CN107002247A - The alkaline coating composition based on cerium for pretreatment of metal surface - Google Patents

The alkaline coating composition based on cerium for pretreatment of metal surface Download PDF

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Publication number
CN107002247A
CN107002247A CN201480082091.6A CN201480082091A CN107002247A CN 107002247 A CN107002247 A CN 107002247A CN 201480082091 A CN201480082091 A CN 201480082091A CN 107002247 A CN107002247 A CN 107002247A
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composition
cerium
iii
weight
component
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曹慧敏
万宗跃
万小山
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Henkel China Co Ltd
Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Priority to CN202210192809.3A priority Critical patent/CN114561636A/en
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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
    • C23C22/60—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 alkaline aqueous solutions with pH greater than 8
    • C23C22/62—Treatment of iron or alloys based thereon
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/08—Anti-corrosive paints
    • 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
    • C23C22/60—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 alkaline aqueous solutions with pH greater than 8
    • C23C22/66—Treatment of aluminium or alloys based thereon
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D13/00—Electrophoretic coating characterised by the process
    • C25D13/12—Electrophoretic coating characterised by the process characterised by the article coated
    • C25D13/16—Wires; Strips; Foils
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D13/00—Electrophoretic coating characterised by the process
    • C25D13/20—Pretreatment
    • 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
    • C23C2222/00—Aspects relating to chemical surface treatment of metallic material by reaction of the surface with a reactive medium
    • C23C2222/20—Use of solutions containing silanes

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Metallurgy (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Chemical Treatment Of Metals (AREA)
  • Paints Or Removers (AREA)

Abstract

The present invention relates to the alkaline aqueous composition for metal pretreated substrate, wherein the composition is based on cerium cation source and there is the organosilan of amido functional group.Purposes the present invention also relates to the method for the metal pretreated substrate based on the alkaline aqueous composition and its in corrosion pretreatment.

