CN1777700B

CN1777700B - Method for coating metallic surfaces with a mixture containing at least two silanes

Info

Publication number: CN1777700B
Application number: CN2004800109314A
Authority: CN
Inventors: M·瓦尔特; A·舍内; C·容; K·布朗; T·科尔伯格; N·克利姆
Original assignee: Chemetall GmbH
Current assignee: Chemetall GmbH
Priority date: 2003-02-25
Filing date: 2004-02-25
Publication date: 2012-11-14
Anticipated expiration: 2024-02-25
Also published as: CN1777699B; CN1798813A; CN1777699A; DE10308237A1; DE10308237B4; CN1777700A

Abstract

The invention relates to a method for doping a waterborne combination on the metal surface, which comprises an optional organic solvent and other components which are used for preprocess before doping or the process of the metal surface. The method is characterized in that, besides water, the combination comprises: a) at least a hydrolysable and/or at least partial hydrolysable Fluorine-free silane and b) at least a hydrolysable and/or at least partial hydrolysable Fluorinated silane, wherein, the silane in the combination is water soluble or becomes water soluble because of the hydrolytic reaction and/or the chemical reaction before doped on the metal surface. The method further relates to a corresponding combination.

Description

Method with the mixture coating metal surfaces that contains at least two kinds of silane

Technical field

The present invention relates to comprise at least a no silicon fluoride and at least a fluorine containing silane and, the method for the waterborne compositions coating metal surfaces of optional organic membrane-forming agent and/or other component.The invention still further relates to the corresponding waterborne compositions of this kind and by the application of the inventive method substrates coated.

Background technology

So far as before the coating to metal, the method that particularly sheet metal strip surface is handled or pre-treatment is the most often adopted based on chromium (VI) compound together with various Application of Additives.Because these class methods relate to toxicology with ecological dangerous, in addition also because to the foreseeable legal restrictions of use that contains the chromic salt method, for a long time, people seek the alternative method of these methods at all areas of metal finishing always.

On the application of principle of silane in the waterborne compositions that the rich siloxanes corrosionproof protection coating of preparation is used is known.Though these coatings have become sophisticated method, but adopt the coating process of the waterborne compositions of main silane to be difficult to carry out in some cases.The coating that forms can not have ideal performance.In addition, exist variety of issue at present aspect clear silane coating extremely thin on the metal base and the defective thereof fully being characterized in interior eye or by optical instrument.The corrosionproof protection ability of formed rich silicon coating is frequent with lacquer sticking power, but always non-, very high, and some situation is even if in suitable field, but still not high enough for specific end use.

In addition, in the design of silane waterborne compositions, adding at least a component that is selected from monomer, oligopolymer and polymkeric substance more or less is appropriate according to finding.In this kind compsn, add silane character and quantity be successful key factor sometimes.Yet; For this purpose the add-on of silane all lower traditionally-the highest usually only 5wt%--and in fact play the effect of a kind of " coupling agent "; Here main purpose is a viscosifying action, particularly between metal base and enamelled coating and, choose wantonly between pigment and organic coating composition; But also the low cross-linking effect can take place on less degree in some cases.The adding of silane is mainly used in aathermoset resin system.

In addition, resin forms a kind of resin compound with the mineral acid blending so that also reach pickling corrosion and improve direct contact the between resin molding and the metallic surface with this with this kind mode, also is known.The shortcoming of this based composition is, because the pickling corrosive nature of treatment solution (dispersion-s) during contacting with each other with base material often stain.This kind contamination causes the accumulation of metal in treatment solution, the permanent change that the result causes the treatment solution chemistry to be formed, and so, the corrosion protection effect just is greatly affected.Because the pickling corrosion, these metals are leached by the metallic surface from pending base material.

WO 00/46310 openly is coated with a kind of method of liquid compsn to the metallic surface, said composition comprises the aminosilane of hydrolysis and the many-silyl-functional silane of hydrolysis, but does not have fluorine containing silane.

DE-A1-101 49 148 describes a kind of water-based paint compositions based on organic membrane-forming agent, thin inorganic particle and lubricant and/or organic inhibitor; Said composition; Although do not contain chromium cpd; But produce the result of excellent in resistance burn into adhesion strength and formability; Especially on steel plate; But also demonstrate; Galvanizing, electro-galvanizing perhaps

Figure DEST_PATH_G00121260150131000D000012

-coating sheet metal strip on; In other words, be difficult to accomplish on the band of corrosionproof protection the corrosion-resistant deficiency of about 1 μ m bed thickness organic film in the metallic surface.Clearly take in the application in this composition, its all component and raw-material character and coating with this publication.

German patent application DE submitted on February 25th, 103 08 237,2003, related to the compsn of similar composition and the correlation method of coating metal surfaces; It is clearly received aspect following for referencial use at this: the hydrolysis of starting material and performance thereof, preparation of compositions or silane, such as the compsn of its enriched material and body lotion form and performance thereof, effect; The shaping of coating, for example, drying, film forming and curing; The composition and the performance of the coating that forms, the various different embodiments of this method in addition.

WO 01/90267 A2 relates to a kind of compsn, and it comprises hydrocarbon compoud containing fluorine silane, tensio-active agent, polymerizable organosilane or the polymerizable silicate of special composition, and catalyzer.The adding of the not mentioned any organic polymer/multipolymer of the document.

WO 02/31062 A2 describes a kind of emulsion; It comprises hydrocarbon compoud containing fluorine silane, tensio-active agent and a kind of silane; It is selected from aminosilane, epoxy silane and hydrosulphonyl silane; And randomly a kind of " film coalescence aid ", the latter is based on silicon-dioxide, titanium oxide, ZIRCONIUM DIOXIDE 99.5, organoalkoxysilane and/or polysilazane.The document is the adding of not mentioned any organic polymer/multipolymer also.

US 2001/0031811 A1 discloses a kind of coating composition; Mainly form: (a) 20～70% two kinds of different silane monomers altogether, (b) 1～60% tetraalkoxysilane, (c) water-soluble organic polymer by following component; (d) nonionogenic tenside; (e) rudimentary aliphatic alcohol, (f) catalytic activity water soluble acid, and (g) water.Randomly, also can add fluoro silane in addition.This kind compsn is intended to be used to produce antireflection coating and photochromic article.

Summary of the invention

The objective of the invention is to overcome the shortcoming of prior art; A kind of method of coating metal surfaces is particularly proposed; It is fit to high surface covered coating part and coating metal band, and the application of this method can be basically or do not contained chromium (VI) compound fully, also in industry, uses extremely easily.

Be surprised to find at present, in waterborne compositions, add a kind of a small amount of fluorine containing silane and just can make the coating of producing more much higher on hydrophobic and corrosion resistance, but significantly do not damage the water-soluble of compsn or it is stable than the comparable coating that does not add fluorine containing silane.Be generally expected that compsn is hydrophobic, it is water-soluble poor more significantly.

This purpose is that the method that adopts a kind of alloy of giving metallic surface, particularly aluminium, iron, copper, magnesium, nickel, titanium, tin, zinc or containing aluminium, iron, copper, magnesium, nickel, titanium, tin and/or zinc to be coated with a kind of waterborne compositions realizes said composition; Optional organic solvent and other component of also can comprising, said compsn can be basically or is not contained chromium (VI) compound fully, is used for further coating pre-treatment before; Perhaps be used for treating coated object randomly-especially band or strip sections-in the operating mode of coating postforming; Processing, it is characterized in that said composition comprises; Except water

A) the no silicon fluoride of at least a hydrolyzable and/or partly hydrolysed at least and

B) at least a hydrolyzable and/or the fluorine containing silane of partly hydrolysed at least, and

C) at least a metal chelator and/or

D) at least a oligomer/polymer/multipolymer,

Component d wherein) monomer/oligomer/polymer/copolymer is than silane (a) and b)) ratio in enriched material and/or in body lotion is between 0.1: 1～10: 1 scope.

