EP2205711A1 - Composition nettoyante pour surfaces métalliques - Google Patents

Composition nettoyante pour surfaces métalliques

Info

Publication number
EP2205711A1
EP2205711A1 EP08839358A EP08839358A EP2205711A1 EP 2205711 A1 EP2205711 A1 EP 2205711A1 EP 08839358 A EP08839358 A EP 08839358A EP 08839358 A EP08839358 A EP 08839358A EP 2205711 A1 EP2205711 A1 EP 2205711A1
Authority
EP
European Patent Office
Prior art keywords
bath
cationic
group
groups
demulsifying
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP08839358A
Other languages
German (de)
English (en)
Other versions
EP2205711B1 (fr
Inventor
Carola Komp
Eckart SCHÖNFELDER
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Chemteall GmbH
Chemetall GmbH
Original Assignee
Chemteall GmbH
Chemetall GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=40243874&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=EP2205711(A1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Chemteall GmbH, Chemetall GmbH filed Critical Chemteall GmbH
Priority to PL08839358T priority Critical patent/PL2205711T3/pl
Publication of EP2205711A1 publication Critical patent/EP2205711A1/fr
Application granted granted Critical
Publication of EP2205711B1 publication Critical patent/EP2205711B1/fr
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • C11D1/721—End blocked ethers
    • 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
    • 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
    • C11D1/38—Cationic compounds
    • C11D1/62—Quaternary ammonium compounds
    • 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
    • C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/10—Objects to be cleaned
    • C11D2111/14—Hard surfaces
    • C11D2111/16—Metals

Definitions

  • surfactant-containing bath solutions cleaning baths, baths
  • non-polar organic contaminants such as Oil (s) or / and other predominantly or completely organic soils such as e.g. Fat (s), soap (s) or / and other metal working aids (s)
  • Drawing aids including anionic organic see compounds and particle dirt are polluted
  • the invention also relates to a suitably soiled bath comprising an aqueous alkaline cleanser composition containing at least one demulsifying nonionic surfactant of the invention and a correspondingly higher concentration concentrate for preparing an aqueous alkaline cleanser composition, inter alia, by dilution with water.
  • the cleaning process for this cleaning composition can be used in particular as a precursor either before the pretreatment of metallic surfaces of substrates before 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 the cleaning of 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 in a demulsifying state.
  • the demulsifying state of the bath in an emulsifying state, and often the cleaning performance has dropped steadily.
  • such a condition can occur after a period of about one day to about 8 weeks. Then the questions arise, in what way the cleaning bath can be brought back into a state of high cleaning performance and what effort this is to drive in the bath care.
  • Bath care means: 1.
  • the high contents of anionic organic compounds in the heavily soiled cleaner bath, in particular on anionic surfactants, prevent the attraction of the oil droplets distributed in the bath by their negative charges of the same type, which are located on the surfaces of the oil droplets. 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 1 to 30 g / L (per liter of bath solution) including the further 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.
  • membrane filtration systems are often used to remove oil and other contaminants from the cleaning zone located in a pre-treatment plant before a Phosphatie- tion zone to allow the most continuous cleaning of the cleaner bath and a consistently high cleaning performance to ensure.
  • an oil separator such as e.g. a sedimentation tank, de-oiler, coalescer, separator, centrifuge or similar oil separation equipment (in particular membrane-free gravity processes and density separation separation) for the separation and removal of oils and other non-polar organic pollutants from the purifier bath and its circulation, wherein the contaminants of the detergent bath continuously accumulate in the oil separator and can be removed there if necessary;
  • an oil separator such as e.g. a sedimentation tank, de-oiler, coalescer, separator, centrifuge or similar oil separation equipment (in particular membrane-free gravity processes and density separation separation) for the separation and removal of oils and other non-polar organic pollutants from the purifier bath and its circulation, wherein the contaminants of the detergent bath continuously accumulate in the oil separator and can be removed there if necessary;
  • a bath In a continuous bath care process, a bath is often approached once in a clean state and continue to use as long as possible, with the pollution with oils and other nonpolar organic contaminants is continuously or repeatedly removed at frequent intervals to a certain extent and the cleaning required substances continuously or repeatedly be added at short intervals in order to operate the cleaner bath with the highest possible cleaning performance and as uniform as possible.