Description

The alkaline coating composition based on cerium for pretreatment of metal surface
Background of invention
Invention field
The present invention relates to the alkaline aqueous composition pre-processed for metallic substrates, wherein composition is based on cerium cation source And the organosilan of aminofunctional.The present invention is also covered by the pre- place of the metallic substrates based on such alkaline aqueous composition The method of reason and its purposes in corrosion pretreatment.
The explanation of correlation technique
In order to avoid metal surface is corroded, often using thin essentially inorganic coating, it at least temporarily with gives anti- Corrosivity and in addition when in method and step of organic face coat in subsequent surfacing apply when it is used as adhesion-promoting layer.It is right In metal parts or the most widely used preprocess method of wire coil be the combination that the passivation based on film such as includes Cr (VI) The phosphorating treatment of thing or routine.Due to toxicity of Cr (VI) systems to both health and environment, non-Cr (VI) system has been researched and developed, its It is typically based on the acidic composition of fluoro metal salt.In other trials, it has been reported that machine silane is in wet-chemical treatment technique The middle validity for forming protective coating.In these substitution methods, seldom it can reach suitable with Cr (VI) conversion coating system Corrosion protection.
Patent US 5292549 discloses the metal coating with the thin silicone film for providing interim corrosion protection Steel plate and the method for applying silicone film, the silicone film can be removed by alkalescence cleaning.The preprocess method of even now is carried For the nontoxic coating not influenceed by humidity, but the steel plate coated to the metal imparts only interim corrosion resistance, And need to remove it before any further coating step.
Patent CN 101098982A disclose the method with Aquo-composition coating metal surfaces, wherein described aqueous group The mixture of compound of the compound comprising silane and Ti, Zr, Al and B.It is reported that such composition is provided and Cr (VI) body It is suitable corrosion resistance, but relies on some complex fluorides and usual a certain amount of free fluorine, particularly as used for pre- place Reason metal material different in same pre-treatment production line.But, fluorine it is harmful to environment and health and therefore when operation so Pretreatment baths when need to use extra employment security measure.But another problem is that fluorine in the operating process of pretreatment baths Concentration can increase, can cause to make in turn on the conversion coating to be formed produce defect excessive fluorine the fact.Therefore, even On the pretreatment line of continuous operation, need to add the fluoride scavengers such as aluminium ion of modulability at present, it is horizontal to maintain to be adapted to Free fluorine.
The method that patent US 2003/0034095A1 disclose processing metallic substrates, it includes being combined with alkalescence pretreatment Thing contacts at least a portion metallic substrates, wherein the alkalescence pretreatment composition is substantially free of chromate, the alkalescence is pre- Treatment compositions include such as stannate, molybdate, vanadate and the cerium compound of hydration；By substrate drying；Clean substrate；And again It is secondary by substrate drying.In a subsequent step, apply based on silane or conventional organic bond such as epoxy resin, silicones, amine Class, alkyd resin, the adhesive coatings of carbamate and acrylic resin.Combined with not chromate-containing alkalescence pretreatment Thing is carried out after conversion coating to exposed metal surface, is handled with the coating composition based on silane.
Therefore, it is still necessary to research and develop the non toxic alternative of Cr (VI) film transformation coating compound, its is easily prepared and in work Safe and reliable bath is maintained with less modulability chemical reagent on industry pre-treatment production line.Such Cr (VI) film conversion Coating composition substitute can be the suitable corrosion resistance of the imparting of the metallic substrates after processing and coating adhesion.
The content of the invention
One object of the present invention covers alkaline aqueous composition, and it is included
A) cerium cation source；
B) at least one silane, it includes the Si-C keys of at least one non-hydrolysable with least one amido functional group With at least one hydrolyzable Si-O key；The weight ratio of component a) and the component b) in terms of Si elements wherein in terms of Ce elements is not More than 5.
Another object of the present invention is the method for metal pretreated part, and it includes combining metal parts with alkaline aqueous The wet-chemical treatment step of thing contact.
The a further object of the present invention be the alkaline aqueous composition be used to pre-processing cold rolling steel, it is hot-strip, zinc-plated The purposes of steel, zinc-plated annealing steel and aluminium.
Embodiment
The present invention is described in more detail in the following paragraphs.Unless there are clear and definite phase antirepresentation, described is each Aspect can be combined with any other aspect.Especially, it is any be expressed as preferred or favourable feature can be with any other table The feature for being shown as preferred or favourable is combined.
In the context of the present invention, unless there is opposite instruction in context.Should according to used in understanding defined below art Language.
Unless there is opposite instruction in context, the singulative " one ", " one kind " and " described " used in text are simultaneously Represent that odd number and plural number refer to thing.
Term " comprising " "comprising" used in text is synonym, and is pardon or open, and is not excluded for Other unrequited member, key element or method and step.
The narration of logarithm value end points is included in all numerical value and fraction in respective scope and the end points described.
All bibliography that the present invention is quoted are incorporated herein by overall quote.
Unless otherwise defined, all terms used in disclosure of the present invention, including technology and scientific terminology, with this hair The implication that the bright technical field those of ordinary skill is generally understood that is identical.By further instructing, by term definition include with More fully understand the teachings of the present invention.
