CN1777699A

CN1777699A - Method for coating metallic surfaces with a composition that is rich in silane

Info

Publication number: CN1777699A
Application number: CNA2004800109259A
Authority: CN
Inventors: H·多姆斯; J·施奈德
Original assignee: Chemetall GmbH
Current assignee: Chemetall GmbH
Priority date: 2003-02-25
Filing date: 2004-02-25
Publication date: 2006-05-24
Anticipated expiration: 2024-02-25
Also published as: CN1798813A; DE10308237A1; DE10308237B4; CN1777700B; CN1777700A; CN1777699B

Abstract

The invention relates to a method for coating a water combination on metal surface, which is used for further pre-treatment before the coating or for treating the metal surface. Besides water, the combination comprises: a) at least a hydrolysable or partially hydrolysable silane; b) at least a metal-chelator; optionally c) at least an organic film-forming agent; d) at least a long chain alcohol used as film-forming additive and/or e) at least an inorganic compound in particle form, wherein the clean pickling and/or pre-treated metal surface closely contacts the water combination; a film is formed on the metal surface, dried and partially or completely tightened through film forming, and the hardening is optionally carried out, wherein the thickness of dried and optionally chosen hardening film is between 0.01 and10Mum. The invention also relates to the corresponding water combination.

Description

Method with Silicon-rich alkane composition coating metal surfaces

Technical field

The present invention relates to contain silane and metal chelator and the method for the waterborne compositions coating metal surfaces of organic membrane-forming agent randomly.The invention still further relates to corresponding waterborne compositions and by the application of the inventive method substrates coated.

Background technology

So far as before spraying paint at metal, particularly the sheet metal strip upper surface handle or pre-treatment the method for normal employing based on chromium (III) and/or chromium (VI) compound together with various Application of Additives.Because these class methods relate to toxicology and ecological dangerous, in addition also because at the foreseeable legal restrictions of the 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 coating self have obtained proof, but adopt the coating process of the waterborne compositions that mainly contains silane to be difficult in some cases use.Formed coating can not have optimum performance.Moreover, can be with the naked eye or fully be characterized in by optical instrument and exist variety of issue at present aspect clear silane coating extremely thin on the metal base and the defective thereof.The corrosionproof protection ability of formed rich silicon coating and lacquer sticking power are frequent, 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 that contains the silane waterborne compositions, add at least a component that is selected from monomer, oligopolymer and polymkeric substance more or less and proved appropriate.In this kind composition, add silane character and quantity be successful determinative sometimes.Yet, so for this purpose the add-on of silane all lower traditionally-the highest usually only 5wt%---just play the effect of a kind of " coupling agent ", here, viscosifying action, particularly between metal base and the enamelled coating and randomly between pigment and organic varnish composition, should be in dominant position, but in some cases, also the low cross-linking effect can take place on less degree.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 in this way and therefore reach the purpose that better directly contacts between resin layer and the metallic surface, also is known.The shortcoming of this based composition is, because the pickling corrosive nature of treatment solution (dispersion) during contacting with each other with base material often stain.This causes the increase of metal concentration in treatment solution, the permanent change that the result causes the treatment solution chemistry to be formed, and so, the corrosion protection effect is just had a greatly reduced quality.Because the pickling corrosion, these metals are dissolved out by the metallic surface from pending base material.

Another shortcoming is, surface discolouration and deepening, become in some occasion dark-grey to hard coal-color, especially under the situation of aluminium or aluminium-containing alloy.The metallic surface of colour-darkening can not be used for decorative use, because this variable color itself is not satisfying from aesthetic theory.Colour-darkening then with the naked eye looks the intensity difference, depends on the thickness of institute's coating.This kind is known as the effect of deepening and should avoids as far as possible.

DE-A-198 14 605 describes a kind of metallic surface closed group compound, and it comprises, except at least a solvent, and at least a silane derivative and colloid silica and/or colloidal silicate.In example, the content of silane is 20wt% (about 200g/l), and the content of silicon dioxide gel or silicate is then between the scope of 10～40wt%.For reducing the wax that the frictional coefficient suggestion adds, perhaps as wetting agent, organic base-material of adding, for example, polypropylene, polyethylene, polyethylene oxide or modified polyorganosiloxane, perhaps since other do not mention former thereby do not mention base-material in more detail all in example, do not adopt.Example is not mentioned any polymeric material except that silane.

The theme of DE-A1-41 38 218 is a kind of solution that contains organic functional silicone and titanic acid ester and/or titanium sequestrant, as generate the back soaker that chromic acidization or passivation contain zinc layer usefulness at the steel component surface.

US 5,053,081 relates to through for example, use the phosphate layer pre-treatment, the metallic surface be coated with method with " back-cleaning solution ", this solution based on a certain amount of 3-aminopropyl triethoxysilane and, the titanium sequestrant of the much lower usefulness tetralkyl titanate of content, beta-diketon and alkanolamine preparation in contrast to this.

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, produce the result of excellent in resistance burn into adhesion strength and formability, especially at Galvalume ^On the steel plate, but also demonstrate, at pot galvanize, electro-galvanizing, Galvalume ^-coating or Galfan ^On the sheet metal strip of-coating, in other words, reach on the band of corrosionproof protection the corrosion-resistant deficiency of about 1 μ m bed thickness organic film difficult on its metallic surface.Clearly take in the application in this composition, its all component and raw-material character and coating with this publication.

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 both had been used for coming the coating metal body surface by dip-coating or spraying, be fit to high surface covered again, for example, be used for sheet metal strip, the application of this method can be basically or is not needed chromium (VI) compound fully, can also as far as possible easily use.Its purpose especially is to improve less than 10 μ m, particularly less than the corrosion resistance of the chromate-free organic coating of 3 μ m dried film thicknesses.

Now be surprised to find, at least a sequestrant, particularly titanium and/or the adding of zirconium sequestrant in containing the silane waterborne compositions can significantly improve the corrosion-resistant and lacquer sticking power of the film that forms thus.The adding of organic inhibitor here also can save usually-situation of the coating of polished steel except.

Also be surprisingly found out that in addition, also might improve very significantly by containing at least a silane but do not contain the corrosion-resistant of film that the waterborne compositions of organic polymer forms, if also add the words of at least a sequestrant, particularly titanium and/or zirconium sequestrant.

This purpose is to adopt a kind of metallic surface of giving, aluminium particularly, iron, copper, magnesium, nickel, titanium, tin, zinc or contain aluminium, iron, copper, magnesium, nickel, titanium, a kind of method of waterborne compositions of being coated with the alloy of tin and/or zinc realizes, said composition can be basically or is not contained chromium (VI) compound fully, be used for further coating pre-treatment before, perhaps be used to treat randomly-especially band of coated object, strip sections or component-in the operating mode of coating postforming, processing, it is characterized in that, said composition comprises, except water

A) silane of at least a hydrolyzable and/or hydrolysis at least in part and

B) at least a metal chelator,

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

The bed thickness of the wherein dry film of crossing and randomly also having solidified is between 0.01～10 μ m, the cured film by peeling off the regulation area and weigh or by with, for example, x-ray fluorescence analysis and corresponding conversion determine that the silicone content of coating determines.

In addition, this purpose is to adopt a kind ofly to be used for before further coating metal pretreated surface or to be used to handle this surperficial waterborne compositions realizing, it is characterized in that said composition except water, also comprises,

A) silane of at least a hydrolyzable and/or hydrolysis at least in part and

B) at least a metal chelator,

Wherein a) than b) the quantity ratio, every kind of situation includes the reaction product that is generated by them, preferably between 0.1: 1～10: 1.

A) than b) the quantity ratio, every kind of situation includes the reaction product that is generated by them, preferably between 0.1: 1～10: 1, especially preferred 0.2: 1～8: 1 quantity ratio, very especially, preferred 0.3: 1～7: 1 quantity ratio especially is about 0.4: 1,0.6: 1,0.8: 1,1: 1,1.2: 1,1.6: 1,2: 1,3: 1,4: 1,5: 1 or 6: 1.

In each case, the quantity of silane and sequestrant, every kind of situation includes the reaction product that is generated by them, especially preferably be 0.05～5wt% independently of one another, in the wet film is benchmark, very especially being the quantity of 0.08～4wt% in each case independently of one another preferably, particularly, is about 0.1,0.2,0.3,0.5,0.8,1,1.5,2,2.5,3 or the quantity of 3.5wt% in every kind of situation independently of one another.

In each case, the quantity of silane and sequestrant, every kind of situation includes the reaction product that is generated by them, especially preferably be 0.2～15wt% independently of one another, in the solids content is benchmark, very especially be the quantity of 0.3～11wt% in each case independently of one another preferably, particularly about, be 0.5,0.8,1,1.5,2,2.5,3,3.5,4,4.5,5,5.5,6,6.5,7,7.5,8,8.5,9,9.5,10 or the quantity of 10.5wt% independently of one another in every kind of situation.

Preferably, at least a silane and the water compatible selected, in other words, this at least a silane and, randomly, its hydrolysis and condensation product can be molten mixed and no problem with all components of waterborne compositions, and can stablize more than several weeks, and it can form indefectible wet film and dry film, the latter, especially fine and close, homogeneous and do not have shrinkage cavity.Specifically, at least a silane of selection provides the possibility of highly corrosion resistant, especially combines with at least a selected sequestrant.

Preferably, at least a sequestrant of selection can be in the presence of other component of waterborne compositions in water dispersion more than stable several weeks, and provide the possibility of highly corrosion resistant.Even more 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 of plan, randomly also can chemically be bonded on the other hand on the layer of paint that preparation applies subsequently.This at least a metal chelator, especially one of following metal chelator: 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.

Mainly contain the waterborne compositions of silane and sequestrant and contain enriched material that the part component of the raw material that polymer composition uses constitutes and preferably have water-content, especially 30～80wt% in 20～85wt% scope as preparation.Enriched material preferably contains at least a silane, comprise the reaction product that generates by it, its content is between 1～60wt%, especially preferred scope between 3～45wt%, very especially preferred scope at 6～45wt%, most preferably 8～40,～35 or～scope of 32wt%, particularly about 8,10,12,14,16,18,20,22,24,26,28,30 or 32.5wt%, and at least a sequestrant, randomly comprise the reaction product that generates by it, its concentration is between the scope of 1～50wt%, especially preferably at 2～40wt%, very especially preferred scope at 3～30wt%, most preferably at 5～25wt%, particularly about 7.5,10,12,14,16,18,20 or 22.5wt%.

