[go: up one dir, main page]

WO1998030732A1 - Agents stabilisants pour l'hydroxylamine dans des solutions de phosphatation contenant du cuivre - Google Patents

Agents stabilisants pour l'hydroxylamine dans des solutions de phosphatation contenant du cuivre Download PDF

Info

Publication number
WO1998030732A1
WO1998030732A1 PCT/EP1997/007185 EP9707185W WO9830732A1 WO 1998030732 A1 WO1998030732 A1 WO 1998030732A1 EP 9707185 W EP9707185 W EP 9707185W WO 9830732 A1 WO9830732 A1 WO 9830732A1
Authority
WO
WIPO (PCT)
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.)
Ceased
Application number
PCT/EP1997/007185
Other languages
German (de)
English (en)
Inventor
Bernd Mayer
Jürgen Geke
Peter Kuhm
Frank Kleine-Bley
Jan-Willem Brouwer
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
Priority to JP53050498A priority Critical patent/JP2002500702A/ja
Priority to BR9714199-2A priority patent/BR9714199A/pt
Priority to EP97954444A priority patent/EP0960220A1/fr
Priority to CA002277336A priority patent/CA2277336A1/fr
Priority to AU58590/98A priority patent/AU5859098A/en
Publication of WO1998030732A1 publication Critical patent/WO1998030732A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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.
  • 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
  • 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 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.
  • 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.
  • the stabilizer is used in particular for copper-containing zinc phosphating solutions that additionally contain up to 2 g / 1 manganese ions.
  • 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.

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)
  • Paints Or Removers (AREA)

Abstract

L'invention concerne une solution de phosphatation aqueuse acide contenant des ions de zinc, des ions de phosphate, des ions de cuivre et de l'hydroxylamine sous forme libre, comme sel ou comme composé entraînant une rupture de l'hydroxylamine et en outre, un ou plusieurs agents stabilisants de l'hydroxylamine, sélectionnés parmi des molécules organiques présentant au moins deux hétéroatomes par molécule ou en cas de polymères, au moins un hétéroatome pour 4 atomes de carbone. L'invention concerne également un concentré aqueux et une solution complémentaire aqueuse pour la solution de phosphatation.
PCT/EP1997/007185 1997-01-08 1997-12-19 Agents stabilisants pour l'hydroxylamine dans des solutions de phosphatation contenant du cuivre Ceased WO1998030732A1 (fr)

Priority Applications (5)

Application Number Priority Date Filing Date Title
JP53050498A JP2002500702A (ja) 1997-01-08 1997-12-19 銅を含有するりん酸塩皮膜形成液におけるヒドロキシルアミンのスタビライザー
BR9714199-2A BR9714199A (pt) 1997-01-08 1997-12-19 Estabilizadores para hidroxilamina em soluções de fosfatação contendo cobre.
EP97954444A EP0960220A1 (fr) 1997-01-08 1997-12-19 Agents stabilisants pour l'hydroxylamine dans des solutions de phosphatation contenant du cuivre
CA002277336A CA2277336A1 (fr) 1997-01-08 1997-12-19 Agents stabilisants pour l'hydroxylamine dans des solutions de phosphatation contenant du cuivre
AU58590/98A AU5859098A (en) 1997-01-08 1997-12-19 Hydroxylamine stabilizers in copper-containing phosphating solutions

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE1997100326 DE19700326A1 (de) 1997-01-08 1997-01-08 Stabilisatoren für Hydroxylamin in Kupfer-haltigen Phosphatierlösungen
DE19700326.5 1997-01-08

Publications (1)

Publication Number Publication Date
WO1998030732A1 true WO1998030732A1 (fr) 1998-07-16

Family

ID=7816929

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP1997/007185 Ceased WO1998030732A1 (fr) 1997-01-08 1997-12-19 Agents stabilisants pour l'hydroxylamine dans des solutions de phosphatation contenant du cuivre

Country Status (8)