Unless otherwise indicated, by the way that " any amount for the compound that weight % " modes quantify should be in the context of the invention Refer to compared to corresponding total composition, amount by weight percentage.When the amount to compound in the way of " ppm " quantifies When, the amount refers to hundred a ten thousandths (10 based on parts by weight-6)。
The present invention relates to alkaline aqueous composition, it is included
A) cerium cation source；
B) at least one silane, its Si-C keys and at least one hydrolyzable Si-O comprising at least one non-hydrolysable Key, wherein Si-C keys carry at least one amido functional group；
The weight ratio of component a) and the component b) in terms of Si elements wherein in terms of Ce elements is no more than 5.
Term as used herein " cerium cation source ", which should refer to work as, is dissolved in water release cerium cation or using cerium in Any compound containing cerium of the complex ion of heart atom.
The property of any combinations thing of the present invention refers to pH value and referred to more than 7, pH for alkalescence is interpreted as the H30 hydroxonium ion at 20 DEG C The activity of sub- concentration is with the 10 negative logarithms bottom of for.
The composition of the present invention can form protective coating by the way that each metal is contacted with the composition in metal surface. Protective coating assigns sufficiently interim corrosion protection to metal surface.Therefore, treated metal parts can be stored provisionally Without the visible corrosion product of significant quantity under conditions of wet or dry.Therefore, metal surface need not can entered In the case of row secondary operation, such treated metal parts is processed further, such as using protectiveness and decoration Property organic coating.
Cerium cation source preferably uses water miscible cerium (III) and/or cerium (IV) salt in the present invention.And it is more preferably water-soluble Cerium (III) and/or cerium (IV) salt be selected from group consisting of：Cerous sulfate (IV) ammonium, cerous nitrate (IV) ammonium, cerous sulfate (IV), Cerous carbonate (III), cerous nitrate (III), cerous acetate (III) and cerium sulphide (III).Even more preferably cerium cation source selected from cerium (III) salt, and it is most preferably selected from cerous carbonate (III), cerous nitrate (III) and cerous acetate (III).
Term as used herein " water solubility " refers to (κ in 20 DEG C of deionized waters<1μScm-1) can dissolve more than 5g/L cerium salt, Uniform solution is still maintained not have visible precipitate within 24h time simultaneously.
The compound a in terms of elemental cerium in the alkaline aqueous composition of the present invention) amount be preferably not less than 0.002 weight Measure %, more preferably no less than 0.02 weight %.When applying usual manner such as spraying or dip-coating, if preparing to apply to metallic substrates Composition described in water soluble salt concentration be less than 0.002 weight %, the content of active component is very few and can not form protection Property coating.On the other hand, according to the compound a in cerium source in the alkaline aqueous composition of the present invention) preferably do not surpassed in terms of Ce elements 2 weight % are crossed, because the composition of the cerium with higher amount tends to assemble or generates precipitation.In another preferred embodiment In, Aquo-composition can be directly used by conventional application method, and not more than 0.2 weight is therefore included in the Aquo-composition Measure %, more preferably no more than 0.12 weight %, the even more preferably not more than 0.08 weight % compound a in terms of Ce elements) To ensure the optimal formation of thin diaphragm.
The silane of aminofunctional preferably has below general formula structure (I)：
(H2N-[(CH2)mNH]n(CH2)p)y-Si-X(4-y) (I)
Hydrolyzable substituent X is each independently selected from not more than 4 carbon atoms, the alkane of preferably no more than 2 carbon atoms Epoxide；M and p are each independently the integer in 1-4 scopes；N is the integer in 0-8 scopes, preferably 0-3；And y is 1-3 scopes In integer, and preferably y be equal to 1.
Preferably, the silane of aminofunctional is selected from γ aminopropyltriethoxy silane, gamma-amino propyl group trimethoxy Base silane, aminoethylaminopropyl trimethoxy silane, aminoethylaminopropyl triethoxysilane, aminoethylamino Diethylaminobutyyl trimethoxy silane and its hydrolysate, derivative, oligomer, condensation product and mixture.
Unexpectedly, the pH value of composition plays a crucial role in the forming step of conversion coating.With good anti-corruption Corrosion transformation of energy coating can be produced only in the range of certain pH.So as in the present invention for the aqueous of pretreatment of metal surface Composition is adjusted to alkalescence.In preferred embodiments, alkaline aqueous composition has at least 8 pH value, but does not preferably surpass Cross 12, more preferably no more than 10.PH value regulator is to be selected from basic matterial, is preferably selected from NaOH, KOH, NH3And NH4HCO3And One or more in alkanolamine.
The stability of the alkaline aqueous composition of component a) and component b) the scale effect present invention.Group in terms of elemental cerium Weight ratio a) with the component b) in terms of elemental silicon is divided to be less than 5 and preferably smaller than 4, more preferably less than 3.If the ratio is more than 5, composition is unstable so that directly generating precipitation.
In preferred alkaline aqueous composition, the weight ratio is at least 0.1 and more preferably at least 0.5.If the ratio Example is less than 0.1, and composition tends to produce on the metallic substrate shows worse coating in salt spray test.When the weight ratio Optimum condition is reached during in the range of 0.5-3.
It is a feature of the present invention that particularly being formed when further organic coating is applied by alkaline aqueous composition Coating can fully avoid the corrosion of metallic substrates.Therefore, the present invention is independent of substantially by chromate, phosphate or element The formation of the coating of Zr, Ti and/or Hf hydroxide/oxide composition.Therefore, in alkaline aqueous composition of the invention, Element M n, Zn or the respective contents of Fe are less than 500ppm, preferably smaller than 100ppm.Also, it is preferred that each leisure of element Zr, Ti or Hf Content in alkaline aqueous composition is less than 50ppm, more preferably small 10ppm, even more preferably less than 5ppm.In addition, with element P Calculate, phosphatic content is preferably smaller than 1000ppm, more preferably less than 100ppm.
