EP2010696B1 - Procédé de nettoyage désémulsifiant de surfaces métalliques - Google Patents

Procédé de nettoyage désémulsifiant de surfaces métalliques Download PDF

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Publication number
EP2010696B1
EP2010696B1 EP07727340.7A EP07727340A EP2010696B1 EP 2010696 B1 EP2010696 B1 EP 2010696B1 EP 07727340 A EP07727340 A EP 07727340A EP 2010696 B1 EP2010696 B1 EP 2010696B1
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EP
European Patent Office
Prior art keywords
bath
oil
cationic
demulsifying
group
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EP07727340.7A
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German (de)
English (en)
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EP2010696A1 (fr
Inventor
Stella Bauerochse
Carola Komp
Ralph Berg Van Den
Peter Claude
Franz Dressler
Joachim Geldner
Zafer YÜKSEL
Eckart SCHÖNFELDER
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Chemetall GmbH
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Chemetall GmbH
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Priority to EP10173888.8A priority Critical patent/EP2253741B1/fr
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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B08—CLEANING
    • B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
    • B08B3/00—Cleaning by methods involving the use or presence of liquid or steam
    • B08B3/04—Cleaning involving contact with liquid
    • B08B3/08—Cleaning involving contact with liquid the liquid having chemical or dissolving effect
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/835—Mixtures of non-ionic with cationic compounds
    • 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
    • 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
    • C23G1/14—Cleaning or pickling metallic material with solutions or molten salts with alkaline 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
    • C23G1/14—Cleaning or pickling metallic material with solutions or molten salts with alkaline solutions
    • C23G1/16—Cleaning or pickling metallic material with solutions or molten salts with alkaline solutions using inhibitors
    • C23G1/18—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
    • 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
    • C23G1/14—Cleaning or pickling metallic material with solutions or molten salts with alkaline solutions
    • C23G1/19—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
    • C23G5/00—Cleaning or de-greasing metallic material by other methods; Apparatus for cleaning or de-greasing metallic material with organic solvents
    • C23G5/06—Cleaning or de-greasing metallic material by other methods; Apparatus for cleaning or de-greasing metallic material with organic solvents using emulsions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/72—Ethers of polyoxyalkylene glycols
    • C11D2111/16—

Definitions

  • non-polar organic contaminants e.g. Oil (s) and / or other predominantly or wholly organic soils such as e.g. Fat (s), soap (s) or / and other metalworking aids (s) such as e.g. Ziehosmittel including anionic organic compounds and particle dirt
  • an aqueous, alkaline, surfactant-containing bath solution cleaning bath,
  • the cleaning process may be used in particular as a precursor either before the pretreatment of metallic surfaces of substrates prior to painting, before the treatment or passivation of metallic surfaces such as e.g. Tapes or parts or before cleaning with an industrial washer or as an intermediate cleaning stage e.g. before a transmission or engine production serve.
  • the cleaning baths for cleaning metallic objects which are intended to remove the contaminants, in particular from the metal processing and from the corrosion protection, from the metallic surfaces of metallic objects, are initially driven in a demulsifying state.
  • the demulsifying state of the bath in an emulsifying state, and often the cleaning performance has dropped steadily.
  • Bath care means in this case: 1.
  • the high contents of anionic organic compounds in the heavily soiled cleaning bath, especially on anionic surfactants prevent by their same negative charges, which are located on the surfaces of the oil droplets, the attraction of distributed in the bath oil droplets with each other. They thus prevent the coalescence of the oil droplets to larger oil droplets and thus the demulsifying effect of forming larger droplets and the separation of oil, which could then possibly even accumulate on the bath surface, where it could easily be removed.
  • the heavily soiled cleaning baths often have an oil content in the range of 1 to 6 or even to 30 g / L (per liter bath solution) including the other soiling, a content of fats, soaps and other anionic organic compounds in the range of 0.3 to 3.5 g / L and a content of surfactants often in the order of about 1 g / L.
  • Such heavily soiled cleansing baths often have high levels of oils and other contaminants, including various surfactants.
  • a total organic bath content e.g. Approximately 10 g / L are possibly about 6 g / L oils, about 3 g / L fats and soaps and about 0.5 to 2 g / L surfactants, of which, however, often only contents in the range of about 30 to 70% by weight of nonionic surfactants which are required for cleaning, and often even about 0.3 g / L of emulsifiers from the pollution, wherein in the fats, soaps and emulsifiers about 1.5 to 3 g / L so-called anionic organic compounds are contained, some of which eg are added to the corrosion inhibitors and lubricants and hydrolyze also from fats by reaction in an alkaline medium and form anionic organic compounds.
  • anionic organic compounds such as u.a. anionic surfactants often occur in soiling.
  • a bath In a continuous bath care process, a bath is often approached once in a clean state and as long as possible continue to use the pollution with oils and other non-polar organic contaminants is continuously or repeatedly removed at short intervals to a certain extent and the substances required for cleaning be continuously or repeatedly added at short intervals to operate the cleaning bath with the highest possible cleaning performance and as uniform as possible.
  • the surfaces of membranes of membrane filtration processes can easily cover with grease, particle dirt and other contaminants and clog the pore channels of the membranes, so that they then, for. must be cleaned by rinsing. Every single-bin filtration process is extremely labor-intensive and cost-intensive.
  • the cleaning bath is used in particular as a precursor before the pretreatment of surfaces of substrates before painting or before the treatment or passivation of the metallic surfaces or before the use of an industrial car wash or for intermediate cleaning.