Mainly contain the water-content that the bath lotion composition of the waterborne compositions of silane and sequestrant preferably has 80～99.9wt% scope, preferably between the scope of 90～99.8wt%, especially preferably at 94～99.7wt%, most 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 at least a silane, comprise the reaction product that generates by it, its content is between 0.01～10wt%, especially preferably between 0.05～7wt%, very especially preferred scope between 0.1～5wt%, most preferably 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 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 the reaction product that is generated by them, those of titanium, hafnium and/or zirconium particularly, preferably account for the 20wt% at least of the solids content of this kind composition, especially at least 30wt%, especially preferably 40wt% at least, very especially preferred 50wt% at least, most preferably every kind of situation at least 60,70,80,90,94,95,96,97,98 or 99wt%.Said composition especially preferably mainly contains: water, at least a silane and/or its reaction product, at least a sequestrant in every kind of operating mode, the optional reaction product that generates by it and randomly of comprising, certain content is selected from following material: alcohol, acid are as 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 and sequestrant, the total content of other compound comprises additive, be generally the highest 20wt% of the solids content of silane and sequestrant, preferably the highest 15wt%, especially preferably the highest 10wt%, very especially preferred the highest 5wt%, most preferably the highest 1 or 2wt%.

Though at least a silane, comprise the reaction product that generates by it,, randomly comprise the reaction product that generates by it with at least a sequestrant, 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,, may there be optimum value in these scopes because in some cases.

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 by adding acid, if chemical system is allowed selected pH value and still kept stable.Yet, if add acid just to neutralization, in fact the pickling corrosion can or can not take place.Can preferably also add solvent, for example alcohol is stablized this silane.

The typical thickness of planting the coating that bath lotion composition forms thus between 0.01～1 μ m or～0.6 μ m, usually between 0.015～0.25 μ m.

The adding of at least a silane (a) is provided between base material and the exsiccant protective membrane and forms and to the advantage of the adhesion bridge of enamelled coating that may apply subsequently and/or plastic coating, therefore also reach the improvement of coating with lacquer sticking power.Another advantage is; suitable silane/siloxane generates bonding bridge in the dry-run protection film; it can improve the intensity and/or the flexibility of coating matrix material greatly, and to the sticking power of base material, reaches the purpose of improving sticking power thereby reach in many systems of spraying paint.

Mainly contain sequestrant and silane, perhaps except that sequestrant and silane, mainly contain synthetic resins, waterborne compositions, preferably contain at least a acyloxy silane in each case, a kind of organoalkoxysilane, a kind of silane such as aminoalkylsilane 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 such as glycidoxy silane with at least one epoxide group, 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 are formed chemically corresponding to the siloxanes of above-mentioned silane.The reaction product of silane is known in principle in this type of system, therefore just lists no longer one by one.Therefore, they also will no longer further be mentioned hereinafter, but be included under the item of term " silane ".

Said composition can comprise, for example, at least a silane is with at least a alcohol of certain content, for example, the mixture of ethanol, methyl alcohol and/or propyl alcohol, the content of alcohol is the highest 8wt% usually, is benchmark, preferably the highest 5wt% in the silane contents, especially preferably the highest 1wt%, very especially preferably the highest 0.5wt%.Specifically, this mixture and comprising, for example, at least a silane, be selected from least a amino-silane, for example, bis-amino-silane, contain or do not contain at least a alkoxyl group-silane such as tri-alkoxy-silyl-propyl group-four sulfane or at least a vinyl silanes and at least a two-silyl-aminosilane or at least a two-silyl-many sulphur-silane and/or at least a two-silyl-aminosilane or at least a aminosilane and at least a many-silyl-functional silane.Chain length is between 2～5 carbon atoms and to contain those silane/siloxane that are fit to the functional group that reacts with polymkeric substance be particularly preferred.

This waterborne compositions preferably contains at least a following silane that is selected from:

Glycidoxyalkyl trialkoxysilanes,

The methacryloxy alkyltrialkoxysilaneand,

(trialkoxysilyl) alkyl-succsinic acid-silane,

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 and

Acetoxysilane.

Waterborne compositions preferably contains the following silane of at least a selection:

3-glycidoxy propyl-triethoxysilicane,

The 3-glycidoxypropyltrime,hoxysilane,

3-methacryloxypropyl triethoxyl silane,

The 3-methacryloxypropyl trimethoxy silane,

3-(triethoxysilyl) propyl group-succsinic acid-silane,

Aminoethyl aminopropyl methyldiethoxysilane,

Aminoethyl aminopropyl methyl dimethoxysilane,

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

β-(3, the 4-epoxycyclohexyl) ethyl trimethoxy silane,

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) diethylenetriamine,

N-(γ-trimethoxy-silylpropyl) diethylenetriamine,

N-(γ-triethoxysilylpropyltetrasulfide) dimethylene triamine,

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

Poly-(aminoalkyl) ethyl dialkoxy silicane,

Poly-(aminoalkyl) methyl dialkoxy silicane,

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

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

Vinyltriacetoxy silane.

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 at first 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, polysiloxane and reaction product thereof and derivative here, and they are commonly referred to as " silane " mixture.Because the normally very complicated chemical reaction that takes place here, and analysis and post-treatment can be very expensive, so can't describe further concrete silane or other reaction product.

Yet, substituting certain at least a no silicon fluoride of content in silane contents, this part content can comprise unique fluorine containing silane, perhaps at least, substitutes no silicon fluoride, at least a fluorine containing silane.

So this waterborne compositions preferably contains at least a silane, be selected from fluorine containing silane: in each case, at least a acyloxy silane, a kind of organoalkoxysilane, a kind of silane such as aminoalkylsilane with at least one amine groups, 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 such as glycidoxy silane with at least one epoxide group, 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 are formed chemically corresponding to the siloxanes or the polysiloxane of above-mentioned silane, the latter comprises at least a group in each case, and it has 1 or have at least one fluorine atom.

So specifically, waterborne compositions comprises at least a fluoroalkyl alkyl silane, at least a have 1,2,3,4,5,6,7,8,9,10,11, the silane of 12 or 13 each silane of fluorine atom, at least a perfluorination silane, at least a list-fluoro silane, at least a based on Ethoxysilane and/or based on the fluoro silane of methoxy silane and/or at least aly have at least one functional group such as an amino group, fluoro silane, cocondensation compound form particularly, for example

The fluoroalkyl dialkoxy silicane,

Fluoro aminoalkyl propyl trialkoxy silane,

The fluoromethane sulphonate,

The fluoropropyl alkyl-dialkoxysilanes,

Triphenyl silicon fluoride, tri-alkoxy silicon fluoride,

The trialkyl silicon fluoride and/or

Ten trifluoro octyltrialkoxysilane.

So said composition especially preferably contains at least a fluorine containing silane, it comprises at least two amino groups and at least one optional fluorizated ethyl and/or at least one optional fluorizated methyl group.

In waterborne compositions, at least a silane, the content that comprises the reaction product that is generated by it is preferably between 0.1～80g/l, 0.2～50g/l particularly, especially preferred 0.3～35g/l, very especially preferred 0.5～20g/l, most preferably 1～10g/l.

Preferably, have lower or do not have the bath lotion composition of membrane-forming agent content to comprise silane, comprise by it and other component and choose the reaction product that generates wantonly, its content 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 0.4,0.6,0.8,1.0,1.1,1.2,1.3,1.4,1.5,1.6,1.7,1.8,1.9,2.0,2.1,2.2,2.4,2.6,2.8,3.0,3.2,3.4,3.6 or 3.8wt%, and at least a sequestrant, comprise the optional reaction product that generates by it, its content 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%.

In waterborne compositions, at least a sequestrant b), randomly comprise the reaction product that generates by it, content preferably between 0.05～80g/l, 0.1～50g/l particularly.

At least a metal chelator preferably is selected from the sequestrant complex compound based on methyl ethyl diketone acid group, acetylacetic ester, acetone acid group, Alkylenediamine, amine, lactate, carboxylic acid, citrate and/or glycol.

At least a metal chelator is preferably based on:

The methyl ethyl diketone acid group,

Alkali metal lactate,

Alkanolamine,

Alkyl etheric acid root,

Alkylenediamine tetrem acid group,

DL-Lactic acid ammonium salt,

Citrate,

The dialkyl group citrate,

Dialkyl-citrate,

Two alkylene triamine,

The acetylacetic ester of the two alkyl of two different alkoxyl groups,

The two alkyl acetylacetic esters of diisopropoxy,

Two-just-alkoxyl group-two alkyl acetylacetic esters,

Hydroxy alkylidene ethylenediamine triacetic acid root,

Trialkanolamine and/or

Three alkylidene group tetramines.

These metal chelators especially play the organometallic compound in the stabilize water and are bonded to the metallic surface or to painting of applying or the effect on the corresponding coating.If if they in waterborne compositions, only have low reactivity and they under the processing condition that adopted, decompose at least in part and discharge be used in conjunction with and/or the metal ion of chemical reaction, then suitable especially.If their hyperergies, then organometallic compound will react with other chemical compound such as silane prematurely.Preferably, sequestrant is hydrophilic, to hydrolysis-stable, and the stable and/or formation stabilised hydrolysate to water.Preferably, the silane of selection or sequestrant and water compatible and in addition also compatible and have a same performance of mentioning at silane or sequestrant with the front with selected organic membrane-forming agent.

Preferably, a) than b) the quantity ratio, every kind of situation includes the reaction product that is generated by them, preferably between 0.1: 1～10: 1, especially preferred 0.2: 1～8: 1 quantity ratio, very especially, preferred 0.3: 1～7: 1 quantity ratio, particularly about 0.4: 1,0.6: 1,0.8: 1,1: 1,1.2: 1,1.6: 1,2: 1,3: 1,4: 1,5: 1 or 6: 1.

Especially preferredly be, the content of silane and sequestrant under every kind of situation, every kind of situation includes the reaction product that comprises silane and inner complex that is generated by them, independently of one another between 0.05～5wt%, in the wet film is benchmark, and very especially preferred every kind of situation is the quantity of 0.08～4wt% independently of one another, particularly, under every kind of situation, be about 0.1,0.2,0.3,0.5,0.8,1,1.5,2,2.5,3 or 3.5wt% independently of one another.

Especially preferredly be, in each case, the quantity of silane and sequestrant, every kind of situation includes the reaction product that comprises silane and inner complex that is generated by them, especially preferably be 0.2～15wt% independently of one another, in the dry matter content is benchmark, very especially be the quantity of 0.3～11wt% in each case independently of one another preferably, particularly about, be 0.5,0.8,1,1.5,2,2.5,3,3.5,4,4.5,5,5.5,6,6.5,7,7.5,8,8.5,9,9.5,10 or the quantity of 10.5wt% independently of one another in every kind of situation.

