CN106574372A - Method for coating metal surfaces, substrates coated in this way, and use thereof - Google Patents

Method for coating metal surfaces, substrates coated in this way, and use thereof Download PDF

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Publication number
CN106574372A
CN106574372A CN201580015618.8A CN201580015618A CN106574372A CN 106574372 A CN106574372 A CN 106574372A CN 201580015618 A CN201580015618 A CN 201580015618A CN 106574372 A CN106574372 A CN 106574372A
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coating
composition
aforementioned
copolymer
conversion
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CN106574372B (en
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K.德迈耶雷
T.维卢迈特
M.瓦尔特
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Chemetall GmbH
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Chemetall GmbH
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    • 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
    • C23C22/40—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 molybdates, tungstates or vanadates
    • C23C22/44—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 molybdates, tungstates or vanadates containing also fluorides or complex fluorides
    • 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
    • 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
    • C23C22/361—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 titanium, zirconium or hafnium compounds
    • 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
    • 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
    • C23C22/82—After-treatment
    • C23C22/83—Chemical after-treatment

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  • 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)
  • Chemical Treatment Of Metals (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Paints Or Removers (AREA)

Abstract

The invention relates to a method for coating metal surfaces with an acidic aqueous conversion composition which contains: in total 0.01 to 1 g/l of TiF6 2+, ZrF6 2+ and/or HfF6 2 calculated as ZrF6 2+, 0 or 0.01 to 1 g/l in each case of Fe2+, Mn and/or Zn ions, of which at least one type of these ions is present in a content range from 0.01 to 1 g/l, 0 or 0.01 to 2 g/l of organic polymer and/or copolymer, 0 or 0.01 to 2 g/l of ultrafine particulate SiO2, approximately 0 or 0.01 to 10 g/l of at least one surfactant, approximately 0 or 0.05 to 10 g/l of anions of carbonate, nitrate and/or sulphate, and 0 or 0.001 to 2 g/l of carboxylate and/or sulphonate anions, wherein the content of molybdate and/or of P-containing oxy anions is in each case < 0.1 g/l or is approximately 0 g/l, and wherein the composition has a pH value in the range from 2.5 to 6.5. The invention also relates to a corresponding coating and to the use of the substrates coated in this way.

Description

The method of coating metal surfaces, the substrate for thus coating and application thereof
The present invention relates to be used in particular for substituting alkaline phosphating, such as the conversion coating coating gold of the use optionally coloring of ferric solid-acid The purposes of the method for metal surface, the substrate with metal surface of corresponding coating and these coated substrates.
Have been described with manufacturing alkali metal phosphate coating, this especially as the pretreatment layer before japanning in individual example The method of type coating.Fresh untapped alkali metal phosphate solution generally hardly or only contains a small amount of aluminum, ferrum and zinc.Except extremely Outside the ion of a kind of few alkali metal and/or ammonium, the acidic alkali metal aqueous phosphatic also containing phosphate anion and by In pickling effect of these solution to metal surface, they are also containing dissolving the metal for such as aluminum, ferrum and/or zinc from metal surface Ion and Jing pickling metal material trace alloying component.During alkali metal phosphating in alkali metal phosphate layer What is primarily formed is mutually corresponding phosphate, oxide and/or the hydroxide of the metal from the surface of base substrate to be processed Thing.
Alkali metal phosphate solution and/or coating are also referred to as liquor ferri phosphatis and/or painting when being used on ferrum and Steel material Layer.Alkali metal phosphate coating is according to Werner Rausch: Die Phosphatierung von Metallen , Saulgau 1988（Referring particularly to the 109-118 page）Also commonly referred to as so-called " non-into stratotype phosphatization " layer.This term It is misleading, because here is also thin for cambium layer, but their Zinc phosphatings for example more various types of than other phosphate layers Much.The alkali metal phosphate solution is all the time containing at least one alkali metal for being improved content, such as sodium and/or ammonium.
It is alkali metal phosphating generally to be carried out in simple and economical mode.But the alkali metal phosphate coating of high-quality although Limited corrosion protection is also only provided after secondary follow-up anti-corrosion treatment, it is usual a) on cold-rolled steel sheet thickness 60 to 80 it is micro- It is little that the powder lacquer coat based on epoxy-polyester powder paint of rice tests 500 in the salt spray test according to the NSS of DIN 50021 When, corrosion protection is not better than, i.e., not less than the subsurface corrosion of 3 mm（Unterwanderung）, and/or generally b) for cold The wet paint coating based on polyurethane-isocyanate paint of 60 to 80 microns of thickness is according to the NSS's of DIN 50021 on rolled steel plate 500 hours in salt spray test, corrosion protection is not better than, i.e., not less than the subsurface corrosion of 4 mm, and generally c) for cold-rolled steel The powder lacquer coat based on epoxy-polyester powder paint of 60 to 80 microns of thickness is according to the cold of DIN EN ISO 2409 on plate Condensate weather（KK）Test 240 hours in test, paint adhesion strength is not better than in cross-cut test, i.e., not less than GT 3.
Therefore, in alkali metal phosphating, it is often necessary to apply the second conversion coating of additional applying, in most of the cases also The even at least one follow-up enamelled coating for applying.Such multistep processes are not only especially complex, and the additional bath of needs and/or place Area and also optionally additional rinsing step and/or drying steps are managed, and is gone back cost intensive and is taken.Apply with alkali metal phosphate The paint adhesive force of layer is generally also not enough, so that must have additional conversion coating before japanning, such as based on lithium zirconium and/or silicon Alkane.Thus the cladding process becomes especially complicated and expensive.High phosphate levels in alkali metal phosphating are also unfavorable, because must answer The phosphate in waste water is disposed miscellaneously.
It is alkali metal phosphating generally to apply in multiple steps, wherein be primarily only cleaned in the first step, and Stratification in two steps.Then rinse and/or rinse again.
The purpose of the present invention is to find easily apply and with as environmentally friendly as possible composition and producing ratio high-quality alkali The Aquo-composition of metal phosphate coating more high corrosion protection.