  • a cleaning bath contains, in addition to water, at least one surfactant and optionally also at least one substance (builder) of the scaffold, e.g. in each case at least one borate, carbonate, hydroxide, phosphate, silicate, if appropriate at least one organic solvent or / and optionally at least one additive, such as, for example, at least one defoamer and optionally at least one introduced oil and possibly further contamination.
  • At least one nonionic surfactant is typically added to the aqueous cleaning bath. Due to the contamination of the metallic surfaces but often anionic organic compounds, Oils and / or often other non-polar organic pollutants, especially fats and / or soaps, introduced.
  • the cleaning bath preferably no anionic and / or amphoteric surfactants are added, because can not be demulsified with these surfactants.
  • DE 40 01 595 A1 allegedly teaches demulsifying cleaners based on a special combination of nonionic surfactants (alkyl ethoxylates), monocarboxylic acids, anionic surfactants (alkyl sulfates, alkylpolyglycol ether sulfates and / or alkylarylsulfonates) and optionally builders.
  • nonionic surfactants alkyl ethoxylates
  • monocarboxylic acids alkyl sulfates, alkylpolyglycol ether sulfates and / or alkylarylsulfonates
  • anionic surfactants alkyl sulfates, alkylpolyglycol ether sulfates and / or alkylarylsulfonates
  • optionally builders optionally builders.
  • a cationic organic compound is not described.
  • EP 0 249 164 A1 describes new improved cationic surfactants which provide a sufficient demulsifying effect on anionic contamination and aims at improved corrosion protection of the treated parts.
  • DE 32 47 431 A1 relates to the spontaneous demulsification due to the addition of a cationic surfactant or cationic surfactant and a cationic polymer.
  • WO 2006/058570 A1 discloses a detergent concentrate based on certain glycol ethers, polyethyleneimine as emulsion breaker and cationic surfactant.
  • DE 40 14 859 A1 describes the use of combinations of cationic and nonionic surfactants in aqueous compositions for cleaning hard surfaces.
  • An object of the invention is to propose a method in which a cleaning bath for soiled metallic surfaces is easier or less expensive for oil (s), other nonpolar organic soils such as e.g. Grease (s), particulate soil, soap (s) or / and other metalworking aids (s) such as grease. Drawing aids can be cleaned.
  • Another object is to propose a cleaning process, with which even with heavy contamination of the cleaning bath with anionic organic compounds can be driven demulsifying.
  • the process according to the invention is in particular a) before the treatment, before the passivation or / and for the corrosion protection of the metallic surfaces with an aqueous, surfactant-containing bath, b) before the so-called pretreatment of metallic surfaces of substrates e.g. before painting e.g. with a pretreatment composition (conversion treatment) such as e.g. by phosphating, before joining, before forming or / and before painting, c) before use of an industrial washing plant or / and d) as intermediate cleaning, e.g. used before a gear or engine production.
  • conversion treatment such as e.g. by phosphating, before joining, before forming or / and before painting
  • bath bath solution
  • cleaning bath any distinction is made between bath, bath solution and cleaning bath and therefore mostly spoken of the "bath”.
  • the term also includes, for example, a solution, e.g. is applied by spraying.
  • the aqueous alkaline surfactant-containing bath used for the alkaline purification preferably has a pH in the range of pH 7 to 14, especially in the range of pH 8 to 12, especially in the range of pH 9 to 11.
  • oil is intended to mean, on the one hand, an "oil-containing composition” which is a composition based on many compounds having a substantially oil-containing character, comprising at least one base oil and typically also at least one anionic organic compound, such as For example, contains at least one compound based on petroleum sulfonate.
  • oil in the context of this application also means at least one base oil from this oil-containing Composition.
  • At least one base oil but also fat (s), soap (s), which at least one (further) anionic organic compound and / or some other substances added to the base oil and their reaction products, in particular with water, interfere with the soiling of the bath. because it reduces the cleaning performance of the bath or even brought to a standstill.
  • the at least one anionic organic compound acts on the state of the bath.
  • oils which may contribute to the pollution of the bath, are often naphthenic and / or aliphatic oils in question. These oils are most commonly called machining oils. They may also be used e.g. referred to and / or used as quench oils, hardening oils, scouring oils, anticorrosive oils, coolant emulsions, coolants oils, cutting oils and / or forming oils.
  • oils in the bath according to the invention may in principle also be high, such as 1 g / L, 5 g / L or 10 g / L
  • the content of either oil (s) (in the narrow spinning) or oil-containing composition ( oil (s) including other contaminants, which may be partially derived from the components of the oils, but also from chemical reactions of the components of the oil-containing composition) in the bath especially in continuous operation preferably not more than 3 g / L, especially not more than 2.5, 2, 1.5, 1, 0.8, 0.6, 0.4, 0.2 or 0.1 g / L or preferably in the range of 0.01 to 3 g / L, more preferably in the range of 0.02 to 2.2 g / L or from 0.03 to 1.5 g / L, most preferably in the range of 0.05 to 1 g / L.
  • samples are taken in the middle of the bath, in which only little or no shares of oil-containing phase can be found on the bath surface, especially in a demulsifying state.
  • the content of the cleaning bath of oil (s) including further soiling in the range of 0.03 to 2 or from 0.05 to 1 g / L and the content of surfactants in the range of 0.05 to 0.7 g / L is maintained.
  • oil (s), grease (s), soap (s), metalworking aids such as e.g. Pulling aids and / or possibly even particulate matter occur, which come as the oil (s), in particular from the metal processing and / or anti-corrosion agents.
  • Particulate matter may be present as a mixture based essentially on dust, abrasion, e.g. of metallic material (s), rubber, plastic (s) and / or abrasive (s), metallic chips, weld or / and weld beads.