Particularly, in composition with higher membrane-forming agent content, component [a)+b)]: quantity ratio c), every kind of situation includes the reaction product that is generated by them, and be benchmark in the wet film, especially preferably between 2: 70～20: 70, very especially preferably between 3.5: 70～17: 70, particularly about 5: 70,6: 70,7: 70,8: 70,9: 70,10: 70,11: 70,12: 70 and 14: 70.Here concerning component a) than components b) or conversely, preferably taking a kind of component is about 1.2～4 times of high numerical value of another component concentration.Component [a)+b)]: quantity ratio c), every kind of situation includes the reaction product that is generated by them, and be benchmark in the solids content, especially preferably between 2: 70～20: 70, very especially, preferred 3.5: 70～17: 70 quantity ratio, especially about 5: 70,6: 70,7: 70,8: 70,9: 70,10: 70,11: 70,12: 70 and 14: 70.

Particularly, in the composition that has than the low filming agent content, component [a)+b)]: quantity ratio c), every kind of situation includes the reaction product that is generated by them, and be benchmark in the wet film, especially preferably from more than or equal to 0.2: 7 to the highest 20: 7, very especially preferably from compared the highest 12: 7 more than or equal to 0.5: 7 quantity or from more than or equal to 1: 7 to the highest 8: 7, especially about 0.4: 7,0.6: 7,0.8: 7,1.2: 7,1.5: 7,2: 7,3: 7,4: 7,5: 7,6: 7,7: 7,9: 7,10: 7,11: 7,13: 7,14: 7 and 16: 7.Here may be preferably, to component a) than components b) or conversely, take 1.2～4 times high numerical value of a kind of component concentration for another component concentration.

Component content a), comprise the reaction product that generates by it and be benchmark in the solids content, especially preferred scope between 0.4～10wt%, very especially, preferred 0.8～8wt%, particularly about 1.2,1.5,1.8,2.1,2.4,2.7,3,3.3,3.6,3.9,4.2,4.5,4.8,5.1,5.5,6,6.5,7 or 7.5wt%.

Components b) content, comprise the reaction product that generates by it, and be benchmark in the solids content, especially preferably between 0.3～10wt%, very especially preferably between 0.8～8wt%, especially about 1.2,1.5,1.8,2.1,2.4,2.7,3,3.3,3.6,3.9,4.2,4.5,4.8,5.1,5.5,6,6.5,7 or 7.5wt%.

Particularly, in composition with higher membrane-forming agent content, amount of component b) content, in the solids content is that benchmark is especially preferably between 10～95wt%, very especially preferably between 30～90wt%, especially about 35,40,45,50,55,60,63,66,69,72,75,78,81,84 or 87wt%.

Particularly, in composition with higher membrane-forming agent content, component d)---at least a long-chain alcohol-content, in the solids content is that benchmark is especially preferably between 0.01～2wt%, very especially preferably between 0.1～1wt%, be in particular about 0.12,0.15,0.18,0.21,0.24,0.27,0.30,0.33,0.36,0.39,0.42,0.45,0.48,0.51,0.55,0.60,0.65,0.7,0.75,0.8,0.9 or 0.95wt%.

Particularly, organic membrane-forming agent c) content is benchmark in composition solid content, between 10～45wt%, preferred 10～40wt%, especially preferred 10～35wt%, particularly 10～30 ,～25 or～20wt%.This waterborne compositions can be used as bath lotion composition and/or as enriched material, preferably contains organic membrane-forming agent c), its content is between 0.1～980g/l, especially preferably between 2～600g/l, very especially preferably between 50～550g/l, 150～450g/l especially.Preferably, add 2～100 parts of organic membrane-forming agents, especially preferred 10～60 parts, very especially preferred 15～45 parts, per 100 weight parts waters.But particularly, under situation about having than the composition of low filming agent content, can be used as bath lotion composition and/or as the waterborne compositions of enriched material, preferably contain organic membrane-forming agent c), its content from more than or equal to 0.01 to the highest 98g/l, especially preferably from more than or equal to 0.1 to the highest 60g/l, very especially preferably from more than or equal to 0.5 to the highest 50g/l, particularly from more than or equal to 2 to the highest 45g/l.

In some cases, the high-content of organic membrane-forming agent can appear at, and particularly, in the ultra-violet curing system, wherein may not contain or only contain a small amount of volatile constituent such as organic solvent and/or residual monomer in system.Mainly or uniquely during drying film forming and/or randomly the coating of portion of hot-physical solidification be that the inventive method is especially preferred.With regard to teachings herein, the term multipolymer preferably also comprises segmented copolymer and graft copolymer.

Organic membrane-forming agent preferably contains a certain proportion of at least at least a polymkeric substance and/or at least a multipolymer, and its acid number is between 3～120, especially preferably between 3～80, very especially preferably between 4～60.

Organic membrane-forming agent preferably contains at least a polymkeric substance of at least one certainty ratio and/or at least a multipolymer, and its minimum film-forming temperature MFT is between-10～+ 99 ℃, and is especially preferred 0～90 ℃, particularly initial from 5 ℃; Very advantageously be, if organic membrane-forming agent contains at least two kinds in the starting stage at least, particularly, thermoplastic polymer and/or multipolymer-because its thermoplastic properties-these components-under the situation that can point out minimum film-forming temperature-have minimum film-forming temperature between 5～95 ℃ is further being handled and will lost at least in part or reduce between the reaction period to thermoplastic component, especially at least 10 ℃, at this moment, these polymkeric substance and/or multipolymer are one of at least, with in these polymkeric substance and/or the multipolymer at least the second kind compare, A) has the minimum film-forming temperature that differs at least 20 ℃ with the minimum film-forming temperature of other component, B) have the second-order transition temperature that differs at least 20 ℃ with the second-order transition temperature of other component, and/or a C) have a fusing point that differs at least 20 ℃ with the fusing point of other component.Preferably, the film-forming temperature of one of these at least two kinds of components is between 10～40 ℃, and the film-forming temperature of another kind of component is between 45～85 ℃.Long-chain alcohol can impel temporary transient reduction second-order transition temperature here and they to a certain degree be become match each other.After applying, long-chain alcohol can be overflowed, so stay next second-order transition temperature than high film during applying.So these exsiccant films softness both within reason is divided only and is clamminess.The second-order transition temperature of these synthetic resins and fusing point be usually near the film-forming temperature scope, in other words mostly 0～110 ℃ scope.

In another kind of embodiment preferred, can use the mixture of organic membrane-forming agent, wherein the glass transition temperature Tg of some membrane-forming agent is basic identical and/or close at least.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, if the minimum film-forming temperature of organic membrane-forming agent is positioned at one of these temperature ranges-can point out minimum film-forming temperature.

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

Organic membrane-forming agent preferably is made of at least a component, and this component in every kind of operating mode, joins in the waterborne compositions with the form of at least a solution, dispersion, emulsion, micro emulsion and/or suspensoid.The term dispersion also comprises sub-term emulsion, solution, micro emulsion and suspensoid here.

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 composition between 3～50 scopes.The component of the organic membrane-forming agent that adds is optional to be 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.In the high acid value interval, do not need usually the stabilizing treatment on membrane-forming agent enforcement positively charged ion, negatively charged ion and/or the space.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 acrylate, ethene, polyester, urethane, silicone polyester, epoxide, phenol, vinylbenzene, melamino-formaldehyde, 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 each case, contain the synthetic resins of certain proportion independently of one another based on acrylate, 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 or even its solution of stabilization on positively charged ion, negatively charged ion and/or the space.Term acrylate with regard to teachings herein, comprises acrylate, polyacrylic acid, methacrylic ester and methacrylate.

Organic membrane-forming agent can preferably comprise at least a component that is selected from following compounds,

Vinylformic acid-polyester-polyurethane ester copolymer,

Vinylformic acid-polyester-polyurethane-styrol copolymer,

Acrylate,

Acrylate-methacrylic ester, optional area 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 acrylate and cinnamic synthetic resin mixture and/or multipolymer,

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

The synthetic resin mixture of acrylate 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, polyvinyl alcohol, polyvinylphenol, Polyvinylpyrolidone (PVP) and/or poly aspartic acid, particularly with the multipolymer of phosphorous vinyl compound.Preferably in waterborne compositions, also add a kind of conductive polymers.

Fusing point between 60～95 ℃ scope based on acrylate or based on the synthetic resins of ethylene-acrylic acid, perhaps fusing point particularly between 60～120 ℃ synthetic resins, is very especially preferred in 20～160 ℃ of scopes.

Preferably, organic membrane-forming agent of adding of 30wt% can comprise the thermoplastic resin that can be configured as film at least, and its content especially preferably is 50wt% at least, very especially preferred 70wt% at least, most preferably at least 90 or the content of 95wt% at least.In addition, organic membrane-forming agent also can comprise certain content, residual content under some situation (residual contents), other additive of at least a monomer under the various situations, oligopolymer, emulsifying agent, dispersion usefulness, a kind of solidifying agent, light trigger and/or cationic polymerizable material.Other content of additive of monomer, oligopolymer, emulsifying agent and dispersion usefulness is generally less than 5wt%, usually less than 2wt%, and may be less than 1wt%.Solidifying agent and can choose the composition of cross-linkable masses of correspondence of adding subsequently wantonly and the corresponding measure that for this reason should take is known in principle.

The molecular weight of the synthetic resins that is added can be preferably at least 1,000 μ, especially preferred at least 5,000 μ, the scope of very especially preferred 20,000～200,000 μ.Each thermoplastic component that can join the organic membrane-forming agent in the waterborne compositions preferably has between 20,000～200,000 μ, the molecular weight in especially preferred 50,000～150, the 000 μ scope.

Organic membrane-forming agent can preferably contain 40wt% high-molecular weight polymer at least, especially preferred 55wt% at least, very especially preferred 70wt% at least, 85wt% at least most preferably, particularly 95wt% at least.Particularly, if the organic membrane-forming agent of 85wt% comprises high-molecular weight polymer at least, then usually with regard to unnecessary adding solidifying agent, for example, isocyanic ester, or light trigger, for example, benzophenone, carry out heat or radical crosslinking, correspondingly crosslinkable synthetic resins to be reaching coating excellent properties of the present invention, because just can need not to implement crosslinked at that rate, only just forms fine and close, solid, high quality thin film by film forming.

, particularly, in the film process that takes place between dry epoch, thereby organic fine particles is bonded to each other and densification forms the dense non-porous film, and is appropriate if polymkeric substance and film coalescence aid are selected, and method is carried out under proper condition.The technician is familiar with this class material and processing conditions in principle.This film can have especially high-quality performance, although bed thickness is so thin, is preferably confirmed by following embodiment between 0.5～3 this fact of μ m.Known to the applicant, cross as the polymeric coating that mainly comprises through film process from unexposed so far, a kind of dried film thickness is organic, not chromate-containing coating less than the basic of 4 μ m bed thickness, can form so high lacquer sticking power and corrosion resistance on sheet metal strip.Coating of the present invention is at least with to contain the chromic salt organic coating suitable at least.