Wherein the silane in the said composition is water miscible or particularly, by the hydrolysis reaction of (further) before the paint metallic surface and/or chemical reaction and become water miscible,

Wherein cleaning, pickled, cleaning are crossed and/or pretreated metallic surface contacts with this waterborne compositions, and on the metallic surface, form film, and this film carries out drying and optional subsequently and additionally is cured,

Wherein dry cross and the bed thickness of the optional film that has also solidified between 0.001～10 μ m, the cured film through peeling off the regulation area and weigh it or through with, for example, x-ray fluorescence analysis and corresponding conversion confirm that the silicone content of coating confirms.

This purpose also realizes through a kind of waterborne compositions corresponding to claim 25.

Its dependent claims further develops this method.Application can be seen in claim 26 and claim 27.

Among the application, this silane is characterised in that the staple of product generally all has available commercial.The silane that comprises in the waterborne compositions (enriched material or body lotion) be monomer, oligopolymer, polymkeric substance, multipolymer and/or with other component by hydrolysis reaction, condensation reaction and/or the further reaction product that generates of reaction.This reaction mainly occurs in the solution, in drying or randomly during coating curing.With regard to teachings herein, term " silane " is used to refer to silane, silanol, siloxanes, ZGK 5 and reaction product thereof or verivate here, and they are " silane " mixture normally.Owing to the normally very complicated chemical reaction that takes place, and analyze and operate very complicacy here, so can't provide further concrete silane or other reaction product.

The silane that meets this illustration purpose will be regarded as water miscible, in the silane compsn, have 0.05g/l at least if they are always said in room temperature, preferred 0.1g/l at least, more preferably 0.2g/l or solubleness in the water of 0.3g/l at least at least.This does not also mean that, any in these silane singlely a kind ofly must have this minimum solubleness, but say, reaches these minimum numerical value fifty-fifty.

In waterborne compositions, preferably have at least a silane that is selected from no silicon fluoride: in every kind of situation, be selected from least a acyloxy silane, a kind of organoalkoxysilane, a kind of silane with at least one amino group such as aminoalkylsilane, a kind of silane with at least one succsinic acid group and/or succinic anhydride group, a kind of two-silyl-silane, a kind of silane with at least one epoxide group such as glycidoxy silane, a kind of (methyl) acrylic (acrylato) silane, a kind of many-silyl-silane, a kind of urea groups silane, a kind of vinyl silanes and/or at least a silanol and/or at least a its composition be chemically corresponding to the siloxanes of above-mentioned silane.It comprises at least a silane and/or (in every kind of operating mode) at least a monomer, dimerization, oligomeric and/or polymerization silanol and/or (in every kind of operating mode) at least a monomer, dimerization, oligomeric and/or polymer siloxane, at this term " oligopolymer " even contain tripolymer.

Specifically, this waterborne compositions contains at least a no silicon fluoride, be selected from or based on:

Glycidoxyalkyl trialkoxysilanes,

The methacryloxy alkyltrialkoxysilaneand,

Aminoalkyl aminoalkyl alkyl-dialkoxysilanes,

(oxirane ring alkyl) alkyltrialkoxysilaneand,

Two-(trialkoxysilyl alkyl) amine,

Two-(trialkoxysilyl) ethane,

(epoxy alkyl) trialkoxy silane,

The aminoalkyl trialkoxy silane,

The urea groups alkyltrialkoxysilaneand,

N-(trialkoxysilyl alkyl) Alkylenediamine,

N-(aminoalkyl) aminoalkyl trialkoxy silane,

N-(trialkoxysilyl alkyl) two alkylene triamine,

Many (aminoalkyl) alkyl-dialkoxysilanes,

The isocyanuric acid ester of three (trialkoxysilyl) alkyl,

The urea groups alkyltrialkoxysilaneand with

Acetoxysilane.

Especially preferably contain at least a silane, be selected from or based on:

3-glycidoxy propyl-triethoxysilicane,

The 3-glycidoxypropyltrime,hoxysilane,

3-methacryloxypropyl triethoxyl silane,

The 3-methacryloxypropyl trimethoxy silane,

Aminoethyl aminopropyl methyldiethoxysilane,

Aminoethyl aminopropyl methyl dimethoxysilane,

β-(3, the 4-epoxycyclohexyl) ethyl triethoxysilane,

β-(3，4-Huan Yanghuanjiji)Yi Jisanjiayangjiguiwan,

β-(3, the 4-epoxycyclohexyl) Union carbide A-162,

β-(3, the 4-epoxycyclohexyl) methyltrimethoxy silane,

γ-(3, the 4-epoxycyclohexyl) propyl-triethoxysilicane,

γ-(3, the 4-epoxycyclohexyl) propyl trimethoxy silicane,

Two (triethoxysilylpropyltetrasulfide) amine,

Two (trimethoxy-silylpropyl) amine,

(3,4-epoxy butyl) triethoxyl silane,

(3,4-epoxy butyl) Trimethoxy silane,

γ-An Bingjisanyiyangjiguiwan,

γ-An Bingjisanjiayangjiguiwan,

γ-urea groups propyl trialkoxy silane,

N-(3-(trimethoxysilyl) propyl group) ethylene diamine,

N-β-(aminoethyl)-γ-An Bingjisanyiyangjiguiwan,

N-β-(aminoethyl)-γ-An Bingjisanjiayangjiguiwan,

N-(γ-triethoxysilylpropyltetrasulfide) NSC 446,

N-(γ-trimethoxy-silylpropyl) NSC 446,

N-(γ-triethoxysilylpropyltetrasulfide) dimethylene triamine,

N-(γ-trimethoxy-silylpropyl) dimethylene triamine,

Gather (aminoalkyl) ethyl dialkoxy silicane,

Gather (aminoalkyl) methyl dialkoxy silicane,

Three (3-(triethoxysilyl) propyl group) isocyanuric acid ester,

Three (3-(trimethoxysilyl) propyl group) isocyanuric acid ester with

Vinyltriacetoxy silane.

Preferably; Waterborne compositions comprises at least a silane that is selected from fluorine containing silane: be selected from every kind of operating mode at least a acyloxy silane, a kind of organoalkoxysilane, a kind of silane with at least one amino group such as aminoalkylsilane, a kind of silane with at least one succsinic acid group and/or succinic anhydride group, a kind of two-silyl-silane, a kind of silane with at least one epoxide group such as glycidoxy silane, a kind of (methyl) acrylic (acrylato) silane, a kind of many-silyl-silane, a kind of urea groups silane, a kind of vinyl silanes and/or at least a silanol and/or at least a its composition be chemically corresponding to the siloxanes or the ZGK 5 of above-mentioned silane; Wherein comprise at least one such group in every kind of operating mode, this group contains one or contain at least one fluorine atom.

Specifically; Waterborne compositions comprise at least a fluoroalkyl alkyl silane, at least a list-, two-or three-functional fluoro silane, at least a list-, two-or three-fluoro silane, at least a based on Ethoxysilane and/or based on the fluoro silane and/or at least a fluoro silane of methoxy silane with at least one functional group such as amino group; Cocondensation compound form particularly; For example, fluoroalkyl dialkoxy silicane, fluoro-aminoalkyl propyl trialkoxy silane, fluoro methanesulfonates, fluoro propyl group alkyl-dialkoxysilanes, triphenyl fluoro silane, tri-alkoxy fluoro silane, trialkyl fluoro silane and/or 13 fluoro octyltrialkoxysilane.

Particularly preferably be, compsn comprises at least a such silane, and it comprises at least two amino groups and contains at least one ethyl group and/or at least one methyl group.

All silane a) and b) quantity, comprise the optional reaction product that generates with other composition, altogether preferably between 0.01～100g/l, in enriched material; Perhaps 0.002～12g/l is in body lotion.In the operating mode of enriched material; This quantity is more preferably between 0.05～80g/l; Very preferably in the scope of 0.1～60g/l, particularly about 0.5,1,2,3,4,5,6,7,8,9,10,11,12,13,14,15,16,17,18,20,22.5,25,27.5,30,35,40,45,50 or 55g/l.Under the situation of body lotion; This quantity is more preferably between 0.005～5g/l; Very preferably in the scope of 0.01～3g/l, particularly about 0.05,0.1,0.2,0.3,0.4,0.5,0.6,0.7,0.8,0.9,1.0,1.1,1.2,1.3,1.4,1.5,1.6,1.7,1.8,2.0,2.25,2.5 or 2.75g/l.The common water of the dilution of enriched material, only the mixture of water and at least a organic solvent is implemented occasionally, specifically can be diluted to 1.5～30 times, and common 2～20 times, particularly 3～12 times.

