CN100554509C - Use the method for itaconic acid homopolymers or multipolymer passivating metallic surfaces - Google Patents

Use the method for itaconic acid homopolymers or multipolymer passivating metallic surfaces Download PDF

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CN100554509C
CN100554509C CNB2005800280976A CN200580028097A CN100554509C CN 100554509 C CN100554509 C CN 100554509C CN B2005800280976 A CNB2005800280976 A CN B2005800280976A CN 200580028097 A CN200580028097 A CN 200580028097A CN 100554509 C CN100554509 C CN 100554509C
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multipolymer
acid
methylene
water
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CN101006201A (en
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F·克利佩尔
M·克卢格莱恩
G·舍尔尼科
A·格特里齐
F·迪奇
H·维特勒
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BASF SE
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/82—After-treatment
    • C23C22/83—Chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/08—Anti-corrosive paints
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/07—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing phosphates
    • C23C22/08—Orthophosphates
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/48—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 not containing phosphates, hexavalent chromium compounds, fluorides or complex fluorides, molybdates, tungstates, vanadates or oxalates
    • C23C22/53—Treatment of zinc or alloys based thereon
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/48—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 not containing phosphates, hexavalent chromium compounds, fluorides or complex fluorides, molybdates, tungstates, vanadates or oxalates
    • C23C22/56—Treatment of aluminium or alloys based thereon
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/78—Pretreatment of the material to be coated

Abstract

The present invention relates to a kind of by make the method for its passivation with the acidic aqueous solution-treated metallic surface of containing at least a itaconic acid homopolymers or multipolymer.The invention still further relates to can be by the passivation layer and the metallic surface of the inventive method acquisition.

Description

Use the method for itaconic acid homopolymers or multipolymer passivating metallic surfaces
The present invention relates to a kind of by make the method for its passivation with the acidic aqueous preparation process metal surfaces that comprises at least a itaconic acid homopolymers or multipolymer.The invention still further relates to can be by the passivation layer and the metallic surface of this method acquisition.
The anti-corrosive treatment of modern metallic substance is carried out in multistage operations usually, and the metallic surface of handling is contained many different layers usually.
The anti-corrosion protection of metal parts has important economic implications.Simultaneously, also more and more stricter to the requirement of anti-corrosion protection.An one example is that present newer vehicle is all assured the antirust perforation phase up to 12 years.
In the equal anti-corrosive treatment of aluminium surface and galvanized metal surfaces particularly importantly of technology and economic aspect, described galvanized metal is the iron and the steel of the zinc-plated or galvanizing of electrochemistry especially.The anti-corrosion protection that zinc provides is based on such fact, and promptly zinc is than the stronger and first thus corrosion zinc of the own alkalescence of metallic substance itself.Itself is kept perfectly metallic substance, as long as it is still by zinc layer covering continuously.
In the presence of atmosphericoxygen, at first form thin oxide layer on zinc or zinc alloy, the aluminum or aluminum alloy surface and delay more or less according to external conditions to below corrosion of metal corrode.
In order to strengthen the provide protection of this oxide skin, usually extra Passivation Treatment is carried out on the aluminum and zinc surface.In this treating processes, make part dissolving metal to be protected and mix again immediately in the oxide film on the metallic surface.This film is similar with the oxide film that exists in any case, but provides higher protection.It is commonly referred to as passivation layer.In many cases, it has also improved the adhesivity that is coated to the enamelled coating on the metal.Therefore use term " conversion coating " to replace term " passivation layer " with the free burial ground for the destitute usually, also use term " pretreatment layer " or " aftertreatment layer " sometimes according to the position of this processing in manufacturing processed.Passivation layer relatively approaches and has usually and is no more than 3 microns thickness.
In order to strengthen anti-corrosion protection, on passivation layer, apply extra (lacquer) layer usually.This system generally includes the combination of the two-layer or more multi-layered enamelled coating that is used for different purposes separately.They are used to protect passivation layer and metal to resist corrosive gases and/or liquid and to resist physical abuse, and for example aggregate chips also is used for purposes attractive in appearance certainly.Enamelled coating usually than the passivation bed thickness many.Typical thickness is 5 microns to 400 microns.
Passivation can be used for permanent anti-corrosion protection or only is used for interim anti-corrosion protection.Temporary protection only is used for the storage of metal sheet or other metal works or transportation and removes in final first being processed.
So far usually by using CrO 3Acidic aqueous solution handle the workpiece need protection and obtain zinc or the lip-deep passivation layer of aluminium.The mechanism of this passivation is complicated.It comprises that metallic zinc or aluminium are from surface dissolution and respectively with amorphous zinc-chromated oxide or aluminium-chromated oxide form redeposition.But these layers can also comprise from the foreign ion of treatment soln and/or other composition.Under situation about handling, can not get rid of a certain amount of Cr (VI) and mix passivation layer especially with chromic acid.
For fear of with carcinogenic Cr (VI) solution-treated, proposed with acid Cr (III) aqueous solution process metal surfaces.As an example, can be referring to US 4,384,902 or WO/40208.Yet increasing customer requirement uses up completely without the method for chromium and carries out passivation on the market.For fear of using Cr (VI) and Cr (III), the use of polymkeric substance is more and more important.
DE-A 195 16 765 discloses the Chrome-free and the no fluoride method of the conversion coating that is used to make Zn or Al metallic surface.The acidic solution that is used for passivation comprises water-soluble polymers, phosphoric acid and aluminum chelate.Perhaps, also can use (methyl) polymerizing acrylic acid thing and multipolymer.
DE-A 197 54 108 discloses the chromium-free waterborne corrosion resistant composition of the hexafluoro-negatively charged ion, vanadium ion, cobalt ion and the phosphoric acid that comprise Ti (IV) and/or Zr (IV).Perhaps, also can add various film-forming polymers, comprise carboxylic multipolymer, for example vinylformic acid/maleic acid.
JP-A 2001-164377 discloses the production of the blackplate that the black shell of Production Example such as consumption electronic product uses.With the lacquer metallic sheet that contains metal ion, water-soluble polymers, aqueous polymer dispersion and acid.An embodiment mentions the water-soluble polymers of 70% vinylformic acid and 30% methylene-succinic acid.The document is not openly used the itaconic acid copolymer passive metal.
JP-A 2001-158969 discloses and has been used for the metallic surface, the setting coat that contains 50% to 98 weight % aqueous polymer dispersion, metal ion, water-soluble polymers and acid of the metallic surface of particularly described black shell.An embodiment mentions the water-soluble polymers of 70% vinylformic acid and 30% methylene-succinic acid.The document is not openly used the itaconic acid copolymer passive metal.
JP-A 2003-027202 discloses a kind of method of using the compositions-treated steel plate galvanized that is made of metallic compound, water-soluble organic resin and acid.This polymkeric substance can especially comprise by carboxylic monomer and other carboxylic monomer or contain the multipolymer that the monomer of OH forms.Embodiment mentions the multipolymer of 70% vinylformic acid and 30% methylene-succinic acid.The document does not point out how to prepare this polymkeric substance fully.
Our present unexposed application DE 103 53 845 (unexposed when the priority date of this specification sheets) discloses the method for using 50 weight % to 99.9 weight % (methyl) vinylformic acid, 0.1 weight % to 50 weight % to comprise the acidic comonomer of ethylenically unsaturated dicarboxylic and choosing the multipolymer passivating metallic surfaces of 0 other comonomer of weight % to 30 weight % wantonly.Dicarboxylic acid can for example be a methylene-succinic acid.But the document is not pointed out the concrete preparation method of polymerization of itaconic acid thing fully.
Except realizing extraordinary anti-corrosion protection, deactivation method, particularly Chrome-free method also need to meet a series of technical requirementss.