The final drying of this kind film may need several days, and substantially dry is then just finished within the several seconds.The curing here may need several Zhou Caineng to reach final drying and solid state in some cases, if the words that do not have heat or radical crosslinking to take place here.The words that require, curing can be owing to crosslinked and quicken extraly or strengthen, for example, pass through irradiation, as adopt ultraviolet rays, perhaps by heating, and/or also on less degree by, for example, contain free NCO group compound adding and and the oh group of hydroxyl group polymkeric substance between reaction.

Coating is preferably made dry and film forming basically or fully dry up and is solidified.Yet alternatively, coating also can partly be made dry and film forming dry up and partly harden by photochemidal activity ray, cationoid polymerisation and/or heat cross-linking or solidify.In this kind operating mode, optional at least a light trigger and/or at least a solidifying agent and correspondingly crosslinkable resin can join in this waterborne compositions.

The pH value of the organic membrane-forming agent in the waterborne compositions is not if add further compound, generally between 0.5～12.Mainly contain synthetic resins, also have silane and sequestrant as the pH value of the waterborne compositions of solids content preferably between 1～6 or 6～10.5---depend on that this program is sour or carry out in alkaline range, especially preferably between 6.5～9.5, very especially preferably between 7～9.2.

In a kind of conversion scheme of embodiment, organic membrane-forming agent preferably only contains water-soluble synthetic resin, particularly be less than or equal to stable those in 9 the solution in the pH value, and/or this organic membrane-forming agent contains the synthetic resins of at least a hydroxyl group.Yet if this pH value is in a single day because of the storage of synthetic resins or its mixture descends, useful is with the pH value, and especially, if not the pH value of the dispersion that can use at any time adjusts back to the meta-alkalescence scope, for example, and by adding sodium hydroxide solution.Organic membrane-forming agent also can have such composition, that is, it randomly only comprises water-soluble synthetic resin, especially is less than or equal to stable those in 5 the solution in the pH value.

Preferably and/or, the acid groups of synthetic resins is by ammonia, amine or alkanolamine such as morpholine, dimethylethanolamine, diethylethanolamine or trolamine, and/or by alkali metal compound, for example, the sodium hydroxide neutralization.These add material then as stablizer.

" film forming " is interpreted as by the film forming process of the material with high organic content, for example, by polymeric dispersions, at first is that polymer beads is converted into the homogeneous film during this period, preferably in room temperature or the temperature that improves slightly.Here usually refer to the fusion of big polymer beads.Here film occurs in drying and polymer beads by the effect of all the other film coalescence aid and during plastifying randomly from the film forming of water medium.The adding of employing that the film forming of film can be by thermoplastic polymer or multipolymer and/or the material by playing temporary transient softening agent effect improves.Film coalescence aid plays a kind of special solvent, thereby the surface of its softening polymer beads also makes it be able to fusion.Here advantageously, these softening agent on the one hand, keep one sufficiently long period so that can work to polymer beads in the time at one section sufficiently long in waterborne compositions, thus and then evaporation and overflowing from film.On the other hand also advantageously, during drying process, also have certain content residuary water to have certain sufficiently long time.In appropriate film process, form a kind of transparent film, rather than oyster white or even Powdered film because this will show that film forming is hindered.For reaching as far as possible perfectly film forming, the temperature of the lip-deep wet film of paint must be higher than minimum film temperature (MFT), and polymer beads is just soft to be condensed to being enough to because have only at that time.Here particularly advantageously be that these softening agent are not or in fact do not change the pH value of waterborne compositions.Here the selection not a duck soup of suitable film coalescence aid usually needs the mixture of at least two kinds of film coalescence aid at this.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 ethylene glycol monobutyl ether, glycol monoethyl ether, methyl glycol, glycol propyl ether, glycol hexyl ether, diethylene glycol methyl ether, diethylene glycol ethyl ether, butyl carbitol, the glycol ether hexyl ether, perhaps polypropylene glycol ether, for example, propylene glycol monomethyl ether, the dipropylene glycol monomethyl ether, the tripropylene glycol monomethyl ether, the propylene glycol monobutyl ether, the dipropylene glycol monobutyl ether, the tripropylene glycol monobutyl ether, propylene glycol one propyl ether, dipropylene glycol one propyl ether, tripropylene glycol one propyl ether, the propylene glycol phenylate, the diisobutyrate of neopentyl glycol, polytetrahydrofuran, polyethers-polyvalent alcohol and/or polyester-polyvalent alcohol.Be different from film forming, crosslinked for the thermofixation that reaches organic coating in the temperature that requires at least 120 ℃ traditionally.

Mainly contain sequestrant and silane or mainly contain in the inventive method of composition that synthetic resins adds sequestrant and silane relating to, waterborne compositions can comprise at least a following component e that is selected from),

e ₁) at least a particle form mineral compound, its average particulate diameter is measured by scanning electronic microscope, 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 and

e ₈) at least a chromium (VI) compound.

Preferably, the powder of fine dispersion, dispersion or suspensoid, for example, carbonate, oxide compound, silicate or vitriol, particularly colloid and/or amorphous granular are as the mineral compound e of particle form ₁) add.Particle based on the compound of at least a aluminium, barium, cerium, calcium, lanthanum, silicon, titanium, yttrium, zinc and/or zirconium preferably adds as the particle form mineral compound.Preferably be based on aluminum oxide, barium sulfate, cerium dioxide, silicon-dioxide, silicate, titanium oxide, yttrium oxide, zinc oxide and/or zirconic particle as what the particle form mineral compound added.

Preferably, mean particle size is used as the particle form mineral compound between the particle of 6～200nm, especially preferred 7～150nm, and very especially preferred 8～90nm is more preferably between 8～60nm, most preferably between 10～25nm's.These particles also can be the form of gel or colloidal sol.Particle is stabilization treatment in addition, for example, under alkaline condition, disperses so that reach preferably.The particle form mineral compound disperses the adding of the boron of usefulness not need, and does not also use in example.Preferably, larger particles has the form of being partial to strip or elongated particle.

The waterborne compositions that can be used as bath lotion composition and/or use as enriched material preferably contains at least a particle form mineral compound, its content is between 0.1～500g/l, especially preferred 10～200g/l, very especially preferred 30～100g/l is most preferably between 3～60g/l.Preferably, add 0.1～50 part of at least a particle form mineral compound, especially preferred 0.5～20 part, very especially preferred 0.8～10 part, per 100 weight parts waters.In the middle of the particle form mineral compound, can keep coating of the present invention transparent, in other words, colourless or white those, for example, aluminum oxide, barium sulfate, silicate, silicon-dioxide, colloid silica, zinc oxide and/or zirconium white are particularly preferred, so that keep the visual signature of metallic surface to try one's best as seen, are not altered.

Also may be selected to be the higher or high conductivity particle that is used to weld and randomly adds, for example, weisspiessglanz, iron phosphide, tungsten, zinc and zinc alloy can make them randomly be projected into layer of the present invention mean particle size in addition slightly so that they are had.

The content of organic membrane-forming agent and the ratio of particle form mineral compound content in waterborne compositions can change in wide region; Particularly, it can be less than or equal to 25: 1.Preferably, this ratio between from more than or equal to 0.05: 1 to the highest 15: 1 scope, especially preferably from more than or equal to 0.2: 1 to the highest 12: 1, very especially preferably from more than or equal to 0.5: 1 to the highest 10: 1, particularly from more than or equal to 1: 1 to the highest 8: 1 scope.

In waterborne compositions, the ratio of the content of at least a silane and particle form mineral compound content equally also can change in wide region; Particularly, it can be less than or equal to 25: 1.This ratio preferably between from more than or equal to 0.01: 1 to the highest 15: 1 scope, especially preferably from more than or equal to 0.05: 1 to the highest 8: 1, very especially preferably from more than or equal to 0.08: 1 to the highest 4: 1, especially from more than or equal to 0.1: 1 to the highest 2: 1.

Preferably, adopt at least a paraffin, polyethylene and the polyacrylic wax of being selected from as lubricant e2), particularly a kind of oxidized petroleum waves, at the content of this wax in waterborne compositions preferably between 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 form of moisture or positively charged ion, negatively charged ion and/or spatial stabilityization, because at that rate, it can keep uniform distribution 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.It is favourable that but only the containing of wax is only under coating of the present invention is a kind of situation of processing layer, because the existence of wax in pretreatment layer may be unfavorable to japanning.Can add lubricant and/or binder to reduce the frictional coefficient of coating, particularly at shaping.Paraffin, polyethylene and oxidic polyethylene, recommended especially this purpose that is used for.

Preferably, at least a wax is together with containing ethene and polymerizing acrylic acid thing mixture and/or multipolymer, for example, ethylene/acrylic acid copolymer as this lubricant, randomly adds at least a other synthetic resins at this, specifically, according to wax and contain quantity ratio between the ethylene and acrylic acid copolymer and equal 0.02: 1～2: 1, especially preferred 0.05: 1～1: 1, added in very especially preferred 0.1: 1～0.5: 1.

In waterborne compositions (bath lotion composition), the content of organic membrane-forming agent can change in wide region with the ratio of the content of lubricant; Specifically, it can be more than or equal to 2: 1.Preferably, this ratio is between 3: 1～50: 1, especially preferred 10: 1～20: 1.

Waterborne compositions preferably contains at least a organic inhibitor e ₃), particularly based on amine, the long-chain alkanolamine of preferred at least a alkanolamine-preferably, the complex compound of at least a TPA-amine, for example, butyric ester-4-the ethyl morpholine of acid affixture-4-oxo-4-p-methylphenyl, the zinc salt of 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 metal-salt of dodecyl-naphthene sulfonic acid, at least a toluene propionic acid, the amino of 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, the content of this 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 evaporable.May 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.Particularly preferred 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.The adding of at least a organic inhibitor only just needs for the metallic surface that is very difficult to protect usually, and for example, the polished steel surface is because the present composition has very high corrosion inhibition or restraining effect.Advantageously, the right and wrong-surface of galvanized steel that be coated with, particularly cold-rolled steel (CRS).

In waterborne compositions (bath lotion composition), the content of organic membrane-forming agent can change in wide region with the ratio of the content of at least a organic inhibitor; Specifically it can be less than or equal to 500: 1.This ratio is preferably between 5: 1～400: 1, especially preferred 10: 1～100: 1.

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 scanning electronic microscope, 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.

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 alkanolamine that can slowly evaporate and oxyhydroxide such as sodium hydroxide solution and potassium hydroxide solution especially, but the alkanolamine of preferred evaporation rapidly, ammonia and based on the compound of morpholine and alkanolamine.They have the neutral of making synthetic resins and become water-solvable and mix, perhaps from about 150 initial acid numbers, and also water-soluble effect.

