WO2005033364A1 - Procedes pour decaper des surfaces metalliques au moyen d'alcynols alcoxyles - Google Patents

Procedes pour decaper des surfaces metalliques au moyen d'alcynols alcoxyles Download PDF

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Publication number
WO2005033364A1
WO2005033364A1 PCT/EP2004/010719 EP2004010719W WO2005033364A1 WO 2005033364 A1 WO2005033364 A1 WO 2005033364A1 EP 2004010719 W EP2004010719 W EP 2004010719W WO 2005033364 A1 WO2005033364 A1 WO 2005033364A1
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WIPO (PCT)
Prior art keywords
acid
weight
water
pickling
chr
Prior art date
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PCT/EP2004/010719
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German (de)
English (en)
Inventor
Frank Dietsche
Thomas Heidenfelder
Helmut Witteler
Original Assignee
Basf Aktiengesellschaft
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Publication date
Priority claimed from DE2003145801 external-priority patent/DE10345801A1/de
Application filed by Basf Aktiengesellschaft filed Critical Basf Aktiengesellschaft
Priority to EP04765569A priority Critical patent/EP1670972A1/fr
Priority to BRPI0414711-1A priority patent/BRPI0414711A/pt
Priority to CA002539246A priority patent/CA2539246A1/fr
Priority to MXPA06002924A priority patent/MXPA06002924A/es
Priority to JP2006530013A priority patent/JP2007507607A/ja
Priority to US10/573,979 priority patent/US20070034606A1/en
Publication of WO2005033364A1 publication Critical patent/WO2005033364A1/fr

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Classifications

    • 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
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
    • C23G1/04—Cleaning or pickling metallic material with solutions or molten salts with acid solutions using inhibitors
    • C23G1/06—Cleaning or pickling metallic material with solutions or molten salts with acid solutions using inhibitors organic inhibitors
    • 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
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
    • C23F11/04—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in markedly acid liquids
    • 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
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
    • 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
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
    • C23G1/04—Cleaning or pickling metallic material with solutions or molten salts with acid solutions using inhibitors
    • C23G1/06—Cleaning or pickling metallic material with solutions or molten salts with acid solutions using inhibitors organic inhibitors
    • C23G1/068—Cleaning or pickling metallic material with solutions or molten salts with acid solutions using inhibitors organic inhibitors compounds containing a C=C bond
    • 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
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
    • C23G1/08—Iron or steel
    • 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
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
    • C23G1/08—Iron or steel
    • C23G1/088—Iron or steel solutions containing organic acids

Definitions

  • the present application relates to a method for pickling metallic surfaces by treating the metallic surface with a composition which comprises water, at least one acid, an alkali alkoxylate and optionally further additives.
  • a composition which comprises water, at least one acid, an alkali alkoxylate and optionally further additives.
  • the alkali alkoxylate is used together with a complexing agent.
  • pickling In the case of pickling, the surface of a material is treated with a pickle and thereby changed chemically. Unwanted surface layers are removed and protective or effect layers are built up if necessary.
  • pickling primarily serves to remove various oxide layers, such as rust or scale layers, and / or other contaminants, such as greases, oils or lime, from the surface and / or to activate and / or protect the surface.
  • An example of a protective treatment is acid phosphating of an iron or steel surface.
  • An essential element here is a pickling attack on the metal.
  • phosphating with an acidic Zn-phosphate solution a large amount of H + ions are consumed by the acid attacking the metal directly on the metal surface, as a result of which the pH increases locally. Only then is the solubility product for zinc phosphate exceeded, so that zinc phosphate is deposited on the surface in a thin layer.
  • aqueous, inorganic or organic acids in particular hydrochloric acid, phosphoric acid or sulfuric acid, and generally auxiliaries such as surfactants are used.
  • the acid should attack the surface layers and possibly also the metal itself, it is generally undesirable if too large amounts of metal are dissolved.
  • a lot of pickling acid is consumed and the pickling contaminated with dissolved metal ions. Accordingly, the pickling bath has to be renewed frequently.
  • the surface - especially with iron or nickel - can also be damaged by so-called hydrogen embrittlement.
  • Preparations for pickling are therefore usually added to pickling inhibitors which are intended to prevent the dissolving of the base material or at least to slow it down considerably without significantly impeding the dissolution of the surface layers. Pickling using inhibitors is also sometimes called "saving pickling".