In another preferred embodiment, the respective contents of element Ni, Co or Cu are less than 100ppm, preferably smaller than 10ppm is to avoid the electroless plated metal of substrate.
Cover the method for metal pretreated substrate in another object of the present invention, it is included metallic substrates with the present invention's The wet-chemical treatment step of alkaline aqueous composition contact.It is unrestricted and can be by normal using the method for alkaline aqueous composition Any method in rule technology applies wet film progress as impregnated, spraying or passing through squeegee.Preferably by metallic substrates with combining Thing is contacted by impregnating or spraying.Usually, metallic substrates are preferably clean before alkaline aqueous composition is applied or gone Greasy dirt, and preferably it is more than 5nm conversion coating without any thickness.After wet-chemical treatment step but it is any enter one Before the organic coating of step is applied and carry out or without middle cleaning step in the case of, metallic substrates are preferred dry with Obtain can be with most of organic coating optimum adhesions protective coating.Such further organic coating is preferably selected from powder coating Or electrocoat.In particularly preferred embodiments, before powder coating is applied, directly the alkali of metallic substrates and the present invention is made Property Aquo-composition contact wet-chemical treatment step after, be rinsed step and subsequent drying steps.
The rinsing step of the present invention, it is characterised in that this is a kind of work for replacing in other unused active components and previously having adhered to Property component in the case of it is unique be individually directed to washing off being present in adhere in the wet film in metallic substrates and come from any elder generation The method of the active component of preceding wet-chemical treatment step.Active component in this sense be equal to such amount dissolving or Scattered any chemical compound in the liquid phase, such amount is in each wet-chemical treatment step in being realized on metal surface At least 1mg/m2Area load.Complete to rinse using flushing liquor such as deionized water.
It is characterised by the drying steps by purposefully applying heat by adhesion according to the drying steps of the present invention Wet film is dried.
The alkaline aqueous composition of the present invention can be applied to selected from cold rolling steel, hot-strip, galvanized steel, zinc-plated annealing The consumption and use time of the metallic substrates of steel and aluminium, preferably alkaline aqueous composition can be effectively in the tables of metallic substrates Face reaches at least 1mg/m2, more preferably at least 5mg/m2, but preferably more than 100mg/m2In terms of elemental cerium element load.
Embodiment
Hereinafter, the alkaline aqueous composition and metal pretreatment methods of the present invention are illustrated by embodiment.
Weight ratio according to table 1, based on including 0.5 weight % cerous nitrate Ce (NO3)3·6H2O and each organosilan The concentrate of content prepare a large amount for the treatment of compositions of table 1.The pH of each treatment compositions is adjusted to each with ammonia or ammonium hydrogen carbonate From value.In table 1, " A " represents that JH A110 (γ aminopropyltriethoxy silane) and " B " represent Z6610 (gamma-aminos Propyl trimethoxy silicane) and the expression of " concentration " row：[component a) weight+component b) weight]/each treatment compositions it is total Weight.
According to following conventional treatment method, the compositions-treated cold-rolled steel sheet (CRS) of table 1 is used.
Step I- cleanings/degreasing
CRS steel is infiltrated at room temperature with the water-reducible 3 weight %Ridoline-1022R of deionization and 0.3 weight Measure in %Ridoline-1020S mixture 5 minutes；
Step II- formation conversion coatings
CRS was contacted with according to the treatment compositions of table 1 in 4 minutes by infiltration；
Step III- is rinsed
By CRS panel deionized water (κ<1μScm-1) rinse and then dried in about 120 DEG C of baking oven；
Step IV- paints
The powder coating electrostatic coating of polyester and epoxy resin composition (EA067Z, from Akzo) will be based on using spray gun To produce the coating of 60-80 μ m-thicks on to CRS panel.
Table 1
Method of testing：
The CRS panel of coating is subjected to neutral salt spray test (NSST, Neutral Salt Spray Test, according to ASTM B117-03).In above-mentioned test after exposure 500h, the corrosion of powder coating is layered by the maximum creep on scriber Evaluated.
For performance test, if 500h NSST creep numerical value is not more than 2mm, it is considered as acceptable.And work as 500h NSST creep numerical value is not more than 1.5mm, and it is considered as well, and if 500h NSST creep numerical value is not more than 1.0mm, it is considered as non- Chang Hao.
Tested for anti-flash rusting, make another group of steel plate, the step of only carrying out I-III and the step for omitting administration powder coating Rapid IV.If after drying steps III, without there is visible red rust on 15 minutes inner panels, then the plate, which is considered as, does not dodge Rust.Therefore, after drying, appearing in table 1 for any flash rusting is expressed as "Yes" in the time range of 15 minutes.
For steady dissolution test, if processed some plates (~0.1m during one week2/ L) composition solution Keep clean, do not generate visible precipitate, then solution is considered as stabilization.In table 1, it is marked as "Yes".Otherwise, it is labeled For "No".
The result listed according to table 1, it is seen that the corrosion resistance of composition of the invention is influenceed by Multiple factors.It is described The factor includes the concentration and the pH value of composition of component a) and component b) weight ratio, component a) and component b).
Embodiment and comparative example prove that the composition of the present invention can make metallic substrates from sudden strain of a muscle on pre-treatment production line Rust, while the corrosion layering of the metallic substrates of coating can be avoided fully.