A) and b) the preferred every kind of situation of quantitative proportion between 1: 0.01～1: 4; More preferably 1: 0.03～1: 3 quantitative proportion; Very preferably 1: 0.05～1: 2.5 quantitative proportion; Especially; In every kind of operating mode, at least 1: 0.08,1: 0.12,1: 0.16,1: 0.2,1: 0.25,1: 0.3,1: 0.35,1: 0.4,1: 0.45 or 1: 0.5 or particularly, the highest 1: 2.5 in every kind of operating mode, 1: 2.2,1: 2,1: 1.8,1: 1.6,1: 1.4,1: 1.2,1: 1.1,1: 1,1: 0.9,1: 0.8,1: 0.7 or 1: 0.6.The concrete optimum value of this quantitative proportion but can fluctuate, yet, depend on used silane a) and b) and their hydrolysis what state.

Preferably, the choice criteria of waterborne compositions should satisfy: greater than 60wt%, particularly greater than 80wt% silane have good water-solvability and, during processing, have good stability by enriched material or the compsn of body lotion form of its preparation.The length of this process period can change between 2h to 6 month, decided as requested.The good stability here is meant, compsn only takes place not have as far as possible or slight deposition, and do not have as far as possible or slight chemistry and/or physical change only take place.Should be basic preferably transparent by the compsn of silane and solvent composition.In this connection, the compound of preferably selecting to be generated in like this reaction/step by this silane relatively major part has the structure that can be considered ladder structure, and is particularly most or even all be those silane, those reactions and the process step of ladder structure.

Possibly particularly preferably be, in waterborne compositions, add at least two kinds of different no silicon fluorides, optional even 3 or 4 kind of different no silicon fluoride.In the middle of multiple possible combination; The especially preferably following combination of use: at least a sense trialkoxy silane and at least a pair-trialkoxy silane, at least a aminosilane and at least a pair-trialkoxy silane, at least a pair-trialkoxy silane and at least a vinyl silanes, at least a pair-trialkoxy silane and at least a urea groups silane, at least a vinyl silanes and at least a pair-trialkoxysilyl propyl silane, at least a aminoalkylsilane and at least a pair-trialkoxysilyl propyl silane, at least a pair-tri-alkoxy-silyl propyl group four sulfanes and at least a pair-trialkoxysilyl propyl silane, at least a no silicon fluoride of cyanato and/or epoxide group and the different with it no silicon fluorides of containing; And, optional add in addition at least a urea groups silane, at least a many-silyl-silane, at least a two-during trialkoxysilyl propyl group four sulfanes and/or at least a other trialkoxy silane one of make up to these.

Also maybe be particularly advantageous be, in waterborne compositions, add at least two kinds of different fluorine containing silanes, optional even 3 or 4 kind of different fluorine containing silane.

Preferred especially combination: in every kind of operating mode, at least a organosilane, a kind of organofunctional silane and a kind of fluoro silane, particularly, in every kind of operating mode, at least a aminosilane, a kind of many-silyl-silane and a kind of fluoro silane.

Maybe be advantageously, with each single silane, the hydrolysis of only single a kind of ground, if their fully hydrolysis as yet, so that, optionally store individually, subsequently they are joined in the compsn.Chemical reaction or condensation reaction are also chosen wantonly during hydrolysis and are taken place.Yet even if at that time, hydrolysis and/or chemical reaction or condensation reaction also can further be carried out, choose wantonly at lay up period, but in some operating mode, even after in the compsn that joins enriched material or body lotion form.

Though waterborne compositions is referred to as solution in this manual, but be not necessarily proper solution, especially because only possibly could confirm whether indication solution is true solution usually through other analysis.Specifically, waterborne compositions also can be suspensoid and/or emulsion, especially when adding particle, particularly during inorganic particle.

Waterborne compositions comprises, as solvent, and water, the wherein content of water in solvent mixture at least: greater than 50wt%, in the operating mode of enriched material; And greater than 75wt%, in the operating mode of bath lotion composition.The content of water in solvent mixture under the situation of enriched material, preferably is 60wt% at least, more preferably 70wt% at least, 80wt% at least very very preferably, particularly 90wt% at least.The content of water in solvent mixture under the situation of bath lotion composition, preferably is 80wt% at least, more preferably 85wt% at least, 90wt% at least very very preferably, particularly 95wt% at least.Other solvent beyond dewatering, in other words, organic solvent particularly; For example; The content of ethanol, methyl alcohol, propyl alcohol and/or Virahol, on the one hand, can be join in enriched material or the body lotion and/or can in enriched material or body lotion, generate through chemical reaction.Yet from the consideration of environment, preferably, the content of organic solvent maintains alap level.In view of the reason of process engineering, preferred sometimes certain content of organic solvent or low organic solvent content, but in some operating mode, because chemical reaction, organic solvent is again inevitably, only if remove it later on artificially.

Waterborne compositions comprises and is not more than 0.2g/l chromium, preferably is not more than 0.1g/l chromium, and more preferably no more than 0.02g/l chromium, wherein this chromium content possibly come from, and particularly, carries secretly and/or from corrosion operation and/or chromium plating to chrome-bearing alloy.Further preferably, greater than the iron of 0.8g/l, manganese with the zinc, contain other heavy metal except altogether no longer in addition.

In the present invention's first particularly preferred embodiment; Waterborne compositions comprise silane a) and b), water and; Optional at least a organic solvent such as methyl alcohol, ethanol, Virahol and/or propyl alcohol, at least a alkaline reagents such as ammonia, at least a acid reagent such as acetate and/or Glacial acetic acid min. 99.5; At least a tensio-active agent is so that reduce surface tension and coating metal surfaces evenly and reliably; For example, at least a nonionic, at least a negatively charged ion, at least a positively charged ion and/or at least a amphoterics, and/or at least a additive such as at least a sanitas and/or at least a biocides.

The water-content that the body lotion of the waterborne compositions of main silane is formed is between 80～99.9wt%; More preferably between 90～99.8wt%; 94～99.7wt% very preferably; 96～99.6wt% particularly is in particular for about 91,91.5,92,92.5,93,93.5,94,94.5,95,95.5,96,96.5,97,97.5,97.9,98.2,98.5,98.8,99.1 or 99.4wt%.

Except that silane and solvent, the quantity of other component generally is no more than 5g/l altogether in body lotion, preferably is no more than 3g/l altogether, more preferably is no more than 1.5g/l altogether, but maybe be correspondingly higher in enriched material.

In the present invention second and the third particularly preferred embodiment variant, at least a component that is selected from following 11 kinds of components is by the extra compsn that joins first kind of particularly preferred embodiment variant:

C) metal chelator,

D) monomer, oligopolymer, polymkeric substance and/or multipolymer,

E) be selected from the component of at least a following component,

e ₁) at least a particle form mineral compound, its average particulate diameter is measured by sem, between 0.005～0.3 μ m diameter,

e ₂) at least a lubricant,

e ₃) at least a organic inhibitor,

e ₄) at least a anti-corrosion pigment,

e ₅) at least a neutralization with and/or the reagent used of the spatial stabilityization of synthetic resins,

e ₆) at least a organic solvent,

e ₇) at least a siloxanes,

e ₈) at least a long-chain alcohol and

e ₉) at least a tensio-active agent.

Preferred especially sequestrant content; Comprising the reaction product by its generation in every kind of operating mode, between 0.01～15wt%, is benchmark in the solids content of bath lotion composition; Be the amount of 0.03～11wt% independently of one another in every kind of operating mode more preferably; Especially, generally, be 0.05,0.1,0.5,1,1.5,2,2.5,3,3.5,4,4.5,5,5.5,6,6.5,7,7.5,8,8.5,9,9.5,10 or the amount of 10.5wt% independently of one another under every kind of situation.