By realizing this purpose, the conversion composition with the method for acidic aqueous conversion composition coating metal surfaces It is solution or dispersion, it is characterised in that it contains：
The TiF of the ionic speciess of 0.01 to 1 g/L altogether6 2+、ZrF6 2+And/or HfF6 2+, by ZrF6 2+Calculate,
The Fe of respective 0 or 0.01 to 1 g/L2+, Mn and/or Zn ions, wherein at least one type is dense 0.01 to 1 g/L's Exist in the range of degree, wherein it is preferred that there is Mn and/or Zn ions,
Based on solid content meter, 0 or 0.01 to 2 g/L in pH value<Stable organic polymer and/or copolymer under 6.5,
Measure in scanning electron microscope and based on solid content meter, the mean diameter of 0 or 0.01 to 2 g/L<0.3 micron micro- Grain SiO2,
At least one surfactant of about 0 or 0.01 to 10 g/L,
The ion selected from carbonate, nitrate anion and sulfate radical of about 0 or 0.05 to 10 g/L, or even ought there is CO3 2+Or SO4 2+ When be converted into NO3 +, and
Calculate by corresponding anion, the carboxylate radical and/or sulfonate radical that or hardly do not damage stratification of 0 or 0.001 to 2 g/L Anion,
Wherein press MoO4 2+The molybdic acid radical content of calculating and/or by PO4 3+The oxo-anions containing P for calculating（Oxyanion）Content Respectively<0.1 g/L or about 0 g/L
And wherein described acidic aqueous compositions have 2.5 to 6.5, preferably 3.0 to 5.5 pH value.
TiF6 2+、ZrF6 2+And/or HfF6 2+Ion it is substantially equivalent and interchangeable in the acidic aqueous conversion composition, But ZrF6 2+Ion usually comes at the optimal properties with conversion coating made by it.Preferably, the acidic aqueous compositions TiF6 2+、ZrF6 2+And/or HfF6 2+Content be 0.05 to<1 g/L, 0.1 to 0.8 g/L, 0.15 to 0.50 g/L or 0.20 to 0.33 g/L。
It is preferred here that, should acidic aqueous conversion composition only Fe2+For the cations of ion, it is based on Fe2+, Mn and Zn ion total content meters, this content at least partly be derived from intentional additive.Manganese and zinc ion and limited Fe in degree2+Ion is substantially equivalent and interchangeable in the acidic aqueous conversion composition, but manganese and/or zinc ion usually come at With the optimal properties of conversion coating made by it.It is especially excellent if manganese and zinc are added in the acidic aqueous conversion composition Choosing is to realize that manganese content is higher than Zn content.They preferably comprise the Fe of 0 or 0.01 to 0.3 g/L or 0.02 to 0.15 g/L2+ The Mn ions and/or 0.01 to 1 g/L or the Zn ions of 0.1 to 0.6 g/L of ion and 0.01 to 1 g/L.Its is particularly preferred The Zn of the Mn ions containing 0.1 to 0.6 g/L or 0.2 to 0.4 g/L and/or 0.1 to 0.6 g/L or 0.2 to 0.4 g/L from Son.
Preferably, basic phosphate free（< 0.1 g/L PO4）Or complete phosphate free（About 0 or just 0 g/L PO4）Operated.In each method modification, especially because entrainment and impurity, it is impossible to which PO is pressed in exclusion4 3+Calculate 0.001 With<Phosphate content between 0.1 g/L.It is furthermore preferred that or even in basic phosphate free（< 0.1 g/L PxOy）Or Complete phosphate free（About 0 or just 0 g/L PxOy）Operated phosphate free.
Addition organic polymer and/or organic copolymer can help to, and can further improve the conversion being made from it and apply Layer property and can optionally omit follow-up japanning.Preferably, the organic polymer of the acidic aqueous conversion composition and/or The content of organic copolymer is 0.01 to 3 g/L, 0.1 to 2.5 g/L, 0.2 to 2 g/L, 0.4 to 1.5 g/L or 0.6 to 1.2 g/L.The organic polymer and/or copolymer are preferably based on (methyl) acrylate/(methyl) acrylic acid and/or vinyl acetate Ester-acrylic copolymer.
If in the case of omitting japanning, the passivation layer coating made by and in the case of corrosion protection, can be described as sky White corrosion protection.
Addition ultrafine particle SiO2（Particularly<0.3 micron）Such as SiO2Nanoparticle can have and addition organic polymer And/or the positive effect that organic copolymer is similar, but difference is generally placed upon stratification, and therefore in SiO2Coating in situation is more equal It is even.
Substantially at least one nonionic, anion, cation and/or zwitterionic surfactant can be added.Here Particularly preferably add at least one nonionic surfactant.
Generally cation is added by water soluble salt and add the anion selected from carbonate, nitrate anion and sulfate radical.Nitre Acid group here is particularly preferred.
As replacement or supplement to these aniones, for example carboxylic acid can be added by acetic acid and/or manganese carboxylate substantially Root anion simultaneously is commonly available to prevent or reduce the anion of mineral acid.Substantially can add all types of carboxylic acids and they Derivant, such as salt and ester, it is water miscible and stable in the pH value range, material composition without complexity, in water Formed anion, the type according to anion and amount do not damage stratification and optionally with the alkali metal and/or alkaline earth for being not involved in stratification Metal ion forms complex.
These particularly including aliphatic carboxylic acid and single-, two- and/or polycarboxylic acid, such as hydroxy carboxylic acid.It is cloudy in addition carboxylate radical During ion, it should be noted that they do not damage stratification, because such as citrate and some other independent chelating agent can optional bases The type of anion damages stratification with measuring.
The addition here of one of at least one sulfonic acid, such as methanesulfonic acid, acylamino- sulfonic acid and/or its derivant is favourable, with Serve as accelerator and/or serve as additional gegenion.