  • alkynols such as 2-butyne-1,4-diol, 1-propyn-3-ol or 1-ethynyl-cyclohexanol
  • pickling inhibitors examples include US 3,658,720, US 3,969,260 or JP-A 60-208 * 487.
  • WO 99/32687 discloses the use of 2-butyne-1,4-diol as an inhibitor in the acid phosphating of one-sided galvanized steel strip.
  • Alkaline alkoxylates are known in principle, for example from DE-A 2241 155. They are used, inter alia, as gloss additives in the electrodeposition of nickel or cobalt, as disclosed by US 3,804,727, 3,814,674 or US 4,832,802. Alkoxylated alkynols are not classified as toxic or carcinogenic.
  • US 3,004,925 discloses the use of ethoxylated butynediol derivatives and ethoxylated propinol derivatives as a corrosion inhibitor in aqueous solutions.
  • the OH groups are each modified with - (CH 2 -CH 2 O) x groups, where x has the value from 3 " to 25.
  • the alkynols disclosed additionally have one or more alkyl, aryl, cycloalkyl and Aralkyl groups Unsubstituted butynediol or propargyl alcohol is not disclosed.
  • compositions for removing lacquers from surfaces which have 10 to 50% water, 3 to 15% of a peroxide and 40 to 70% ethyl lactate.
  • the composition can also optionally have ethoxylated butynediol as a corrosion inhibitor and an acid.
  • a composition which comprises 55 to 60% butyrolactone, 30 to 32% aqueous hydrogen peroxide, 9.5% formic acid, 1% ethoxylated butanediol, 0.5% Na EDTA and 4% surfactants.
  • the object of the present invention was to provide a method for pickling metallic surfaces in which butynediol or propinol are replaced by suitable substitutes, and in which a better pickling inhibition is nevertheless achieved. Accordingly, a process has been found for pickling metallic surfaces, in which the metallic surface is treated with an acidic aqueous preparation which comprises at least the following components:
  • the pickling inhibitor is used in combination with a water-soluble complexing agent.
  • the method according to the invention can in principle be used for pickling various types of metallic surfaces.
  • the metals can be pure metals as well as alloys. Examples include surfaces made of iron, cast iron, steel, nickel, zinc, brass or aluminum, in each case meaning the uppermost metal layer which comes into direct contact with the preparation.
  • the metallic surface can also be, for example, surface-tempered steels, such as hot or galvanized steels.
  • the method is particularly suitable for pickling surfaces made of (cast) iron, steel or aluminum, very particularly preferably for steel surfaces.
  • the method is particularly suitable for pickling the surface of strip metals, such as steel or aluminum strips.
  • the metallic surfaces can be both external surfaces of metallic materials, such as the surface of metallic strips, metal sheets or irregularly shaped workpieces such as machine parts. But it can also be internal surfaces, such as the inner surfaces of pipelines, boilers, chemical plants or the like.
  • pickling includes the phosphating of metallic surfaces.
  • Unwanted surface layers can in particular be inorganic layers, for example largely oxidic layers such as rust layers, scale layers or layers which are formed when metals, for example steel, are rolled.
  • the preparation used for the process according to the invention comprises, as component (a), water and at least one acid in a total amount of from 60 to 99.99% by weight.
  • component (a) water and at least one acid in a total amount of from 60 to 99.99% by weight.
  • the total amount of water and acid is preferably 70 to 99.99% by weight and very particularly preferably 80 to 99.99% by weight.
  • the acid can be an inorganic acid such as, for example, hydrochloric acid, hypo- and chlorous acid, sulfuric acid, phosphoric acid or phosphorous acid or else an organic acid such as, for example, formic acid, methanesulfonic acid, acetic acid, citric acid, succinic acid or amidosulfonic acid. Mixtures of different acids can of course also be used, for example mixtures of hydrochloric acid and phosphoric acid.
  • the acid is preferably hydrochloric acid, sulfuric acid, methanesulfonic acid or phosphoric acid.
  • the amount of water and acid depends on the one hand on the intended use of the preparation and also on the type of acid. While in special cases the solvent can only consist of concentrated (i.e. 85%) phosphoric acid when using phosphoric acid, higher dilutions are advantageous when using acids other than phosphoric acids. If acids other than phosphoric acid are used, the preparation generally comprises at least 50% by weight of water, preferably at least 60% by weight of water. The total amount of water in the preparation is calculated as the sum of the water which is added together with the acid and from which is added in pure form or in the form of solutions of other materials.