Preferably; Selected at least a silane and water compatible, that is, satisfy: at least a silane and/or; Optional its hydrolysis and condensation product can dissolve with all components of waterborne compositions and mix; And do not destroy, and can keep the time that surpasses several weeks, and it can form particularly fine and close, homogeneous and not have the indefectible wet film and the dry film of shrinkage cavity.Specifically, at least a silane of selection can provide the possibility of highly corrosion resistant, especially combines with at least a selected sequestrant.

Preferably, at least a sequestrant of selection can be stablized a couple of days or several weeks in water dispersion in the presence of other component of waterborne compositions, and the possibility of highly corrosion resistant is provided.In addition, advantageously, at least a silane and at least a sequestrant on the one hand, all can be chemically bonded on the contacted with it metallic surface, randomly also can chemically be bonded on the other hand on the spraying paint that preparation applies subsequently.This at least a metal chelator; Especially aluminium, boron, calcium, iron, hafnium, lanthanum, magnesium, manganese, silicon, titanium, yttrium, zinc, zirconium and/or at least a lanthanon, for example, cerium; Perhaps; For example, contain the mixture of the lanthanon of cerium, especially preferably be selected from aluminium, hafnium, manganese, silicon, titanium, yttrium and zirconium.

The waterborne compositions of main silane and sequestrant and preferably have 20～95wt% scope interior water-content, particularly 30～90wt% as containing the enriched material of polymer compsn with the part component of raw material.This enriched material preferably contains silane, comprises the reaction product that is generated by it, and its content is between 0.1～60wt%; More preferably 0.2～45wt%, very preferably 0.3～35wt%, particularly 0.5～32wt%; Especially be about 0.8,1,2,4,6,8,10,12,14,16,18,20,22.5,25,27.5 or 30wt%, and preferably comprise at least a sequestrant, the optional reaction product that generates by it that comprises; Its content is between 0.1～50wt%, more preferably 0.2～40wt%, very especially preferred 0.3～30wt%; 0.5～25wt% particularly especially is about 00.75,1,2,4,6,8,10,12,14,16,18,20 or 22.5wt%.

The water-content that the bath lotion composition of the waterborne compositions of main silane and sequestrant preferably has 80～99.9wt% scope wherein also can comprise a part of at least a organic solvent.The content of water and/or at least a organic solvent is preferably between the scope of 90～99.8wt%; Preferably at 94～99.7wt%; Especially preferably in the scope of 96～99.6wt%, particularly about 95,95.5,96,96.5,97,97.5,97.9,98.2,98.5,98.8,99.1 or 99.4wt%.

Bath lotion composition preferably contains silane; Comprise by it and other components and choose the reaction product that generates wantonly, its content is between 0.01～10wt%, especially preferably between 0.05～7wt%; Very especially preferred scope between 0.1～5wt%; Particularly at 0.2～4wt%, especially about 0.4,0.6,0.8,1.0,1.1,1.2,1.3,1.4,1.5,1.6,1.7,1.8,1.9,2.0,2.1,2.2,2.4,2.6,2.8,3.0,3.2,3.4,3.6 or 3.8wt%, and preferably contain at least a sequestrant; Comprise the optional reaction product that generates by it; Its concentration is between 0.01～10wt%, especially preferably between 0.05～7wt%, very especially preferably between 0.1～5wt%; Most preferably between 0.2～4wt%, particularly about 0.3,0.4,0.5,0.6,0.7,0.8,0.9,1.0,1.1,1.2,1.3,1.4,1.6,1.8,2.0,2.2,2.4,2.6,2.8,3.0,3.2,3.4,3.6 or 3.8wt%.

The content of at least a silane and at least a sequestrant; Every kind of situation all comprises those of the reaction product, particularly titanium, hafnium and/or the zirconium that are generated by them, preferably accounts for the 20wt% at least of the solids content of this kind compsn; Especially at least 30wt%; Especially preferably 40wt% at least, very especially preferred 50wt% at least, particularly every kind of situation at least 60,70,80,90,94,95,96,97,98 or 99wt%.Said composition especially preferably mainly contains: water, in every kind of operating mode at least a silane and/or its reaction product, at least a sequestrant, the optional reaction product and the optional certain content that are generated by it of comprising is selected from following material: alcohol, acid are like carboxylic acid and lipid acid, for example; Acetate; And/or mineral acid, and other influences the material of pH value, for example; Ammonia, and additive and impurity.Except silane with the sequestrant, the total content of other compound comprises additive; Generally be up to the 20wt% of the solids content of silane and sequestrant, preferably the highest 15wt%, especially preferably the highest 10wt%; Very especially preferred the highest 5wt%, particularly the highest 1 or 2wt%.

Though at least a silane comprises the reaction product that is generated by it, with at least a sequestrant; The optional reaction product that generates by it that comprises, between ratio, can be preferably between 0.8: 1～1.2: 1; But be surprisingly found out that, this ratio also can, particularly; Between 0.2: 1～0.5: 1 or 2: 1～5: 1,, possibly there is optimum value in these scopes because in some situation.

The pH value of this kind bath lotion composition can, particularly, 3～9.5 scope is especially preferably between 3.5～9, particularly between 4～8.8.For regulating the pH value, particularly can add the mixture of a kind of weak acid or rare strong acid or acid.Specifically, at least a acid, for example, carboxylic acid or lipid acid, for example, acetate, and/or mineral acid, and other influences the material of pH value, for example, ammonia all can use.Bath lotion composition in some cases, can be lowered to about 3.5 pH value through adding acid, if chemical system is allowed selected pH value and still kept stable.Can preferably also add solvent, for example alcohol is stablized this silane.

The typical layers thickness of planting the coating that bath lotion composition forms thus is between 0.01～0.6 μ m, usually between 0.015～0.25 μ m.

As silane, the present composition also can comprise organic monomer, oligopolymer, polymkeric substance and/or multipolymer.With regard to teachings herein, term " multipolymer " preferably also comprises segmented copolymer and graft copolymer.

The acid number of synthetic resins is preferably between 3～100, and especially preferred 3～60 or 4～50.Particularly, add the multipolymer of acid number in hydrotropisms's compsn between 3～50 scopes.Randomly, the component of organic membrane-forming agent of adding is a part neutral.Organic membrane-forming agent preferably can comprise the multipolymer of at least a acid number of certain proportion between 3～80 scopes, particularly account for add the 50wt% at least of synthetic resins.Interval at high acid value, need not implement the stabilizing treatment on positively charged ion, negatively charged ion and/or the space usually to membrane-forming agent.Yet,, just needed this kind stabilizing treatment usually at low acid number.Therefore, advantageously adopt synthetic resins or its mixture of (partly) stabilization.

Waterborne compositions preferably contains at least a synthetic resins; For example; Organic polymer, multipolymer and/or its mixture are particularly based on the synthetic resins of propenoate, ethene, polyester, urethane, silicone polyester, epoxide, phenol, vinylbenzene, carbamide, melocol and/or vinyl.Organic membrane-forming agent can preferably at least a polymkeric substance and/or the synthetic resin mixture of at least a multipolymer; They; In every kind of situation, contain the synthetic resins of certain proportion independently of one another based on propenoate, epoxide, ethene, melocol, phenol, polyester, urethane, vinylbenzene, styrene butadiene and/or vinyl.It here also can be synthetic resins or polymkeric substance and/or its dispersion-s or even its solution of stabilization on positively charged ion, negatively charged ion and/or the space.Term " propenoate " with regard to teachings herein, comprises propenoate, ROHM, methacrylic ester and methacrylate.

Organic membrane-forming agent can preferably comprise at least a component based on following compounds:

Vinylformic acid-polyester-polyurethane ester copolymer,

Vinylformic acid-polyester-polyurethane-styrol copolymer,

Propenoate,

Propenoate-methacrylic ester, optional band free acid and/or vinyl cyanide,

The ethylene-propylene acid mixture,

Ethylene-acrylic acid copolymer,

Ethylene-acrylic acid-polyester copolymer,

Ethylene-acrylic acid-polyurethane copolymer,

Ethylene-acrylic acid-polyester-polyurethane ester copolymer,

Ethylene-acrylic acid-polyester-polyurethane-styrol copolymer,

Ethylene-acrylic acid-styrol copolymer,

Have the combination of the vibrin and the melamine formaldehyde resin of free carboxy group,

Based on propenoate and cinnamic synthetic resin mixture and/or multipolymer,

The synthetic resin mixture of styrene-based-divinyl and/or multipolymer,

The synthetic resin mixture of propenoate and epoxide and/or multipolymer,

Based on the polyester of the vinylformic acid-modification of carboxyl group, together with carbamide and ethylene-acrylic acid copolymer,

Polycarbonate-polyurethane,

Polyester-polyurethane,

Vinylbenzene,

Vinylbenzene-vinyl acetate between to for plastic,

Vinyl acetate between to for plastic,

Vinyl ester and/or

Vinyl ether.