At least a organic solvent e ₆) can randomly also join in the inventive method.At least a water soluble mixes and/or water-soluble alcohol, a kind of glycol ethers or n-methyl-2-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 propylene glycol, 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, use hardly or without organic solvent, may be except a small amount of alcohol.

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

Not only can be basically or do not contain chromium (VI) compound fully according to coating of the present invention, and do not contain chromium (III) compound, and can not damage quality.Although with regard to content of the present invention, do not plan to add environmentally harmful chromium cpd e usually ₈), for example, Cr particularly ⁶⁺Those, but under situation about adopting, but can answer customer requirement that this compound is provided.This waterborne compositions that does not preferably contain or do not contain substantially chromium (VI) compound has the highest only 0.05wt% chromium content and is containing the chromium metallic surface---at chromium-free metal surface and the highest 0.2wt% chromium content---; The chromium content that appears in the body lotion can be dissolved out from the metallic surface by pickling corrosion, can trace from the impurity that contains, produce or can from before body lotion or from container and pipeline, bring.Preferably, do not join chromium in the waterborne compositions consciously.

Yet; also can advantageously adopt and have at least a the inventive method that contains chromium cpd of certain content; if plan in wide region and keep the corrosionproof protection effect highly reliably; particularly protective layer impaired after, this may be by due to transportation, storage and the mechanical stress between erecting stage of handling base material after the substrate surface with treatment solution of the present invention.So, can add, for example, sodium dichromate 99, potassium bichromate and/or ammonium dichromate.So the content of chromium (VI) compound is preferably between 0.01～100g/l, especially preferred 0.1～30g/l.

Preferably, waterborne compositions also can contain at least a alkaline linking agent, based on titanium, hafnium and/or zirconium as positively charged ion and/or based on carbonate or volatile salt as negatively charged ion, at the content of this this kind linking agent in waterborne compositions preferably between 0.01～3wt%, especially preferred 0.02～1.8wt%, very especially preferred 0.05～1wt%.

Preferably, waterborne compositions contains at least a additive, the additive of particularly at least a being selected from-at least a biocides, at least a defoamer and/or at least a wetting agent.

Preferably, do not have acid, particularly do not have mineral acid and/or organic carboxyl acid to join in the waterborne compositions-in some cases, be hidden in except the acid traces in the starting material.Particularly, it does not contain or is substantially free of mineral acid and/or organic carboxyl acid, the most important thing is not contain mineral acid.

Waterborne compositions of the present invention does not preferably contain free fluorochemical, the complex fluorides of adding, for example, and hexafluoro metatitanic acid or hexafluoro zirconate and/or the fluorochemical of bonding otherwise.

Preferably, waterborne compositions does not contain or is substantially free of heavy metal.Particularly, the content of cadmium, nickel, cobalt and/or copper should maintain extremely low-level and should not add.Yet with regard to the present composition, the pickling corrosion is carried out so slowly usually, so that does not have steel-refining agent, and for example, chromium or nickel can come out from the steel surface dissolution.

The particularly advantageous present composition mainly contains, particularly, at least a multipolymer, for example, based on vinylformic acid-polyester-polyurethane, vinylbenzene, cinnamic acrylic ester and/or ethylene-acrylate, as membrane-forming agent, at least a silane, at least a sequestrant, at least a film coalescence aid based on long-chain alcohol, at least a particle form mineral compound, the latter is particularly based on aluminum oxide, aluminium phosphide, ferric oxide, iron phosphide, mica, lanthanide oxide, for example, based on cerium oxide, moly-sulfide, graphite, carbon black, silicate, silicon-dioxide, colloid silica, zinc oxide and/or zirconium white, randomly at least a lubricant, for example, wax, randomly at least a wetting agent, for example, polysiloxane, randomly at least a organic inhibitor and other additive randomly, for example, particularly, defoamer.

The metallic surface preferably is in the state that harsh output is come, cleaned or cleaned.That term " clean metal surface " here refers to is non--metal that cleaned, and for example, firm galvanized surface need not to clean thereon, the surface of perhaps just having cleaned.

Preferably, this waterborne compositions does not apply pretreatment compositions and in advance by on the direct paint metallic surface.For some purposes, may be favourable but may be to apply at least a pretreatment layer in advance, for example, based on the alkali metal phosphate agent, contain the zinc phosphoric acid agent, contain the pretreating agent of rare earth metal such as cerium and/or at least a silane.

For mainly preparing bath lotion composition by enriched material by diluting with water, or preparation is added solution so that at long body lotion operating period adjusting bath lotion composition, the preferred employing contained great majority or whole bath lotion composition component but do not contain the waterborne compositions of at least a particle form mineral compound usually almost, and wherein this particle form mineral compound is preferred preserves separately and add separately.Also can advantageously add reaction and dry accelerant separately, for example, the alkylbenzyldimethylasaltsum saltsum of tosic acid.Enriched material and add solution with regard to single component, is concentrated to 5～10 times of the concentration that is equivalent to bath lotion composition.Yet in some cases, " enriched material " also can directly be used as bath lotion composition, randomly does dilution in advance slightly, for example, and 5～30%.

In the methods of the invention, waterborne compositions can be preferably 5～50 ℃ temperature, and especially preferred 10～40 ℃, very especially preferred 18～25 ℃, or 30～95 ℃ temperature paint metallic surface.In the methods of the invention, the metallic surface can preferably remain on 5～60 ℃ of temperature in the scope during coating applies, especially preferably at 10～55 ℃, and very especially preferred 18～25 ℃, perhaps in some cases, also can be at 50～120 ℃.In the methods of the invention, drying can preferably be carried out under the circulating air temperature in 20～400 ℃ of temperature ranges in the metallic surface of coating, preferred 40～120 ℃, perhaps at 140～350 ℃, very especially preferably, perhaps under 160～300 ℃ PMT (peak value metal temperature), carry out-depend on the chemical constitution of organic membrane-forming agent at 60～100 ℃.The dry needed residence time and drying temperature are inversely proportional to basically: for example, the material of image-tape material and so on, 1～3s under 100 ℃, perhaps at 250 ℃ of following 1～20s, the chemical constitution that depends on synthetic resins or polymkeric substance, perhaps at 20 ℃ of following 30min, the combination with the vibrin of free hydroxyl group group and melamine formaldehyde resin then can't be at the temperature drying that is lower than 120 ℃.On the other hand, the shaping component of coating especially depend on wall thickness, must the dry much longer time.Especially be fit to this drying based on recirculating air, induction, drying plant infrared and/or microwave.In the methods of the invention, the coating band can preferably be wound into coiled material, randomly after being cooled to 40～70 ℃ of temperature in the scope.

In the methods of the invention, waterborne compositions can preferably can apply by roller coat, overflow, scraper coating, spraying, spraying, brushing or dip-coating, and randomly uses roller floating subsequently.

The bed thickness of coating of the present invention is preferably between 0.1～6 μ m, especially preferred 0.2～5 μ m, very especially preferred 0.25～4 μ m, particularly 0.3～2.5 μ m.

The coating performance of pendulum-rocker hardness and flexibility is important to the coating that is rich in organic polymer/multipolymer only generally.Be coated with at least one layer of paint or at least one coating as layer of paint if coating of the present invention also will add afterwards, then T (font)-pliability test is with regard to particularly important.

This drying and randomly again the solidified film preferably have the pendulum-rocker hardness of 30～190s, preferred 50～180s adopts K nig pendulum hardness tester to measure according to DIN 53157.Yet in some cases, K nig pendulum-rocker hardness is preferably between 60～150s, especially preferred 80～120s.Between the pendulum-rocker hardness of 100～150s appear at usually can be UV-crosslinked coating in, the preferred value of the pendulum-rocker hardness of 40～80s can then appear at non-can be UV-crosslinked coating or based on, for example, not or hardly in the coating of the polymeric dispersions of chemically crosslinked.The layer that produces according to the present invention is only prepared testing at sample chemically identical but that have an enough thick thick coating, and the thick shallow layer of the highest 10 μ m is not carried out.

This drying and randomly again the solidified film preferably have certain flexibility, so that basically according to DIN ISO 6860 about the shaft rod bending test of 3.2mm～38mm diameter mandrel rod in after the bending of taper mandrel rod-but must not the tear test zone-crackle of not being longer than 2mm forms, these crackles, if form, can be wetting with copper sulfate subsequently, be deposited on the cracking metallic surface of exposing by copper due to variable color detect.The term here " basically " is meant and all characterizes thicker film traditionally, Just because of this, also carries out copper sulfate test here subsequently, it can disclose (otherwise) defective that can't see in some cases.The zone that the proof of flexibility adopts shaft rod bending test also will so be shaped subsequently is immersed in the method that detects defective in the copper-bath can provide reproducible test-results, and has the advantage that does not need for this reason to carry out expensive corrosion test, this corrosion test, for example, to last 240 hours, under some situation, look the chemical constitution and the roughness of metallic surface, can cause different results, therefore can only on limited extent, be compared to each other.In the metallic surface of meta-alkalescence, for example, aluminium alloy will carry out this test, need at first do once cleaning by pickling to the metallic surface before coating, so that remove zone of oxidation basically.

To being coated with according to the present invention, and be coated with subsequently in T font-pliability test of implementing with the shaping component (metal sheet) of coiled material spraying, the area ratio of delamination face is preferably only the highest by 8%, especially preferably the highest by 5%, very especially preferably the highest by 2%, at this but optimum value is about 0%, so that generally only chap.Spraying paint based on the coiled material coating of silicone polyester to be preferably used for this purpose, in the typical simultaneous test especially for the coiled material of coating.Yet here, whether chap and the size of crackle, depend on used person's character of spraying paint basically.

In the methods of the invention, in each case, be selected from printing-ink, paper tinsel, spray paint, preferably paint should drying and randomly again on the solidified film as at least one coating of the material that sprays paint, powder coating, tackiness agent and/or adhesive carrier.

In every kind of operating mode, be selected from functional paint, tackiness agent and/or the adhesive carrier of lacquer, polymkeric substance, lacquer, plastics, for example, from-adhesive film, but at least one coating paint this partly or on complete drying or the solidified film, particularly a kind of wet shot lacquer, powder paints, plastic coating, tackiness agent, particularly coiled material coating usefulness.Be coated with metallic element, particularly band or strip sections according to the present invention, can stand to be shaped, spray paint with this waterborne compositions, be coated with polymkeric substance, for example, PVC, printing, gluing, hot soldering, welding and/or by clamping or other interconnection technique is connected to each other perhaps is connected to the processing on other element.These methods are known as the coating of sheet metal strip for building in principle.Generally speaking, at first implement another type and spray paint or be coated with, reshape subsequently.If coating of the present invention is spraying or is coated with plastics, usually just can't not set up soldering or be welded to connect a little if do not remove coating at least partly, unless, for electric welding, in film of the present invention, be incorporated into high-content conductive particle and/or conductive polymers, and coating subsequently is thin extraordinarily.