Can be immersed in by the workpiece that will need passivation and carry out passivation in the passivating dip.Workpiece in bulk (for example screw) can place the cylinder that is used for this purpose, and with this cylinder dipping.Big workpiece also can be installed on the suitable frame, and with this framework dipping.Use pickling process, the technician relatively freely determines the duration of contact between passivating dip and the workpiece, and so even can obtain quite thick passivation layer.Duration of contact can be in minute rank.When this technology of use, the complicated workpiece of assembling earlier for example, welds together zinc-plated as a whole then and passivation from steel part usually.
In order to make plate-shape metal workpiece, for example trolley part, car body component, instrument case, elevation of building coating, top ceiling or window profiled material, for example, by suitable technology, for example punching, boring, folding, die mould and/or deep-draw are with sheet metal forming.If suitable, the big parts of assembling motor-vehicle bodies and so on by many single parts are welded together.Its starting material generally include long metal strip, and it is made by the rolling metal and in order to store and transport the form that is known as " volume " that is rolled into.
The industrial zinc-plated and passivation of in continuous device, carrying out these metal strips.For zinc-plated, at first, make the metal strip operation by galvanizing rig, for example the fused zinc groove by further passivation device, for example remains groove then, or rinsing device.Usually, carry out further procedure of processing continuously: for example clean or rinse step, or passivation layer is applied first enamelled coating.The metal strip operation is 50 to 100 meters/minute by the typical rate of continuous device.This means that metallic surface and passivation are short with the duration of contact between the preparation.Usually only there is the time of several seconds to be used for handling.Therefore, even industrial suitable method also must can provide gratifying result under short contacting time.
Therefore; the purpose of this invention is to provide the improved of a kind of metallic surface that is used for passivation zinc, zinc alloy, aluminum or aluminum alloy; the method of preferred Chrome-free, it compared with prior art provides improved anti-corrosion protection and wherein only needs metallic surface and passivation just can realize still gratifying result with the short contacting time between the preparation.Especially, also should implement this method continuously.
Therefore the present invention provides a kind of method of passivating metallic surfaces, wherein handles described surface with the acidic aqueous preparation that contains at least a water-soluble itaconic acid homopolymers or multipolymer, and this polymkeric substance is made of following monomer units:
(A) methylene-succinic acid of 0.1 weight % to 100 weight %,
(B) at least a monoethylenically unsaturated monocarboxylic of 0 weight % to 99.9 weight % and
(C) 0 weight % to 40 weight % at least a is except that (A) with other ethylenically unsaturated monomer (B), and it contains acidic group,
And/or
(D) 0 weight % to 30 weight % at least a be except that (A), (B) with other ethylenically unsaturated monomer (C),
Amount under every kind of situation is all based on all monomeric total amounts of incorporating in the multipolymer,
Wherein multipolymer can obtain by radical polymerization in being lower than 120 ℃ aqueous solution.
In a preferred embodiment of the invention, the metallic surface is the surface of metal strip, further preferably, carries out passivation by continuous processing.
The present invention also provides can also provide the metallic surface of containing this passivation layer by the passivation layer on the metallic surface of this method acquisition.
Be surprised to find that, and use known polymer, for example compare during vinylformic acid-maleic acid, use the polymerization of itaconic acid thing obviously more corrosion-resistant by the metallic surface that the inventive method obtains.Especially unexpectedly, show than the much better anticorrosive provide protection of synthetic itaconic acid copolymer under higher temperature being lower than 120 ℃ of synthetic itaconic acid copolymers among the present invention.
Vinylformic acid-itaconic acid copolymer manufactured according to the present invention is compared with vinylformic acid-maleic acid and is produced obvious improved passivation.Itaconic acid copolymer has the residual monomer content lower than corresponding maleic acid.By replacing toxilic acid with methylene-succinic acid, can in polymkeric substance of the present invention, obtain higher dicarboxylic acid content, this is of value to inactivating performance equally.
Detailed Description Of The Invention is as follows:
Can pass through the metallic surface of the inventive method passivation particularly including lowpriced metal surface.Described surface can be the surface of iron, steel, zinc, zinc alloy, aluminum or aluminum alloy for example.
The inventive method is specially adapted to the metallic surface of passivation zinc, zinc alloy, aluminum or aluminum alloy.These can be the structure that is made of described metal or alloy fully or the surface of workpiece.Perhaps, they can be that structure can be made of other material with the surface of the structure of zinc, zinc alloy, aluminum or aluminum alloy coating: for example, and other metal, alloy, polymkeric substance or matrix material.Described surface can be the surface of galvanized iron or steel especially.In a specific embodiments of this method, it is the surface of the steel of the surface of metal strip, particularly electrogalvanizing or galvanizing.
Zinc alloy or aluminium alloy are known to the skilled.The technician is according to the type and the amount of required final application choice alloying constituent.The typical composition of zinc alloy that is used for hot dipping method is particularly including Al, Pb, Si, Mg, Sn, Cu or Cd.The zinc alloy of electrolytic deposition generally includes Fe, Co, Ni or Mn.The typical composition of aluminium alloy is particularly including Mg, Mn, Si, Zn, Cr, Zr, Cu or Ti.Described alloy can also be the Al/Zn alloy, and wherein Al and Zn exist with about equally amount.The steel that scribbles these alloys is commercially available.
Passivation comprises one or more with preparation and contains the methylene-succinic acid unit, and if ticket olefinic unsaturated monocarboxylic and optional other monomer as the homopolymer and/or the multipolymer of structural unit.
Used polymkeric substance is water-soluble or water dispersible at least.For the present invention, term " water-soluble " is intended to show that used multipolymer should be evenly water-soluble.Term " water dispersible " is meant, although solution is not limpid fully, the polymkeric substance uniform distribution therein and do not have a sedimentation.Preferred water miscible polymkeric substance.
Used multipolymer preferably should be unlimited molten mixed with water, even all absolute necessary under this not all situation.But the water-soluble of them must reach the degree that can carry out passivation by the present invention at least.
Usually, used multipolymer should have at least 50 grams per liters, preferred 100 grams per liters, the more preferably solubleness of at least 200 grams per liters.
The technician in water-soluble polymers field will appreciate that the solubleness of polymkeric substance in water that contains COOH depends on the pH value.Therefore, selected reference point all is the required pH value of specific final application in each case.May under another pH value, have enough solubleness at the multipolymer that has under the pH value estimating the insufficient solubleness of purposes.
Be used to prepare homopolymer used according to the invention or the monomer of multipolymer (A) is a methylene-succinic acid:
Figure C20058002809700081
Methylene-succinic acid also can use with its salt form: for example, and as alkali metal salts or ammonium salt.In addition, can also use the derivatives from itaconic acid that in the aqueous solution, is hydrolyzed into methylene-succinic acid easily, for example corresponding acid anhydride, monoesters or diester or acid amides.Recognize, also can use the mixture of these derivatives.
Polymkeric substance used according to the invention can be the homopolymer of methylene-succinic acid, or preferred copolymer.
The amount of methylene-succinic acid in polymkeric substance is 0.1 weight % to 100 weight %, preferred 10 weight % to 50 weight %, more preferably 15 weight % to 45 weight %, very preferably 20 weight % to 40 weight %, 25 weight % to 35 weight % for example, this numeral is based on all monomeric summations in the polymkeric substance.
Polymkeric substance used according to the invention can also contain one or more monomers (B) of maximum 99.9 weight %.They are monoethylenically unsaturated monocarboxylics.
The example of suitable monoethylenically unsaturated monocarboxylic (B) comprises the C of vinylformic acid, methacrylic acid, Ba Dousuan, vinylacetic acid or monoethylenically unsaturated dicarboxylic acid 1-C 4Monoesters.Preferred monomers is vinylformic acid and methacrylic acid, preferred especially vinylformic acid.
Recognize, also can use the mixture of two or more different monoethylenically unsaturated monocarboxylics.
The amount of all monomers (B) is total up to preferred 50 weight % to 90 weight %, more preferably 55 weight % to 85 weight %, very preferably 60 weight % to 80 weight %, for example 65 weight % to 75 weight %.