  • the surfaces of the membranes of membrane filtration processes can easily be coated with grease, particulate dirt and other contaminants and clog the pore channels of the membranes, so that they then become e.g. must be cleaned by rinsing. Every membrane filtration process is extremely labor-intensive and cost-intensive.
  • the cleaner bath is used in particular as a precursor before the pretreatment of surfaces of substrates prior to 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 detergent bath contains not only water but at least one surfactant and optionally also at least one substance (builder) of the detergent structure such as For example, in each case at least one borate, carbonate, hydroxide, phosphate, silicate, optionally at least one organic solvent or / and optionally at least one additive such as at least one defoamer and optionally at least one entrained oil and optionally further contamination.
  • At least one nonionic surfactant is typically added to the aqueous detergent bath. Due to the contamination of the metallic surfaces but often anionic organic compounds, oils and / or often other non-polar organic contaminants, especially fats and / or soaps, are introduced.
  • the cleaner bath is constantly maintained in a demulsifying state.
  • the demulsifying state of the detergent bath is achieved by the addition or by the content of at least one nonionic surfactant according to the invention.
  • no anionic or / and amphoteric surfactants are added to the demulsifying detergent bath, because they can not be demulsified with these surfactants.
  • DE 102006018216 A1 teaches processes for demulsifying purification and mentions a multiplicity of surfactants and cationic organic polymers which are fundamentally possible for the design of a demulsifying purification process.
  • demulsifying surfactants certain classes of nonionic or cationic surfactants are listed with their basic composition.
  • DE 102006018216 A1 and its associated foreign applications are expressly incorporated into this application, in particular with regard to the purification processes and effects.
  • a further object is to propose an aqueous cleaner composition which can be used for demulsifying even if the cleaner bath is heavily contaminated with anionic organic compounds.
  • an aqueous alkaline cleaning composition for cleaning metallic surfaces which contains at least one demulsifying nonionic surfactant, based on e-ethoxylated alkyl alcohols having one or two alkyl groups having in each case an average of 7.5 to 16.5 carbon atoms and having on average from 5.5 to 18.5 EO groups per alkyl group, and with one or two end-capping compounds, at least one end-capping compound being an isopropyl, isobutyl, tertiarybutyl or / and benzyl group, said surfactant being non-propoxylated.
  • the invention is also achieved with a soiled bath containing an aqueous alkaline cleaning composition containing the at least one nonionic surfactant of the invention which acts as a de-emulsifier and a contaminant.
  • the invention is further achieved with an aqueous concentrate for an aqueous alkaline cleaning composition, wherein the at least one demulsifying nonionic surfactant of the invention is contained in a higher concentration by a factor of 5 to 5,000 than in the aqueous alkaline detergent composition obtainable therefrom.
  • water of city water quality or / and fully desalted water is used to dilute the concentrate.
  • the concentrate is mixed with water by a factor in the range of 50 to 3500, from 100 to 3000 or from 200 to 2500, more preferably in the range of 300 to 2000 or of 400 to 1500 or of 500 to 1000.
  • This concentrate is used to prepare an aqueous alkaline detergent composition, inter alia, by dilution with water, but optionally also by adding further substances, such as, for example, scaffolds and / or additives.
  • demulsifying nonionic surfactants based on ethoxylated alkyl alcohols according to the invention are outstandingly suitable for an alkaline aqueous demulsifying cleaner composition with regard to their cleaning performance, their demulsifying action and their low foaming tendency, in particular simultaneously because of all three properties.
  • the at least one demulsifying nonionic surfactant according to the invention acts demulsifying.
  • the demulsifying nonionic surfactant according to the invention has a benzyl group in at least one end group closure. In particular, it has only one end group closure.
  • the alkyl groups may independently of one another be linear or branched, which are independently saturated or unsaturated.
  • a plurality of demulsifying nonionic surfactants according to the invention having a significantly different molecular structure may be present in the detergent composition according to the invention in accordance with the main claim.