Yet; Organic membrane-forming agent also can preferably contain; As synthetic resins; Certain content is based on organic polymer, multipolymer and/or its mixture of polymine, Z 150PH, polyvinylphenol, PVP K120 and/or SAP 73, particularly with the multipolymer of phosphorous vinyl compound.Preferably in waterborne compositions, also add a kind of conductive polymers.

In second kind of particularly preferred embodiment variant of the present invention; Component d)--monomer/oligomer/polymer/copolymer--and the compound weight ratio of silane in enriched material and/or body lotion; Preferably between 0.1: 1～10: 1; More preferably 0.2: 1～5: 1, very preferably 0.3: 1～3: 1, particularly be up to 2: 1 or the highest 1.5: 1 value.In the operating mode of this kind embodiment variant, silane not only can play, and only on less degree, does not perhaps play " coupling agent " usually.

In the third particularly preferred embodiment variant of the present invention; Component d)--monomer/oligomer/polymer/copolymer--and the compound weight ratio of silane in enriched material and/or body lotion; Preferably between 3: 1～200: 1, more preferably 8: 1～120: 1, very preferably 12: 1～100: 1.。In the operating mode of this kind embodiment variant, silane in many cases can be partly, mainly or fully play the effect of " coupling agent ".Specifically, in the operating mode of this kind embodiment variant, advantageously use a kind of long-chain alcohol e usually ₈) as film coalescence aid, the latter provide between film stage make between glass transition temperature Tg or the minimum film-forming temperature MFT close to each other or the coupling effect.So, can make the film that forms by organic substance have the structure of special homogeneous, thereby the performance of this type coating is played favorable influence.

In a kind of particularly preferred embodiment in this connection, can use the mixture of organic membrane-forming agent, wherein the glass transition temperature Tg of at least a portion membrane-forming agent is basic identical and/or close.Here especially preferredly be that the glass transition temperature Tg of some organic membrane-forming agent is between 10～70 ℃ scope, very especially preferably between 15～65 ℃, particularly between 20～60 ℃ at least.So organic membrane-forming agent preferably contains at least a polymkeric substance of at least one certainty ratio and/or at least a multipolymer, its minimum film-forming temperature MFT is between-10～+ 99 ℃, especially preferably between 0～90 ℃, especially since 5 ℃ or from 10 ℃.Here especially preferredly be, at least two kinds, if not whole, as long as the minimum film-forming temperature of organic membrane-forming agent is positioned at one of these TRs-can point out minimum film-forming temperature.

At this especially advantageously, whole organic membrane-forming agents during drying form film.Particularly preferably be, the synthetic resins of in waterborne compositions, sneaking into is 80wt% at least, and 90wt% has thermoplastic properties especially at least.

Here the selection of suitable film coalescence aid and remarkable; The mixture that usually needs at least two kinds of film coalescence aid.Particularly advantageous film coalescence aid is so-called long-chain alcohol; Particularly have those of 4～20 carbon atoms; For example; Butyleneglycol, butyl glycol (Butyl glycol), butyldiglycol, glycol ether such as terepthaloyl moietie monobutyl ether, glycol monoethyl ether, methyl glycol, glycol propyl ether, glycol hexyl ether, diethylene glycol methyl ether, diethylene glycol ethyl ether, butyl carbitol, glycol ether hexyl ether; Perhaps polypropylene glycol ether; For example, diisobutyrate, THF homopolymer, polyethers-polyvalent alcohol and/or the polyester-polyvalent alcohol of Ucar 35 monomethyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, Ucar 35 monobutyl ether, dipropylene glycol monobutyl ether, tripropylene glycol monobutyl ether, Ucar 35 one propyl ether, dipropylene glycol one propyl ether, tripropylene glycol one propyl ether, Ucar 35 phenylate, neopentyl glycol.Be different from film forming, crosslinked for the thermofixation that reaches organic coating in the temperature that requires at least 120 ℃ traditionally.

In the 4th kind of particularly preferred embodiment variant of the present invention, taked appropriate measure forming a kind of hydrophobic surface owing to be hydrophobic, thus should the surface and/or surface micro-structure have self-cleaning performance.In this connection, might make this surface micro-structure,,,, and have microstructure in the structure of nanometer and/or micrometer range through appropriate process method through the formation of organic granular through the adding of organic and/or inorganic particle.The particle that adds preferably has uneven surface and/or complex geometric shapes and/or association largely or is associated, and the result forms a kind of aggregate or agglomerate of coarse largely or tool complicated shape.This process can pass through to add the different particle of granularity, in other words, and the particle that different mean particle sizes and/or different grain size distribute, and promoted.The surface of the coating that generates by mode like this preferably has such microstructure, that is, and and the microstructure of a kind of medium fineness that superposes at least in part above that.This coating can be based upon on the compsn of especially preferred first, second or the third embodiment variant.

Moreover, also have other embodiment preferred, wherein, particularly, there is at least a e of being selected from ₁)～e ₉) component and randomly, also have amount of component b) or d) one of at least, in addition, randomly, add at least a monomer/oligomer/polymer/copolymer and/or add at least a particle form mineral compound.

As lubricant e ₂); At least a paraffin, Vilaterm and the polyacrylic wax of being selected from of preferred employing, particularly a kind of oxidized petroleum waves, wherein the content of wax in waterborne compositions is preferably between the scope from 0.01～5wt%; Especially preferably from 0.02～3.5wt%, very especially preferably from 0.05～2wt%.Preferably, as the fusing point of the wax of lubricant between 40～165 ℃, especially preferably between 50～160 ℃, particularly 120～150 ℃.Particularly advantageously be; Except fusing point between 120～165 ℃ lubricant; Also add fusing point between 45～95 ℃ or the second-order transition temperature lubricant between-20～+ 60 ℃, specifically its consumption accounts for 2～30wt% of total solids level, preferred 5～20wt%.Yet the latter also can advantageously use separately.

The particularly advantageous wax that is to use the dispersion-s form of aqueous dispersion or positively charged ion, negatively charged ion and/or spatial stabilityization, because at that rate, it keeps equally distributed form easily in waterborne compositions.Waterborne compositions preferably contains at least a lubricant, and it also is a binder simultaneously randomly, and its content is between 0.1～25g/l, the content of especially preferred 1～15g/l.

Waterborne compositions preferably contains at least a organic inhibitor e ₃), particularly based on amine, preferred at least a alkanolamine one is the long-chain alkanolamine preferably; The complex compound of at least a TPA-amine; For example, the zinc salt of the sour affixture-butyric ester-4-ethyl morpholine of 4-oxo-4-p-methylphenyl, at least a aminocarboxylic acid, the zinc salt of 5-nitro-m-phthalic acid or the zinc salt of cyanic acid, the polymeric ammonium salts of at least a lipid acid, at least a sulfonic acid; For example; The amino metal-salt of dodecyl-naphthene sulfonic acid, at least a toluene propionic acid, 2-sulfydryl-benzothiazolyl-succsinic acid and transition metal complex or at least a its amide, at least a conductive polymers and/or at least a mercaptan, wherein the content of organic inhibitor in waterborne compositions can be preferably between the scope of 0.01～5wt%; Especially preferred 0.02～3wt%, very especially preferred 0.05～1.5wt%.

At least a organic inhibitor preferably at room temperature is not easy to evaporable.Maybe be also advantageously, it is easy to be dissolved in the water and/or is easy to be dispersed in the water, particularly reaches more than the 20g/l.Preferred especially compound is alkylamino ethanol especially, for example, and dimethylaminoethanol, and based on the complex compound of TPA-amine, for example, the complex compound of N-ethylmorpholine and 4-methyl-γ-oxo-benzenebutanoic acid.The purpose that adds this inhibiter is to realize or further strengthens certain powerful relatively corrosion inhibition.