  • Component (b) in the preparation used for the process according to the invention is 0.01 to 2% by weight of at least one alkali alkoxylate of the general formula
  • indices n and n 'independently of one another are from 1 to 10. It is known to the person skilled in the art that such alkoxy groups can be obtained in particular by oxalkylation or starting from technical polyglycols.
  • the values mentioned stand for n thus for average chain lengths, whereby the average value does not of course have to be a natural number, but can also be any rational number. It is preferably n and n 'and a number from 1 to 3.
  • the radicals R 1 in (I) and (II) each independently represent H or methyl.
  • the alkyleneoxy groups can be groups derived exclusively from ethylene oxide units or groups derived exclusively from propylene oxide. Of course, however, these can also be groups which have both ethylene oxide units and propylene oxide units.
  • the amount of (I) and / or (II) also depends on the type and amount of acid used and the temperature at which the preparation is to be used. The higher the acid concentration, the higher the concentration of pickling inhibitor (I) and / or (II) used should generally be. The higher the temperature, the higher the concentration of the pickling inhibitor should normally be.
  • the amounts specified below have proven particularly useful for use at room temperature:
  • the amount of such additives is 0 to 38% by weight, preferably 0.01 to 30% by weight and particularly preferably 0.1 to 20% by weight.
  • Auxiliaries are in particular 0.01% by weight to 20% by weight of at least one surface-active substance. 0.1 to 10% by weight and particularly preferably 0.5 to 8% by weight of the surface-active substance are preferably used.
  • suitable surface-active substances include conventional anionic, cationic or nonionic surfactants.
  • Alkoxylated C 8 -C 22 alcohols such as fatty alcohol alkoxylates, oxo alcohol alkoxylates and Guerbet alcohol ethoxylates:
  • the alkoxylation can be carried out using ethylene oxide, propylene oxide and / or butylene oxide.
  • Block copolymers or statistical copolymers can be present. They usually contain 2 to 1 mol of alcohol 50 mol, preferably 3 to 20 mol, of at least one alkylene oxide.
  • Preferred alkylene oxide is ethylene oxide.
  • the alcohols preferably have 10 to 18 carbon atoms.
  • Alkylphenol alkoxylates especially alkylphenol ethoxylates, which contain C 6 -C 14 alkyl chains and 5 to 30 mol alkylene oxide / mol.
  • N-alkyl glucamides fatty acid amide alkoxylates, fatty acid alkanolamide alkoxylates and block copolymers of ethylene oxide, propylene oxide and / or butylene oxide.
  • Suitable anionic surfactants are, for example:
  • Sulfated alkoxylated C 8 -C 22 alcohols (alkyl ether sulfates): Compounds of this type are prepared, for example, by first alkoxylating a C 8 -C 22 , preferably a C 10 -C 18 alcohol, for example a fatty alcohol, and that Alk-oxylation product then sulfated. Ethylene oxide is preferably used for the alkoxylation.
  • Linear C 8 -C 20 alkylbenzenesulfonates LAS
  • linear C 9 -C 13 alkylbenzenesulfonates and alkyltoluenesulfonates LAS
  • Alkane sulfonates in particular C 8 -C 24 -, preferably C 0 -C 18 alkane sulfonates.
  • Soaps such as the Na and K salts of C 8 -C 24 carboxylic acids.
  • Ester quats especially quaternary esterified mono-, di- and tjalkanolamines which are esterified with C 8 -C 22 -carboxylic acids;
  • Imidazoline quats in particular 1-alkylimidazolinium salts of the formulas III or IV
  • R 2 C Cse alkyl or C 2 -C 25 alkenyl; R 3 CC 4 alkyl or hydroxy-C C alkyl; R 4 CC 4 alkyl, hydroxy-dC 4 alkyl or a radical R 4 - (CO) -X- (CH 2 ) p - (X: -O- or -NH-; p: 2 or 3), where at least one R 2 is C 7 -C 22 alkyl.
  • Nonionic surfactants are preferably used.
  • the preparation used particularly preferably comprises one or more water-soluble complexing agents as further components.
  • the complexing agents work synergistically with the pickling inhibitor. It has been found that complexing agents as an additive to pickling acids accelerate the removal of metal. However, if they are used in combination with the alkoxylated alkinols used as pickling inhibitors according to the invention, the inhibiting effect of the pickling inhibitor is not reduced by the complexing agent, but on the contrary is even increased. In experiments, the inhibitory effect could be improved by up to 60% by adding a complexing agent.
  • the complexing agent is a water-soluble, at least bidentate ligand, which is able to form chelate complexes.