  • the anionic organic compounds belong predominantly to the polar organic contaminants and generally each carry at least one carboxyl group, hydroxycarboxyl group, phosphate group, phosphonate group, sulfonate group and / or sulfate group. These compounds are generally readily soluble in water in alkaline medium. They are amphiphilic, anionic organic compounds such as e.g. anionic surfactants, petroleum sulfonate (s), aminocarboxylic acid (s), soap (s) or / and derivatives thereof. They often act as corrosion inhibitors and / or as lubricants. They are often added as additives to the oils. The oils as additives such as e.g. as corrosion inhibitors, forming aids, formulation additives, biocides, etc.
  • added substances can each be independently polar or non-polar, uncharged or anionically charged. However, the majority of these additives are usually also part of the anionic organic compounds. However, the remaining substances of these additives are usually present in comparatively small amounts. Often they do not bother or not materially.
  • Fats and fatty oils can often hydrolyze in aqueous alkaline media, forming soaps, which are also the anionic organic compounds may include, for example, based on caprylic acid, lauric acid, oleic acid, palmitic acid and / or stearic acid, in particular based on Alkalicaprylaten, alkali laurates, Alkalioleaten, Alkalipalmitaten, and / or Alkalistearaten such as sodium stearate or / and potassium stearate or especially corresponding further carboxylates. Fats and fatty oils can form hydrolyzed compounds (soaps) in the water, which often have surfactant-like properties that can be (side by side) polar and / or non-polar.
  • the pollution usually contains at least one oil, often also at least one anionic organic compound.
  • oil (s) with a lot of additives
  • there is often a limit to the demulsifying driving style of the bath because the content of anionic organic compounds, which is taken up in the bath when cleaning, is too high.
  • the initial or pre-existing demulsifying power of the bath decreases with increasing soiling e.g. by anionic organic compound (s) and can be easily depleted when the levels of anionic organic compounds are too large, because the anionic organic compounds can accumulate in the bath and limit the cleaning performance of the bath more and more.
  • An initially demulsifying demulsifying surfactant may then lose its demulsifying effect in the bath.
  • a demulsifying surfactant has a demulsifying effect under the usual conditions of a cleaning bath, but can lose its demulsifying effect, in particular by the entry of or / and the reaction to anionic organic compounds.
  • the process according to the invention is carried out for cleaning processes and baths with contaminations which have contents of anionic organic compounds, in particular contents of anionic organic compounds in the range from 0.2 g / l to very high contents, for example of the order of about 100 g / L.
  • the contents are in the range of 0.25 to 60 g / L or in the range of 0.3 to 40 g / L, particularly common in the range of 0.35 to 30 g / L or in the range of 0.4 to 20 g / L, most often in the range of 0.45 to 15 g / L, in the range of 0.5 to 10 g / L or in the range of 0.55 to 5 g / L
  • They can still be driven according to the invention easy and good demulsifying, if the corresponding contents contained in the bath or / and appropriate additions are added.
  • anionic organic compounds in many embodiments to values of not more than e.g. 50 g / L as e.g. limited by the use of a centrifugal system to throw off the dirt from the surface of the bath.
  • a centrifugal system to throw off the dirt from the surface of the bath.
  • Phosphating before joining and / or before forming, it may be recommended, if possible not more than e.g. 5 g / L of anionic organic compounds in an aqueous, alkaline, surfactant-containing bath. In a body cleaning plant in the automotive industry, it may be necessary, not more than e.g. Allow 1 g / L of anionic organic compounds in the cleaning bath to drive the system continuously and without special bath care measures.
  • anionic organic compounds in a cleaning bath can affect in some systems due to also contained certain types of oil (s) in the pollution even at very low levels on the demulsifying effect of the bath: ZB often enough already about 0.05 or about 0.1 g / L of anionic organic compounds in order to reduce or even completely prevent the demulsifying effect, which also depends inter alia on the nature of the substances present.
  • the size of the primary-cleaned oil droplets is usually very small, i. H. often of a diameter approximately in the range of 0.5 to 5 or even to 50 microns.
  • a large interface between oil and water is generally energetically unfavorable, so the chemical system tends to coalesce several small oil droplets into at least one larger one. This process is also called coalescence.
  • the method according to the invention can be optimized in the fine range.
  • This radius of curvature is preferably set in some embodiments, that the oil in a moving bath just not demulsified and that an oil-containing phase is therefore not or not yet accumulates more strongly on the surface of the bath, but in a dormant bath such as B. in a separating vessel (oil separator) spontaneously separates and accumulates on the surface of the bath as oil-containing, often other contaminants than oil-containing phase.
  • demulsifying state can be improved by the possible renewed addition of at least one cationic organic compound, which may in particular also be at least one surfactant or / and at least one cationic polymer such as at least one cationic polyelectrolyte can be maintained.
  • a state of the bath is also referred to as demulsifying state, in which the constituents of the oil-containing composition, ie in particular oil (s) and anionic organic compound (s), separate off and, in particular, also on the bath surface as an oil-containing phase accumulate and remove.
  • the bath can be cleaned ("maintained") in a simple manner by skimming the dirt from the bath surface.
  • Demulsification is caused by small droplets of oil converging to give larger drops of oil. If the oil drops are large enough, they can float to the surface of the bath and continue to accumulate there. This process may be due to levels of emulsifiers and / or to anionic organic. Compounds are impaired or even suppressed.
  • the demulsifying state of a bath is darari recognizable that when the bath movement is diminished or felt, an oil-containing phase separates spontaneously and optionally accumulates on the surface of the bath and / or in rare cases on the bottom of the bath container as an oil-containing phase, while In a certain or strong bath movement no oil-containing phase separates.