Randomly, multipolymer of the present invention can also comprise at least a and (A) of 0 weight % to 40 weight % and (B) different other ethylenically unsaturated monomer (C).Monomer (C) contains at least one acidic group in each case.Particularly preferably, they all are that monoene belongs to monomer in each case.Monomer (C) is a free redical polymerization.
Monomer (C) can for example be the monomer (C2) of carboxylic monomer (C1), phosphoric acid group and/or phosphonyl group or the monomer (C3) that contains sulfonic acid group.
Monomer (C) can also use with its salt form: for example, and as alkali metal salts or ammonium salt.In addition, can also use the derivative that in the aqueous solution, is hydrolyzed into the monomer (C) of free acid easily, for example acid anhydride, monoesters or diester or acid amides.Recognize, also can use the mixture of these derivatives.
The example of carboxylic monomer (C1) particularly including, ethylenically unsaturated dicarboxylic, for example toxilic acid, methylfumaric acid, citraconic acid, fumaric acid or methylene radical propanedioic acid.Preferred monomers (C1) is toxilic acid and/or maleic anhydride.
The example of suitable monomers (C2) comprises vinyl phosphonate, the mono phosphoric acid ester vinyl ester, the allyl group phosphonic acids, the mono phosphoric acid ester allyl ester, 3-butenyl phosphonic acids, mono phosphoric acid ester-3-butenyl esters, mono phosphoric acid ester (4-vinyloxy group butyl) ester, vinylformic acid phosphonato ethyl ester, methacrylic acid phosphonato ethyl ester, mono phosphoric acid ester (2-hydroxyl-3-vinyloxy group propyl group) ester, mono phosphoric acid ester (1-phosphonato methyl-2-vinyloxy group ethyl) ester, mono phosphoric acid ester (3-allyloxy-2-hydroxypropyl) ester, mono phosphoric acid ester (2-allyloxy-1-phosphonato methylethyl) ester, 2-hydroxyl-4-vinyloxy group methyl isophthalic acid, 3,2-two oxa-phosphuranes and 2-hydroxyl-4-allyloxy methyl isophthalic acid, 3,2-two oxa-phosphuranes.Can also use monomeric salt and/or ester, the especially C of phosphoric acid and/or phosphonyl group 1To C 8If monoalkyl, dialkyl group and suitable trialkyl ester.
A kind of preferred monomer (C2) is vinyl phosphonate or its hydrolyzable ester.
The example that contains the monomer (C3) of sulfonic acid group comprises allyl sulphonic acid, methallylsulfonic acid, styrene sulfonate, vinyl sulfonic acid, allyloxy Phenylsulfonic acid or 2-acrylamido-2-methyl propane sulfonic acid, 2-(methacryloyl) ethylsulfonic acid and their an alkali metal salt.
Recognize, also can use the mixture of two or more different monomers (C).The preferred monomer (C2) that uses carboxylic monomer (C1) and phosphoric acid group and/or phosphonyl group.
If there is monomer (C), their amount is preferred 0.1 weight % to 20 weight %, more preferably 0.2 weight % to 15 weight %, very preferably 0.5 weight % to 10 weight % altogether.
If monomer (C) comprises the monomer of phosphoric acid group and/or phosphonyl group, vinyl phosphonate particularly, then verified is that appropriate vol is 5 weight % to 40 weight %, preferred 10 weight % to 30 weight %, more preferably 12 weight % to 28 weight %, very preferably 20 weight % to 25 weight %.
In addition, randomly, this multipolymer can contain at least a and (A), (B) of 0 weight % to 30 weight % and (C) ethylenically unsaturated monomer of other different free redical polymerizations (D).In addition, do not re-use other monomer.
Monomer (D) is used to finely tune the character of multipolymer.They are selected according to required multipolymer character by the technician.Monomer (D) also is a free redical polymerization.
Preferably, they also are that monoene belongs to unsaturated monomer.Yet under specific circumstances, can also use the monomer that contains two or more polymerizable groups on a small quantity.This can make this public affairs polymers be cross-linked to small degree.
The example of monomer (D) comprises (methyl) acrylic acid C 1To C 8Alkyl ester or C 1To C 4Hydroxyalkyl acrylate, for example (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) propyl acrylate, (methyl) isopropyl acrylate, (methyl) butyl acrylate, (methyl) Ethyl acrylate, (methyl) 2-EHA, (methyl) Hydroxyethyl acrylate, (methyl) Propylene glycol monoacrylate or butane-1,4-glycol mono acrylic ester.Pure composition in (methyl) acrylate also can be an alcohol alcoxylates.Can mention the alkoxylate C that contains 2 to 80 mole ethylene oxides, propylene oxide, oxybutylene or its mixture especially at this 1To C 18Alcohol.The example of these alkoxylated polymerization products comprises polyoxyethylene glycol (methyl) methyl acrylate or the C that reacts with 3,5,7,10 or 30 mole ethylene oxides 13/ C 15(methyl) acrylate of oxo alcohol, and/or their mixture, (methyl) vinylbenzene, maleimide, N-alkyl maleimide, toxilic acid monoamide or toxilic acid monoesters.
What be fit to equally is vinyl or allyl ethers, for example, methylvinylether, ethyl vinyl ether, propyl vinyl ether, IVE, 2-ethylhexyl vinyl ether, vinyl cyclohexyl ether, vinyl 4-hydroxyl butyl ether, decave, dodecyl vinyl, octadecyl vinyl ether, 2-(diethylamino) ethyl vinyl ether, 2-(di-n-butyl amino) ethyl vinyl ether or methyl glycol ether vinyl ether and corresponding allylic cpd.Can also use vinyl ester, for example vinyl-acetic ester or propionate.
The monomeric example of alkalescence comprises acrylamide and AAM, for example acrylamide, Methacrylamide, N tert butyl acrylamide or N-methyl (methyl) acrylamide.Can use the alkaline monomer of 1-vinyl imidazole and N-vinyl pyrrolidone and so in addition.
The example of cross-linking monomer comprises the molecule that contains two or more ethylenically unsaturated groups, two (methyl) acrylate for example, for example two (methyl) vinylformic acid glycol ester or butane-1,4-glycol two (methyl) acrylate; Or poly-(methyl) acrylate, for example trimethylolpropane tris (methyl) acrylate; Or two (methyl) acrylate of oligo alkylene glycols or polyalkylene glycol, for example two, three or TEG two (methyl) acrylate.Other example comprises (methyl) vinyl acrylate or butyleneglycol divinyl ether.
Recognize, can also use the mixture of different monomers (D).The total amount of used all monomers (D) is 0 weight % to 30 weight % based on all used monomer total amounts of present method.Preferably, this amount is 0 weight % to 20 weight %, more preferably 0 weight % to 15 weight %, very preferably 0 weight % to 10 weight %.If there is cross-linking monomer (D), its amount should be no more than 5 weight % based on all used monomer total amounts of present method, preferred 2 weight % usually.This amount can for example be 10ppm to 1 weight %.
The technician selects used monomeric property quality and quantity according to required passivation.When doing like this, the technician will consider that polymkeric substance is water-soluble or the fact of water dispersible.Therefore, those skilled in the art only use with the amount that can not produce negative effect and may damage the water miscible monomer of polymkeric substance.
Special preferably approximately 25 weight % to 30 weight % methylene-succinic acids and the acrylic acid multipolymer of about 70 weight % to 75 weight %, particularly about 26 weight % to 28 weight % methylene-succinic acids and the acrylic acid multipolymer of about 72 weight % to 74 weight %.
In addition, the terpolymer of special preferably approximately 23 weight % to 30 weight % methylene-succinic acids, about 67 weight % to 75 weight % vinylformic acid and about 0.1 weight % to 10 weight % vinyl phosphonate, the terpolymer of particularly about 25 weight % to 27 weight % methylene-succinic acids, about 68 weight % to 70 weight % vinylformic acid and about 3 weight % to 5 weight % vinyl phosphonates.