Substantially, by MoO4Calculate 0 or 0.01 to<0.5 g/L, particularly 0.02 to 0.3 g/L, 0.01 to 0.1 g/L Molybdic acid salt content be preferred.The addition of molybdate only just has proven to favourable when few addition is added.
Especially because may pollutant effluents and optionally due also to more serious sludge is formed（This is likely to result in complexity Waste water and/or sludge treatment）, should avoid adding the oxo-anions containing P, such as orthophosphoric acid root, condensed phosphoric acid root and phosphonate radical. Especially in the case of the oxo-anions containing P, due to Environmental compatibility and due to avoiding expensive disposal, preferably without containing The oxo-anions of P, and preferably it should be noted that as far as possible the entrainment of the oxo-anions containing P is not come in.
In the case of the method for the invention, the acidic aqueous compositions preferably contain in addition, it is basic by or by following group Divide and constitute：
The ion of the lithium of 0.03 to 5 g/L, sodium and/or potassium altogether,
The ammonium ion of 0 or 0.05 to 5 g/L,
Co and/or Ni ions of about 0 or 0.05 to 0.3 g/L altogether,
Respective 0 or 0.01 to 0.8 g/L by ClO3 -The chlorate anions of calculating, by NO2Nitrite anions of calculating and/or by H2O2Meter The peroxide of calculation,
0 or 0.01 to 0.5 g/L by F-The free fluoride ion of calculating, and
0 or 0.01 to 0.2 g/L by VO4 3-The vanadic acid radical ion of calculating.
Generally, lithium, sodium, potassium and/or ammonium content are cannot be avoided substantially to realize charge balance and not only add multivalence sun Ion, such as heavy metal ion.In monovalent cation, sodium ion is especially preferred.They are in the acidic aqueous conversion combination In thing it is substantially equivalent and be used interchangeably and be typically adjust pH necessary to.
As in many cladding processes, the addition here of cobalt and/or nickel is still advantageously implemented more preferable corrosion protection, very If being debatable to Environmental compatibility and work hygiene to these elements.
Sometimes at least one accelerator must be added, particularly adds chlorate, nitrite and/or peroxide.But It is that here should be noted that suitable amount, such as much smaller than the NO of 1 g/L2Content.In at least one accelerator of addition, Ke Yijia Rapid-result layer and can improve thus made by coating property.Here should avoid being excessively added for accelerator, with unlike embodiment Damage stratification in the case of B40 like that.The addition of nitroguanidine not yet confirms favorably.
（One or more）Composite fluoride（Komplexflorid）Content typically result in low free fluoride ion alone Content.The content of at least one fluoride and/or addition may cause the free fluoride ion content of Lve Genggao.It is particularly conducive to contain The free fluoride ion content of the substrate surface of aluminum presses F-Calculate and be usually 0.01 to 0.5 g/L.
The addition of at least one vfanadium compound can significantly improve corrosion protection.
Here cannot be excluded, and the additional elements content of the metal surface of substrate and device is due to the acidic aqueous conversion combination The pickling of thing is acted on and simultaneously optionally even accumulated in bath composition in the bath, particularly Fe2+Ion and alloying element and Their ion.
On the other hand, generally also cannot exclude in the case of current painting method and device, marginally carry secretly from Other device regions, such as from the ion and content of material of the cleaning for using before, although optionally being rinsed using water. Especially, the alkali metal of certain content, ammonium, chelating agent, surfactant, the anionic impurity of cleaning bath and/or additional impurities And/or thus its ion can be entrained in the bath composition of the present invention.But, it is not that absolutely essential offer individually clean in advance step It is rapid to be input into substantially exclude foreign ion by chemical treatment solution.At its best, can be with living containing surface Property agent but without buider（Reinigergerüst）Water be cleaned step.
On the one hand, can be cleaned before conversion coating, to be cleaned before substrate is contacted with the Aquo-composition, Especially by alkaline clean.On the other hand, supplement or replace this cleaning, the Aquo-composition can also contain at least one Surfactant is planted, so that cleaning and conversion coating（）Carry out in Same Way step.
It is preferred that not to or only intentionally add in the aqueous conversion composition following：Such as respective most 0.1 g/L carboxylic acids, Phosphate, phosphonate and/or calcium, chromium, chromate, cobalt, copper, magnesium, molybdenum, nickel, the compound and/or ion of vanadium and/or stannum and/or Silane/silanol/siloxanes/polysiloxanes.Silane/silanol/siloxanes and polysiloxanes represent silane, silanol, silica Alkane and/or polysiloxanes, because generation silanol and/or silicon can be exceedingly fast in water and in the coating with such as silane as raw material Oxygen alkane, can also produce polysiloxanes sometimes（Depending on respective chemistry definition）.
The content of the alkaline-earth metal of the acidic aqueous conversion composition, such as calcium and/or magnesium is preferably not more than 0.2 g/ altogether L, to prevent from being precipitated in the presence of fluoride as far as possible.
Following variant is particularly preferred：
The acidic aqueous conversion composition have 2.5 to 6.5 pH value and contain, by or be made up of following component altogether substantially：
Modification A:
By ZrF6 2+Calculate, the TiF of the ionic speciess of 0.01 to 1 g/L6 2+、ZrF6 2+And/or HfF6 2+, and
The Fe of respective 0 or 0.01 to 1 g/L2+, Mn and/or Zn ions, wherein at least one type of these ions 0.01 to Exist in the content range of 1 g/L,
And based on solid content meter, the mean diameter of optional 0.01 to 2 g/L<0.3 micron of microgranule SiO2, and/or
At least one surfactant of optional 0.01 to 10 g/L, and
<0.1 g/L PO4Phosphate content.