Can preferably be used as wire rod according to substrates coated of the present invention, band, sheet metal or rolling component wiry, the flower twisted wire, steel band, metal sheet, lining, wire cloth, motorcar body or its component, or motor vehicle, trailer, the component of mobile house or guided missile, lid, cover, lamp, lamp (light), the traffic signals modulation element, furniture or furnishing elements, the household electrical appliance component, frame, section bar, the shaping component of complicated shape, crash barrier, well heater or hedge element, collision bumper, the component of at least one pipe and/or section bar, window, door or bicycle frame or item of hardware, for example, screw, nut, flange, spring, or spectacle-frame.

The inventive method is to above-mentioned, on the one hand, and rich chromic salt anacidity; or on the other hand, to containing sour method, before particularly spraying paint in the sheet metal strip surface preprocessing technical field; alternative method, with these methods mutually specific energy be provided at the better result of anti-corrosion protection and lacquer sticking power aspect.

In addition, also can adopt the inventive method to handle but not need subsequently aftertreatment by the metallic surface of traditional way cleaning, for example, water or suitably the back cleaning solution clean.The inventive method is particularly suitable for applying treatment soln by smoother roller or by so-called roller spreader, and wherein treatment soln can not need further intermediate processing steps (dry technology on the spot) applying the back convection drying.So, process is simplified greatly, for example, compare with conventional spray paint or dip-coating method, particularly process, for example with having cleaning subsequently, those of chromating or phosphoric acid zinc impregnation are compared, and only produce the rinse water of very a small amount of washing unit after work is finished, because do not need cleaning process after applying, this compares with the existing Chrome-free method of operating by the method for spraying the back cleaning solution and also represents an advantage.These rinse water can join in the new a collection of bath lotion composition once more.

Here, be easy to use coating polymkeric substance of the present invention, optional chromate-free and do not need to apply in advance extra pretreatment layer, therefore contain polymeric coating, as coating or the Al-and the floating layer of Zn-of metal by applying, just can reach the metallic surface, particularly AlSi-, ZnAl-such as Galfan ^, AlZn-such as Galvalume ^, ZnFe-, ZnNi-such as Galvanneal ^And the outstanding permanent protection of other zinc alloy.In addition, coating of the present invention proves also and is particularly suitable for highly perishable metallic surface that for example, those of iron and Steel Alloy particularly on cold-rolled steel, advantageously add at least a inhibiter this moment in waterborne compositions.By this kind measure, the formation that wink becomes rusty between the dry epoch of cold-rolled steel (CRS) surface treatment liquid can be inhibited.

So can obtain the lower and comparatively friendly anti-corrosion protection of a kind of cost to environment; it does not need expensive ultra-violet curing yet but only depends on dry and film forming and randomly be aided with " general chemistry " curing in addition; that is, usually said " heat cross-linking " just can solidify fully.Yet, in some cases, may interestedly be in a special procedure of processing, to obtain harder coating rapidly.So, advantageously, add at least a light trigger and select at least a ultraviolet-curable polymer component, rely on the partial cross-linked of photochemical activation radiation, particularly uv-radiation to reach.So coating of the present invention can be by the photochemical activation radiation be partly solidified and is finished partly solidified by dry and film forming or heat cross-linking.This to fast-motion conveyor line on apply during or for initial stage crosslinked (curing) particularly important.Here so-called UV-crosslinked content can account for all possible solidified 0～50%, preferred 10～40%.

The advantage with basic or complete chromate-free coating of polymkeric substance of the present invention is-especially bed thickness under the situation of 0.5～3 μ m-it is transparent and slight painted, therefore for example zinc-plated or Galvalume ^The metallicity on surface and typical construction still can clearly be seen clearly with keeping the shape or substantially seeing through coating with keeping the shape.Moreover so thin coating also allows welding, without a doubt.

Polymeric coating of the present invention also be very easy to be shaped in addition, therefore can regulate it so that coating, dry and randomly solidify and randomly pass through long-time after, it still is in relative plasticity, rather than hard, brittle state.

The present invention contains polymeric coating and is easy to spray paint with most of varnish or plastics Lacquer finish.The present invention contains and sprays paint after polymeric coating can carry out or with plastic paint coating, for example, and by being coated with PVC such as powder coated, wet shot lacquer, overflow, roller coat, brushing or dip-coating.Adopt the present invention of this kind measure paint to contain on the polymeric coating formed solidified coating and also can apply 2 or 3 layers usually and spray paint or plastic layer, generally have the bed thickness of 5～1,500 μ m altogether.

Polymeric coating of the present invention also can not go wrong in the reverse side foaming, for example uses the polyurethane insulating foams plastics, so that produce 2-sheet sandwich element, perhaps can easily be coated with the traditional structure tackiness agent, for example adopts like that in automobile making.

Coating of the present invention at first can be used as prime coat.They be particularly suitable for need not, but also be fit to the pretreatment layer that applies before at least one.This kind pretreatment layer, so, especially can be based on the phosphatic coating of phosphoric acid salt, particularly ZnMnNi, perhaps based on phosphoric acid salt, silane and/or based on fluoride complex, inhibiter, phosphoric acid salt, polymkeric substance and/or fine dispersion particulate mixture.

Adopt coating of the present invention can obtain a kind of pretreatment layer or prime coat, they can form a kind of coating system that is equivalent to best Chromium coating system with spraying paint of applying subsequently.

The inventive method is with description so far and/or at rich aluminium base or in the superior part that base material-particularly steel substrate-method of upward enforcement is compared that is coated with aluminium-containing alloy---it does not cause the substrate surface deepening, do not make the milky white shape delustring of substrate surface yet, therefore can be used for decorative constructure and/or building component and do not need additional colour to spray paint.The aesthetic qualities of metallic surface remains unchanged.

Coating of the present invention is extra cheap, environmental friendliness and adopting on big technical scale easily.

Surprisingly, 0.5～2 μ m although bed thickness is only had an appointment can produce the high no chromium thin film of abnormal quality with coat of synthetic resin of the present invention.

Making us very surprised is; by in waterborne compositions, adding metal chelator; no matter can reach unexpectedly the film that forms thus significantly improving on anti-corrosion protection and lacquer sticking power---mainly containing sequestrant and silane, still except sequestrant and silane, also mainly containing in the waterborne compositions of synthetic resins.

The viscosifying action of silane and reaction product thereof, particularly at metal base and between spraying paint, randomly between pigment and organic varnish component, for example also will show on the composition described in the embodiment example here, or even show on the itself, as long as the existence side by side of polymkeric substance and sequestrant.Once find unexpectedly, under the situation of high-content high-molecular weight polymer and multipolymer, do not need to contain low-molecular-weight organic matter matter, just can reach the remarkable improvement of film performance by the adding sequestrant.High-molecular weight polymer and multipolymer may take place crosslinked owing to the existence of sequestrant, and this is particularly conducive to those film forming systems that does not contain solidifying agent and light trigger.By this kind measure, can avoid, adopt exposure at high temperature and as the free radical irradiation of additional expensive procedure of processing as heat cross-linking.

Embodiment

Example and Comparative Examples:

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

A) mainly based on the composition of sequestrant and silane:

Be the preparation aqueous concentrates, at least 2 weeks of silane ageing of at least a partial hydrolysis, and hydrolysis randomly also takes place whereby.Subsequently, add the contained metal chelator of table 1.Subsequently, this enriched material dilutes with water, randomly adds the reagent of regulating the pH value, and for example, ammonia is so that obtain available treatment solution immediately.In every kind of operating mode, at least 3 hot-dip galvanizing sheet steels or Galvalume ^Steel plate contacts by the also dry alignment processing liquid with 25 ℃ of roller coat.So the metal sheet of handling is placed under 90 ℃ of PMT and carries out drying, tests their anti-corrosion protection ability subsequently.

Example E1～E8 comprises Comparative Examples CE4, shows to add sequestrant, the perhaps influence of sequestrant and polymeric blends.At example E9～E12, and among E13～E17, the quantity of silane and sequestrant has improved, and meanwhile, the add-on of inorganic particle has reduced, and is the add-on difference of polymeric blends in the difference of this this two series.At last, the bed thickness in example E9 and E18～E20 changes.

Table 1:Based on sequestrant and silane and, also comprise the composition of inorganic particle in some cases, concentration data is unit with wt%, handles that to bathe then be g/l

Example/Comparative Examples	B1	B2	B3	VB4	B5	B6	B7	B8	B9	B10	B11	B12	B13	B14	B15	B16	B17	B18	B19	B20
Example/Comparative Examples	B1	B2	B3	VB4	B5	B6	B7	B8	B9	B10	B11	B12	B13	B14	B15	B16	B17	B18	B19	B20	Enriched material
Organofunctional silane A	15	15	15	30	-	15	15	3.3	1.7	5.1	7.5	11.6	2	1.2	3.3	5.1	7.8	1.7	1.7	1.7	Enriched material
Organofunctional silane A	15	15	15	30	-	15	15	3.3	1.7	5.1	7.5	11.6	2	1.2	3.3	5.1	7.8	1.7	1.7	1.7	Organofunctional silane B	-	-	-	-	15	-	-	-	-	-	-	-	-	-	-	-	-	-	-	-
Titanium-inner complex D	17.5	17.5	17.5	-	-	-	-	3.9	2	5.9	8.8	13.7	3.1	1.3	3.9	5.9	9.1	2	2	2	Organofunctional silane B	-	-	-	-	15	-	-	-	-	-	-	-	-	-	-	-	-	-	-	-
Titanium-inner complex D	17.5	17.5	17.5	-	-	-	-	3.9	2	5.9	8.8	13.7	3.1	1.3	3.9	5.9	9.1	2	2	2	Zirconium-inner complex E	-	-	-	-	17.5	-	-	-	-	-	-	-	-	-	-	-	-	-	-	-
Zirconium-inner complex F	-	-	-	-	-	17.5	-	-	-	-	-	-	-	-	-	-	-	-	-	-	Zirconium-inner complex E	-	-	-	-	17.5	-	-	-	-	-	-	-	-	-	-	-	-	-	-	-
Zirconium-inner complex F	-	-	-	-	-	17.5	-	-	-	-	-	-	-	-	-	-	-	-	-	-	Titanium-inner complex G	-	-	-	-	-	-	17.5	-	-	-	-	-	-	-	-	-	-	-	-	-
SiO ₂-particle＜0.2 μ m	-	-	-	-	-	-	-	11	13	9	6	-	7	9	6	4	-	13	13	13	Titanium-inner complex G	-	-	-	-	-	-	17.5	-	-	-	-	-	-	-	-	-	-	-	-	-
SiO ₂-particle＜0.2 μ m	-	-	-	-	-	-	-	11	13	9	6	-	7	9	6	4	-	13	13	13	Ethanol/methyl alcohol	Do not add optional formation
Ammonia	Add and be used to regulate pH value to 8.3 on a small quantity																				Ethanol/methyl alcohol	Do not add optional formation
Ammonia																					Polymeric blends	-	-	-	-	-	-	-	7	7	7	7	7	4.5	4.5	4.5	4.5	4.5	7	7	7
Water	67.5	67.5	67.5	70	67.5	67.5	67.5	74.8	76.3	73	70.7	67.7	83.4	84	82.3	80.5	78.6	76.3	76.3	76.3	Polymeric blends	-	-	-	-	-	-	-	7	7	7	7	7	4.5	4.5	4.5	4.5	4.5	7	7	7
Water	67.5	67.5	67.5	70	67.5	67.5	67.5	74.8	76.3	73	70.7	67.7	83.4	84	82.3	80.5	78.6	76.3	76.3	76.3	Add up to	100	100	100	100	100	100	100	100	100	100	100	100	100	100	100	100	100	100	100	100
Each batch processing is bathed																					Add up to	100	100	100	100	100	100	100	100	100	100	100	100	100	100	100	100	100	100	100	100
Each batch processing is bathed																					Enriched material	10	20	30	20	20	20	20	53	53	53	53	53	53	53	53	53	53	40	27	13
Water	90	80	70	80	80	80	80	47	47	47	47	47	47	47	47	47	47	60	73	87	Enriched material	10	20	30	20	20	20	20	53	53	53	53	53	53	53	53	53	53	40	27	13