  • the ligand comprises acidic groups, preferably COOH groups.
  • the complexing agent has at least two COOH groups. It is preferably a two- to six-toothed ligand, particularly preferably a two- to four-toothed ligand.
  • the coordinating groups are arranged in a chelating ligand in such a way that the ligand can form one or more rings together with the metal, in particular five-membered rings.
  • the ligand can also have other atoms or groups which are capable of forming coordinative bonds to metal ions.
  • OH groups and nitrogen-containing groups such as primary, secondary and tertiary amino groups should be mentioned here in particular. Tertiary amino groups are preferred.
  • Complexing agents preferred for carrying out this invention are ligands which are derived from compounds having primary amino groups and in which the H atoms on the amino group are substituted by -CH 2 -COOH groups.
  • Examples include ethylenediaminetetraacetic acid (EDTA), diethylenetriaminepentacetic acid (DTPA), hydroxyethylethylenediaminetriacetic acid (HEDTA), nitrilotriacetic acid. acid (NTA) or methylglycinediacetic acid (MGDA).
  • Ethylene diamine tetraacetic acid and methyl glycinediacetic acid are preferably used to carry out the present invention, and methyl glycinediacetic acid is very particularly preferred.
  • the complexing agents can be used in the form of acids or in the form of salts.
  • the complexing agents can also be polymeric complexing agents.
  • Suitable polymeric complexing agents are in particular those which are derived from polymers which have primary and / or secondary amino groups and in which the H atoms on the amino groups are wholly or partly substituted by —CH 2 —COOH groups.
  • Preferred polymer complexing agents are polyethyleneimines modified with -CH 2 -COOH groups. As a rule, at least 50%, preferably at least 60% and particularly preferably at least 75% of the H atoms on the amino groups should be substituted. The preparation of such polymeric complexing agents is described in WO 2004/001099.
  • the complexing agent is generally used in an amount of from 0..01 to 10% by weight. Preferably 0.1 to 10% by weight and particularly preferably 0.1 to 5% by weight are used
  • the weight ratio of complexing agent to pickling inhibitor is generally 100: 1 to 1: 100, preferably 50: 1 to 1:50 and particularly preferably 5: 1 to 1:10. Depending on the acid concentration, the following quantities have proven particularly useful for use at room temperature:
  • the pH of the composition is determined by the person skilled in the art depending on the desired
  • a preparation which is particularly preferred for carrying out the method according to the invention is:
  • the amounts are very particularly preferably: (a) 70 to 98.9% by weight, (b) 0.1 to 2% by weight, (c) 0.5 to 15% by weight, and (d) 0.5 up to 10% by weight.
  • the pickling inhibitors used according to the invention are used together with water-soluble cationic, nitrogen-containing polymers (V) which contain quaternized ammonium groups
  • R 5 or R 5 ' are the same or different and represent a saturated or unsaturated, substituted or unsubstituted aliphatic radical, a saturated or unsaturated, substituted or unsubstituted alicyclic radical or a substituted or unsubstituted araliphatic radical.
  • the groups A connecting the ammonium groups are hydrocarbon groups, in particular alkylene groups, into which further functional groups and / or heteroatoms can also be incorporated. For example, non-adjacent groups can be replaced by -O atoms or N atoms.
  • Suitable functional groups are in particular urea groups -NC-CO-NH-.
  • X is chosen by the person skilled in the art depending on the desired properties.
  • Particularly suitable polymers usually have a molecular weight of 1000-100000 g / mol, preferably 1500-50000 g / mol and particularly preferably 2000-20000 g / mol.
  • the cationic polymers V are preferably one which has two different connecting groups A 'and A ".
  • Group A is a group which has alkylene units and urea units:
  • k and k 'independently of one another represent a natural number from 1 to 5, preferably 2 or 3.
  • R 6 and R 6' independently of one another represent H or a straight-chain or branched aikyl radical having 1 to 12 C atoms.
  • R 6 or R 6 ' are preferably selected from the group of H, -CH 3 or -C 2 H 5 , particularly preferably R 6 or R 6' is H.
  • the group A is a straight-chain or branched alkylene group with 2 - 20 C atoms.
  • non-adjacent, non-terminal C atoms can also be substituted by one or a plurality of identical or different heteroatoms such as O, S and / or N.
  • O-substituted radicals are preferred.
  • I stands for a natural number from 1 to 3.
  • a " is particularly preferably -CH 2 CH 2 -O-CH 2 -CH 2 -.