In another embodiment of the present invention, verified suitable is, the terpolymer of about 10 weight % to 30 weight % methylene-succinic acids, about 50 weight % to 70 weight % vinylformic acid and about 10 weight % to 30 weight % vinyl phosphonates, the terpolymer of particularly about 15 weight % to 25 weight % methylene-succinic acids, about 55 weight % to 65 weight % vinylformic acid and about 15 weight % to 25 weight % vinyl phosphonates.
Make the radical polymerization in aqueous solution of used monomer.
Term " water-based " is meant that solvent for use or thinner contain water as its main component.Yet, outside dewatering, can also have water miscibility organic solvent composition.This may be that the solvability of improvement some monomer, particularly monomer (D) in reaction medium is necessary.
Therefore, solvent for use or thinner contain the water of the 50 weight % that account for the solvent total amount at least.In addition, can also use one or more water miscibility solvents.Can mention alcohol especially at this, the example is single alcohol, for example ethanol, propyl alcohol or Virahol; Glycol, for example ethylene glycol, Diethylene Glycol or polyalkylene glycol or their derivative.Preferred alcohol is propyl alcohol and Virahol.Water-content is preferably at least 70 weight %, more preferably at least 80 weight %, very preferably at least 90 weight %.Very particularly preferably only make water.
Be known to the skilled on the implementation principle of free radical addition polymerization.
The suitable polymerization starter of preferred use causes the free radical addition polymerization.Yet perhaps it can also for example cause by suitable radiation.Radical initiator should dissolve in the reaction solvent, and is preferably water miscible.
In heat-activatable polymerization starter, preferred decomposition temperature is 30 to 150 ℃, particularly 50 to 120 ℃ initiator.This temperature value is usually directed to 10 hour transformation period.
As initiator, can use all compounds that under polymerizing condition, resolve into free radical, for example, inorganic peroxy compounds, for example peroxidation dithionate, especially peroxidation two ammonium sulfate, potassium persulphate, preferred peroxidation two sodium sulfate, the sulfuric peroxide hydrochlorate, hydroperoxide, percarbonate and hydrogen peroxide and the material that is known as redox initiator.The preferred water soluble starter that uses.In some cases, the mixture that uses different initiators is favourable, for example the mixture of hydrogen peroxide and peroxidation two sodium sulfate or potassium persulphate.Can use the mixture of hydrogen peroxide and peroxidation two sodium sulfate with any required ratio.
Suitable organic peroxy compound is a diacetyl peroxide, di-t-butyl peroxide, the peroxidation diamyl, dioctanoyl peroxide, didecanoyl peroxide, dilauroyl peroxide, dibenzoyl peroxide, peroxidation two toluoyls, succinyl peroxide, t-butyl peroxy-acetate, tert butyl permaleic acid, t-butylperoxy isobutylate, cross the PIVALIC ACID CRUDE (25) tert-butyl ester, cross the sad tert-butyl ester, cross the neodecanoic acid tert-butyl ester, t-butylperoxyl benzoate, tert-butyl peroxide, t-butyl hydroperoxide (water-soluble), cumene hydroperoxide, cross-the 2 ethyl hexanoic acid tert-butyl ester and mistake diamino acid diisopropyl ester.
In addition, preferred initiator is an azo-compound.They dissolve in organic solvent, usually for example be 2,2 '-azo two (4-methoxyl group-2, the 4-methyl pentane nitrile), 2,2 '-azo two (2 Methylpropionic acid) dimethyl ester, 1,1 '-azo two (hexanaphthene-1-nitrile), 1-[(cyano group-1-methylethyl) azo] methane amide, 2,2 '-azo two (N-cyclohexyl-2-methyl propanamide), 2,2 '-azo two (2, the 4-methyl pentane nitrile), 2,2 '-azo two (2-methylbutyronitrile), 2,2 '-azo two [N-(2-propenyl)-2-methyl propanamide], 2,2 '-azo two (N-butyl-2-methyl propanamide).Yet, preferred their water solubles, usually for example be 2,2 '-azo two [2-(5-methyl-2-tetrahydroglyoxaline-2-yl) propane] dihydrochloride, 2,2 '-azo two [2-(2-tetrahydroglyoxaline-2-yl) propane] dithionate dihydrate, 2,2 '-azo two [N-(2-propyloic)-2-methyl-prop amidine] tetrahydrate, 2,2 '-azo two 2-[1-(2-hydroxyethyl)-2-tetrahydroglyoxaline-2-yl] and propane } dihydrochloride, 2,2 '-azo two { 2-methyl-N-[1,1-two (methylol)-2-hydroxyethyl] propionic acid amide, 2,2 '-azo two [2-methyl-N-(2-hydroxyethyl) propionic acid amide], 2,2 '-azo two [2-(2-tetrahydroglyoxaline-2-yl) propane] dihydrochloride, 2,2 '-azo two (2-methyl propanamide) dihydrochloride, 2, [2-(3,4 for 2 '-azo two, 5,6-tetrahydropyrimidine-2-yl) propane] dihydrochloride, 2,2 '-azo two [2-(2-tetrahydroglyoxaline-2-yl) propane], 2,2 '-azo two 2-methyl-N-[2-(1-hydroxyl butyl)] propionic acid amide }.
In addition, other preferred initiator is a redox initiator.Redox initiator comprise at least a above-mentioned peralcohol as oxidation component and for example comprise xitix, glucose, sorbose, ammonium or basic metal hydrosulphite, hydrosulphite, thiosulphate, hyposulfite (hyposulfite), pyrosulfite or sulfide or the methylol sodium hydrosulfite 90min as reduction components.As the reduction components in the redox catalyst, preferably use xitix or Sodium Pyrosulfite.With respect to used monomeric amount in the polymkeric substance, the amount of used reduction components for example is 1 * 10 in the redox catalyst -5To 1 mole of %.
Combine with initiator and/or redox initiator system, can also use transition-metal catalyst, for example the salt of iron, cobalt, nickel, copper, vanadium and manganese.The example of suitable salt comprises ferric sulfate (II), cobalt chloride (II), single nickel salt (II) and cupric chloride (I).The consumption of reductibility transition metal salt is generally 0.1 to 1000ppm based on the monomer total amount.Particularly advantageous combination is, for example combination of hydrogen peroxide and iron (II) salt is for example in each case based on the hydrogen peroxide of 0.5 weight % to 30 weight % of monomer total amount with based on 0.1 to 500ppm FeSO of monomer total amount 4* 7H 2The combination of O.
The example of suitable light trigger is phenyl methyl ketone, benzoin ether, benzyl dialkyl ketone and their derivative.Their soluble or water solubles hardly, but may be dissolved in alcohol, therefore can realize disperseing.
The preferred thermal initiator that uses, preferred water-soluble azo compounds and water-soluble peralcohol.Preferred especially inorganic peroxy compounds, especially hydrogen peroxide, particularly peroxidation two sodium sulfate or its mixture, optional and 0.1 to 500ppm FeSO 4* 7H 2The O combination.Especially preferred hydrogen peroxide.
Recognize, also can use the mixture of different initiators, prerequisite is that they can not have a negative impact each other.The technician determines amount according to required multipolymer.Usually use 0.05 weight % to 20 weight % based on all monomer total amounts, preferred 0.1 weight % to 15 weight %, the more preferably initiator of 0.2 weight % to 8 weight %.
In addition, can also use suitable conditioning agent, for example mercaptoethanol in known mode in principle.Preferably do not use conditioning agent.
Can also in the presence of alkali, carry out polymerization.Make monomeric acidic-group thus, particularly carboxyl neutralizes wholly or in part.
Available alkali for example comprises NaOH, KOH or NH 3Amine also is suitable.