  • the demulsifying nonionic surfactant according to the invention is at least one ethoxylated alkyl alcohol having one or two alkyl groups having in each case on average 7.5 to 14.5 carbon atoms and especially with on average 5.5 to 18.5 EO groups per alkyl group and with one or two end group closures, of which at least one end group closure is an isopropyl, isobutyl, tert-butyl or / and benzyl group, in particular at least one benzyl group End-cap is, wherein the surfactant is not propoxylated.
  • it has only one alkyl group.
  • the alkyl groups may independently be linear or branched, which are independently saturated or unsaturated.
  • the demulsifying nonionic surfactant according to the invention is particularly preferably at least one ethoxylated alkyl alcohol having one or two alkyl groups having an average of in each case 7.5 to 12.5 carbon atoms and in particular having an average of 7.5 to 14.5 EO groups per alkyl group and having one or two end group closures, of which at least one end group closure is an isopropyl, isobutyl, tertiary butyl or / and benzyl group, in particular in each case at least one tertiary butyl or / and benzyl group, in particular at least one benzyl group is an end group closure, the surfactant not being is propoxylated.
  • it has only one alkyl group.
  • the alkyl groups may independently be linear or branched, which are independently saturated or unsaturated.
  • the demulsifying nonionic surfactant according to the invention is very particularly preferably at least one ethoxylated alkyl alcohol having an average of 8.5 to 11.5 carbon atoms and in particular having an average of 9.5 to 12.5 EO groups per alkyl group and having a benzyl group as end group closure, wherein the surfactant is not propoxylated.
  • the alkyl group may be linear or branched, it may be saturated or unsaturated.
  • Two alkyl groups are gemini Surfactants.
  • Each alkyl group may, where appropriate, independently of one another each have one or more aromatic, substituted aromatic, phenolic or / and substituted phenolic groups, particular preference being given to amino, hydroxyl, carboxyl, carbonyl or / and nitro groups as substituents.
  • an alkyl group of the at least one demulsifying surfactant according to the invention contains on average 7.5 to 16.5 carbon atoms, in particular on average 7.5 to 14.5, 8.5 to 12.5 or 8.5 to 11, 5 carbon atoms, and an average of 5.5 to 18.5 EO groups, in particular 6.5 to 16.5 on average, 7.5 to 14.5 or 9.5 to 12.5 EO groups (ethylene oxide groups), in each case on average 7.5 to 12.5, 8.5 to 11, 5 or 9.5 to 10.5 EO groups.
  • each alkyl group independently of one another preferably contains chlorine, ethyl, methyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, isopentyl, hexyl, isohexyl or benzyl, in particular benzyl, tert-butyl or butyl.
  • the at least one demulsifying surfactant may be demulsifying in an aqueous alkaline cleaning composition which is optionally soiled, without and in contact with at least one cationic organic compound such as at least one cationic surfactant and / or at least one cationic organic polymeric compound.
  • the at least one cationic organic compound may chemically react in the detergent composition with the at least one nonpolar organic compound and / or with the at least one anionic organic compound. These chemical reactions are often very fast.
  • the reactants form mostly heavy or / and not water-soluble and often inactive compounds, which can often accumulate on the bath surface and optionally on the bottom of the bath container and / or on its walls. These can often be removed from the bathroom comparatively easily.
  • the demulsifying nonionic surfactant according to the invention acts in this case in particular by its specific molecular geometry. It has The task is to cleanse strongly, to foam as little as possible and to have the greatest possible demulsifying effect. Due to a low foaming tendency in the usual applications, it is also suitable for spray applications.
  • the cleaning composition according to the invention may preferably additionally comprise at least one further nonionic surfactant, at least one amphiphilic surfactant, at least one cationic surfactant, at least one cationic organic polymer, at least one scaffold, at least one corrosion inhibitor and / or at least one further additive and, if appropriate, corresponding Contain counterions to the amphiphilic surfactants, cationic surfactants or / and cationic polymeric compounds.
  • no anionic surfactants, no further anionic organic compounds, with the exception of at least one anionic solubilizer or / and no non-polar organic compounds are intentionally added to the cleaner composition according to the invention. In some embodiments, it is advisable not to intentionally add polymeric cationic compounds.
  • the detergent composition according to the invention does not contain any cationic polymeric compounds based on polyethyleneimine or / and no corrosion inhibitor.
  • the cleaner composition of the invention may preferably additionally contain at least one ethoxylated-propoxylated nonionic surfactant, in particular having a cloud point below 20 0 C.