Waterborne compositions preferably contains at least a corrosion-inhibitive pigments e of 0.1～80g/l ₄).These comprise that particularly, various silicate are based on pure aluminium silicate, aluminosilicate, aluminium alkaline earth metal silicate and alkaline earth metal silicate.Corrosion-inhibitive pigments preferably has the average particulate diameter of 0.01～0.5 μ m diameter, measures according to sem, particularly 0.02～0.3 μ m.The all kinds corrosion-inhibitive pigments is known in principle.As if yet the adding one of at least of these pigment in principle not necessarily but can provide possible alternate embodiment variant.

Be used for and acid number, particularly between the acid groups of 5～50 synthetic resins and/or make it the reagent e that spatial stabilityization is used ₅), can be a kind of low volatility alkanolamine and oxyhydroxide such as sodium hydroxide solution and potassium hydroxide solution especially, but preferred high volatile volatile alkanolamine, ammonia and based on the compound of morpholine and alkanolamine.They have the neutral of making synthetic resins and become water soluble and mix, perhaps under the situation of the acid number of about 150 beginnings even water-soluble.

At least a organic solvent e ₆) also can choose wantonly and join in the inventive method.At least a water soluble mixes and/or water-soluble alcohol, a kind of glycol ethers or N-Methyl pyrrolidone and/or water; The organic solvent that can be used as organic polymer; And under the situation that adopts solvent mixture; Particularly at least a long-chain alcohol, for example, the mixture of Ucar 35, a kind of ester-alcohol, a kind of glycol ethers and/or butyleneglycol and water.Yet, preferably, only add entry in many cases, do not add any organic solvent.If with an organic solvent, then its content is preferably between 0.1～10wt%, 0.25～5wt% particularly, very especially preferred 0.4～3wt%.Under the situation that band is produced, then preferably only adopt water, hardly with or do not use organic solvent, maybe be except a small amount of alcohol.

Also advantageously adopt at least a wetting agent in addition, so that can apply wet film and bed thickness homogeneous equably along whole area, so that fine and close and do not have a flaw.Many wetting agents are fit to this purpose in principle, and preferred acrylate, silane, ZGK 5, long-chain alcohol are because they can reduce the surface tension of waterborne compositions.Especially at least a ZGK 5 e of preferred adding ₇).

At least a tensio-active agent e ₉) adding can help to improve the present composition the wetting of metallic surface and improve coating, particularly be coated with homogeneous more.In this connection, significantly improvement effect especially can be obtained under the coarse especially situation in surface.Be fit to reach the tensio-active agent that varied type is arranged, particularly nonionic, positively charged ion, both sexes and the AS of this purpose.0.01 a small amount of adding of～0.4g/l scope is just enough usually.

The present composition also can be used as in coating operation in advance, like the back-cleaning solution after the conversion coated operation.As convertible coating, for example, can at first apply a kind of being coated with and expect on the metallic surface; This coating is based at least a organic and/or mineral acid, and is optional together with further additive, based on the bonderize agent; For example; Based on iron, calcium, magnesium, manganese and/or zinc, this treatment agent is again by the preparation of complicated fluoride solution or dispersion-s, and they are based on phosphonate, based at least a silane/siloxane and/or ZGK 5 and/or based on rare earth compound.Therefore, this kind solution or back cleaning solution are particularly suitable for not painting or not applying the corrosionproof protection as the polishing material of lacquer coating.Based on rare earth compound such as cerium oxide, convertible coating especially can be used on the surface of rich aluminium, magnesium, titanium and/or zinc.

Embodiment

Instance and Comparative Examples:

Below described instance be intended to describe in more detail theme of the present invention.

A) compsn of high level silane:

Be the preparation aqueous concentrates; Prepared a kind of aqueous mixture according to table 1; Preparation is used for not passing through as yet the silane of prehydrolysis; In containing the said mixture of Glacial acetic acid min. 99.5 and alcoholic acid, prehydrolysis is more than at least 3 days in acidic medium, under room temperature and the stirring at least a silane, and wherein employed silane is not in prehydrolysis form as yet.Subsequently, this has become the silane of prehydrolysis form optional adding, and system is carried out violent stirring, and with the optional room temperature that is stored in of preparation.Subsequently, enriched material with water dilution and, optional pH value regulator such as ammonia and/or the Glacial acetic acid min. 99.5 of adding is so that obtain ready-to-use processing body lotion.Then, in every kind of operating mode, the metal sheet that the cleaning of at least 5 CRSs (CRS) or two-sided hot-dip galvanized steel sheet is crossed contacts with dry corresponding treatment solution with 25 ℃ by roller coat.The metal sheet of so handling is tested its corrosionproof protection effect subsequently 90 ℃ of PMT dryings.Enriched material and composition and the performance of handling body lotion, and the performance of coating is summed up in table 1 and 2.

Silane A and B are not fluorine-containing, and silane C is fluorine-containing.Silane A is the aminofunctional trialkoxy silane, in joining compsn before only hydrolysis about 2h.Silane B passes through hydrolysis before and stores about 3 days two-trialkoxy silane in joining compsn.Silane C is the fluoroalkyl organoalkoxysilane of water-soluble aminoalkyl functional, is that hydrolysis in advance just joins in the compsn later with storing for a long time.These details have characterized the character of the main composition that comprises in the available commercial product.The silane that exists in the waterborne compositions (enriched material or body lotion) be monomer, oligopolymer, polymkeric substance, multipolymer and/or with the reaction product of other component through hydrolysis reaction, condensation reaction and/or other reaction.These reactions mainly occur in the solution, between dry epoch and, during the optional coating curing.Term " silane " is used to refer to silane, silanol, siloxanes, ZGK 5 and reaction product thereof and verivate here, and they are " silane " mixture normally.Used enriched material and body lotion prove that all to stablize a week above and do not change or do not precipitate.Do not add ethanol.Those ethanol that comprise in the compsn are uniquely from chemical reaction.

Polymkeric substance D is a kind of easy film forming thermoplastic polymer based on ethoxylate.Polymkeric substance E is a polyethylene and ethylene copolymers.The mean particle size of silica dioxide granule is about 200nm.Monoethanolamine MEA BASF and/or ammonia are added in the body lotion so that regulate the pH value.In addition, in the operating mode of instance of the present invention/Comparative Examples CE 10 and IE 11～IE 20, added the nonionogenic tenside of about 0.1g/l quantity in every kind of situation.The effective wetting of the metallic surface that this of tensio-active agent kind of adding helps to clean especially under the complicated or coarse especially metallic surface situation, is realized even film forming in shape.Adopt these compsns, prepared the coating that dry film is significantly smaller than 1 μ m.

Here formed film is all transparent, homogeneous and densification.In all operating modes, except CE2, film is Show Color on steel plate not all.The structure of metallic surface, gloss and color look the only very little variation of generation before and after coating.More kinds of silane comprise than the small proportion fluorine containing silane, and the combination of composition all shows the obvious improvement effect to corrosionproof protection, when promptly the add-on of convenient fluorine containing silane is fewer.In this kind operating mode, in other words further coating, had not both had priming paint not have on the finish coat paint silane coating yet.The corrosionproof protection value wherein 5 is represented worst-case value from 0 up to 5.The system that selection is made up of no silicon fluoride and/or fluorine containing silane shows and is worth with them, because all these combinations all provide highly stable solution.

So between 0.02～0.16 μ m, great majority are between 0.02～0.12 μ m for the thickness of the coating of preparation--the sort of situation that applies of fluctuation when comprising beginning--.

Contact angle adopts DIGIDROP contact angle appearance, and company provides by the GBX scientific instrument, adopts redistilled water, and every block of plate is measured 5 times.Contact angle is big more, and the surface is hydrophobic more.Under the situation of experiment CE 2, be different from the plate of other coating, the steel plate of this coating demonstrates golden yellow rust, and this can have a negative impact for contact angle.In addition, find that contact angle not only only depends on the silane that applies, and depends on the surface treatment effect, for example, the pH value.Be surprised to find, in these experiment conditions, it is strict related between the corrosion resistance of hydrophobicity, contact angle and the coating system of coating surface, to exist amazing ground at present.