The example of suitable amine comprises straight chain, ring-type and/or side chain C 1-C 8Single-, two-and trialkylamine, straight or branched C 1-C 8Single-, two-or trialkanolamine, especially single-, two-or trialkanolamine, straight or branched C 1-C 8Single-, two-or the straight or branched C of trialkanolamine 1-C 8Alkyl oxide, oligomeric amine and polyamine such as diethylenetriamine or polymine, heterocyclic amine such as morpholine, piperazine, imidazoles and piperidines, or some arylamine such as benzotriazole or tolyl-triazole.Amine also can alkoxyization, particularly ethoxylation.Can advantageously improve thus and have water-soluble than the amine of long alkyl chain.
The technician can carry out appropriate selection from these amine.
Preferred straight or branched C 1-C 8Single-, two-or trialkanolamine, preferred especially single-, two-and trolamine and/or corresponding ethoxylated product.
If use alkali, then degree of neutralization should be no more than 30 moles of % of monomeric all acidic-group total amounts usually.Preferably, degree of neutralization is no more than 20 moles of %, more preferably no more than 10 moles of %.
Very particularly preferably do not use alkali.
Alkali can before the polymerization or among add.Preferably, adding before the polymerization or when being not later than polymerization and beginning.Alkali can disposablely add, or adds in the corresponding period in maximum and entire reaction period.Alkali can add in the monomer feed.Preferably, alkali is included in the initial charge of polymerization before beginning.
According to the present invention, carry out polymerization being lower than under 120 ℃ the temperature.In addition, the technician can change this temperature according to the character and the required result of used monomer, initiator in wide limit.What determine in this article is about 60 ℃ minimum temperature.Can in polymerization process, keep steady temperature, or can distribute by controlled temperature.Polymerization temperature is preferably 75 to 115 ℃, and more preferably 80 to 110 ℃, preferred especially 90 to 108 ℃, very preferably 95 to 105 ℃.
Polymerization can be carried out in the device that is usually used in the free radical addition polymerization.When operating more than the boiling point at the mixture of water or water and other solvent, in suitable pressurized vessel, operate, otherwise operation can under atmospheric pressure be carried out.Polymerization is preferably under atmospheric pressure carried out.Polymerization can for example be carried out under refluxing.
About polymerization, confirm that usually suitable is to comprise methylene-succinic acid and/or its derivative in initial charge in aqueous solution.After this, equally suitably be metered into monocarboxylic acid and initiator in hydrotropisms's solution.Verified suitable feed time is 0.5 hour to 24 hours, preferred 1 hour to 12 hours.
Thus, make the concentration of reactive higher monocarboxylic acid in aqueous solution keep relatively low.This has reduced the trend of monocarboxylic acid and himself reaction and has made the methylene-succinic acid unit mix multipolymer more equably.When the optional monomer (C) that uses and/or (D) during sluggish, also advantageously they are included in the initial charge with methylene-succinic acid.Yet, recognize that they also can dropwise add subsequently.Add therein after all monomers, can also have for example 0.5 to 3 hour the afterreaction time.This guarantees that polyreaction carries out as far as possible fully.
The technician can certainly implement polymerization in another way.
The synthetic polymkeric substance can separate from aqueous solution by ordinary method known to the skilled: for example, and evaporating solns, spraying drying, lyophilize or precipitation.
Yet particularly preferably, the polymkeric substance after the polymerization does not separate from aqueous solution fully; But resulting polymers solution is directly used.
In order to make this directly further use easier, the amount of aqueous solvent should make the concentration of polymkeric substance in solvent be fit to this application when beginning.Verified specially suitable concentration is 15 weight % to 75 weight % based on all components total amount, preferred 20 weight % to 65 weight %, more preferably 25 weight % to 60 weight %, for example 45 weight % to 55 weight %.
Polymkeric substance of the present invention solvable can be dispersed in the water at least or water-content in the aequeous solvent mixture of at least 50 weight %, the technician will appreciate that the solubleness that is rich in the polymkeric substance of COOH can highly depend on the pH value.PH value when therefore being used for passivation with reference to polymkeric substance here, in other words, with reference to acidic solution, 0.5 to 6 pH scope particularly.Term " water dispersible " is meant, although solution is not limpid fully, still uniform distribution is therein and do not have a sedimentation for polymkeric substance.Described polymkeric substance is preferably water-soluble polymers.
The pH value of polymers soln preferably less than 4, is more preferably less than 3 usually less than 5.
The molecular weight M of multipolymer w(weight average) is 5000 to 2000000 gram/moles, preferably at least 10000 gram/moles, more preferably at least 15000 gram/moles.Usually, M wBe 20000 gram/moles to 1000000 gram/moles, preferred 30000 gram/moles are to 900000 gram/moles, more preferably 40000 gram/moles are to 800000 gram/moles, very preferably 50000 gram/moles are to 700000 gram/moles.It is determined according to required final application by the technician.
The preparation of polymkeric substance used according to the invention is acidic aqueous preparation.
Polymkeric substance of the present invention can be used in particular for process metal surfaces.For this reason, polymkeric substance of the present invention can be used as the component of corresponding preparaton especially: for example, and as the component of sanitising agent, pickle solution, corrosion control composition and/or passivation preparaton.
Multipolymer of the present invention can be particularly advantageous for passivating metallic surfaces or be used for forming passivation layer on metal.Usually use term " conversion coating " and also use term " pretreatment layer " to replace term " passivation layer " sometimes with the free burial ground for the destitute.Multipolymer of the present invention is specially adapted to chromium-free deactivation.
Can be by any metallic surface of polymer treatment of the present invention, particularly passivation.Yet preferred surface is low or the surface of the surface of high quality steel or zinc, zinc alloy, aluminum or aluminum alloy.These can be the structure that is made of described metal and/or alloy fully or the surface of workpiece.Perhaps they can be that structure can be made of other material with the surface of the structure of zinc, zinc alloy, aluminum or aluminum alloy coating, for example, and other metal, alloy, polymkeric substance or matrix material.Described surface can be the surface of galvanized iron or steel especially.In a specific embodiments of present method, it is the surface of the steel of the surface of metal strip, particularly electrogalvanizing or galvanizing.In a further preferred embodiment, described surface can be the body of a motor car surface.
Zinc alloy or aluminium alloy are known to the skilled.The technician is according to the type and the amount of required final application choice alloying constituent.The typical composition of zinc alloy that is used for hot dipping method is particularly including Al, Pb, Si, Mg, Sn, Cu or Cd.Exemplary alloy composition in the zinc alloy of electrolytic deposition is Ni, Fe, Co and Mn.The typical composition of aluminium alloy is particularly including Mg, Mn, Si, Zn, Cr, Zr, Cu or Ti.
Described alloy can also be the Al/Zn alloy, and wherein Al and Zn exist with about equally amount.The steel that scribbles these alloys is commercially available.
The solvent or the thinner that are used for multipolymer are water or the aequeous solvent mixture that contains at least 50 weight % water.If use aqueous mixture, this mixture preferably contain at least 65 weight %, more preferably at least 80 weight %, the very preferably water of at least 95 weight %.This tittle is all based on the total amount of all solvents in each case.Other composition of mixture can be the water miscibility solvent.Example comprises single alcohol as methyl alcohol, ethanol or propyl alcohol, higher alcohols such as ethylene glycol or polyether glycol, and ether alcohol such as butyl glycol or methoxypropanol.
Preferably only make water as solvent.
Copolymer concentration in the preparation is determined according to required final application by the technician.The thickness of passivation layer for example depends on selected Technology, but can also depend on the viscosity of the composition that is used for passivation.Generally speaking, verified suitable concentration is 0.01 grams per liter to 500 grams per liter, preferred 0.1 grams per liter to 200 grams per liter, more preferably 0.5 grams per liter to 5 grams per liter.Described concentration is based on the instant preparation.Usually, can at first prepare enriched material, make water or optional other solvent mixture only on the spot they are diluted to desired concn.
Preparation used according to the invention is a tart.It has 0.5 to 6 pH value usually, can be according to base material and mode of administration and the narrower pH scope of selection of time that exposes in preparation according to the surface.For example, for handling the aluminium surface, the pH value preferably is adjusted to 2 to 4 scope, under the situation of handling zinc or galvanized steel, preferably is adjusted to 1 to 5 scope.