  • no emulsifier or in individual embodiments only a small amount of at least one emulsifier of up to 0.5 g / L is intentionally added to the bath, preferably up to 0.2 g / L, particularly preferably up to 0.05 g / L, especially if the bath has little or no bath movement.
  • At least one emulsifier may also be introduced by the pollution.
  • the demulsifying surfactants and the cationic organic compounds act as demulsifiers.
  • the nonionic surfactants used for the purification also often act as demulsifiers. In particular, they act as emulsifiers if the arrangement of the surfactant molecules on the oil droplet does not lead to excessive curvature.
  • the droplet size of the oil droplets clarifies the Bath condition: The smaller the oil droplets, the more emulsifying the bath, and the larger the oil droplets are, the more demulsifying the bath is.
  • the process of coalescence is reduced or even suppressed by the presence of anionic organic compounds in the bath, as the anionic organic compounds absorbed on the oil droplets charge the oil droplets of the same name, which in turn leads to a repulsion of the oil droplets with each other. Due to the addition of e.g. Of cationic organic compounds, this anionic charge can be partially or even completely neutralized, so that further a demulsifying state and the coalescence of the oil droplets can proceed.
  • the content of anionic organic compounds in the bath solution is e.g. determined by Epton titration and that appropriate amounts of at least one cationic organic compound are added to the bath.
  • the total amounts of cationic organic compounds contained in the bath are therefore preferably to be selected so that the demulsifying state is reached again or / and continued to the desired extent. It may be advantageous in some embodiments, if a just demulsifying, but not yet a strong demulsifying state is set.
  • the at least one demulsifying surfactant contained in the bath and / or added to the bath is preferably selected from nonionic surfactants and / or from cationic surfactants, in particular from nonionic demulsifying surfactants and / or from cationic demulsifying surfactants .
  • all cationic surfactants can be obtained by interaction with at least one anionic organic Compound demulsifying effect.
  • many nonionic surfactants have a demulsifying effect, in particular due to their molecular geometry, polarity of the total molecule or / and the surfactant mixture.
  • the at least one demulsifying surfactant serves to reduce the surface tension, to clean, to demulsify, to adjust the emulsifying or demulsifying properties or / and to reduce the foaming tendency.
  • the at least one demulsifying, especially cationic and / or nonionic, surfactant also acts as a demulsifying surfactant as long as the conditions of use are such that it is in a demulsifying state that is substantially dependent on the chemical composition, the nature and amount of the contaminants , depends on the salt content and the temperature of the bath as well as on the type and performance of Badum stiilzung or pumps.
  • the levels of demulsifying surfactants in the cleaning bath in the dipping process are in the range of 0.2 to 10 g / L, usually independent of whether they are continuous or batch processes.
  • At least one demulsifying surfactant is selected from the group of nonionic surfactants and is in particular at least one based on ethoxylated alkyl alcohols with end capping and ethoxylated-propoxylated alkyl alcohols with end capping, wherein the alkyl group of the alkyl alcohols - saturated or unsaturated, branched or unbranched - has an average number of carbon atoms in the range of 6 to 22 carbon atoms, each having either linear or branched chain formation, wherein the alkyl group optionally has one or more aromatic and / or phenolic groups, the ethylene oxide chain optionally each averaging 2 has up to 30 ethylene oxide units, wherein the propylene oxide optionally has in each case on average 1 to 25 propylene oxide units and wherein an end group closure in particular with an alkyl group - saturated or unsaturated, branched or unbranched - having an average of 1 to 8 carbon atoms.
  • demulsifying surfactants or / and of nonionic surfactants are proportionately removed with the contaminants from the cleaning baths and must therefore be replenished accordingly in order to maintain or reset the cleaning performance.
  • These surfactants are usually subject to no chemical reactions, usually remain in solution and thus usually remain proportionately or largely preserved in the bath, but are proportionately removed with the contaminants from the bath.
  • At least one cationic organic compound contained in and / or added to the cleaning bath is preferably selected from the group consisting of cationic surfactants and cationic polymers.
  • cationic polymers as in the other places, where not the other polymeric variants are listed, for a selection from the group consisting of cationic polymers, cationic copolymers, cationic block copolymers and cationic graft copolymers.
  • the cationic organic compounds serve in particular to produce and / or enhance the optionally weakly demulsifying, too weakly demulsifying or even missing demulsifying mode of action and action of the bath containing at least one demulsifying nonionic surfactant due to the demulsifying action of the at least one cationic organic compound and / or to maintain the demulsifying driving style and effect of the bath as long as possible or even permanently. Due to the demulsifying procedure, oil is separated from the bath and extends the service life of the bath.
  • 1 to 1,000,000 quaternary ammonium groups or / and 1 to 1,000,000 nitrogen-containing heterocyclic positively charged groups having 5 or 6 ring atoms in one molecule may occur, in each case independently of one another preferably 5 to 800,000, particularly preferably 15 to 600,000, most preferably 25 to 400,000.
  • 5 to 1,500,000 units of a monomer building block or several different monomer building blocks can occur in one molecule, in each case independently of one another, preferably 25 to 1,100,000, particularly preferably 75 to 600,000, very particularly preferably 100 to 200,000.
  • these can be arranged, if appropriate in specific regions, randomly, isotactically, syndiotactically, atactically and / or in blocks, for example as block copolymers or graft copolymers.
  • this term includes, as elsewhere, also those in which the other polymeric variants are not listed, for a choice from the group consisting of cationic polymers, cationic copolymers, cationic block copolymers and cationic graft copolymers - the at least one alkyl Group - saturated or unsaturated, branched or unbranched - each independently 3 to 160 carbon atoms, more preferably 5 to 120 carbon atoms, most preferably 8 to 90 carbon atoms.