Variant B:
By ZrF6 2+Calculate, the TiF of the ionic speciess of 0.01 to 1 g/L6 2+、ZrF6 2+And/or HfF6 2+,
The Fe of respective 0 or 0.01 to 1 g/L2+, Mn and/or Zn ions, wherein at least one type of these ions 0.01 to Exist in the content range of 1 g/L, and
Based on the g/L of solid content meter 0.01 to 2 in pH value<Stable organic polymer and/or copolymer under 6.5,
And the mean diameter based on optional 0.01 to 2 g/L of solid content meter<0.3 micron of microgranule SiO2,
With at least one surfactant of optional 0.01 to 10 g/L,
With the anion selected from carbonate, nitrate anion and sulfate radical of optional 0.05 to 10 g/L, or even when there is CO3 2+Or SO4 2+When be converted into NO3 +, and
The carboxylate radical and/or sulfonate radical that or hardly do not damage stratification of optional 0.001 to 2 g/L are calculated by corresponding anion Anion,
Wherein press MoO4 2+The molybdic acid radical content of calculating and/or by PO4 3+The oxo-anions content containing P for calculating is respectively<0.1 G/L or about 0 g/L.
Variant C:
By ZrF6 2+Calculate, the TiF of the ionic speciess of 0.01 to 1 g/L6 2+、ZrF6 2+And/or HfF6 2+,
The Fe of respective 0 or 0.01 to 1 g/L2+, Mn and/or Zn ions, wherein at least one type of these ions 0.01 to Exist in the content range of 1 g/L, and
By MoO4 2+Calculate 0.01 to<The molybdic acid radical content of 0.5 g/L,
And based on optional 0.01 to 2 g/L of solid content meter in pH value<Stable organic polymer and/or copolymer under 6.5,
With the mean diameter based on optional 0.01 to 2 g/L of solid content meter<0.3 micron of microgranule SiO2,
With at least one surfactant of optional 0.01 to 10 g/L,
With the anion selected from carbonate, nitrate anion and sulfate radical of optional 0.05 to 10 g/L, or even when there is CO3 2+Or SO4 2+When be converted into NO3 +, and
The carboxylate radical and/or sulfonate radical that or hardly do not damage stratification of optional 0.001 to 2 g/L are calculated by corresponding anion Anion,
Wherein press MoO4 2+The molybdic acid radical content of calculating be 0.01 to<0.5 g/L and by PO4 3+The oxo-anions containing P for calculating Content is<0.1 g/L or about 0 g/L.
For all three variant, preferred addition M and/or Zn ions, and Fe2+Ion concentration is preferably only turned by the acidity The pickling effect for changing compositionss goes out from pickling in the metallic substrates of rich ferrum.Optionally to the subsequent japanning of the coating at least one times.
Particularly preferably following acidic aqueous conversion composition, its be solution or suspension and contain, it is basic by or by following Component is constituted：
By ZrF6 2+Calculate, altogether the TiF of the ionic speciess of 0.01 to 1 g/L6 2+、ZrF6 2+And/or HfF6 2+,
At least one type of the Mn and/or Zn ions of 0 or 0.01 to 1 g/L, wherein these ions is in the dense of 0.01 to 1 g/L Exist in the range of degree,
The Fe of 0 or 0.01 to 0.3 g/L2+Ion,
Wherein preferably there is Mn and/or Zn ions,
Based on solid content meter, 0 or 0.01 to 1 g/L in pH value<Stable organic polymer and/or copolymer under 6.5,
With scanning electron microscopy measurement and based on solid content meter, the mean diameter of 0 or 0.01 to 1 g/L<0.3 micron of microgranule SiO2,
At least one surfactant of about 0 or 0.01 to 6 g/L,
The anion selected from carbonate, nitrate anion and sulfate radical of about 0 or 0.05 to 6 g/L, or even ought there is CO3 2+Or SO4 2+When be converted into NO3 +, and
Calculate by corresponding anion, the carboxylate radical and/or sulfonate radical that or hardly do not damage stratification of 0 or 0.001 to 1 g/L Anion,
Wherein press MoO4 2+The molybdic acid radical content of calculating and/or by PO4 3+The oxo-anions content containing P for calculating is respectively<0.1 G/L or about 0 g/L, and
Wherein the Aquo-composition has 2.5 to 6.5, preferably 3.0 to 5.5 pH value.
The acidic aqueous compositions particularly preferably also contain, it is basic by or be made up of following component：
The lithium of 0.01 to 5 g/L, sodium and/or potassium ion altogether,
The ammonium ion of 0 or 0.05 to 5 g/L,
Co and/or Ni ions of about 0 or 0.05 to 0.2 g/L altogether,
Respective 0 or 0.01 to 0.4 g/L by ClO3 -The chlorate anions of calculating, by NO2Nitrite anions of calculating and/or by H2O2Meter The peroxide of calculation,
0 or 0.01 to 0.5 g/L by F-The free fluoride ion of calculating, and
0 or 0.01 to 0.1 g/L by VO4 3-The vanadic acid radical ion of calculating.
The present invention bath composition here preferably by with water with 5:1 to 40:1 coefficient of dilution dilutes one or two Concentrate is preparing.Second concentrate can contain for example, at least a kind of surfactant and can also be aqueous.Fluorion Here also can be used as single fluoride, bifluoride（Bifluorid）And/or added in the form of respective acids.Free fluoride ion contains Amount is usually 0.01 to 0.2 g/L.
For the acidic aqueous conversion composition, preferably by with such as electrical conductivity of about 200 to 600 μ S/cm from Water or by deionized water be used for the batch of material and for supplementing the bath in liquid level and for the after conversion coating Once flushing.
After this first time rinsing step, according to standard only as last flushing, rinsed using the deionization of deionized water It is necessary, to prevent salt component（Salzfracht）It is dried, this can cause poor corrosion protection.
In galvanizing by dipping（HDG）Paint adhesive force and corrosion protection on steel is often slightly worse than cold-rolled steel（CRS）Plate.If drop Zn content in the low or even completely omitted acidic aqueous conversion composition, the coating performance on hot-dip galvanized steel sheet is usual To improve.
Fe2+Ion concentration does not generally make coating performance be deteriorated, but has confirmed, Fe2+Ion is gradually oxidized to Fe3+And sink Drop is used as bath sludge.Here, the acidic aqueous conversion composition preferably has manganese and/or zinc ion content.