On the one hand, polymkeric substance or the character of multipolymer and the pH value of concentration control preparation that can be by containing COOH, and therefore acquisition pH automatically.In this, should consider that because preparation, the COOH group in the polymkeric substance is neutralization wholly or in part in some cases.
As another selection, preparation can also comprise at least a organic or inorganic acid or its mixture.The example of suitable acid comprises the acid of phosphorus, sulphur or nitrogen such as phosphoric acid, phosphonic acids, sulfuric acid, sulfonic acid such as methylsulfonic acid, amido sulfonic acid, tosic acid, m-nitrobenzene sulfonic acid and derivative thereof, nitric acid, hydrofluoric acid, hydrochloric acid, formic acid or acetate.Acid is preferably selected from HNO 3, H 2SO 4, H 3PO 4, formic acid and acetate.Preferred especially H 3PO 4And/or HNO 3Recognize, also can use the mixture of different acid.
On the contrary, if suitable, also can use alkali to improve the pH value.
The phosphonic example comprises 1-hydroxyl ethane-1; 1-di 2 ethylhexyl phosphonic acid (HEDP), 2-phosphinylidyne butane-1; 2,4-tricarboxylic acid (PBTC), amino three (methylene phosphonic acids) (ATMP), ethylene diamine four (methylene phosphonic acid) (EDTMP) or diethylenetriamine five (methylene phosphonic acid) (DTPMP).
The character of acid and concentration are determined according to required final application and pH value by the technician in the preparation.Generally speaking, verified suitable concentration is 0.01 grams per liter to 30 grams per liter, preferred 0.05 grams per liter to 3 grams per liter, more preferably 0.1 grams per liter to 5 grams per liter.
Preparation can also be chosen other component that comprises except that described component wantonly.
The optional component that exists for example can be transition metal ion and transistion metal compound, for example ion of Ce, Ni, Co, V, Fe, Zn, Zr, Ca, Mn, Mo, W, Ti, Zr, Hf, Bi, Cr and/or lanthanon and compound.They can also be the compounds of main group element such as Si and/or Al.These compounds can use with the form of separately water complex.Yet they also can cooperate with other part, the fluoride complexes of Ti (IV), Zr (IV) or Si (IV) for example, or oxometallic acid root, for example MoO 4 2-Or WO 4 2-In addition, can also use and the typical title complex that forms the part of inner complex, for example ethylene diaminetetraacetic acid (EDTA), diethylene triaminepentaacetic acid(DTPA) (DTPA), hydroxy ethylene ethylenediamine triacetic acid (HEDTA), nitrilotriacetic acid(NTA) (NTA) or methylglycine oxalic acid (MGDA).
Other optional components comprises surface active cpd, inhibiter or typical electroplating additives.The technician is according to carrying out appropriate selection in feasible in principle optional components of required application and their amount.The particularly preferred inhibiter that can be used in combination with the polymerization of itaconic acid thing comprises benzotriazole and/or tolyl-triazole.
In order to finely tune its character, preparation can also comprise other water-soluble polymers as additional component.The example of these polymkeric substance is particularly including the polymkeric substance that contains carboxylate radical of the above-mentioned definition that does not only correspond to composition.The example that can mention comprises poly-(methyl) vinylformic acid and (methyl) vinylformic acid and other monomeric (being total to) polymkeric substance that contains acidic group, and other monomer for example is toxilic acid, fumaric acid, Ba Dousuan or vinylacetic acid.The amount of these extra multipolymers is determined according to the required character of passivation layer by the technician.Yet, the common not 30 weight % of used all amount of polymers of should exceed of amount, preferred 20 weight %, more preferably 10 weight %.
Described passivation is preferably the essentially chromium-free passivation.This is meant can only add the character of small additions of chromium compound with the fine setting passivation layer at most.Its amount is based on composition all components should exceed 2 weight % not, preferred 1 weight %, more preferably 0.5 weight %.If the use chromium cpd preferably should use Cr (III) compound.But in each case, it is so low so that the amount of the Cr on the passive metal (VI) is no more than 1 milligram/square metre that Cr (VI) content should keep.
Particularly preferably, passivation is a chromium-free deactivation; In other words, used preparation does not contain the Cr compound fully.Yet, the small additions of chromium that described " Chrome-free " is not precluded within this technology indirect and was not intended to originally bring into.In fact, if use the inventive method passivation to contain the alloy of chromium as alloying constituent, chrome-bearing steel for example, the small additions of chromium in the then pending metal always may be by this method formulations employed dissolving, and therefore itself by mistake enters preparation.Even using these metals and having under gained result's the situation, this method also still is regarded as " Chrome-free ".
In the method for passivating metallic surfaces of the present invention, with preparation by spraying, dip-coating or rolling process metal surfaces.After the dip-coating operation, can remove excessive treatment soln from workpiece by making excessive treatment soln drip-dry; Under the situation of metal sheet, tinsel or analogue, perhaps for example can remove excessive treatment soln by extruding or striking off.In treating processes, other component of used at least polymkeric substance and preparation is combined closely thereby produce between surface and component by the metallic surface chemisorption.Usually carry out under room temperature or higher temperature with the preparation processing, single this do not got rid of the possibility of lesser temps in principle.Usually, handle at 20 to 90 ℃, preferred 25 to 80 ℃, more preferably 30 to 60 ℃ are carried out.For this reason, can heat the bath that contains preparaton in the bath by thermometal is immersed in, but also can reach the temperature of rising automatically.
Can after handling, use scavenging solution, particularly remove the resistates of preparation used according to the invention to get on from the surface with the water rinse surface.
Processing can also be the processing that is known as no rinsing operation, wherein with treatment soln convection drying and do not carry out rinsing in drying oven immediately after it is used.
Can be discontinuously with preparation and linking agent process metal surfaces, or especially, carry out continuously.Continuous processing is specially adapted to handle metal strip.The metal strip operation is by preparation groove or preparation spray equipment, and optional groove or the spray equipment of passing through, and optional by other pre-treatment or after-treatment device.
Treatment time is determined according to required layer character, the composition that is used to handle and technology final condition by the technician.It can maybe can be two minutes or more of a specified duration far below one second.Under the situation of continuous processing, verified specially suitable be make the surface contact 1 to 60 second with preparation.
After handling, remove solvent for use.It can be at room temperature by removing at the air at room temperature single vaporization.
Perhaps, can be by suitable assist measure, for example by heating and/or making air-flow, particularly airflow come secondary solvent to remove by treat surface.Can be for example by the IR projector or, or for example by dry auxiliary-solvent evaporation in drying tunnel.For dry, verified suitable temperature is 30 ℃ to 160 ℃, preferred 40 ℃ to 100 ℃, and more preferably 50 ℃ to 80 ℃.This is meant the temperature of metallic surface; Must set higher dryer temperature, it is suitably selected by the technician.
The inventive method is chosen wantonly and is comprised one or more pre-treatment step.For example, before passivation, can be with preparation clean metal surface used according to the invention for example to remove grease or oil.Can also be before passivation pickled surface to remove oxidate, dirt, interim anti-corrosion protection and analogue.If suitably, also additionally need be these pre-treatment step after and between use the water rinse surface, the resistates of removal rinsing solution or Acidwash solution.
Passivation layer can also be crosslinked.For this reason, for example linking agent can be sneaked into used preparation, prerequisite is that described linking agent can not react in preparation.Perhaps at first handle metal, handle this layer with suitable crosslinking agent then, for example spray this layer with cross-linking agent solution with preparation.
Suitable crosslinking agent should be for water-soluble or dissolve in above-mentioned aequeous solvent mixture at least.The example of suitable crosslinking agent is particularly including containing at least two those linking agents that are selected from the crosslinked group of azirane group, ethylene oxide group or thiirane.Disclose the further details of suitable crosslinking agent in our application WO 2005/042801, it is quoted hereby and incorporates this paper into.