  • This nonionic surfactant can act as a defoamer.
  • the cleaning composition according to the invention most preferably at least temporarily contains at least one cationic surfactant or / and at least one cationic organic polymer, in particular at least one quaternary ammonium compound having one or two aromatic and / or substituted aromatic groups selected from amphiphilic compounds.
  • gene of the general formula (I) for the chemical reaction with non-polar organic compounds and / or anionic organic compounds, in particular from contaminants.
  • the at least one cationic surfactant may preferably be a quaternary ammonium compound having one or two aromatic and / or substituted aromatic groups in the detergent composition of the invention.
  • the at least one cationic surfactant is selected from amphiphilic compounds of general formula (I)
  • N represents ® nitrogen as the quaternary ammonium compound
  • R 1 is an alkyl group - saturated or unsaturated - with an average number of carbon atoms in the range of 8 to 18 carbon atoms, in each case either a linear or branched chain form, the alkyl group R 1 is optionally a or more or may be replaced by those wherein R 2 is hydrogen,
  • EO x
  • polyether chain of the formula "- CH 2 - CH 2 - O -" with x 1 to 50 units with or without end-capping, especially with a methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl or benzyl group)
  • At least one cationic surfactant has one or two benzyl groups.
  • the at least one cationic organic compound may preferably be present at or near such level in the detergent composition of the present invention as is required for its substantial or complete chemical reaction with the nonpolar organic compounds and / or anionic organic compounds present in the detergent composition ,
  • the cleaning composition according to the invention preferably contains a content of cationic organic compounds in the bath immediately prior to its chemical reaction - in particular in discontinuous operation - in an amount in which the stoichiometric ratio of cationic organic compounds to anionic organic compounds in the bath is in the range of 0.1: 1 to 10: 1 is maintained.
  • the contents of the at least one demulcent surfactant according to the invention based on ethoxylated alkyl alcohols with end group closure and the contents of the at least one cationic organic compound in the cleaner composition according to the invention can preferably be selected approximately or at least such that the cleaner composition is in the weakly anionic region, in the weak cationic range or charge neutral.
  • the cleaning composition according to the invention is often in a range from -0.005 g / L to +0.025 g / L, in particular depending on its concentration of active compounds, from -0.02 g / L to +0.08 g / L or from - 0.1 g / L to + 0.2 g / L of cationic organic substances.
  • the values can be within a range of - 0.1 g / L to + 0.4 g / L of cationic organic substances, which is probably due to the test method, only if the content of especially polar substances in the bath is high. A narrower tolerance than mentioned here is advantageous.
  • the Epton two-phase titration is performed by undercoating the detergent composition to be tested with dichloromethane after dilution with demineralized water and after neutralization under control with pH paper, and using a cationic substance solution as a reagent and a cationic dye-based indicator mixture anionic dye is titrated with vigorous stirring.
  • the stirring is interrupted again and again to await the separation of the two phases.
  • the end point approaches, the emulsion that forms by the vigorous stirring is becoming more easily separated so that titration is more careful and stirring is continued between them until the end point is reached.
  • the end point is when the red color from the dichloromethane phase has completely disappeared and given way to a mostly pale greenish blue or colorless or purple coloration.
  • the consumption of the reagent can then be converted to the molar content of anionic constituents.
  • the cleaner composition When working in an industrial plant, it is difficult to meet and maintain the charge neutral state of the cleaner composition. Therefore, the cleaner composition will often be able to work only weakly anionic or weakly cationic. However, these areas and the charge neutral point in between are the most favorable work areas.
  • the metering of the at least one cationic compound for the cleaning composition according to the invention it is possible to work in such a way that a particular degree of soiling of non-polar organic compounds and / or anionic organic compounds in the cleaning composition has been established, especially or especially. that is, that has enriched a certain amount of nonpolar organic compounds and / or anionic organic compounds in the detergent composition, an amount of at least one cationic compound is added to the soiled detergent composition.
  • These difficult or / and not water-soluble compounds can be removed relatively easily from the bath, as a rule. They can be largely or completely removed, for example, by removing dirt, such as oil and / or other dirt, for example, be skimmed off.