  • the counterions to the amphiphilic compounds and to the cationic polymers are preferably anions selected from the group consisting of alkyl sulfate, carbonate, carboxylate, halide, nitrate, phosphate, phosphonate, sulfate or / and sulfonate-based ions.
  • ions based on halide such as, for example, bromide and / or chloride or / and ions based on carboxylate can also be used as counterions especially such as acetate, benzoate, formate, gluconate, heptonate, lactate, propionate, fumarate, maleate, malonate, oxalate, phthalate, succinate, tartrate, terephthalate and / or citrate occur.
  • the cationic polymers only or essentially only monovalent ions preferably occur as counterions.
  • Both the cationic organic compounds and the anionic organic compounds are usually polar and water-soluble.
  • the ions neutralize.
  • the cations in particular the alkalis and / or alkaline earths, in particular ammonium, sodium and / or potassium ions and the anions, in particular chloride ions, enter the aqueous solution and can remain there. Due to the removal, losses such as by discharging and / or circulation of the bath solution, the amount of water is always replenish, so that in many cases, the salts do not accumulate too much.
  • the cationic organic compounds and the anionic organic compounds often form salified with ionic interaction reaction products, which are mostly very hydrophobic, water-insoluble adducts. Therefore, these reaction products accumulate more in the oil-containing soils and / or in the oil-containing phase and can be removed with them. These reaction products interfere because they are very hydrophobic and behave like oils disturbing.
  • a content of cationic organic compounds is added to the bath, in particular in discontinuous operation, in an amount in which the stoichiometric ratio of cationic organic compounds to anionic organic compounds is in the range of 0, 9: 1 to 1: 1 is held.
  • not more than 1 g / L of cationic organic compounds particularly preferably not more than 0.1 g / L, very particularly preferably not more than 0.01 g / L cationic organic compounds.
  • the bath is usually only weakly or very weakly demulsifying. If the at least one cationic organic compound is present in excess in the bath compared to the unreacted anionic organic compounds present, then the bath is emulsifying and contains little oil (s) and / or contaminants associated therewith, but the cleaning performance has usually already decreased. In a middle range of this ratio of cationic organic compounds to the present unreacted anionic organic compounds in the bath is usually both the demulsifying effect of the bath, as well as its cleaning performance high and at the same time the content of oil (s) and / or associated pollution low or very low. Therefore, it is advisable to work in many variants, such as the limit of cationic behavior to anionic behavior. Higher cleaning performance is also associated with a better cleaning result.
  • the cleaning bath additionally contains at least one scaffold, that is at least one builder, and / or this is added to the bath.
  • the scaffold of the scaffold can help to create an rusting effect such as flash rusting on steel or white rust formation
  • the scaffold may preferably contain at least one borate-based builder such as e.g. Orthoborate (s) or / and tetraborate (s), of silicate (s) such as e.g. Metasilicate (s), orthosilicate (s) or / and polysilicate (s), phosphate (s) such as e.g. Orthophosphate (s), tripolyphosphate (s) or / and pyrophosphate (s), at least one alkaline medium e.g. based on potassium hydroxide solution, sodium hydroxide solution, sodium carbonate, sodium bicarbonate, potassium carbonate or / and potassium bicarbonate, at least one amine such as e.g.
  • a borate-based builder such as e.g. Orthoborate (s) or / and tetraborate (s), of silicate (s) such as e.g. Metasilicate (s), orthosilicate (s) or / and polysilicate (s), phosphat
  • monoalkylamine s
  • trialkylamine s
  • monoalkanolamine s
  • / and trialkanolamine s
  • Monoethanolamine triethanolamine, methyldiethanolamine or / and at least one complexing agent, e.g. based on carboxylate (s) such as e.g. Gluconate or / and heptonate, sodium nitrilotriacetic acid (NTA) or / and phosphonate (s), e.g. HEDP included.
  • carboxylate s
  • NTA sodium nitrilotriacetic acid
  • s e.g. HEDP included.
  • the content of builders is in particular either 0 or in the range of 0.1 to 290 g / L or of 0.2 to 120 g / L, preferably 0 or in the range of 0.5 or from 1 to 100 g / L or from 1.5 to 48 g / L, more preferably 0 or in the range of 3 to 25 g / L.
  • levels of builders are used in spraying processes in the range of 1 to 50 g / L, in the case of immersion processes in the range of 2 to 100 g / L, usually irrespective of whether they are continuous or discontinuous processes.
  • the bath contains at least one additive such as a corrosion inhibitor and / or at least one additive is optionally added to the bath again.
  • a corrosion inhibitor for example, those based on alkylamidocarboxylic acid (s), aminocarboxylic acid (s), alkylhexanoic acid (s) and / or boric acid ester (s), in particular their amine salt (s), may be present in the bath and / or added to the bath.
  • the content of corrosion inhibitor (s) is in particular 0 or in the range of 0.01 to 10 g / L, preferably 0 or in the range of 0.1 to 3 g / L, particularly preferably 0 or in the range of 0, 3 to 1 g / L.
  • At least one additive such as at least one biocide and / or at least one defoamer may be contained in the bath and / or added to the bath, especially in the range of 0.01 to 0.5 g / L.
  • the bath may also contain at least one pickling inhibitor and / or be added to it.
  • Pickling inhibitors help to reduce or prevent the alkaline attack of the cleaning bath especially on surfaces of aluminum, magnesium, zinc or / and their alloys. They often act quite selectively depending on the type of metallic surfaces to be protected, so that they are partially used in certain mixtures.
  • the bath content of the pickling inhibitors is preferably 0 or in the range of 0.01 to 10 g / L, particularly preferably in the range of 0.1 to 8 g / L.