The inventive method can obtain passivation layer on the metallic surface.We do not know the definite structure and the composition of passivation layer.But except the amorphous oxide of the aluminium of routine or zinc and suitable other metal of words, described layer also comprises the reaction product of polymkeric substance, and suitable, also comprises the reaction product of other component in linking agent and/or the preparaton.The composition of passivation layer is inhomogeneous usually; On the contrary, each component shows concentration gradient.
The thickness of passivation layer is regulated according to required layer character by the technician.Usually, thickness is 0.01 to 3 micron, preferred 0.1 to 2.5 micron, and more preferably 0.2 to 2 micron, most preferably 0.3 to 1.5 micron, for example 1 to 2 micron.Thickness can for example be subjected to the property quality and quantity of used component and the influence of exposure duration.In addition, can use technical data to influence thickness: for example to use roller or scraper plate to remove the treatment soln of excessive use.
Hypothetical layer has the specific density of 1 kg/liter, before the metallic surface is exposed in the composition used according to the invention and afterwards, determines layer thickness by the differential weighing.Hereinafter, regardless of the actual specific density of layer, " layer thickness " always is meant the variable that records thus.These thin layers are enough to obtain excellent anti-corrosion protection.This thin layer has guaranteed to keep the size of passivation workpiece.
This specification sheets further provides the metallic surface of containing passivation layer of the present invention.Passivation layer is applied directly on the actual metal surface.In a preferred embodiment, described metallic surface is to contain zinc or Zinc alloy coated steel metal strip, has applied passivation layer of the present invention thereon.Described surface can also be the body of a motor car that applies with passivation layer of the present invention.
The metallic surface that has passivation layer can be covered by one or more layers color or effect enamelled coating according to known way in principle.Under the situation of two-layer or more multi-layered enamelled coating, typical paint, their composition and typical level preface are known to the skilled in principle.
Passivation of the present invention can be used in the different process segments.It can for example carry out in steel maker.In this case, steel bar can be with continuous processing zinc-plated and after zinc-plated immediately by handling passivation with preparation used according to the invention.The passivation in this stage is called " aftertreatment " usually by the technician.
Described passivation can only be interim, in order to store and transportation in and/or further preventing to corrode in the procedure of processing, but remove before the permanent anti-corrosion protection carrying out.Can be by cleaning from the surface removal acid copolymer with alkaline aqueous solution.
Perhaps, processing can be permanent anti-corrosive treatment, its stay on the metal strip or the workpiece of complete moulding on and provide extra lacquering for it.The passivation in this stage is called " pre-treatment " usually by the technician.
If passivation and suitable painted metals plate, bar or other semi-finished metal product can further be processed to form metal works, for example body of a motor car.This must use at least one separating step and a forming step usually.Be assembled into bigger parts by single parts subsequently.Moulding comprises the shape that changes material, common and tool in contact.Moulding for example can comprise compression molding, for example rolling or embossing; The stretching compression molding, rolls curved (roll-bending) or bends at for example cold drawn, deep-draw; Drawing and forming for example elongates or widens; Brake forming, for example bending, edging or deburring; And shear forming, for example reverse or misplace.
Compare when using the itaconic acid copolymer that obtains at comparatively high temps, passivating method of the present invention obtains much better anti-corrosion protection.
The following example is used for more elaborating the present invention:
Measuring method:
By H.Fikentscher, Cellulose-Chemie, the 13rd volume, the method for 58-64 and 71-74 page or leaf (1932) is to measure the K values at 25 ℃ in the aqueous solution of 1 weight % in concentration, by gel permeation chromatography M wValue.
Polymer manufacture
Comparative Examples 1:
The multipolymer of 75 weight % vinylformic acid and 25 weight % toxilic acids
6 boost and be enclosed in the gram maleic anhydride of 480 in 1 liter of deionized water and 22.5 milligrams of ferric sulfate in the power reactor what have paddle stirrer, temperature monitoring and nitrogen inlet.
With this initial charge under nitrogen atmosphere 115 to 120 ℃ of heating.When arriving this temperature,, and be 30% superoxol and 300 ml deionized water through being metered into 115 gram concentration in 5 hours with uniform acceleration with the 1670 gram vinylformic acid of uniform acceleration through being metered in 1.2 liters of deionized waters in 4 hours.In polymerization process,, make pressure remain on 3 to 4 crust by careful relief pressure.
Cooling produce solid content be 45.6% and K value (in deionized water 1%) be 26.0 light yellow limpid polymers soln.
Comparative Examples 2:
Vinylformic acid/methylene-succinic acid (73/27) multipolymer, in pressure reactor 120 ℃ of polymerizations
6 444 gram methylene-succinic acids, 15.5 milligram of seven ferric sulfate hydrate and the 889 gram deionized waters of packing in the power reactor that boost that having paddle stirrer, temperature monitoring, nitrogen inlet and two opening for feeds.
This initial charge is heated to 120 ℃ under nitrogen atmosphere.When arriving this temperature, with uniform acceleration through being metered into the incoming flow 1 that constitutes by 1188.0 gram vinylformic acid and 926 gram deionized waters in 5 hours, and with the incoming flow 2 of uniform acceleration through being metered into by 81.6 gram hydrogen peroxide (concentration is 30%) and 177 gram deionized waters formations in 6 hours.After incoming flow 1 finishes, further add 133 gram deionized waters.With reaction mixture 120 ℃ of restir 2 hours.In polymerization process,, make pressure remain on 3 to 4 crust by careful relief pressure.With this batch of material dilute with water.
Cooling produce solid content be 17.9% and K value (concentration 1% in deionized water) be 83.5 light yellow limpid polymers soln.By 1H NMR spectrum does not detect any free methylene-succinic acid.
Embodiment 1
The multipolymer of vinylformic acid and methylene-succinic acid (73/27) is at 100 ℃ of pressure polymerizations not
In the stirred pot that has paddle stirrer and internal thermometer, 111.0 gram methylene-succinic acids are dissolved in 250 gram deionized waters, after adding 3.875 milligram of seven ferric sulfate hydrate (II), with solution reflux (internal temperature: 98 ℃) slightly.Subsequently,, add the incoming flow 1 that constitutes by 297.0 gram vinylformic acid and 398.0 gram deionized waters, and, add the incoming flow 2 that constitutes by 6.12 gram peroxidation, two sodium sulfate in 180 gram water through 6 hours through 5 hours.After incoming flow 1 finishes, with this system 98 ℃ of restir 2 hours.This produce solid content be 36.4% and K value (concentration 1% in deionized water) be 59.6 faint yellow limpid polymers soln.By 1H NMR spectrum does not detect any free methylene-succinic acid.
Embodiment 2
The multipolymer of vinylformic acid and methylene-succinic acid (73/27) is at 100 ℃ of pressure polymerizations not
In the stirred pot that has paddle stirrer and internal thermometer, 111.0 gram methylene-succinic acids are dissolved in 250 gram deionized waters, after adding 3.875 milligram of seven ferric sulfate hydrate (II), with solution reflux (internal temperature: 98 ℃) slightly.Subsequently, through 5 hours, add the incoming flow 1 that constitutes by 297.0 gram vinylformic acid and 398.0 gram deionized waters, and, add the incoming flow 2 that constitutes by 20.4 gram hydrogen peroxide (concentration is 30%) in 180 gram water through 6 hours.After incoming flow 1, with this system 98 ℃ of restir 2 hours.Dilute this batch of material with 750 gram water fraction parts altogether.This produce solid content be 15.0% and K value (concentration 1% in deionized water) be 115.2 faint yellow limpid polymers soln.By 1H NMR spectrum does not detect any free methylene-succinic acid.