Example/Comparative Examples		B1	B2	B3	VB4	B5	B6	B7	B8	B9	B10	B11	B12	B13	B14	B15	B16	B17	B18	B19	B20
Example/Comparative Examples		B1	B2	B3	VB4	B5	B6	B7	B8	B9	B10	B11	B12	B13	B14	B15	B16	B17	B18	B19	B20	Handle and bathe
Water		968	936	904	936	936	936	936	866.6	874.5	857.0	844.8	828.9	912.2	915.3	906.3	896.8	886.7	905.1	936.1	969.3	Handle and bathe
Water		968	936	904	936	936	936	936	866.6	874.5	857.0	844.8	828.9	912.2	915.3	906.3	896.8	886.7	905.1	936.1	969.3	Organometallics		17	34	51	-	34	34	34	20.7	10.6	31.3	46.6	72.6	16.4	6.9	20.7	31.3	48.2	8.0	5.4	2.6
Silane		15	30	45	64	30	30	30	17.5	9.0	27.0	39.8	61.5	10.6	6.4	17.5	27.0	41.3	6.8	4.6	2.2	Organometallics		17	34	51	-	34	34	34	20.7	10.6	31.3	46.6	72.6	16.4	6.9	20.7	31.3	48.2	8.0	5.4	2.6
Silane		15	30	45	64	30	30	30	17.5	9.0	27.0	39.8	61.5	10.6	6.4	17.5	27.0	41.3	6.8	4.6	2.2	Vinylformic acid-polyester-polyurethane-multipolymer		-	-	-	-	-	-	-	15	15	15	15	15	9.7	9.7	9.7	9.7	9.7	11.4	7.7	3.7
Copolymer in cinnamic acrylic ester		-	-	-	-	-	-	-	16.7	16.7	16.7	16.7	16.7	10.7	10.7	10.7	10.7	10.7	12.6	8.4	4.1	Vinylformic acid-polyester-polyurethane-multipolymer		-	-	-	-	-	-	-	15	15	15	15	15	9.7	9.7	9.7	9.7	9.7	11.4	7.7	3.7
Copolymer in cinnamic acrylic ester		-	-	-	-	-	-	-	16.7	16.7	16.7	16.7	16.7	10.7	10.7	10.7	10.7	10.7	12.6	8.4	4.1	Colloid SiO ₂		-	-	-	-	-	-	-	58.3	68.9	47.7	31.8	-	37.1	47.7	31.8	21.2	-	52	35.1	16.9
Polysiloxane		-	-	-	-	-	-	-	1	1	1	1	1	0.6	0.6	0.6	0.6	0.6	0.8	0.5	0.2	Colloid SiO ₂		-	-	-	-	-	-	-	58.3	68.9	47.7	31.8	-	37.1	47.7	31.8	21.2	-	52	35.1	16.9
Polysiloxane		-	-	-	-	-	-	-	1	1	1	1	1	0.6	0.6	0.6	0.6	0.6	0.8	0.5	0.2	Defoamer		-	-	-	-	-	-	-	1	1	1	1	1	0.6	0.6	0.6	0.6	0.6	0.8	0.5	0.2
Long-chain alcohol		-	-	-	-	-	-	-	3.3	3.3	3.3	3.3	3.3	2.1	2.1	2.1	2.1	2.1	2.5	1.7	0.8	Defoamer		-	-	-	-	-	-	-	1	1	1	1	1	0.6	0.6	0.6	0.6	0.6	0.8	0.5	0.2
Long-chain alcohol		-	-	-	-	-	-	-	3.3	3.3	3.3	3.3	3.3	2.1	2.1	2.1	2.1	2.1	2.5	1.7	0.8	The pH-value		8.3	8.3	8.3	8.3	8.3	8.3	8.3	8.3	8.3	8.3	8.3	8.3	8.3	8.3	8.3	8.3	8.3	8.3	8.3	8.3
Film properties																						The pH-value		8.3	8.3	8.3	8.3	8.3	8.3	8.3	8.3	8.3	8.3	8.3	8.3	8.3	8.3	8.3	8.3	8.3	8.3	8.3	8.3
Film properties																						Layer is heavy, g/m ²		0.2	0.4	0.6	0.2	0.4	0.4	0.4	0.8	0.8	0.8	0.8	0.8	0.5	0.5	0.5	0.5	0.5	0.6	0.4	0.2
Salt spray test ASTM B117-73: the % after the surface corrosion	48h	10	＜2	0	30	＜2	＜2	＜2	0	0	0	20	30	0	0	0	30	40	0	0	0	Layer is heavy, g/m ²		0.2	0.4	0.6	0.2	0.4	0.4	0.4	0.8	0.8	0.8	0.8	0.8	0.5	0.5	0.5	0.5	0.5	0.6	0.4	0.2
	48h	10	＜2	0	30	＜2	＜2	＜2	0	0	0	20	30	0	0	0	30	40	0	0	0	96h	20	10	＜2	60	10	10	10	0	0	0	30	40	0	0	0	40	60	0	0	＜2
	120h	40	20	5	90	20	20	20	＜2	0	＜2	50	60	0	0	0	50	80	0	＜2	5	96h	20	10	＜2	60	10	10	10	0	0	0	30	40	0	0	0	40	60	0	0	＜2
	120h	40	20	5	90	20	20	20	＜2	0	＜2	50	60	0	0	0	50	80	0	＜2	5	240h	60	40	10	100	40	40	40	10	0	10	70	80	10	＜2	10	70	100	＜2	5	10
	360h	100	60	30	100	60	60	60	20	＜2	30	100	100	20	5	30	100	100	5	10	30	240h	60	40	10	100	40	40	40	10	0	10	70	80	10	＜2	10	70	100	＜2	5	10

Here transparent, the homogeneous of the film of Xing Chenging and densification.The film that forms shows does not have variable color, and following metallic surface does not have deepening (darkening).This in fact seeing particularly advantageous structure, gloss and the color of metallic surface in order to see through coating with keeping the shape.The combination of sequestrant and silane causes, compares with the composition that does not contain organic metallic compound, under very low bed thickness condition, very significantly improves aspect anti-corrosion protection.Other examples show that also particularly the higher dosage inorganic particle in this operating mode, based on the silicon-dioxide of mean particle size 10～20nm, further adds contribution to corrosion-resistant making.Here be surprised to find, surpass a spot of this kind particulate adding the content increase and the anti-corrosion protection of inorganic particle are significantly increased.What be taken aback is, although have part high-content inorganic particle, still can form a kind of densification of anti-mechanical effect later in the coating film forming, but the film of deflection.Heavy roughly the drawing with the micron divided by 1.1 of layer is the bed thickness of unit.With the naked eye estimate with regard to the corrosive area ratio.Because a small amount of synthetic resins, so this film has the performance of inactivating performance rather than thin organic coating, the latter can be shaped.Though the film that about 0.75 μ m of example 9 is thick is thicker really than the inorganic passivation film of typical rich chromic salt, demonstrate at least good equally corrosion-resistant, moreover, be different from rich chromate coating, be easy to be shaped.

Claims

1. one kind is coated with a kind of method of waterborne compositions to the metallic surface, and said composition can be basically or do not contained chromium (VI) compound fully, is used for the pre-treatment before the further coating, perhaps is used for handling, and it is characterized in that said composition comprises, except water,

A) silane of at least a hydrolyzable and/or hydrolysis at least in part and

B) at least a metal chelator,

The bed thickness of the wherein dry film of crossing and randomly also having solidified is between 0.01～10 μ m.

2. the method for claim 1 is characterized in that, said composition also comprises,

C) at least a organic membrane-forming agent, it comprises the organic polymer and/or the multipolymer of at least a water-soluble or water-dispersion, and its acid number is between 3～250, and wherein the content of organic membrane-forming agent is benchmark in the solids content, is 10～45wt%, and

D) Ren Xuan at least a long-chain alcohol is as film coalescence aid.

3. claim 1 or 2 method is characterized in that waterborne compositions 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 and

e ₈) at least a chromium (VI) compound.

4. the method for any one in the above claim, it is characterized in that, organic membrane-forming agent is a kind of synthetic resin mixture, comprise at least a polymkeric substance and/or at least a multipolymer, they comprise the synthetic resins of certain content based on acrylate, epoxide, ethene, melocol, phenol, polyester, urethane, vinylbenzene, styrene butadiene and/or vinyl.

5. the method for any one in the above claim, it is characterized in that, organic membrane-forming agent also comprises, as synthetic resins, certain content is based on organic polymer, multipolymer and/or its mixture of polymine, polyvinyl alcohol, polyvinylphenol, Polyvinylpyrolidone (PVP) and/or poly aspartic acid, particularly with the multipolymer of phosphorous vinyl compound.

6. the method for any one is characterized in that in the above claim, and organic membrane-forming agent comprises at least a acid number of certain content between 3～80 multipolymer, and specifically, its content accounts for the 50wt% at least of the synthetic resins of adding.