  • the at least one cationic organic compound is preferably added to the detergent composition only when a certain minimum amount of nonpolar organic compounds and / or anionic organic compounds are incorporated in the detergent bath and therefore included in the detergent composition.
  • the content of the at least one cationic organic compound in the cleaner composition is preferably present temporarily Zero, very low or comparatively low.
  • the cleaning composition according to the invention is in particular a) before the treatment, before the passivation and / or corrosion protection of metallic surfaces with an aqueous, surfactant-containing bath, b) before the so-called pretreatment of metallic surfaces of substrates, for example, before painting with, for example a pretreatment composition (conversion treatment) such as by phosphating, before joining, before forming or / and before painting, c) before using an industrial process Washer and / or d) used as an intermediate cleaning eg before a gear or engine production.
  • a pretreatment composition conversion treatment
  • bath bath solution
  • detergent bath a solution that is applied, for example, 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, in particular in the range of pH 8 to 13 or of pH 8 to 12, very particularly in the range of pH 9 to 11 ,
  • oil in the context of this application also means at least one base oil from this oil-containing composition.
  • oils which may contribute to the pollution of the bath, often come naphthenic and / or aliphatic oils in question. These oils are most commonly called machining oils. Under certain circumstances, they are also referred to and / or used as quenching oils, hardening oils, scouring oils, anticorrosive oils, cooling lubricant emulsions, cooling lubricant oils, cutting oils and / or forming oils.
  • oils in the bath according to the invention in principle also high values such. 1 g / L, 5 g / L or 10 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 cleaner bath of oil (s) including further contaminants 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 or from 0.1 to 1, 6 g / L is maintained, which is particularly dependent on the system and the driving style.
  • it does not always have to be a base oil as soiling, especially if the soils are remnants of a deep-drawing grease and / or a cold-working soap.
  • particulate soils also occur which, like the oil (s), originate in particular from metalworking and / or from agents for corrosion protection.
  • Particulate matter can occur as a mixture essentially on the basis of dust, abrasion, for example of metallic material (s), rubber, plastic (s) o / / and abrasive (s), metallic chips, Sch detailschmauch and / or welding 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 to form soaps, which may also include the anionic organic compounds, such as on the basis of caprylic acid, lauric acid, oleic acid, palmitic acid or / and stearic acid, especially based on Alkalicaprylaten , Alkaline laurates, alkali metal ethers, Alkalipalmitaten and / or alkali metal stearates such as sodium stearate or / and potassium stearate or in particular corresponding further carboxylates. From fats and fatty oils, hydro- lysed compounds (soaps) which often have surfactant-like properties which may be (side by side) polar and / or non-polar.
  • anionic organic compounds such as on the basis of caprylic acid, lauric acid, oleic acid, palmitic acid or / and stearic acid, especially based on Alkalicaprylaten , Alkaline laur
  • 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 performance 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 can then lose its demulsifying effect in the bath.
  • a demulsifying surfactant has a demulsifying effect under the usual conditions of a detergent bath, but in particular can lose its demulsifying effect by the entry of and / or the reaction to anionic organic compounds.
  • the process according to the invention is intended 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, more often in the range of 0.35 to 30 g / L or in the range of 0.4 to 20 g / L, more particularly 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
  • you can still easily and according to the invention good demulsifying if the corresponding Keep in the bath or / and appropriate additives are added to it.
  • 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 centrifuge system for removing the dirt from the surface of the bath.
  • a centrifuge system for removing the dirt from the surface of the bath.
  • Phosphating, before joining or before forming may be recommended, if possible not more than e.g. 5 g / L of anionic organic compounds in an aqueous, alkaline, surfactant-containing bath.
  • 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 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, ie often of a diameter in the range of about 0.5 to 5 or even up to 50 microns.
  • 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 enriched more strongly on the surface of the bath, but in a dormant bath such , B. in a separating vessel (oil separator) separates spontaneously and accumulates on the surface of the bath as oil-containing, often other contaminants than oil-containing phase.
  • a separating vessel oil separator
  • the demulsifying state can be maintained by the optionally 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.
  • a state of the bath is also referred to as demulsifying state, in which the constituents of the oil-containing composition, that is to say oil (s) and anionic organic compound (s), are deposited and, in particular, also on the bath surface as an oil-containing phase accumulate and remove.