  • Boric acid (s), silicate (s) and / or phosphonate (s) can be used as the pickling inhibitor (s), among others.
  • the anionic organic compounds which are optionally present in the bath and are usually derived only from soils, in particular the anionic surfactants, are rendered less water-soluble, preferably by a chemical reaction with at least one cationic organic compound or / and with polyvalent cations.
  • the resulting insoluble compounds accumulate on the bath surface at least partially, especially in the oil-containing phase, and can then be removed from the bath as needed.
  • These surfactants are usually derived mainly from the contaminants.
  • the amphoteric surfactants and phosphate esters which usually also originate only from the contaminants, generally do not react chemically in this manner and generally remain dissolved in the bath solution as they are. All of these surfactants are preferably not intentionally added to the bath as they may interfere with demulsification and excessive foam tendency, especially.
  • the total content of all active ingredients in the bath is in the range from 1 to 300 g / L or from 1.5 to 150 g / L, preferably in the range from 2 to 50 g / L or from 3 to 30 g / L, more preferably in the range from 4 to 20 g / L, from 5 to 15 g / L or from 5.5 to 12 g / L.
  • a cleaning method in many embodiments that accumulate not more than 10 g / L of anionic organic compounds in the bath until bath care, and it is particularly preferred, not more than 5 g / L or not more than 3.5 g / L, most preferably not more than 2 g / L of anionic organic compounds in the bath.
  • cationic organic compounds formed over a few hours to about 2 days, often about 1 to 15 cm thick layer of oil (s) and nonpolar organic compounds on the bath surface as an oil-containing phase, which then in a simple manner, for example can be removed mechanically and / or by lifting the bath level and draining.
  • the amount of cationic organic compounds to be added in this case can be determined either accurately by Epton titration, by chromatography or simply, accurately and effectively by adding several proportions of cationic organic compounds in order to determine the latter method. after which amount no significant amounts of oil (s) and nonpolar organic compounds are deposited more and float to the bath surface, so the bath is no longer demulsified.
  • anionic organic compounds and cationic organic compounds in the context of this application mean the corresponding unreacted compounds and not the adducts resulting therefrom.
  • the bath solution can also be applied in at least one cleaning zone, for example by spraying or / and by spraying and brushing.
  • the at least one substrate may optionally also be treated electrolytically, ie by electrolytic cleaning.
  • these, but also other variants of the method are also suitable for tapes.
  • the applied pressure is in the cleaning process often substantially at atmospheric pressure, when printing in circulation processes, for example by injection flooding (up to about 50 bar) is dispensed with, while often worked in injection molding with injection pressures in the range of 0.1 to 5 bar becomes.
  • the temperatures are in the cleaning process - depending partially on the chemical composition - preferably in the range of 5 to 99 ° C, more preferably in the range of 10 to 95 ° C, wherein spraying often in the range of 40 to 70 ° C and dipping often in Range of 40 to 95 ° C are applied.
  • the nonionic surfactants typically have an HLB in the range of 5 to 12, often in the range of 6 to 12. Surfactants are preferably effective at HLB values ⁇ 10, especially at ⁇ 9 demulsifying.
  • substrates in the form of sheets, coils (strips), wires, parts or / and composite components are cleaned.
  • the substrates which are cleaned according to the invention preferably have metallic surfaces of iron, steel, stainless steel, galvanized steel, metal-coated steel, aluminum, magnesium, titanium or / and their alloys.
  • cleaning processes have been found which can be practiced, or possibly permanently, with significantly lower levels of oil (s) including other contaminants than heretofore available in the art with such contaminants, and where the initial high cleaning performance can be sustained over time while in the processes of the prior art often decreases continuously, if no membrane filtration processes are used:
  • oil contaminated metallic surfaces has a content of oil (s), including other soiling when soiled, of at least 0.7 g / L and often in the range of 0.8 to 1.2 g / L eg in automobile systems with bath care and at least 1.5 g / l and often up to approx.
  • the cleaning baths with a content of oil (s) including further pollution at heavy pollution in the range of at least 0.05 to at least 1 g / L depending on the type of equipment and use and often in the order of about 0.5 g / L, for example, in automobile systems with bath care or in the order of about 8 g / L of oil (s) including further pollution eg in general industrial plants without bath care are used.
  • the content of the cleaning bath of oil (s), including other contaminants can often be maintained in the range of 0.05 to 1 g / L, while in typical prior art cleaning processes, the content of the cleaning bath of oil (s) includes often further in the range of 0.7 to 6 g / L or / and the content of surfactants in the range of 0, 3 to 1.5 g / L.
  • cleaning methods were found that are relatively easy to use and their consumption costs are slightly higher depending on the initial conditions by the hitherto unnecessary addition of cationic organic compounds or due to decreasing consumption of chemicals due to increased cleaning power consumption costs of about the same or even lower level than before require.
  • the substrates purified by the process according to the invention can be used for phosphating, in particular for alkali phosphating, e.g. for iron phosphating, for manganese phosphating or for zinc phosphating and / or for coating with at least one treatment or pretreatment composition based on silane / siloxane / polysiloxane, titanium / zirconium compound, iron oxide / cobalt oxide, chromate, oxalate, phosphonate phosphate or / and organic polymer / Copolymer or / and for coating with at least one composition based on a substantially organic polymeric composition, with a welding primer, with a galvanic coating, with an enamel coating, with anodization, with a CVD coating, with a PVD Coating or / and be used with a temporary anti-corrosion coating.
  • alkali phosphating e.g. for iron phosphating, for manganese phosphating or for zinc phosphating and / or for coating with at
  • the cleaning zones are made to resist phosphating two zones: 1 alkaline degreasing and 2nd alkaline degreasing. In both degreasing baths, substantially the same aqueous composition is used.