Country Link
EP (1) EP0960220A1 (fr)
JP (1) JP2002500702A (fr)
AU (1) AU5859098A (fr)
BR (1) BR9714199A (fr)
CA (1) CA2277336A1 (fr)
DE (1) DE19700326A1 (fr)
TR (1) TR199901460T2 (fr)
WO (1) WO1998030732A1 (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20160149226A (ko) 2014-04-30 2016-12-27 리오 페어발퉁스 아게 금속 부품을 산세하고 인산염 처리하기 위한 처리 장치 및 처리 방법

Citations (9)

* Cited by examiner, † Cited by third party
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
JPS5869842A (ja) * 1981-10-20 1983-04-26 Nisshin Kako Kk ヒドロキシルアミンの安定化剤
JPS5869841A (ja) * 1981-10-20 1983-04-26 Nisshin Kako Kk 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
DE3412712A1 (de) * 1983-04-04 1984-10-04 Fuji Photo Film Co., Ltd., Minami-Ashigara, Kanagawa Farbentwickler und verfahren fuer die behandlung eines farbphotographischen silberhalogenidmaterials unter verwendung des farbentwicklers
WO1990014615A1 (fr) * 1989-05-23 1990-11-29 Eastman Kodak Company Procede ameliore de developpement photographique en couleur
EP0695817A1 (fr) * 1994-08-05 1996-02-07 Itb S.R.L. Solution aqueuse acide de phosphation et procédé de phosphatation de surfaces métalliques
EP0633950B1 (fr) * 1992-03-31 1996-05-15 Henkel Kommanditgesellschaft auf Aktien Procede de phosphatation exempte de nickel
WO1997030190A1 (fr) * 1996-02-19 1997-08-21 Henkel Kommanditgesellschaft Auf Aktien Phosphatation du zinc avec faible quantite de cuivre et de manganese

Patent Citations (9)

* Cited by examiner, † Cited by third party
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
JPS5869842A (ja) * 1981-10-20 1983-04-26 Nisshin Kako Kk ヒドロキシルアミンの安定化剤
JPS5869841A (ja) * 1981-10-20 1983-04-26 Nisshin Kako Kk 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
DE3412712A1 (de) * 1983-04-04 1984-10-04 Fuji Photo Film Co., Ltd., Minami-Ashigara, Kanagawa Farbentwickler und verfahren fuer die behandlung eines farbphotographischen silberhalogenidmaterials unter verwendung des farbentwicklers
WO1990014615A1 (fr) * 1989-05-23 1990-11-29 Eastman Kodak Company Procede ameliore de developpement photographique en couleur
EP0633950B1 (fr) * 1992-03-31 1996-05-15 Henkel Kommanditgesellschaft auf Aktien Procede de phosphatation exempte de nickel
EP0695817A1 (fr) * 1994-08-05 1996-02-07 Itb S.R.L. Solution aqueuse acide de phosphation et procédé de phosphatation de surfaces métalliques
WO1997030190A1 (fr) * 1996-02-19 1997-08-21 Henkel Kommanditgesellschaft Auf Aktien Phosphatation du zinc avec faible quantite de cuivre et de manganese

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
PATENT ABSTRACTS OF JAPAN vol. 007, no. 026 (P - 172) 2 February 1983 (1983-02-02) *
PATENT ABSTRACTS OF JAPAN vol. 007, no. 161 (C - 176) 15 July 1983 (1983-07-15) *
PATENT ABSTRACTS OF JAPAN vol. 009, no. 013 (P - 328) 19 January 1985 (1985-01-19) *

Also Published As

Publication number Publication date
DE19700326A1 (de) 1998-07-09
JP2002500702A (ja) 2002-01-08
EP0960220A1 (fr) 1999-12-01
TR199901460T2 (xx) 1999-11-22
AU5859098A (en) 1998-08-03
BR9714199A (pt) 2000-03-28
CA2277336A1 (fr) 1998-07-16