Aquo-composition containing surfactant can help to further to improve defat and/or the cleaning after pickling or at least The defat before conversion coating is omitted, and it is possible thereby to cleaning is cleaned and omitted in one kettle way and in conversion coating Carry out.
In the method for the invention, at least one is preferably made to have the substrate of metal surface aqueous with this in processing component Compositionss contact the time of 1 second to 10 minutes, particularly 0.5 to 10 minute.Particularly preferably the contact time of 1 to 10 minute, special It it is not or preferably 0.5 to 6 minute in dipping, particularly in spraying.Therefore even for these compositionss, it is possible to use With alkali metal phosphating middle identical process time, this is easy to the conversion coating from the invention of alkali metal phosphating device conversion cost.Cause It is in alkali metal phosphating, generally also using 3 to 5 minutes.Or, if also rinsed with water after band coating（It is flushed Journey）, the present invention compositionss also can be applied on band.In band coating, metal tape is preferably set to connect with the Aquo-composition Touch the time of 1 second to 2 minutes.
In the method for the invention, the substrate with metal surface when contacting with the Aquo-composition preferably have 5 to 90 DEG C, preferably 15 to 70 DEG C or 30 to 60 DEG C of temperature.On the other hand, the Aquo-composition with the substrate with metal surface It is also preferred that with 35 to 70 DEG C or 45 to 60 DEG C of temperature during contact.The temperature of these compositionss therefore can with it is alkali metal phosphating In it is identical, wherein 50 to 55 DEG C of temperature is usually used.At a temperature of 50 to 55 DEG C, obtain most uniform conversion coating and Most uniform enamelled coating is obtained after japanning.
Also this purpose is realized with according to the coated substrate with metal surface of present invention coating.
It is preferred here that, thus made by coating have 0.3 to 3 micron thickness degree and/or by x-ray fluorescence Analyser（RFA）The zirconium measured by element in the conversion coating for measuring and/or total applied amount of titanium are 1 to 300 milligram/square Rice or preferably 15 to 150 millis gram/m.
Thus coating here made by is preferably also coloured, iris or Lycoperdon polymorphum Vitt.In the coating made by thus, preferably There are the interference colours of single order or higher order or interference colours occur with color during ion color addition.These colors with alkali metal Those in phosphate coating are same or like.These colors are typically facilitated and substantially estimate the thickness of coating and to a certain degree The uniformity and/or quality of upper coating.If this is even feasible under bigger viewing distance, this especially has for cladding process Profit.
Particularly with the use of special high-quality, thus made by conversion coating of the present invention preferably then with water or use Aqueous rear rinse solution, those particularly containing silane, organic polymer and/or organic copolymer are rinsed and optionally also gone up Paint.Aqueous rear rinse solution, such as Gardolene containing phenolic resin can be used®D95 or based on silane Gardolene®D6890 is rinsed after carrying out.
The aqueous rear rinse solution particularly preferably containing it is each it is at least one a) selected from alkaline earth metal cation, aluminium cations, The cation of titanium cation, yttrium cation and heavy metal cation, b) organic polymer and/or copolymer, c) silane, silane Alcohol, siloxanes and/or polysiloxanes, and/or d) composite fluoride, wherein composite fluoride also represent corresponding fluoric-containing acid.It is special Not, the amino silane and/or double-silicyl silane with, two or even more amino is herein preferred Silane.
In a particularly preferred the inventive method, with the acidic aqueous compositions of the present invention coating, Ran Houren are applied Rinsed from water and/or hereafter optionally rinsed again with Aquo-composition, and to the subsequent japanning of at least one coating made by thus At least one times.
In a particularly preferred the inventive method, using being based on ZrF is pressed6 2+Calculate the ionic speciess of 0.01 to 1 g/L TiF6 2+、ZrF6 2+And/or HfF6 2+Or only ZrF5 2+With the Fe of 0 or 0.01 to 1 g/L2+, Mn and/or Zn ions（Wherein these At least one type of ion exists in the content range of 0.01 to 1 g/L）And based on solid content meter optional 0.01 to 2 The mean diameter of g/L<0.3 micron of microgranule SiO2And/or at least one surfactant and base of optional 0.01 to 10 g/L This phosphate free and the acidic aqueous compositions of the invention substantially without phosphonate apply coating, then optionally with water rinse with/ Or optionally hereafter with based on zirconium composite fluoride, silane and/or in pH value<Stable organic polymer/copolymer contains under 6.5 Water composition is rinsed again, and can then japanning is at least one times at least one coating made by thus.Due to the acidity of the present invention Surface-active contents in Aquo-composition, can optionally omit advance cleaning.
Thus the conversion coating of the present invention made by can not contain organic polymer and during without organic copolymer at it, excellent It is selected in subsequently without water or preferably without aqueous rear rinse solution, particularly containing silane, organic polymer and/or organic copolymer It is dried in the case of those flushings of thing and optional also japanning.
Or, if the conversion coating of the present invention contains organic polymer and/or copolymer made by thus, preferably not Use in the case of coating it with priming paint, paint or binding agent.
Thus the conversion coating of the present invention made by also can rinsed optionally at least with water and/or with aqueous rear rinse solution Priming paint, paint or binding agent is once used to coat preferably at least once afterwards.Therefore, even if in the case of these compositionss, it is also possible to Optionally successfully use and alkali metal phosphating middle identical process step, order and method.
Thus coating made by can represent alkali metal phosphate coating, such as ferrum system phosphate coating in excellent mode Succedaneum.
Described at least one according to the present invention coating the substrate with metal surface be preferably used as Constracture unit, as appearance Device, as structure or connecting element, as bar elements, as calandria element, the molded body as complicated molding and/or use Make the component during building industry, energy technologies, car construction, equipment construction, household electrical appliance construction or machinery are built.
, it is surprising that obtained with the aqueous conversion composition of the present invention there is excellent anticorrosive, excellent paint to adhere to The exceptional overcoat of power and generally obvious color.In the case that rinse solution improves coating performance after being subsequently not used, in steel table Corrosion resistance on face is about the same with high-quality Zinc phosphating good and is therefore significantly better than the alkali metal phosphating process of high-quality Corrosion resistance.When using additional rear rinse solution, or even the corrosion resistance of achievable high-quality Zinc phosphating.