  • the bath can be cleaned 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 can be impaired or even suppressed by levels of emulsifiers and / or anionic organic compounds.
  • the demulsifying state of a bath is recognizable by the fact that with reduced or no movement of the bath, an oil-containing phase separates spontaneously and optionally accumulates on the surface of the bath and / or in rare cases at the bottom of the bath container as an oil-containing phase while if there is some or no movement of the cleaner composition, no oil-containing phase separates.
  • no emulsifier is added to the bath or in individual embodiments only a small amount of at least one emulsifier of up to 0.5 g / L is intentionally added, 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 demulsifiers when the arrangement of the surfactant molecules on the oil droplet does not lead to excessive curvature.
  • the droplet size of the oil droplets illustrates the bath state: the smaller the oil droplets, the more emulsifying the bath, and the larger the oil droplets are, the more demulsifying the bath is.
  • 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.
  • demulsifying surfactant which is contained in the bath and / or added to the bath is selected from nonionic surfactants, in particular from the nonionic demulsifying surfactants according to the invention, and / or from cationic demulsifying surfactants .
  • nonionic surfactants in particular from the nonionic demulsifying surfactants according to the invention, and / or from cationic demulsifying surfactants .
  • all cationic surfactants can act as demulsifiers through interaction with at least one anionic organic compound.
  • nonionic surfactants have a demulsifying effect, in particular on account of their molecular geometry, polarity of the total molecule or of 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 least At least one demulsifying, especially cationic and / or non-ionic surfactant also acts as a demulsifying surfactant as long as the conditions of use are such that it is in a demulsifying state which depends essentially on the chemical composition, the type and amount of Pollution, the salinity and the temperature of the bath as well as the type and performance of Badum stiilzung or pumps depends.
  • Both the contents of total demulsifying surfactants and the contents of the demulsifying nonionic surfactants according to the invention in the aqueous alkaline detergent composition are preferably in the range from 0.01 to 60 g / L or from 0.03 to 30 g / L, particularly preferably in the range from 0.05 to 20 g / L, very particularly preferably in the range from 0.08 to 15 g / L or from 0.1 to 10 g / L. They are then often in the range of 0.5 to 8 g / L or from 1 to 6.5 g / L or from 2 to 5 g / L.
  • contents of demulsifying surfactants and contents of the demulsifying nonionic surfactants according to the invention in spray processes in the range from 0.1 to 5 g / l are used, in the dipping process in the range from 0.2 to 10 g / l, usually independently whether they are continuous or batch processes.
  • the demulsifying nonionic surfactants of the invention in the aqueous alkaline detergent composition are preferably in the range of 0.01 to 6 g / L or 0.03 to 3 g / L more preferably in the range from 0.05 to 2 g / L, very particularly preferably in the range from 0.08 to 1.5 g / L, from 0.1 to 1 g / L or from 0.12 to 0, 7g / L.
  • the levels of cationic surfactants or / and cationic organic polymers are preferably in the range of 0.1 to 100 g / L or 0.3 to 60 g / L at the time of their addition to the soiled alkaline aqueous cleaner composition and before they chemically react , especially preferably in the range from 0.5 to 40 g / L, very particularly preferably in the range from 0.8 to 20 g / L or from 1 to 10 g / L. They are then often in the range of 2 to 8 g / L or from 3 to 6 g / L.
  • the demulsifying nonionic surfactants of the invention in the aqueous alkaline detergent composition are preferably in the range of 0.01 to 6 g / L or 0.03 to 3 g / L particularly preferably in the range from 0.05 to 2 g / L, very particularly preferably in the range from 0.08 to 1.5 g / L, from 0.1 to 1 g / L or from 0.12 to 0, 7g / L.
  • the levels of cationic surfactants and / or cationic organic polymers are preferably at zero, trace levels, or in the range of 0.001 to 5 g, preferably after the chemical reaction of the cationic surfactants or / and the cationic organic polymers with the contaminants in the aqueous alkaline cleaner composition / L or from 0.003 to 3 g / L, more preferably in the range of 0.005 to 2 g / L or from 0.01 to 1.5 g / L, most preferably in the range of 0.05 to 1 g / L or from 0.1 to 0.5 g / L.