Similar Documents

Publication Publication Date Title
DE3751666T2 (de) Flüssige konzentrierte Zusammensetzung zur Herstellung von Phosphatierlösungen die Mangan enthalten
DE2845439C2 (de) Bad zur galvanischen Abscheidung von Überzügen aus Zinn oder Zinnlegierungen
DE2904402A1 (de) Phosphatierungsmittel
EP0454211B1 (fr) Procédé pour appliquer des couches de phosphates sur des surfaces métalliques
DE2600636C3 (de) Chromatisiertes Stahlblech und Verfahren zur Herstellung von chromatisiertem, galvanisch verzinktem Stahlblech
DE69423647T2 (de) Zusammensetzung und verfahren zur behandlung von magnesiumenthaltenden metallen und daraus hergestelltes produkt
DE3812076C2 (fr)
DE4241134A1 (de) Verfahren zur Phosphatierung von Metalloberflächen
DE3024932C2 (fr)
EP2706132A1 (fr) Electrolyte zinc-nickel sans acide borique
DE3780078T2 (de) Korrosionsbestaendige beschichtung.
EP2492371A1 (fr) Solution de passivation sans cobalt et procédé de séparation de couches de passivation sans cobalt sur des surfaces de zinc et d'alliage de zinc
EP0662164B1 (fr) Procede de phosphatation de surfaces en acier galvanisees
EP0960220A1 (fr) Agents stabilisants pour l'hydroxylamine dans des solutions de phosphatation contenant du cuivre
DE69024774T2 (de) Verfahren zur chemischen Konversion von Metallgegenständen, verwendetes Bad dafür und Konzentrat zur Herstellung des Bades
AT390605B (de) Korrosionsinhibierende wasserzusaetze und verfahren zu ihrer herstellung
DE2414650C3 (de) Stromlos arbeitendes wässriges Verkupferungsbad
DE1817355A1 (de) Bad zum Abscheiden von metallischem Kupfer ohne Stromzufuhr von aussen
DE974503C (de) Verfahren zur Herstellung von UEberzuegen auf Metallen
DE2516252C3 (de) Elektrolyt für die galvanische Goldabscheidung
EP1206589B1 (fr) Catalyseur pour la phosphatation de surfaces metalliques
CH680449A5 (fr)
DE2948999C2 (de) Wässriges, saures Bad zur galvanischen Abscheidung von Gold und Verfahren zur galvanischen Abscheidung von Hartgold unter seiner Verwendung
DE1521512B1 (de) Alkalisches Bad zur stromlosen Kupferabscheidung
DE860445C (de) Verfahren und Loesung zur Behandlung von metallischen Oberflaechen

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AU BR CA CN CZ HU JP KR MX PL RU TR US

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): AT BE CH DE DK ES FI FR GB GR IE IT LU MC NL PT SE

DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
121 Ep: the epo has been informed by wipo that ep was designated in this application
WWE Wipo information: entry into national phase

Ref document number: 1999/01460

Country of ref document: TR

WWE Wipo information: entry into national phase

Ref document number: 1997954444

Country of ref document: EP

WWE Wipo information: entry into national phase

Ref document number: PA/a/1999/006241

Country of ref document: MX

ENP Entry into the national phase

Ref document number: 1998 530504

Country of ref document: JP

Kind code of ref document: A

ENP Entry into the national phase

Ref document number: 2277336

Country of ref document: CA

Ref document number: 2277336

Country of ref document: CA

Kind code of ref document: A

WWE Wipo information: entry into national phase

Ref document number: PV1999-2432

Country of ref document: CZ

WWE Wipo information: entry into national phase

Ref document number: 09341417

Country of ref document: US

WWP Wipo information: published in national office

Ref document number: 1997954444

Country of ref document: EP

WWP Wipo information: published in national office

Ref document number: PV1999-2432

Country of ref document: CZ

WWR Wipo information: refused in national office

Ref document number: PV1999-2432

Country of ref document: CZ

WWW Wipo information: withdrawn in national office

Ref document number: 1997954444

Country of ref document: EP