Claims (14)

1. for the alkaline aqueous treatment compositions of pretreatment of metal surface, it is included
A) cerium cation source；
B) at least one silane, its Si-C keys and at least one hydrolyzable Si-O key comprising at least one non-hydrolysable, its Described in Si-C keys carry at least one amido functional group；
The weight ratio of component a) and the component b) in terms of Si elements wherein in terms of Ce elements is no more than 5.
2. the composition of claim 1, wherein the weight of component a) and the component b) in terms of Si elements in terms of Ce elements is than excellent Choosing is no more than 4, more preferably no more than 3, but more preferably at least 0.1 and more preferably at least 0.5.
3. the composition of any one of foregoing claim, wherein the component b) has below general formula (I) structure：
(H2N-[(CH2)mNH]n(CH2)p)y-Si-X(4-y) (I)
Wherein hydrolyzable substituent X is each independently selected from not more than 4 carbon atoms, the alkane of preferably no more than 2 carbon atoms Epoxide；
Wherein m and p are each independently 1-4 integer；Wherein n is 0-8, preferably 0-3 integer；And wherein y is the whole of 1-3 Number, and preferably y is equal to 1.
4. any one of claim 1-3 composition, wherein the component a) is the water solubility of cerium (III) and/or cerium (IV) The water soluble salt of salt, preferably cerium (III).
5. any one of claim 1-4 composition, wherein the water soluble salt of the cerium (III) and/or cerium (IV) is selected from sulphur Sour cerium (IV) ammonium, cerous nitrate (IV) ammonium, cerous sulfate (IV), cerous carbonate (III), cerous nitrate (III), cerous acetate (III) and vulcanization Cerium (III) and cerium (III) salt is preferably selected from, is more preferably selected from cerous carbonate (III), cerous nitrate (III) and cerous acetate (III).
6. any one of claim 1-5 composition, wherein the content of the component a) in terms of Ce elements is not less than 0.002 weight %, more preferably no less than 0.02 weight %, but preferably no more than 0.2 weight %, more preferably no more than 0.12 weight % are measured, even More preferably no more than 0.08 weight %.
7. any one of claim 1-6 composition, wherein the pH value of the composition is not higher than 12, preferably no greater than 10, But more preferably at least 8.
8. any one of claim 1-7 composition, wherein the respective content of element M n, Zn or Fe that the composition is included Less than 500ppm, preferably smaller than 100ppm.
9. any one of claim 1-8 composition, wherein the respective content of Ni or Co included in the composition is less than 100ppm, preferably smaller than 10ppm, more preferably less than 1ppm.
10. any one of claim 1-9 composition, wherein being calculated with element P, what is included in the composition is phosphatic Content is less than 1000ppm, preferably smaller than 100ppm.
11. a kind of method of metal pretreated substrate, it includes the composition by metallic substrates and foregoing any one claim The wet-chemical treatment step of contact, is preferably contacted by impregnating or spraying.
12. the method for claim 11, wherein being applied after the wet-chemical treatment step but in any further coating Before and carry out or without middle cleaning step in the case of, dry the metallic substrates.
13. the method for claim 11 or 12, wherein further organic coating is applied after the wet-chemical treatment step, It is preferably selected from powder coating or electrocoat, more preferably powder coating.
14. the purposes of any one of claim 1-10 composition, for selected from cold rolling steel, hot-strip, galvanized steel, plating The corrosion pretreatment of the metallic substrates of zinc annealing steel and aluminium.
CN201480082091.6A 2014-09-22 2014-09-22 The alkaline coating composition based on cerium for pretreatment of metal surface Pending CN107002247A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109722661A (en) * 2019-02-23 2019-05-07 沈阳帕卡濑精有限总公司 Rear-earth-doped inorganic agent of a kind of basic silane for Treatment of Metal Surface and its preparation method and application

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