  • Such cationic polymers their production and properties are known in principle, in particular as a cosmetic agent for hair.
  • a cosmetic agent for hair For example, reference is made to DE-A 25 21 960 or DE-A 2 924 230. It is particularly preferably a polymer of the general formula VI:
  • the cationic polymers are preferably used in the same amounts as the complexing agents.
  • complexing agents and cationic polymers can also be used together with the pickling inhibitor.
  • the preparation used can also comprise further components or auxiliaries.
  • water-miscible organic solvents In order to improve the removal of fats during pickling degreasing, it may be advantageous to add small amounts of water-miscible organic solvents to the composition.
  • the amount of optionally added organic solvents is usually 0 to 10% by weight.
  • suitable, water-miscible solvents include monoalcohols such as methanol, ethanol or propanol, higher Al> alcohols such as ethylene glycol or polyether polyols and ether alcohols such as butyl glycol or ⁇ methoxypropanol.
  • further auxiliaries include, for example, foam attenuators such as polypropoxylates or silicone ethers.
  • the type and amount of additional components or auxiliaries are determined by the person skilled in the art depending on the intended use.
  • the amount of optionally added additional aids is usually 0 to 5% by weight.
  • the metallic surface is brought into contact with the aqueous preparation, for example by spraying, dipping or rolling on. After a dipping process, you can remove excess treatment solution drain the workpiece; in the case of sheets, metal foils or the like, however, excess treatment solution can also be squeezed off, for example.
  • the method according to the invention can optionally also comprise one or more pretreatment steps.
  • the metal surface can be cleaned with the preparation used according to the invention prior to pickling, e.g. to remove fats or oils. This is regularly recommended, especially when phosphating.
  • the method can optionally include post-treatment steps. Mention should be made here in particular of rinsing steps in which the treated surface is rinsed with suitable cleaning liquids, in particular water, in order to remove, for example, residues of the preparation used according to the invention from the surface.
  • suitable cleaning liquids in particular water
  • the treatment can be carried out batchwise or continuously.
  • a continuous process is particularly suitable for treating strip metals.
  • the metal strip is passed through a trough or a spray device and optionally through further pre-treatment or post-treatment stations.
  • the temperature and duration of the treatment are determined by the person skilled in the art depending on the desired application. On the one hand, higher temperature accelerates the pickling attack on layers to be removed, but on the other hand also accelerates the pickling attack on the metal itself. In general, the temperature of the treatment is 20 to 80 ° C., without the invention being restricted to this range. The duration of treatment can range from 1 s to several hours. The treatment time is usually shorter at higher temperatures than at lower temperatures. When pickling steel strips, a temperature of 60 to 80 ° C, for example 70 ° C, with contact times of 1 to 10 s has proven particularly useful. Sulfur or hydrochloric acid pickling is particularly suitable for steel strips.
  • the pickling attack on the metal is inhibited significantly more than is the case when using non-alkoxylated pickling inhibitors.
  • Complexing agents work synergistically with the alkoxylated pickling inhibitors and significantly reduce the pickling attack again.
  • the acidic, aqueous composition can be used as a dampening solution for offset printing.
  • the ethoxylated alkynols contained in the formulation advantageously prevent undesirable corrosion on the printing press and printing plates.
  • phosphoric acid or organic acids such as succinic acid are suitable as acids for this application, usually as components of a buffer system.
  • additives known to those skilled in the art can be used as further components for this application.
  • examples include alcohols such as glycerin, hydrophilic polymers such as gum arabic or cellulose derivatives, surface-active substances and biocides.
  • PA- n EO propargyl alcohol, ethoxylated with an average of n ethylene oxide units
  • PAN PO propargyl alcohol, propoxylated with an average of n propylene oxide units
  • BDA - n PO 2-butyne-1,4-diol, propoxylated with an average of n propylene oxide units
  • the alkoxylated used for the process according to the invention was produced in accordance with the regulation disclosed in DE-A 2241 155.
  • Solutions of corrosion inhibitor (if any) and complexing agents (if any) were made up in water.
  • the amounts of corrosion inhibitor and complexing agent are given in Tables 1 to 4.
  • the pH was adjusted with an acid.
  • the total amount was 100 g each.