  • the respective bath life could be doubled depending on the driving behavior, in some cases even at least quadrupled until the entire bath was replaced and thereby renewed.
  • the oil, including the other contaminants was largely contained on the bath surface as an oil-rich phase Enriched fats and other nonpolar organic pollutants.
  • the oil-rich phase contained only 2 to 30 wt .-% aqueous phase including builders and surfactants and even 70 to 98 wt .-% in the essential oil (s) and other constituents of the oil-containing phase.
  • the oil-rich phase could then be skimmed off, for example after one day.
  • the bath had about 0.5 to 1 g / L of oil (s), including the other soiling.
  • the at least one anionic or / and nonionic surfactant which is basically contained in the bath composition, had to be added again since these surfactants were partially removed with the oil-rich phase.
  • the at least one cationic, demulsifying surfactant was not replenished immediately, but only when the contents of oil (s) including further contaminants in the bath have again adjusted to 2.5 to 4 g / L after several weeks.
  • This surfactant was specially selected according to the conditions for the demulsifying procedure.

Claims (15)

  1. Procédé de nettoyage désémulsifiant de surfaces métalliques qui sont le cas échéant salies avec de l'huile (des huiles), avec au moins un autre composé organique non polaire, avec de la (des) graisse(s), avec du (des) savon(s), avec des salissures particulaires ou/et avec au moins un composé organique anionique, au moyen d'un bain de solution aqueux alcalin, contenant des agents tensioactifs (= bain de nettoyage, bain), où, lors du nettoyage des surfaces métalliques, le bain est souillé avec de l'huile (des huiles), avec au moins un autre composé organique non polaire, avec de la (des) graisse(s), avec du (des) savon(s), avec des salissures particulaires ou/et avec au moins un composé organique anionique, caractérisé
    en ce que l'on travaille avec un procédé par immersion,
    en ce que, lors du procédé par immersion, on utilise des teneurs en agents tensioactifs désémulsifiants comprises dans la plage allant de 0,2 à 10 g/L,
    en ce que le bain contient au moins un agent tensioactif désémulsifiant ou/et que celui-ci est ajouté au bain,
    en ce que l'on choisit parmi des agents tensioactifs non ioniques à base d'alcools alkyls éthoxylés à verrouillage de groupe terminal, et d'alcools alkyls éthoxylés-propoxylés à verrouillage de groupe terminal,
    en ce que le bain contient en outre au moins un composé organique cationique ou/et que celui-ci est ajouté au bain,
    en ce que l'on ajoute au bain une teneur en composés organiques cationiques en une quantité où le rapport stoechiométrique entre les composés organiques cationiques et les composés organiques anioniques est maintenu dans la plage allant de 0,7 : 1 à 1,2 : 1, et
    en ce que le bain est maintenu dans un état désémulsifiant, même en cas de salissure croissante, notamment avec au moins un composé organique anionique,
    sachant que l'état désémulsifiant est maintenu par l'ajout éventuellement renouvelé d'au moins un composé organique cationique, et
    sachant que le rayon de courbure des gouttelettes d'huile est classé de manière telle que dans un bain agité, l'huile ne se désémulsifie tout juste pas encore et que par conséquent, une phase contenant de l'huile ne s'enrichisse tout juste pas encore ou pas encore plus intensément à la surface du bain, mais se sépare spontanément dans un bain mort.
  2. Procédé selon la revendication 1, caractérisé en ce que, en service continu, la teneur en huile(s) ou en composition contenant de l'huile (= huile(s) ainsi que d'autres salissures) dans le bain est maintenue à une valeur ne dépassant pas 3 g/L.
  3. Procédé selon la revendication 1 ou 2, caractérisé en ce que l'agent tensioactif désémulsifiant, au nombre d'au moins un, est choisi parmi des agents tensioactifs non ioniques à action désémulsifiante ou/et des agents tensioactifs cationiques à action désémulsifiante.
  4. Procédé selon l'une des revendications précédentes, caractérisé en ce que l'on choisit au moins un agent tensioactif désémulsifiant dans le groupe des agents tensioactifs non ioniques à base d'al- , cools alkyls éthoxylés à verrouillage du groupe terminal et d'alcools alkyls éthoxylés-propoxylés à verrouillage du groupe terminal, sachant que le groupe alkyle des alcools alkyls - saturé ou insaturé, ramifié ou non ramifié - présente un nombre moyen d'atomes de carbone compris dans la plage allant de 6 à 22 atomes de carbone, avec formation de chaîne respectivement linéaire ou ramifiée, sachant que le groupe alkyle présente le cas échéant un ou plusieurs groupes aromatiques ou/et phénoliques, la chaîne oxyde d'éthylène présentant le cas échéant en moyenne respectivement 2 à 30 unités oxyde d'éthylène, la chaîne oxyde de propylène présentant le cas échéant en moyenne respectivement 1 à 25 unités oxyde de propylène, et sachant qu'il y a un verrouillage de groupe terminal notamment avec un groupe alkyle - saturé ou insaturé, ramifié ou non ramifié - avec en moyenne 1 à 8 atomes de carbone.
  5. Procédé selon l'une des revendications précédentes, caractérisé en ce que l'on choisit au moins un composé organique cationique dans le groupe de composés constitué d'agents tensioactifs cationiques et de polymères cationiques.
