according to one or more of Claims 1 to 18.
- the proportions in the supplemental solution may differ from the proportions to be set in the phosphating bath.
- the phosphating solution does not have to contain zinc ions if sufficient zinc ions get into the phosphating bath during the phosphating of galvanized material due to the pickling attack.
- the supplemental solution may have a higher ratio of hydroxylamine to layer-forming cations than the phosphating bath.
- the supplementary solution can only contain hydroxylamine and stabilizer, but no layer-forming components. Accordingly, the invention also includes an aqueous supplementary solution for a phosphating solution according to one or more of Claims 1 to 18, the hydroxylamine in free form as
- a commercially available phosphating bath concentrate was prepared by mixing the following components in the order given:
- An operable phosphating bath is obtained by preparing a 4.8% by weight aqueous solution of this concentrate and adjusting it to a pH of 3.2.
- This phosphating bath is mixed with different amounts of copper ions (as copper sulfate) and stabilizer and at 55 ° C in a drying cabinet stored. After certain times, the residual hydroxylamine content is determined analytically using the so-called "acetone method".
- the initial hydroxylamine content is set as 100% relative and the amounts of hydroxylamine found after certain times are related to this.
- Table 1 shows the residual hydroxylamine content as a function of time when stored at 55 ° C.
- a Cu concentration of 0.11 mmol / 1 corresponding to 7 mg / 1 was set for row A and a Cu concentration of 0.16 mmol / 1 corresponding to 10.2 mg / 1 for row B.
Landscapes
- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
- Chemical Treatment Of Metals (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
Description
Claims
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE1997100326 DE19700326A1 (de) | 1997-01-08 | 1997-01-08 | Stabilisatoren für Hydroxylamin in Kupfer-haltigen Phosphatierlösungen |
DE19700326 | 1997-01-08 | ||
PCT/EP1997/007185 WO1998030732A1 (de) | 1997-01-08 | 1997-12-19 | Stabilisatoren für hydroxylamin in kupfer-haltigen phosphatierlösungen |
Publications (1)
Publication Number | Publication Date |
---|---|
EP0960220A1 true EP0960220A1 (de) | 1999-12-01 |
Family
ID=7816929
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP97954444A Withdrawn EP0960220A1 (de) | 1997-01-08 | 1997-12-19 | Stabilisatoren für hydroxylamin in kupfer-haltigen phosphatierlösungen |
Country Status (8)
Country | Link |
---|---|
EP (1) | EP0960220A1 (de) |
JP (1) | JP2002500702A (de) |
AU (1) | AU5859098A (de) |
BR (1) | BR9714199A (de) |
CA (1) | CA2277336A1 (de) |
DE (1) | DE19700326A1 (de) |
TR (1) | TR199901460T2 (de) |
WO (1) | WO1998030732A1 (de) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN106460185B (zh) | 2014-04-30 | 2020-02-21 | Rio管理有限公司 | 用于酸洗和磷化处理金属部件的处理设备和处理方法 |
Family Cites Families (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS57179843A (en) * | 1981-04-30 | 1982-11-05 | Oriental Shashin Kogyo Kk | Color developer composition for color photographic sensitive silver halide material |
JPS595573B2 (ja) * | 1981-10-20 | 1984-02-06 | 日進化工株式会社 | ヒドロキシルアミンの安定化剤 |
JPS595574B2 (ja) * | 1981-10-20 | 1984-02-06 | 日進化工株式会社 | ヒドロキシルアミンの安定化剤 |
JPS59160142A (ja) * | 1983-03-02 | 1984-09-10 | Fuji Photo Film Co Ltd | ハロゲン化銀カラ−感光材料の処理方法 |
JPH068956B2 (ja) * | 1983-04-04 | 1994-02-02 | 富士写真フイルム株式会社 | ハロゲン化銀カラ−感光材料の処理方法 |
US4975357A (en) * | 1989-05-23 | 1990-12-04 | Eastman Kodak Company | Method of photographic color development using polyhydroxy compounds, metal ions and sequestering agents |
DE4210513A1 (de) * | 1992-03-31 | 1993-10-07 | Henkel Kgaa | Nickel-freie Phosphatierverfahren |
IT1274594B (it) * | 1994-08-05 | 1997-07-18 | Itb Srl | Soluzione fosfatica acquosa acida e processo di fosfatazione di superfici metalliche che la utilizza |
DE19606017A1 (de) * | 1996-02-19 | 1997-08-21 | Henkel Kgaa | Zinkphosphatierung mit geringen Gehalten an Kupfer und Mangan |
-
1997
- 1997-01-08 DE DE1997100326 patent/DE19700326A1/de not_active Withdrawn
- 1997-12-19 CA CA002277336A patent/CA2277336A1/en not_active Abandoned
- 1997-12-19 TR TR1999/01460T patent/TR199901460T2/xx unknown
- 1997-12-19 EP EP97954444A patent/EP0960220A1/de not_active Withdrawn
- 1997-12-19 BR BR9714199-2A patent/BR9714199A/pt unknown
- 1997-12-19 AU AU58590/98A patent/AU5859098A/en not_active Abandoned
- 1997-12-19 JP JP53050498A patent/JP2002500702A/ja active Pending
- 1997-12-19 WO PCT/EP1997/007185 patent/WO1998030732A1/de not_active Application Discontinuation
Non-Patent Citations (1)
Title |
---|
See references of WO9830732A1 * |
Also Published As
Publication number | Publication date |
---|---|
JP2002500702A (ja) | 2002-01-08 |
BR9714199A (pt) | 2000-03-28 |
AU5859098A (en) | 1998-08-03 |
DE19700326A1 (de) | 1998-07-09 |
TR199901460T2 (xx) | 1999-11-22 |
CA2277336A1 (en) | 1998-07-16 |
WO1998030732A1 (de) | 1998-07-16 |
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Legal Events
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RIN1 | Information on inventor provided before grant (corrected) |
Inventor name: BROUWER, JAN-WILLEM Inventor name: KLEINE-BLEY, FRANK Inventor name: KUHM, PETER Inventor name: GEKE, JUERGEN Inventor name: MAYER, BERND |
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