  • Pickling degreaser solution 4 1 g pickling inhibitor (according to Table 5) 3 g non-ionic surfactant: saturated Ci3-oxo alcohol, ethoxylated, on average 8 EO units 0.2 g anionic surfactant: acidic phosphoric acid ester of a fatty alcohol alkoxide 50 g HCI conc. (37% HCI) 45.8 g water water content: 77.3% water + acid content: 95.8%
  • Solution 5 1 g pickling inhibitor (according to Table 5) 3 g non-ionic surfactant: saturated C 3 -oxo alcohol, ethoxylated, on average 8 EO units 3 g 3-nitrobenzenesulfonic acid 0.5 g alkylphenol ether sulfate, Na salt, 40% 50 g HCI conc , (37% HCI) 42.5 g water water content: 74.3% water + acid content: 92.8%
  • Solution 6 2 g pickling inhibitor (according to Table 5) 0.5 g non-ionic surfactant: oleylamine, ethoxylated, on average 12 EO units 0.5 g non-ionic surfactant: saturated C 13 oxo alcohol, ethoxylated, on average 8 EO units 25 g H 2 SO 4 conc. (96%) 72 g water
  • Solution 7 1 g pickling inhibitor (according to Table 5) 12 g non-ionic surfactant: saturated Ci 3 -i 5 -oxoalcohol, ethoxylated, through an average of 8 EO units 5 g dodecylbenzenesulfonic acid 40 g H 3 PO 4 conc. (85%) 42 g water
  • Solution 7a as solution 7, additionally 0.2% by weight methylglycinediacetic acid, (0.2% by weight water less)
  • Solution 9 0.5 g pickling inhibitor with conc. H 2 SO 4 adjusted to pH 1 and dissolved with 50 g / l Fe (II) sulfate.
  • Solution 10 Like solution 9, additional 0.25% by weight methylglycinediacetic acid Solution 11 Like solution 9, additional 0.25% by weight of a polymeric complexing agent (polyethyleneimine, modified with acetic acid groups, Na salt)
  • a polymeric complexing agent polyethyleneimine, modified with acetic acid groups, Na salt
  • Solution 12 As solution 9, additionally 0.25% by weight of a cationic polymer of the general formula
  • test sheets made of St 1.0037, AI 99.9 or Zn 99.8 are immersed in a constant test solution (see solutions 1-7) for 1h or 24h at room temperature and the area-related mass loss is determined gravimetrically using differential weighing.
  • Degreasing A solution of the degreasing bath with the following composition is used in a plastic tub with two flat electrodes (stainless steel or graphite) that are larger than the test plate: 20 g NaOH 22 g Na 2 CO 3 16 g Na 3 PO 4 * 12 H 2 O 1 g ethylenediaminetetraacetic acid (EDTA) 0.5 g non-ionic surfactant: alkylphenol, ethoxylated, on average 10 EO units in approx. 940 ml deionized water.
  • EDTA ethylenediaminetetraacetic acid
  • NaOH, Na 2 CO 3 and Na 3 PO 4 are dissolved in DI water in succession with stirring.
  • EDTA and the surfactant are separately pre-dissolved in demineralized water, with the surfactant solution at a temperature of 50 ° C.
  • the EDTA and surfactant solutions are then added to the sodium hydroxide solution in a measuring cylinder and, after cooling, made up to 1000 ml with demineralized water.
  • Rust removal In a plastic tub with two flat electrodes that are larger than the test plate, a solution of the rust removal bath of the following composition is used: 100 g diammonium citrate in 1000 ml water
  • a sheet of steel measuring 50 mm x 20 mm x 1 mm is wiped with a paper rag and immersed in the degreasing bath between the electrodes at 10 volts and switched as a cathode.
  • the voltage is adjusted so that the current is 1A.
  • the steel sheet is removed and rinsed under running water for five seconds.
  • the steel sheet is immersed at 10 V in the rust removal bath between the electrodes and switched as the cathode.
  • the tension is adjusted so that the
  • the metal sheet size 50 mm x 20 mm x 1 mm, is degreased and derusted electrolytically.
  • the initial mass is determined with the analytical balance.
  • the metal sheet is used immediately after weighing.
  • the prepared metal sheet is placed diagonally in a 200ml glass bottle with test solution.
  • the angle between sheet steel and floor is 35 °.
  • the glass bottle is tightly closed and stored at room temperature. During storage, the glass bottle is shaken briefly once every 6 hours.
  • the metal sheet is removed from the solution, rinsed with demineralized water, brushed with steel wool, rinsed with demineralized water and blown dry with air. The mass is then determined.
  • the gravimetric pickling test is carried out as a tenfold determination and the mean value is formed.