According to finding, in many operating modes, give certain hydrophobic quality of coatingsurface and--can measure--and guarantee that coating has certain thickness, for all being useful as the corrosionproof protection blocking layer from contact angle.Silane has improved the sticking power to the metallic surface here.

The coating of producing with it is fit to be coated with powder paints or with solvent-Ji lacquer in many cases.By contrast, the water-miscible paint compsn then receives rejection.

B) basically based on the back cleaning solution compsn of silane:

As experimentalists and technicians A) operating mode in such preparation aqs soln, but different be, according to table 3 select to form and transformant-coating based on the metal sheet of duraluminum AA 6063 through in the room temperature body lotion, forming coating more than the immersion 1min.

The metal sheet of duraluminum AA 6063 is in advance with according to WO-A1-01/71058, handle based on cerium-rich rare earth conversion of compounds type coating.

Table 3:Silicon-rich alkane solution is as the application of back cleaning solution, with silane not or with the comparison of yellow chromic salt coating:

The layer thickness of the coating of the present invention of producing with this back cleaning solution is between 0.2～0.3 μ m.Coating of the present invention transparent with have a little the flash of light look.Their height homogeneous and very big have improved the corrosion resistance based on the said conversion coating of rich cerium oxide.The steel plate of instance IE 22～IE24 of the present invention, according to the present invention be coated with the back cleaning solution after, have and the comparable corrosion resistance of conventional yellow chromic salt coating, but do not contain environmentally harmful material.With regard to corrosion-resistant, the improvement that reaches is more comprehensive than expection.

Claims

1. one kind is coated with a kind of method of waterborne compositions to the metallic surface,

Said composition also randomly comprises:

Organic solvent and other components,

Said compsn does not contain chromium (VI) compound basically or fully, is used for further coating pre-treatment before, perhaps is used for handling, and the method is characterized in that said composition comprises, except water, and combination:

B) at least a hydrolyzable and/or the fluorine containing silane of partly hydrolysed at least, wherein the content of at least a fluorine containing silane in the waterborne compositions comprises the reaction product that is generated by it, between 0.01～150g/l;

Wherein the silane in the said composition is water miscible or becomes water miscible by the chemical reaction that the paint metallic surface takes a step forward,

Wherein clean and/or pretreated metallic surface contacts with this waterborne compositions, and on the metallic surface, forms film, and this film carries out drying and choose wantonly additionally being cured subsequently,

Wherein dry the mistake also, the thickness of the film that has randomly also solidified is between 0.001～10 μ m.

2. the process of claim 1 wherein that said chemical reaction is a hydrolysis reaction.

3. the process of claim 1 wherein that said metallic surface is a pickled.

4. the method for claim 1 is characterized in that, in waterborne compositions, in every kind of situation, exists

At least

A kind of acyloxy silane, a kind of organoalkoxysilane, a kind of silane with at least one amino group, a kind of silane with at least one succsinic acid group and/or succinic anhydride group, a kind of two-silyl-silane, a kind of have the silane of at least one epoxide group, a kind of (methyl) acrylic silane, a kind of many-silyl-silane, a kind of urea groups silane, a kind of vinyl silanes and/or at least a silanol and/or at least a siloxanes

As no silicon fluoride.

5. the method for claim 4 is characterized in that having one or more of following characteristic:

I) said silane with at least one amino group is aminoalkylsilane;

Ii) said silane with at least one epoxide group is glycidoxy silane.

6. claim 4 or 5 method is characterized in that, said siloxanes is to form chemically corresponding to the siloxanes of said silane.

7. each method among the claim 1-5 is characterized in that, has at least a no silicon fluoride in the said waterborne compositions, be selected from or based on:

Glycidoxyalkyl trialkoxysilanes,

The methacryloxy alkyltrialkoxysilaneand,

Aminoalkyl aminoalkyl alkyl-dialkoxysilanes,

(oxirane ring alkyl) alkyltrialkoxysilaneand,

Two-(trialkoxysilyl alkyl) amine,

Two-(trialkoxysilyl) ethane,

(epoxy alkyl) trialkoxy silane,

The aminoalkyl trialkoxy silane,

The urea groups alkyltrialkoxysilaneand,

N-(trialkoxysilyl alkyl) Alkylenediamine,

N-(aminoalkyl) aminoalkyl trialkoxy silane,

N-(trialkoxysilyl alkyl) two alkylene triamine,

Many (aminoalkyl) alkyl-dialkoxysilanes,

The isocyanuric acid ester of three (trialkoxysilyl) alkyl,

The urea groups alkyltrialkoxysilaneand with

Acetoxysilane.

8. the method for any one among the claim 1-5 is characterized in that, has at least a silane in the said waterborne compositions, be selected from or based on:

3-glycidoxy propyl-triethoxysilicane,

The 3-glycidoxypropyltrime,hoxysilane,

3-methacryloxypropyl triethoxyl silane,

The 3-methacryloxypropyl trimethoxy silane,

Aminoethyl aminopropyl methyldiethoxysilane,

Aminoethyl aminopropyl methyl dimethoxysilane,

β-(3, the 4-epoxycyclohexyl) ethyl triethoxysilane,

β-(3，4-Huan Yanghuanjiji)Yi Jisanjiayangjiguiwan,

β-(3, the 4-epoxycyclohexyl) Union carbide A-162,

β-(3, the 4-epoxycyclohexyl) methyltrimethoxy silane,

γ-(3, the 4-epoxycyclohexyl) propyl-triethoxysilicane,

γ-(3, the 4-epoxycyclohexyl) propyl trimethoxy silicane,

Two (triethoxysilylpropyltetrasulfide) amine,

Two (trimethoxy-silylpropyl) amine,

(3,4-epoxy butyl) triethoxyl silane,

(3,4-epoxy butyl) Trimethoxy silane,

γ-An Bingjisanyiyangjiguiwan,

γ-An Bingjisanjiayangjiguiwan,

γ-urea groups propyl trialkoxy silane,

N-(3-(trimethoxysilyl) propyl group) ethylene diamine,

N-β-(aminoethyl)-γ-An Bingjisanyiyangjiguiwan,

N-β-(aminoethyl)-γ-An Bingjisanjiayangjiguiwan,

N-(γ-triethoxysilylpropyltetrasulfide) NSC 446,

N-(γ-trimethoxy-silylpropyl) NSC 446,

N-(γ-triethoxysilylpropyltetrasulfide) dimethylene triamine,

N-(γ-trimethoxy-silylpropyl) dimethylene triamine,

Gather (aminoalkyl) ethyl dialkoxy silicane,

Gather (aminoalkyl) methyl dialkoxy silicane,

Three (3-(triethoxysilyl) propyl group) isocyanuric acid ester,

Three (3-(trimethoxysilyl) propyl group) isocyanuric acid ester with

Vinyltriacetoxy silane.

9. the method for one of claim 1-3 is characterized in that, in waterborne compositions, exist, in every kind of situation:

At least

A kind of acyloxy silane; A kind of organoalkoxysilane; A kind of silane with at least one amino group; A kind of silane with at least one succsinic acid group and/or succinic anhydride group; A kind of pair-silyl-silane; A kind of silane with at least one epoxide group; A kind of (methyl) acrylic silane; A kind of many-silyl-silane; A kind of urea groups silane; A kind of vinyl silanes and/or at least a silanol and/or at least a its are formed chemically corresponding to the siloxanes or the ZGK 5 of above-mentioned silane; Wherein comprise the group that at least one contains at least one fluorine atom in every kind of situation

As fluorine containing silane.

10. the method for claim 9 is characterized in that, has one or more of following characteristic:

I) said silane with at least one amino group is aminoalkylsilane;

Ii) said silane with at least one epoxide group is glycidoxy silane.

11. the method for one of claim 1-3 is characterized in that, waterborne compositions comprises at least a fluoroalkyl alkyl silane.

12. the method for one of claim 1-3 is characterized in that, waterborne compositions comprise at least a list-, two-or three-functional fluoro silane.