7. the method for any one is characterized in that in the above claim, and organic membrane-forming agent comprises at least a component based on following material:

Vinylformic acid-polyester-polyurethane ester copolymer,

Vinylformic acid-polyester-polyurethane-styrol copolymer,

Acrylate,

Acrylate-methacrylic ester, optional area 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,

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

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

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

Polycarbonate-polyurethane,

Polyester-polyurethane,

Vinylbenzene,

Vinylbenzene-vinyl acetate between to for plastic,

Vinyl acetate between to for plastic,

Vinyl ester and/or

Vinyl ether.

8. the method for any one is characterized in that in the above claim, but the 30wt% at least of organic membrane-forming agent of adding is made up of the film forming thermoplastic resin.

9. the method for any one is characterized in that in the above claim, and the molecular weight of the synthetic resins of adding is 1,000 μ at least.

10. the method for any one is characterized in that in the above claim, and organic membrane-forming agent of adding is made up of 40wt% high-molecular weight polymer at least.

11. the method for any one is characterized in that in the above claim, the acid groups of synthetic resins is with ammonia, amine, for example, morpholine, dimethylethanolamine, diethylethanolamine or trolamine, and/or alkali metal compound such as sodium hydroxide come stabilization.

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

13. the method for any one in the above claim, it is characterized in that, waterborne compositions contains, in every kind of operating mode, at least a acyloxy silane, a kind of organoalkoxysilane, a kind of silane with at least one amino group is aminoalkyl group silane for example, 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 is glycidoxy silane for example, 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 are formed chemically corresponding to the siloxanes of above-mentioned silane.

14. the method for any one is characterized in that in the above claim, composition comprises at least a silane, is selected from:

Glycidoxyalkyl trialkoxysilanes,

The methacryloxy alkyltrialkoxysilaneand,

(trialkoxysilyl) alkyl-succsinic acid-silane,

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 and

Acetoxysilane.

15. the method for any one is characterized in that in the above claim, composition comprises at least a silane, is selected from:

3-glycidoxy propyl-triethoxysilicane,

The 3-glycidoxypropyltrime,hoxysilane,

3-methacryloxypropyl triethoxyl silane,

The 3-methacryloxypropyl trimethoxy silane,

3-(triethoxysilyl) propyl group-succsinic acid-silane,

Aminoethyl aminopropyl methyldiethoxysilane,

Aminoethyl aminopropyl methyl dimethoxysilane,

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

β-(3, the 4-epoxycyclohexyl) ethyl trimethoxy silane,

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) diethylenetriamine,

N-(γ-trimethoxy-silylpropyl) diethylenetriamine,

N-(γ-triethoxysilylpropyltetrasulfide) dimethylene triamine,

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

Poly-(aminoalkyl) ethyl dialkoxy silicane,

Poly-(aminoalkyl) methyl dialkoxy silicane,

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

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

Vinyltriacetoxy silane.

16. the method for any one is characterized in that in the above claim, this at least a silane in waterborne compositions comprises the reaction product that is generated by it, content preferably between 0.1～50g/l.

17. the method for any one in the above claim, it is characterized in that, at least a metal chelator is selected from the sequestrant complex compound based on methyl ethyl diketone acid group, acetylacetic ester, acetone acid group, Alkylenediamine, amine, lactate, carboxylic acid, citrate and/or glycol, this at least a sequestrant wherein, comprising may be by the reaction product of their generations, and the content in waterborne compositions is preferably between 0.1～80g/l.

18. the method for any one is characterized in that in the above claim, at least a metal chelator of selection based on:

The methyl ethyl diketone acid group,

Alkali metal lactate,

Alkanolamine,

Alkyl etheric acid root,

Alkylenediamine tetrem acid group,

DL-Lactic acid ammonium salt,

Citrate,

The dialkyl group citrate,

Dialkyl-citrate,

Two alkylene triamine,

The acetylacetic ester of the two alkyl of two different alkoxyl groups,

The two alkyl acetylacetic esters of diisopropoxy,

Two-just-alkoxyl group-two alkyl acetylacetic esters,

Hydroxy alkylidene ethylenediamine triacetic acid root,

Trialkanolamine and/or

Three alkylidene group tetramines.

19. the method for any one is characterized in that in the above claim, the powder of fine dispersion, dispersion or suspensoid, for example, carbonate, oxide compound, silicate or vitriol, particularly colloid and/or amorphous granular add as the mineral compound of particle form.

20. the method for any one is characterized in that in the above claim, 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.

21. the method for any one is characterized in that in the above claim, based on aluminum oxide, barium sulfate, cerium dioxide, silicon-dioxide, silicate, titanium oxide, yttrium oxide, zinc oxide and/or zirconic particle, adds as the particle form mineral compound.

22. the method for any one is characterized in that in the above claim, waterborne compositions comprises at least a particle form mineral compound of 0.1～500g/l.

23. the method for any one in the above claim, it is characterized in that, waterborne compositions contains at least a organic inhibitor, particularly based on amine, the long-chain alkanolamine of preferred at least a alkanolamine-preferably, the complex compound of at least a TPA-amine, for example, butyric ester-4-the ethyl morpholine of acid affixture-4-oxo 4-p-methylphenyl, at least a alkylamino ethanol, the zinc salt of 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 metal-salt of dodecyl-naphthene sulfonic acid, at least a toluene propionic acid, the amino of 2-sulfydryl-benzothiazolyl-succsinic acid and transition metal complex or at least a its ammonium salt, 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%.

24. the method for any one in the above claim, it is characterized in that, waterborne compositions contains at least a alkaline linking agent, based on titanium, hafnium and/or zirconium as positively charged ion and/or based on carbonate or volatile salt as negatively charged ion, wherein the content of this kind linking agent in waterborne compositions is preferably between 0.01～3wt%.

25. the method for any one is characterized in that in the above claim, does not add mineral acid and/or organic carboxyl acid in waterborne compositions.

26. the method for any one in the above claim, it is characterized in that, at least a glycol that is selected from, for example, the segmented copolymer of oxyethane and propylene oxide, butyleneglycol, propylene glycol and/or decanediol, butyl glycol (Butyl glycol), butyldiglycol, ester-alcohol, ethylene glycol, glycol ether, glycol ethers as two-and triethylene glycol and single-and diether and dme, polyethers, polyoxyethylene glycol, polyglycol ether, polyglycol, polypropylene glycol, propylene glycol, propylene glycol, polypropylene glycol ether, glycol ethers, the diisobutyrate of neopentyl glycol and the long-chain alcohol of derivative thereof, be used as film coalescence aid, wherein the content of long-chain alcohol in waterborne compositions is preferably between 0.01～10wt%.

27. the method for any one in the above claim, it is characterized in that at least a paraffin, polyethylene and the polyacrylic wax of being selected from, particularly a kind of oxidized petroleum waves, be used as lubricant, wherein the content of wax in waterborne compositions is preferably between the scope from 0.01～5wt%.

28. the method for any one is characterized in that in the above claim, at least a wax is used as lubricant together with containing ethene and polymerizing acrylic acid thing mixture and/or multipolymer.

29. the method for any one is characterized in that in the above claim, coating layer portion ground also partly reaches curing by photochemidal activity radiation, cationoid polymerisation and/or heat cross-linking by dry and film forming.

30. the method for any one is characterized in that in the above claim, waterborne compositions comprises at least a additive, the particularly at least a additive that is selected from least a biocides, at least a defoamer and/or at least a wetting agent.

31. the method for any one is characterized in that in the above claim, waterborne compositions is applied on the metallic surface 5～50 ℃ temperature.

32. the method for any one is characterized in that in the above claim, the metallic surface maintains 5～60 ℃ temperature during coating applies.

33. the method for any one is characterized in that in the above claim, the circulating air temperature of the metallic surface of coating temperature between 20～400 ℃ is carried out drying.

34. the method for any one is characterized in that in the above claim, the strip coil coiled coiled material of coating is randomly after the temperature that is cooled to 40～70 ℃ of scopes.

35. the method for any one is characterized in that in the above claim, waterborne compositions applies by roller coat, overflow, scraper coating, spraying, spraying, brushing or dip-coating, and randomly uses roller floating subsequently.

36. the method for any one is characterized in that in the above claim, dry and randomly again the solidified film have the pendulum-rocker hardness of 30～190s, adopt K nig pendulum hardness tester to measure according to DIN 53157.

37. the method for any one in the above claim, it is characterized in that, dry and randomly again the solidified film have certain flexibility, so that basically according to DIN ISO 6860 about the shaft rod bending test of 3.2mm～38mm diameter mandrel rod in after the bending of taper mandrel rod-but must not the tear test zone-less than the long above crackle formation of 2mm, these crackles can be wetting with copper sulfate subsequently, be deposited on the cracking metallic surface of exposing by copper due to variable color detect.

38. the method for any one in the above claim, it is characterized in that, in each case, be selected from printing-ink, paper tinsel, spray paint, be applied to this drying and randomly again on the solidified film as at least one coating of the material that sprays paint, powder paints, tackiness agent and/or adhesive carrier.

39. the method for any one in the above claim, it is characterized in that the metallic element of coating, band or strip sections stand to be shaped, and spray paint, be coated with polymkeric substance, for example, PVC, printing, gluing, hot soldering, welding and/or by clamping or other interconnection technique is connected to each other perhaps is connected on other element.

40. one kind is used for before further coating the metallic surface pre-treatment, perhaps the waterborne compositions that this surface treatment is used is characterized in that, said composition comprises, except water,

A) silane of at least a hydrolyzable and/or hydrolysis at least in part and

B) at least a metal chelator,

41. the waterborne compositions of claim 40 is characterized in that said composition also comprises,

C) at least a organic membrane-forming agent, it comprises the organic polymer and/or the multipolymer of at least a water-soluble or water-dispersion, and its acid number is between 3～250, and

D) Ren Xuan at least a long-chain alcohol is as film coalescence aid.

42. the waterborne compositions of claim 40 or 41 is characterized in that, said composition also comprises at least a particle form mineral compound.

43. according to one of at least method substrates coated in the middle of the above claim 1～39 as the application of following article: wire rod, band, sheet metal or rolling component wiry, the flower twisted wire, steel band, metal sheet, lining, wire cloth, motorcar body or its component, or motor vehicle, trailer, the component of mobile house or guided missile, lid, cover, lamp, lamp (light), the traffic signals modulation element, furniture or furnishing elements, the household electrical appliance component, frame, section bar, the shaping component of complicated shape, crash barrier, well heater or hedge element, collision bumper, component with at least one pipe and/or section bar, window, door or bicycle frame or item of hardware, for example, screw, nut, flange, spring, or spectacle-frame.