  • the efficiency E of the active ingredient can be specified, by means of which the mass loss ⁇ m Pr0be in relation to the mass loss in the corrosion test without inhibitor ⁇ m 0 is set. It applies
  • E ( ⁇ m 0 - ⁇ mprobe) / ⁇ m 0
  • the inhibition efficiency can therefore be 1 (no metal removal), O (in demineralized water), but it can also be ⁇ 0 if the additives lead to accelerated corrosion.
  • Solution 3 was used for the experiments (HCl, pH 3.5).
  • the inhibition efficiency E was determined for steel sheets 1.0037 according to the method generally described above at room temperature after 1 h.
  • the pickling inhibitors and complexing agents specified in Table 4 were used in the amounts specified. The results are summarized in Table 4.
  • alkoxylated pickling inhibitors used according to the invention inhibit considerably better than propargyl alcohol or butynediol. This not only provided a replacement that was less harmful from an ecological point of view, but also a replacement with a better effect. This applies in particular to steel surfaces.
  • complexing agents in a synergistic manner. While the complexing agent used alone accelerates the dissolution of the metal, the combination of complexing agent and pickling inhibitor results in a stronger inhibition than with the pickling inhibitor alone.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Detergent Compositions (AREA)
  • Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)

Abstract

L'invention concerne des procédés pour décaper des surfaces métalliques, par traitement de ces surfaces métalliques au moyen d'une composition contenant de l'eau, au moins un acide, un alcynalcoxylate, et éventuellement d'autres additifs. Dans un mode de réalisation préféré de cette invention, l'alcynalcoxylate est utilisé en association avec un agent complexant.
PCT/EP2004/010719 2003-09-30 2004-09-24 Procedes pour decaper des surfaces metalliques au moyen d'alcynols alcoxyles WO2005033364A1 (fr)

Priority Applications (6)

Application Number Priority Date Filing Date Title
EP04765569A EP1670972A1 (fr) 2003-09-30 2004-09-24 Procedes pour decaper des surfaces metalliques au moyen d'alcynols alcoxyles
BRPI0414711-1A BRPI0414711A (pt) 2003-09-30 2004-09-24 processo para a desoxidação de superfìcies metálicas, e, composições aquosa, ácida para a desoxidação de superfìcies metálicas
CA002539246A CA2539246A1 (fr) 2003-09-30 2004-09-24 Procedes pour decaper des surfaces metalliques au moyen d'alcynols alcoxyles
MXPA06002924A MXPA06002924A (es) 2003-09-30 2004-09-24 Metodo para tratar quimicamente superficies metalicas por el uso de alquinoles alcoxilados.
JP2006530013A JP2007507607A (ja) 2003-09-30 2004-09-24 アルコキシレート化したアルカノールの使用により金属表面を酸洗いする方法
US10/573,979 US20070034606A1 (en) 2003-09-30 2004-09-24 Method for pickling metallic surfaces by using alkoxylated alkynols

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
DE10345801.8 2003-09-30
DE2003145801 DE10345801A1 (de) 2003-09-30 2003-09-30 Verfahren zum Beizen metallischer Oberflächen unter Verwendung von alkoxylierten Alkinolen
DE102004019709 2004-04-20
DE102004019709.1 2004-04-20

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WO2007014967A1 (fr) * 2005-08-04 2007-02-08 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Decapant eliminable sans laisser de residus
JP2007070628A (ja) * 2005-09-02 2007-03-22 Sika Technology Ag 塗料への接着剤及びシーラントの接着性を向上させるための水性接着促進クリーナー組成物
WO2008031781A2 (fr) * 2006-09-15 2008-03-20 Basf Se Utilisation de polymères comprenant des groupes ammonium quaternaire et des groupes urée en tant qu'inhibiteurs de corrosion pour des surfaces de cuivre
WO2008138817A2 (fr) * 2007-05-11 2008-11-20 Basf Se Procédé et composition de désinfection de surfaces sensibles
EP2099268A1 (fr) * 2008-03-07 2009-09-09 Atotech Deutschland Gmbh Composition d'adhésion sans gravure, procédé de préparation d'une pièce de travail et procédé de formation de structures en cuivre sur un substrat de support de circuit