Also surprisingly, alkali metal phosphating excellent succedaneum can be in a relatively simple manner obtained, its is excellent Work and can make in simple and environmentally-friendly and optional identical method.
The surface of various steel bases of the compositionss and the method for the present invention of the present invention used in metal-processing industry It is particularly advantageous in Chemical Pretreatment.Here even can be cleaned in one step and apply simultaneously can japanning conversion Layer is this with conversion coating cleaning, fully sufficient with this three step process method rinsed from water and deionized water is rinsed.Especially It is that bath analysis is operationally very simple, because determining anion and cation with little need for accurate, because pH value and conductance The information of the commonly provided enough chemical conditions with regard to the bath of rate.
The method of the present invention can be used to manufacture coloured, iris, Lycoperdon polymorphum Vitt or colourless（Such as the situation of B40）Passivation layer（It is supreme Paint）Or coloured, iris, Lycoperdon polymorphum Vitt or colourless（Such as the situation of B40）Conversion coating（There is japanning）.Passivation layer is also in itself by turning Coating made by change.Therefore, term " conversion coating " in the sense that the application also include term " passivation layer ", as long as or if Japanning is not for example carried out in the claims.
The method of the present invention can be used as the succedaneum of alkali metal phosphating method or even can be used to substitute zinc system phosphorus in individual example Change method.Can be used in a variety of ways with product made by the method for the present invention, particularly as Constracture unit, as container, As structural detail or connecting element, as bar elements, as calandria element, the molded body as complicated molding and/or Component in building as building industry, energy technologies, car construction, equipment construction, household electrical appliance construction or machinery, and for example use Make calandria, as framework, as sheet material, as liner, as angle bar（Winkel）Or the group as automobile or interior of aircraft Part.
Embodiment and comparative example
Subject of the present invention is explained in more detail by embodiment.These embodiments are using following substrates, method and step, material and mix Compound is carried out.
It is coated using following on-gauge plate：The Gardobond by made by the cold-rolled steel CRS of St14 DC05®C, by phase Gardobond made by the electro-galvanized steel answered®HDG/5 or by made by the AA 5005 of AlMg1 Gardobond®F, from Chemetall GmbH.Unless specifically stated so, using on-gauge plate Gardobond® C。
Prepare the aqueous conversion composition according to table 1.Using Gardobond®The non-ionic surface active of additive H7438 Used as surfactant, it guarantees the extra clean of metal surface for agent.It is stable with potassium hydroxide from Chemetall GmbH The alkaline SiO of change2Dispersion Gardobond®Additive H7157 has 20% solid content and 0.2 micron of particle mean size.Come The AC 2773 of polymeric dispersions 1 based on acrylate from Alberdingk is with 53% solid content.From The VP of 2 VA of copolymer dispersion 294 containing acrylate of Alberdingk have 47% solid content.From Alberdingk The VP of 3 AS of copolymer dispersion 2084 containing acrylate have 53% solid content.Will be poly- at the end of the mixed process Compound, copolymer, SiO2Particle and/or surfactant be added separately to before made by aqueous conversion composition.Individual Not Shi Yan in, add ammonium molybdate.
In embodiment B45 to B48, just absorbed about in bath due to the pickling effect of the acidic conversion compositionss The Fe of 0.02 g/L2+Content.This iron content that pickling goes out hence above in other samples, Fe2+Content is in other samples It is in bath<0.001 to 0.01 g/L.In compositionss B41 and B42, the iron content being previously mentioned in table is intentionally added.
The plate converts coating 3 minutes at 55 DEG C, and when a surfactant is present, this has cleaning action simultaneously.Then Rinsed once with water for industrial use, then deionized water is rinsed, be then dried coated plate at 120 DEG C in drying baker At least 10 minutes.When using different temperatures, obvious quality discrepancy is not observed.
Then, each enamelled coating is applied on the plate of inverted coating：60 to 80 micrometer layer thickness from Akzo The Interpon of Nobel Power Coatings GmbH®700 epoxy-polyester powder paints, 60 to 80 micrometer layer thickness come From Mankiewicz based on polyurethane and the Alexit of isocyanates®Monolayer wet paints or in embodiment B3 15 to The Cathoguard from BASF of 20 micrometer layer thickness®350 Black Cathode dipping lacquers or in embodiment B45 to B48 15 to The Cathoguard from BASF of 20 micrometer layer thickness®800 negative electrode dipping lacquers（KTL）, and subsequently each one according to Daimler Benz automobile makings layer by made by 25-30 micron fillers, 11-15 microns base paint and 40-50 micron varnish.
Determine in the cross-cut method according to DIN EN ISO 2409 before alternately climatic test and after 240 hours The paint adhesive force of the sample of paint.The sample of japanning is determined in the salt spray test according to DIN 50021 in neutral salt spray test NSS The corrosion resistance of product 500 hours.Here applying only one enamelled coating-different from the Normal practice in Asia and North America market.
Surprisingly, obtaining the very high corrosion resistance of 0 mm in B44 after 1000 h in salt spray test.
Using x-ray fluorescence analysis instrument by milli gram/m in units of for apply element zirconium measurement layer weight.Element Zirconium is typically the indicator element of coating quality, wherein being deposited in the case of using identical Aquo-composition according to metallic substrates Different zirconium metal applied amounts.