Embodiment 3
The terpolymer of vinylformic acid, methylene-succinic acid and vinyl phosphonate (69/26/5) is at 100 ℃ of pressure polymerizations not
In the stirred pot that has paddle stirrer and internal thermometer, 111.0 gram methylene-succinic acids are dissolved in 250 gram deionized waters, after adding 3.875 milligram of seven ferric sulfate hydrate (II), with solution reflux (internal temperature: 98 ℃) slightly.Subsequently,, add the incoming flow 1 that constitutes by 297.0 gram vinylformic acid, 22.7 gram vinyl phosphonates and 346.0 gram deionized waters, and, add the incoming flow 2 that constitutes by 42.8 gram hydrogen peroxide in 180 gram water through 6 hours through 5 hours.After incoming flow 1 finishes, with this system 98 ℃ of restir 2 hours.Dilute this batch of material with 700 gram water fraction parts altogether.This produce solid content be 21.2% and K value (concentration 1% in deionized water) be 37.8 faint yellow limpid polymers soln.
Embodiment 4
The multipolymer of vinylformic acid, methylene-succinic acid and vinyl phosphonate
In the stirred pot that has paddle stirrer and internal thermometer, 161.3 gram methylene-succinic acids and 152 vinyl phosphonates (95%) are dissolved in 200 gram deionized waters, after adding 703 milligram of seven ferric sulfate hydrate (II), with solution reflux (internal temperature: 98 ℃) slightly.Subsequently,, add the incoming flow 1 that constitutes by 430.0 gram vinylformic acid and 455 gram deionized waters, and, add the incoming flow 2 that constitutes by 42.5 gram peroxidation, two sodium sulfate in 160 gram water through 6 hours through 5 hours.After incoming flow 1 finishes, with this system 98 ℃ of restir 2 hours.This produce solid content be 48.8% and K value (concentration 1% in deionized water) be 28.2 faint yellow limpid polymers soln.
The passivation of metallic surface
Metallic surface and pre-treatment thereof:
Use (about 100 * 190 * 0.7 millimeter of alkaline zinc plating or hot-dip galvanized steel sheet in each case; Add 20 microns zinc) test.
With alkaline zinc plating steel plate (AV) at cleaning solution (0.5%HCl+0.1%
Figure C20058002809700251
AP10, BASF AG) submergence is about 5 seconds in, and spends ionized water rinsing and dry by blowing immediately.
With hot-dip galvanized steel sheet (HV) in alkaline defatting agent 50 ℃ of submergences 120 seconds, and spend ionized water rinsing and dry immediately by blowing.
The application of preparation used according to the invention
With synthetic polymkeric substance water-soluble (solid content 5 weight %), homogenizing also adds in the dip-coating bath.With the directly submergence 30 seconds in being adjusted to 50 ℃ polymers soln of the metal sheet that cleaned, and in drying at room temperature.Remove the corner of (mask off) passivation plate.
The differential weighing method
Hypothetical layer has the specific density of 1 kg/liter, before the metallic surface is exposed in the composition therefor and afterwards, determines layer thickness by the differential weighing method.Hereinafter, regardless of the actual specific density of layer, " layer thickness " always is meant the parameter that records thus.
The layer thickness that records by the differential weighing method is 1.5 to 3 microns.In the salt fog spray test, measure tolerance time.
Test method
Salt-fog test
Use is according to the result of the salt-fog test of DIN 50021 measurement standard as anticorrosion ability.The corrosion-damaged type that arrives according to the observation differently defines the tolerance time in the corrosion test.
If-forming diameter usually greater than 1 millimeter white point (zinc oxide or aluminum oxide are called white rust), described tolerance time is meant such time, promptly after this time, the infringement outward appearance is equivalent to the DIN EN ISO 10289 in April calendar year 2001, accessories B, the evaluation and test level 8 in the 19th page.
If-forming diameter before the white rust point usually less than 1 millimeter stain (particularly having on the zinc of passivation layer), described tolerance time is meant such time, promptly after this time, the infringement outward appearance is equivalent to the DIN EN ISO 10289 in April calendar year 2001, annex A, the evaluation and test level 8 in the 9th page.
Testing laboratory's volume: 400 liters
The spraying throughput that records according to DIN: 2.2 milliliters/hour
Test-results collects in the table 1.
Figure C20058002809700261
The embodiment of the invention and Comparative Examples show, by the inventive method of using polymerization temperature to carry out passivation less than 120 ℃ polymerization of itaconic acid thing, compares when the polymerization of itaconic acid thing that the higher temperature polymerization is made with using, and obtains much better anti-corrosion protection.It is renderd a service and also is higher than vinylformic acid-maleic acid.

Claims (18)

1. contain the method that at least a acidic aqueous preparation process metal surfaces water-soluble or the water dispersible itaconic acid copolymer makes its passivation by using, wherein said multipolymer is made of following monomer units:
(A) methylene-succinic acid of 15 weight % to 45 weight %,
(B) at least a monoethylenically unsaturated monocarboxylic of 55 weight % to 85 weight %,
(C) vinyl phosphonate of 5 weight % to 40 weight %,
With
(D) Ren Xuan 0 weight % to 30 weight % at least a be except that (A), (B) with other ethylenically unsaturated monomer (C),
Amount under every kind of situation is all based on all monomeric total amounts of mixing in the multipolymer, and multipolymer is by radical polymerization obtains under 120 ℃ the temperature being lower than in aqueous solution.
2. according to the process of claim 1 wherein that the amount of vinyl phosphonate is 10 weight % to 30 weight %.
3. according to the process of claim 1 wherein that multipolymer is the terpolymer of 67 weight % to 75 weight % vinylformic acid, 23 weight % to 30 weight % methylene-succinic acids and 0.1 weight % to 10 weight % vinyl phosphonate.
4. according to the process of claim 1 wherein that multipolymer is the terpolymer of 55 weight % to 65 weight % vinylformic acid, 15 weight % to 25 weight % methylene-succinic acids and 15 weight % to 25 weight % vinyl phosphonates.
5. according to each method in the claim 1 to 4, wherein be aggregated under 90 to 105 ℃ the temperature and carry out.
6. according to each method in the claim 1 to 4, wherein said metallic surface is the surface of zinc, aluminium or its alloy.
7. according to each method in the claim 1 to 4, the amount of chromium is no more than 2 weight % based on the composition all components in this method.
8. according to each method in the claim 1 to 4, wherein said processing is undertaken by rolling, spraying or dip coating.
9. according to each method in the claim 1 to 4, wherein the metallic surface is the surface of metal strip.
10. according to the method for claim 9, wherein metal strip is the steel of electrogalvanizing or galvanizing.
11. according to the method for claim 9, wherein said processing is undertaken by continuous processing.
12., wherein make described surface contact 1 to 60 second with preparation according to the method for claim 9.
13. according to each method in the claim 1 to 4, wherein preparaton also comprises benzotriazole and/or tolyl-triazole.
14. the water-soluble or water dispersible itaconic acid copolymer that constitutes by following monomeric unit:
(A) methylene-succinic acid of 15 weight % to 45 weight %,
(B) at least a monoethylenically unsaturated monocarboxylic of 55 weight % to 85 weight % and
(C) vinyl phosphonate of 5 weight % to 40 weight %,
With
(D) Ren Xuan 0 weight % to 30 weight % at least a be except that (A), (B) with other ethylenically unsaturated monomer (C),
Amount under every kind of situation is all based on all monomeric total amounts of mixing in the multipolymer, and multipolymer is by radical polymerization obtains under 120 ℃ the temperature being lower than in aqueous solution.
15. according to the multipolymer of claim 14, therein ethylene base phosphonic amount is 10 weight % to 30 weight %.
16. according to the multipolymer of claim 14, wherein multipolymer is the terpolymer of 67 weight % to 75 weight % vinylformic acid, 23 weight % to 30 weight % methylene-succinic acids and 0.1 weight % to 10 weight % vinyl phosphonate.
17. according to the multipolymer of claim 14, wherein multipolymer is the terpolymer of 55 weight % to 65 weight % vinylformic acid, 15 weight % to 25 weight % methylene-succinic acids and 15 weight % to 25 weight % vinyl phosphonates.
18., wherein be aggregated under 90 to 105 ℃ the temperature and carry out according to each multipolymer in the claim 14 to 17.
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