13. the method for one of claim 1-3 is characterized in that, waterborne compositions comprise at least a list-, two-or three-fluoro silane.

14. the method for one of claim 1-3 is characterized in that, waterborne compositions comprises at least a based on Ethoxysilane and/or based on the fluoro silane of methoxy silane.

15. the method for one of claim 1-3 is characterized in that, waterborne compositions comprises at least a fluoro silane with at least one functional group.

16. the method for one of claim 1-3 is characterized in that, waterborne compositions comprises at least a fluoro silane with at least one amino group.

17. the method for one of claim 1-3 is characterized in that, waterborne compositions comprises at least a fluoro silane with at least one functional group, and it is a cocondensation compound form.

18. the method for one of claim 1-3; It is characterized in that waterborne compositions comprises fluoroalkyl dialkoxy silicane, fluoro-aminoalkyl propyl trialkoxy silane, fluoro propyl group alkyl-dialkoxysilanes, triphenyl fluoro silane, tri-alkoxy fluoro silane, trialkyl fluoro silane and/or 13 fluoro octyltrialkoxysilane.

19. the method for one of claim 1-3 and 7-16 is characterized in that, silane comprises at least two amino groups and comprises at least one ethyl group and/or at least one methyl group.

20. the method for any one is characterized in that among the claim 1-5, waterborne compositions also comprises at least a metal chelator and/or at least a polymkeric substance.

21. the method for claim 20 is characterized in that, said polymkeric substance is oligopolymer or multipolymer.

22. the method for claim 1 is characterized in that, waterborne compositions also comprises at least a component e), be selected from:

e ₂) at least a lubricant,

e ₃) at least a organic inhibitor,

e ₄) at least a anti-corrosion pigment,

e ₆) at least a organic solvent,

e ₇) at least a siloxanes,

e ₈) at least a long-chain alcohol and

e ₉) at least a tensio-active agent.

23. the method for claim 1; It is characterized in that; Said waterborne compositions comprises organic membrane-forming agent; This organic membrane-forming agent is a kind of synthetic resin mixture, comprises at least a polymkeric substance, and they comprise a certain amount of synthetic resins based on propenoate, epoxide, ethene, melocol, phenol, polyester, urethane, vinylbenzene, styrene butadiene and/or vinyl.

24. the method for claim 23 is characterized in that, said polymkeric substance is a multipolymer.

25. the method for claim 1; It is characterized in that; Said waterborne compositions comprises organic membrane-forming agent; This organic membrane-forming agent also comprises, and as synthetic resins, certain content is based on the organic polymer of polymine, Z 150PH, polyvinylphenol, PVP K120 and/or SAP 73.

26. the method for claim 25 is characterized in that, said polymkeric substance is a multipolymer.

27. the method for claim 26 is characterized in that, said multipolymer is the multipolymer with phosphorous vinyl compound.

28. the method for any one is characterized in that among the claim 23-27, the acid groups of synthetic resins is with ammonia, amine, and/or alkali metal cpd comes stabilization.

29. the method for any one is characterized in that among the claim 23-27, the acid groups of synthetic resins comes stabilization with morpholine, dimethylethanolamine, diethylethanolamine or trolamine.

30. the method for any one is characterized in that among the claim 23-27, the acid groups of synthetic resins comes stabilization with sodium hydroxide.

31. the method for any one is characterized in that among the claim 1-5, waterborne compositions contains the organic membrane-forming agent of 0.1～980g/l.

32. the method for claim 31 is characterized in that, waterborne compositions contains the organic membrane-forming agent of 2～600g/l.

33. the method for any one is characterized in that among the claim 1-5, the content of at least a no silicon fluoride in the waterborne compositions comprises the reaction product that is generated by it, between 0.05～300g/l.

34. the method for claim 20; It is characterized in that; Described at least a metal chelator is selected from the sequestrant complex compound based on methyl ethyl diketone acidifying thing, acetylacetic ester, acetone acidulants, Alkylenediamine, amine, newborn acidulants, carboxylic acid, Citrated thing and/or glycol; Wherein this at least a sequestrant comprises the optional reaction product that is generated by them, and the content in waterborne compositions is between 0.1～80g/l.

35. the method for claim 22 is characterized in that, dispersion-s or suspensoid add as the mineral compound of particle form.

36. the method for claim 22 is characterized in that, the powder of fine dispersion adds as the mineral compound of particle form.

37. the method for claim 35 or 36 is characterized in that, carbonate, oxide compound, silicate or vitriol are added into.

38. the method for claim 35 or 36 is characterized in that, said particle is colloid and/or amorphous granular.

39. the method for claim 22 is characterized in that, the particle based on the compound of at least a aluminium, barium, cerium, calcium, lanthanum, silicon, titanium, yttrium, zinc and/or zirconium adds as the particle form mineral compound.

40. the method for claim 22 is characterized in that, at least a paraffin, Vilaterm and the polyacrylic wax of being selected from is used as lubricant, and wherein the content of wax in waterborne compositions is between the scope from 0.01～5wt%.

41. the method for claim 40 is characterized in that, said wax is a kind of oxidized petroleum waves.

42. the method for any one is characterized in that among the claim 1-5, coating layer portion ground generates through dry and film forming, and/or reaches curing through photochemidal activity radiation, cationoid polymerisation and/or heat cross-linking.

43. the method for any one is characterized in that among the claim 1-5, waterborne compositions comprises at least a additive.

44. the method for claim 43 is characterized in that, said additive is at least a additive that is selected from biocides, skimmer and/or wetting agent.

45. the method for any one is characterized in that among the claim 1-5, the temperature of the metallic surface of coating in 20～400 ℃ force air TR carried out drying.

46. the method for any one is characterized in that among the claim 1-5, waterborne compositions applies through roller coat, flow coat, scraper coating, spraying, spraying, brushing or dip-coating, and optional, uses roller floating subsequently.

47. the method for any one is characterized in that among the claim 1-5, in each case, printing-ink, paper tinsel, spray paint, at least one coating of powder paints, tackiness agent and/or adhesive carrier should drying by paint and randomly again on the solidified film.

48. the method for any one is characterized in that among the claim 1-5, the metallic element of coating, band or strip sections stand to be shaped; Spray paint, be coated with, printing with polymkeric substance; Gluing, welding and/or through clamping or other interconnection technique is connected to each other perhaps is connected on other element.

49. the method for claim 48 is characterized in that, said polymkeric substance is PVC.

50. the method for claim 48 is characterized in that, said welding is hot soldering.

51. one kind is used for before the further coating metal pretreated surface or is used to handle the waterborne compositions on said surface, it is characterized in that said composition comprises, except water, and combination:

B) at least a hydrolyzable and/or the fluorine containing silane of partly hydrolysed at least,

Wherein in every kind of operating mode, a) and b) quantitative proportion, comprise the reaction product that generates by them, between 1: 0.01～1: 4, and

Wherein the silane in the said composition is water miscible or owing to further chemical reaction becomes water miscible.

52. according to the waterborne compositions of claim 51, wherein said chemical reaction is a hydrolysis reaction.

53. according to the application of the method substrates coated one of in the claim 1～50: the wire rod of following article, band, sheet material or part as following article:

Rolling wire, wire cloth, metal sheet, panel, shielding, motorcar body or motorcar body component, or mo(u)lded item, signpost element, radiator element or hedge element, collision bumper, component, window frame or the bicycle frame of the component of motor vehicle, trailer, mobile house or guided missile, lid, cover, lamp, traffic signals modulation element, furniture or furnishing elements, household electrical appliance component, frame, section bar, complicated shape with at least one pipe and/or section bar.

54. according to the application of the method substrates coated one of in the claim 1～50: the wire rod of following article, band, sheet material or part as following article:

The component of processing by at least one pipe and/or section bar.

55. according to the application of the method substrates coated one of in the claim 1～50: steel band, doorframe, screw, nut, flange, spring or spectacle-frame as following article.

56. defined compsn is as the back cleaning solution and/or as the application of polished surface corrosionproof protection with compsn in one of claim 1～52, wherein the back cleaning solution is by on the coating before the paint.

57. the described application of claim 56, wherein the back cleaning solution is by on the paint conversion coating.