In comparative example VB1 and VB2, by embodiments of the invention and in the world in the Gardobond by made by cold-rolled steel® Widely used high-quality is alkali metal phosphating on C plates compares：Exemplary program in alkali metal phosphating（When used in ferrum and Steel material Ferric solid-acid was also referred to as when upper）Using Gardobond®WH carries out operating=Gardobond®A 4976 is on the steel surface Carry out at 55 DEG C 3 minutes, deionized water is rinsed and optionally subsequently used and is based on ZrF6Gardolene®Rinse after D 6800 Rinse 5 minutes after liquid；Then it is dried at least 10 minutes at 120 DEG C in drying baker.To this alternatively, using based on amino silicone The rear rinse solution Gardolene of alkane and surfactant®D 6890, use are based on two kinds of different amino silanes and ZrF6 Rear rinse solution Oxsilan®9810/3 rinses molten using being based on after the AC 2773 of Organic substance dispersion 1 of acrylate Liquid is operated, and is then dried at least 10 minutes at 120 DEG C in drying baker.
The summary of the property of composition of the table 1. containing water-bath and affiliated coated sample and coating
These embodiments show, using the aqueous conversion composition of the present invention although having generally open-and-shut composition and little Content, but obtain under these conditions with the excellent of excellent corrosion resistance, excellent paint adhesive force and generally obvious color Different coating.Using these compositionss, can both obtain serious coloring can also obtain colourless coating.Corrosion resistant in steel surface Corrosion is almost good as high-quality Zinc phosphating and therefore is much better than the alkali metal phosphating corrosion resistance of high-quality（Such as B3 pair Compare VB1）.
In comparative example VB2, only coating performance is determined after second additional conversion processing --- this is different from this Bright embodiment.Paint adhesive force in steel surface is almost good as high-quality Zinc phosphating and therefore is very significantly better than high The alkali metal phosphating paint adhesive force of quality.Additionally, the aqueous conversion composition of the present invention has constitute quite environmentally friendlyly, from occupation Favourable and phosphate free from the point of view of health.
If use afterwards at least one times rear rinse solution after conversion coating of the invention and being rinsed with water, such as Silane-containing, organic polymer and/or those containing organic copolymer, the paint adhesive force realized on the steel surface at least with high-quality Zinc phosphating is equally good, and also realizes corrosion resistance at least good as high-quality Zinc phosphating.
Have confirmed on the whole, the acidic aqueous conversion composition of the present invention is excellent in various types of metal substrate surfaces Strange land replacement is alkali metal phosphating, is not merely suitable for substituting the ferric solid-acid on ferrum and steel surface.Even having been found that should Many metal abilities in process, so that the mixing of different types of metal surface can simultaneously or sequentially be processed in identical bath Thing.
If ZrF6By TiF6Substitute, compared to the layer property for measuring, when being particularly useful on steel, corrosion protection may appoint Select slightly damaged.
When only using zinc as the heavy metal cation for adding, or even in the unexpected earth polar of Zn content holding of coating When low and when without phosphate, the coating of high-quality is also obtained.When only using manganese as heavy metal cation, or even When the manganese content of coating is also unexpectedly extremely low and when without phosphate, the coating of high-quality is also obtained.If while Using manganese and zinc, when without phosphate, when only using one of these heavy metal cations compared with see in some cases Observe slightly damaged.
When only using Fe2+When being used together as heavy metal cation or with Mn and/or Zn ions, high-quality is also obtained Coating.From the Fe of base material2+The acid cleaning process that can pass through caused by reaction is re-supplied from the bath of iron content substrate surface.But, lead to Often due to the circulation of the bath, it is subsequently generally oxidized to Fe3+, and take out from the bath as reactive ingredients.Although addition Fe2+, but also as in embodiment B41 and B42, typically set up 0.025 to 0.1 g/L Fe2+Stable state Fe2+Concentration.
In the case where the more longlasting coating of multiple substrates is for example used, the pickling in acidic aqueous conversion composition is removed Main component and a part of alloying element simultaneously can be accumulated in a certain extent in bath composition, then generally deposited simultaneously in the bath In various cationes, they especially may act on the composition of the coating and can time strategic point act on its property.
If in most of the cases obtaining poor painting completely without heavy metal cation in comparative example VB3 and VB4 Layer.Based on by the measurement of x-ray fluorescence analysis, compared with Zr, Zn and Mn is only deposited with inapparent immeasurablel amount. But, Zr is the key component of this layer and can be used as such as Zr (OH)xFyExist.Zn generally fills in interface of the metal with coating Work as fluoride scavengers, so that less fluoride is incorporated in the layer, this can bring more preferable result according to the understanding of the applicant. Zn and Mn are the components of the only relatively small amount of this layer and therefore can only more accurately detect by electron spectroscopy for chemical analysis XPS/ESCA.
In the test that can be contrasted, when Zr applied layers are most thick, made by coating property it is generally best.But, Zr is applied Plus become with different surface naturies in the case of steel of the layer in the case of the different brackets of steel and in same levels.
In these experiments, the nonionic surfactant of addition further improves CRS Gardobond used®C is marked The cleannes of the metal surface of quasi- plate.Therefore advance cleaning can be omitted.If omitting the surfactant in contrast to this Addition, coating performance is essentially identical, but fully do not clean the risk of metal surface and raise, and this is likely to have layer property negative Face rings.
In the case of addition greater amount molybdenum, it has to be noted that the probability that coating is slightly separated.
Organic polymer, organic copolymer and SiO2The addition of nanoparticle has proven to particularly advantageous.It should be noted herein that When addition is more than 0.5 g/L, does not foam and do not crust to interfere on injection nozzle and wall.

Claims (22)

1., with the method for acidic aqueous conversion composition coating metal surfaces, the conversion composition is solution or dispersion, its It is characterised by that it contains
By ZrF6 2+Calculate, altogether the TiF of the ionic speciess of 0.01 to 1 g/L6 2+、ZrF6 2+And/or HfF6 2+,
The Fe of respective 0 or 0.01 to 1 g/L2+, Mn and/or Zn ions, wherein at least one type of these ions is 0.01 to 1 Exist in the content range of g/L,
Based on solid content meter, 0 or 0.01 to 2 g/L in pH value<Stable organic polymer and/or copolymer under 6.5,
Based on solid content meter, the mean diameter of 0 or 0.01 to 2 g/L<0.3 micron of microgranule SiO2,
At least one surfactant of about 0 or 0.01 to 10 g/L,
The anion selected from carbonate, nitrate anion and sulfate radical of about 0 or 0.05 to 10 g/L, or even ought there is CO3 2+Or SO4 2+When be converted into NO3 +, and
Calculate by corresponding anion, the carboxylate radical and/or sulfonate radical that or hardly do not damage stratification of 0 or 0.001 to 2 g/L Anion,
And by MoO4 2+The molybdic acid radical content of calculating and/or by PO4 3+The oxo-anions content containing P for calculating is respectively<0.1 G/L or about 0 g/L, and
The acidic aqueous compositions have 2.5 to 6.5 pH value.