  6. Procédé selon la revendication 5, caractérisé en ce que l'on choisit au moins un composé organique cationique
    a) parmi des composés amphiphiles qui présentent au moins un groupe ammonium quaternaire ou/et au moins un groupe cyclique avec au moins un atome d'azote comme groupe de tête, sachant que soit l'atome d'azote, au nombre d'au moins un, du groupe cyclique, soit le groupe cyclique comporte au moins une charge positive et présente le groupe alkyle, au nombre d'au moins un, ou, à la place de celui-ci, au moins un groupe aromatique, sachant que le groupe alkyle, au nombre d'au moins un, présente, indépendamment l'un de l'autre - saturé ou insaturé - avec respectivement un nombre moyen d'atomes de carbone compris dans la plage allant de 4 à 22 atomes de carbone, avec formation de chaîne respectivement linéaire ou ramifiée, sachant que le groupe alkyle présente le cas échéant, indépendamment l'un de l'autre - saturé ou insaturé, ramifié ou non ramifié - respectivement un ou plusieurs groupes aromatiques, et sachant que le cas échéant au moins un groupe alkyle peut présenter un nombre différent d'atomes de carbone qu'au moins un autre groupe alkyle,
    b) parmi des polymères cationiques qui, dans le cas de polymères cationiques solubles dans l'eau, sont souvent également des polyélectrolytes cationiques,
    sachant que les polymères cationiques b1) contiennent au moins un groupe ammonium quaternaire et au moins quatre unités d'un élément constitutif monomère, ou
    sachant que les polymères cationiques b2) contiennent au moins un groupe ammonium quaternaire ou/et au moins un groupe ammonium quaternaire ou/et au moins un groupe hétérocyclique à charge positive, contenant de l'azote, avec 5 ou 6 atomes cycliques et au moins cinq unités d'un élément constitutif monomère ou plusieurs éléments constitutifs monomères différents dans au moins une chaîne polymère.
  7. Procédé selon l'une des revendications précédentes, caractérisé en ce que dans les composés amphiphiles ou/et les composés organiques cationiques, il y a comme contre-ions des ions à base de sulfate d'alkyle, carbonate, carboxylate, halogénure, nitrate, phosphate, phosphonate, sulfate ou/et sulfonate.
  8. Procédé selon l'une des revendications précédentes, caractérisé en ce que l'on ajoute au bain - notamment en fonctionnement discontinu - une teneur en composés organiques cationiques, en une quantité où le rapport stoechiométrique entre les composés organiques cationiques et les composés organiques anioniques dans le bain est maintenu dans la plage comprise entre 0,9 : 1 et 1 : 1.
  9. Procédé selon l'une des revendications précédentes, caractérisé en ce que l'on fait en sorte que les composés organiques anioniques, notamment les agents tensioactifs anioniques, soient moins solubles dans l'eau, par le biais d'une réaction chimique avec au moins un composé organique cationique.
  10. Procédé selon l'une des revendications précédentes, caractérisé en ce que le bain contient en plus au moins un adjuvant pour détergent (builder) ou/et que celui-ci est ajouté au bain.
  11. Procédé selon l'une des revendications précédentes, caractérisé en ce que le bain contient en plus au moins un inhibiteur de corrosion ou/et au moins un autre additif ou/et que celui-ci/ceux-ci est/sont ajouté(s) au bain.
  12. Procédé selon l'une des revendications précédentes, caractérisé en ce que la teneur totale de tous les agents actifs dans le bain est comprise dans la plage allant de 1 à 300 g/L.
  13. Procédé selon l'une des revendications précédentes, caractérisé en ce que l'on nettoie des substrats sous forme de tôles, de bobines, de fils métalliques, de pièces ou/et d'éléments composites.
  14. Procédé selon l'une des revendications précédentes, caractérisé en ce que l'on nettoie des substrats qui présentent de préférence des surfaces métalliques en fer, acier, acier inoxydable, acier galvanisé, acier à revêtement métallique, aluminium, magnésium, titane ou/et leurs alliages.
  15. Utilisation des substrats nettoyés conformément au procédé selon les revendications 1 à 14, pour la phosphatation ou/et pour le revêtement avec au moins une composition de traitement ou de traitement préalable à base de silane/siloxane/polysiloxane, composé de titane/zirconium, oxyde de fer/oxyde de cobalt, chromate, oxalate, phosphonate/phosphate ou/et polymère/copolymère organique ou/et pour le revêtement avec au moins une composition à base d'un composé polymère essentiellement organique, avec un primaire de soudage, avec un revêtement galvanique, avec un revêtement d'émail, avec une anodisation, avec un revêtement CVD, avec un revêtement PVD ou/et avec un revêtement anticorrosion temporaire.
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US20100068392A1 (en) 2010-03-18
MX2008013310A (es) 2009-01-09
EP2253741B1 (fr) 2018-05-16
BRPI0711624A2 (pt) 2011-12-06
CN102787320B (zh) 2014-10-29
CN101473068A (zh) 2009-07-01
BRPI0711624B1 (pt) 2018-04-03
US20120273013A1 (en) 2012-11-01
CA2650947A1 (fr) 2007-11-01
EP2253741A3 (fr) 2014-01-08
ZA200809775B (en) 2010-02-24
EP2010696A1 (fr) 2009-01-07
DE102006018216B4 (de) 2008-09-25
WO2007122056A1 (fr) 2007-11-01
DE102006018216A1 (de) 2007-10-31
CA2650947C (fr) 2016-05-24
US20140041693A1 (en) 2014-02-13
US8609195B2 (en) 2013-12-17
ES2586573T3 (es) 2016-10-17
MX318016B (es) 2014-02-12
US20140311533A1 (en) 2014-10-23
CN101473068B (zh) 2012-07-04
US9731331B2 (en) 2017-08-15
CN102787320A (zh) 2012-11-21
ES2684116T3 (es) 2018-10-01
EP2253741A2 (fr) 2010-11-24

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