WO2009121947A1 (fr) * 2008-04-04 2009-10-08 Basf Se Composition polymère acide et son procédé de fabrication
US8901060B2 (en) 2008-11-17 2014-12-02 Basf Se Use of thioglycol ethoxylate as a corrosion inhibitor
EP2231843B1 (fr) 2008-11-28 2015-07-22 Arkema France Utilisation d'acide alcane sulfonique pour elimination de la rouille
CN106222712A (zh) * 2015-12-01 2016-12-14 江苏九天光电科技有限公司 适合于钢带电镀前快速脱脂活化二合一处理剂
WO2017186931A1 (fr) * 2016-04-29 2017-11-02 Chemetall Gmbh Procédé de traitement anticorrosion d'une surface métallique à enlèvement réduit de matière décapée
EP3913111A1 (fr) * 2020-05-20 2021-11-24 Beratherm AG Concentré de nettoyage, solution de nettoyage aqueuse à ph-neutre ainsi que son utilisation
WO2023111687A1 (fr) 2021-12-17 2023-06-22 Cci Holdings, Inc. Système de transfert de chaleur à inhibiteurs organiques non ioniques compatibles avec une exposition au flux dans des opérations de pile à combustible

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JP5992506B2 (ja) 2011-04-14 2016-09-14 ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ 系の表面上のスケール堆積物を溶解および／または抑制する方法
CA2838299A1 (fr) * 2011-06-13 2012-12-20 Akzo Nobel Chemicals International B.V. Resistance amelioree a la corrosion par utilisation d'agents de chelation dans un equipement contenant du chrome
EP2836582A1 (fr) 2012-04-12 2015-02-18 Basf Se Composition de nettoyage pour laver la vaisselle
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DE102016210289A1 (de) * 2016-06-10 2017-12-14 Henkel Ag & Co. Kgaa Verfahren zur reinigenden Vorbehandlung von durch Schweißen zusammengefügten eisenhaltigen Bauteilen
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WO2007014967A1 (fr) * 2005-08-04 2007-02-08 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Decapant eliminable sans laisser de residus
JP2007070628A (ja) * 2005-09-02 2007-03-22 Sika Technology Ag 塗料への接着剤及びシーラントの接着性を向上させるための水性接着促進クリーナー組成物
WO2008031781A2 (fr) * 2006-09-15 2008-03-20 Basf Se Utilisation de polymères comprenant des groupes ammonium quaternaire et des groupes urée en tant qu'inhibiteurs de corrosion pour des surfaces de cuivre
WO2008031781A3 (fr) * 2006-09-15 2008-07-03 Basf Se Utilisation de polymères comprenant des groupes ammonium quaternaire et des groupes urée en tant qu'inhibiteurs de corrosion pour des surfaces de cuivre
WO2008138817A2 (fr) * 2007-05-11 2008-11-20 Basf Se Procédé et composition de désinfection de surfaces sensibles
WO2008138817A3 (fr) * 2007-05-11 2009-02-05 Basf Se Procédé et composition de désinfection de surfaces sensibles
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EP2099268A1 (fr) * 2008-03-07 2009-09-09 Atotech Deutschland Gmbh Composition d'adhésion sans gravure, procédé de préparation d'une pièce de travail et procédé de formation de structures en cuivre sur un substrat de support de circuit
WO2009109391A1 (fr) * 2008-03-07 2009-09-11 Atotech Deutschland Gmbh Composition adhésive non photosensible sans gravure et procédé de préparation d'une pièce à travailler
WO2009121947A1 (fr) * 2008-04-04 2009-10-08 Basf Se Composition polymère acide et son procédé de fabrication
US8901060B2 (en) 2008-11-17 2014-12-02 Basf Se Use of thioglycol ethoxylate as a corrosion inhibitor
EP2231843B1 (fr) 2008-11-28 2015-07-22 Arkema France Utilisation d'acide alcane sulfonique pour elimination de la rouille
CN106222712A (zh) * 2015-12-01 2016-12-14 江苏九天光电科技有限公司 适合于钢带电镀前快速脱脂活化二合一处理剂
WO2017186931A1 (fr) * 2016-04-29 2017-11-02 Chemetall Gmbh Procédé de traitement anticorrosion d'une surface métallique à enlèvement réduit de matière décapée
EP3913111A1 (fr) * 2020-05-20 2021-11-24 Beratherm AG Concentré de nettoyage, solution de nettoyage aqueuse à ph-neutre ainsi que son utilisation
WO2023111687A1 (fr) 2021-12-17 2023-06-22 Cci Holdings, Inc. Système de transfert de chaleur à inhibiteurs organiques non ioniques compatibles avec une exposition au flux dans des opérations de pile à combustible

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JP2007507607A (ja) 2007-03-29
CA2539246A1 (fr) 2005-04-14
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