2. method according to claim 1, it is characterised in that the acidic aqueous compositions contain in addition：
The ion of the lithium of 0.03 to 5 g/L, sodium and/or potassium altogether,
The ammonium ion of 0 or 0.05 to 5 g/L,
Co and/or Ni ions of about 0 or 0.05 to 0.3 g/L altogether,
Respective 0 or 0.01 to 0.8 g/L by ClO3 -The chlorate anions of calculating, by NO2Nitrite anions of calculating and/or by H2O2Meter The peroxide of calculation,
0 or 0.01 to 0.5 g/L by F-The free fluoride ion of calculating, and
0 or 0.01 to 0.2 g/L by VO4 3-The vanadic acid radical ion of calculating.
3. according to the method for claim 1 or 2, it is characterised in that coating made by thus has 0.3 to 3 micron of thickness degree.
4. according to the method for at least one of aforementioned claim, it is characterised in that with x-ray fluorescence analysis instrument measure by unit The zirconium of element measurement and/or total applied amount of titanium are 1 to 300 milli gram/m.
5. according to the method for at least one of aforementioned claim, it is characterised in that coating made by thus is coloured, iris Or Lycoperdon polymorphum Vitt.
6. according to the method for at least one of aforementioned claim, it is characterised in that coating made by thus is alkali metal phosphate The succedaneum of coating.
7. according to the method for at least one of aforementioned claim, it is characterised in that by with water with 5:1 to 40:1 dilution system Number dilutes one or two concentrate to prepare the bath composition.
8. according to the method for at least one of aforementioned claim, it is characterised in that make at least one substrate with metal surface With the time that the Aquo-composition contacts 1 second to 10 minutes.
9. according to the method for at least one of aforementioned claim, it is characterised in that the substrate with metal surface is containing with described With 5 to 90 DEG C of temperature when water composition is contacted.
10. according to the method for at least one of aforementioned claim, it is characterised in that the Aquo-composition with metal With 35 to 70 DEG C of temperature during the substrate contact on surface.
11. according to the method for at least one of aforementioned claim, it is characterised in that in the substrate and the Aquo-composition It is cleaned before contact.
12. according to the method for at least one of aforementioned claim, it is characterised in that the Aquo-composition also contains at least one Plant surfactant and the cleaning and conversion are coated in Same Way step and carry out.
13. according to the method for at least one of aforementioned claim, it is characterised in that conversion coating made by thus subsequently uses water Or with aqueous rear rinse solution, the such solution particularly containing silane, organic polymer and/or organic copolymer is rinsed, and Optional also japanning.
14. according to the method for at least one of aforementioned claim, it is characterised in that if conversion coating is not contained made by thus Organic polymer and without organic copolymer, subsequently without water or with aqueous rear rinse solution, particularly containing silane, organic Such solution of polymer and/or organic copolymer is dried and optional also japanning in the case of rinsing.
15. according to the method for at least one of claim 1 to 13, it is characterised in that if conversion coating contains made by thus Organic polymer and/or copolymer, use in the case where it is coated without priming paint, paint or binding agent.
16. according to the method for at least one of claim 1 to 14, it is characterised in that conversion coating made by thus is with water And/or use priming paint, paint or binding agent to coat at least one times afterwards at least one times with aqueous rear rinse solution flushing.
17. methods according to claim 16, it is characterised in that the aqueous rear rinse solution contains each at least one a) be selected from The cation of alkaline-earth metal, aluminum, titanium, yttrium and heavy metal cation, b) organic polymer and/or copolymer, c) silane, silane Alcohol, siloxanes and/or polysiloxanes and/or d) composite fluoride.
18. according to the method for at least one of aforementioned claim, with the acidity of at least one according to claim 1 and/or 2 Aquo-composition applies coating, is then optionally rinsed with water and/or is optionally rinsed again with Aquo-composition, and to made by thus The subsequent japanning of at least one coating is at least one times.
19., according to the method for at least one of aforementioned claim, with acidic aqueous compositions coating, the compositionss base are applied In
By ZrF6 2+Calculate the TiF of the ionic speciess of 0.01 to 1 g/L6 2+、ZrF6 2+And/or HfF6 2+Or only ZrF5 2+, and
The Fe of respective 0 or 0.01 to 1 g/L2+, Mn and/or Zn ions, wherein at least one type of these ions is 0.01 to 1 Exist in the content range of g/L, and
Mean diameter based on optional 0.01 to 2 g/L of solid content meter<0.3 micron of microgranule SiO2, and/or
At least one surfactant of optional 0.01 to 10 g/L,
And the basic phosphate free of the compositionss and substantially without phosphonate,
Optionally subsequently rinsed with water and/or
Optionally subsequently with based in pH value<Stable organic polymer/copolymer, zirconium composite fluoride and/or silane under 6.5 Aquo-composition is rinsed again, and
To the subsequent japanning of at least one coating made by thus at least one times.
The 20. coated substrates with metal surface, it is coated according to any one of claim 1 to 19.
21. substrates with metal surface by being coated according to the method for at least one of claim 1 to 19 are used as building Element, as container, as structural detail or connecting element, as bar elements, as calandria element, as complicated molding Molded body and/or as building industry, energy technologies, car construction, equipment build, household electrical appliance build or machinery build in The purposes of component.
22. according to the method for at least one of claim 1 to 19 as alkali metal phosphating method or the succedaneum of Zinc phosphating method Purposes.
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