  • the levels of cationic surfactants or / and cationic organic polymers on this scale are maintained in this order of magnitude for longer periods of time in the aqueous alkaline detergent composition, preferably until the next addition of cationic surfactants and / or cationic organic polymers to more soiling ,
  • At least one demulsifying surfactant is preferably selected from the group of nonionic surfactants and is in particular at least one based on ethoxylated alkyl alcohols, ethoxylated-propoxylated alkyl alcohols, ethoxylated alkyl alcohols having one end-capping or two end-group occlusions and being ethoxylated propoxylated alkyl alcohols having one end-capping or two end-capping agents, the alkyl group of the alkyl alcohols being saturated or unsaturated, branched or unbranched - may optionally have an average number of carbon atoms in the range of 6 to 22 carbon atoms in each case either linear or branched chain formation, wherein the alkyl group may optionally have one or more aromatic and / or phenolic groups, wherein the ethylene oxide chain may optionally have in each case on average 2 to 30 ethylene oxide units, the propylene oxide chain optionally each having on average 1 to 25
  • At least one demulsifying surfactant may in particular be selected from the group of nonionic surfactants based on ethoxylated alkylphenols, ethoxylated-propoxylated alkylphenols, ethoxylated alkylphenols having an end-capping and ethoxylated-propoxylated alkylphenols having an end-capping, the alkyl group of the alkylphenols being saturated or unsaturated, branched or unbranched - having an average number of carbon atoms in the range of 4 to 18 carbon atoms, the ethylene oxide chain may optionally each have an average of 2 to 30 ethylene oxide units, the propylene oxide chain optionally each having on average 1 to 25 propylene oxide units and where appropriate, an end-capping especially with an alkyl group - saturated or unsaturated, branched or unbranched - can occur with an average of 1 to 8 carbon atoms.
  • At least one demulsifying surfactant may be selected in particular from the group of nonionic surfactants based on ethoxylated alkylamines in the bath, whose alkyl group - saturated or unsaturated - has an average number of carbon atoms in the range from 6 to 22, in each case linear or branched Chain formation and their polythene has an average number of ethylene oxide units in the range from 3 to 30 or / and whose average number of propylene oxide units is in the range from 1 to 25.
  • At least one demulsifying surfactant may in particular be selected from the group of nonionic surfactants based on surfactants ethoxylated or ethoxylated-propoxylated alkanoic acids whose alkyl group - saturated, unsaturated or cyclic - having an average number of carbon atoms in the range of 6 to 22, respectively linear or branched chain formation and whose polyethylene oxide chain has an average number of ethylene oxide units in the range of 2 to 30 or / and whose average number of propylene oxide units in the range of 1 to 25.
  • nonionic surfactants based on surfactants ethoxylated or ethoxylated-propoxylated alkanoic acids whose alkyl group - saturated, unsaturated or cyclic - having an average number of carbon atoms in the range of 6 to 22, respectively linear or branched chain formation and whose polyethylene oxide chain has an average number of ethylene oxide units in the range of 2 to 30 or / and whose average number of
  • At least one demulsifying surfactant may in particular be selected from the group of nonionic surfactants based on block copolymers which contain at least one polyethylene oxide block and at least one polypropylene oxide block whose polyethylene oxide block has on average a number from 2 to 100 ethylene oxide units and whose polypropylene oxide block averages a number from 2 to 100 propylene oxide units, wherein optionally independently of one another in each case one or more polyethylene oxide blocks or polypropylene oxide blocks can be contained in the molecule.
  • the contents of demulsifying surfactants and / or of other particularly nonionic surfactants are proportionately removed with the contaminants from the cleaning baths and must therefore be correspondingly replenished in order to maintain or reset the cleaning performance.
  • the surfactants which are not cationic surfactants, are usually not subject to chemical reactions, usually remain in solution and thus usually remain proportionately or largely preserved in the bath, but are proportionally removed with the contaminants from the bath. In discontinuous operation, it may be worthwhile to replace the entire bath contents when cleaning the system when removing the dirt (bath replacement).
  • At least one cationic organic compound which is contained in the detergent bath and / or is added to it is preferably selected from the group consisting of cationic surfactants and cationic organic polymers.
  • cationic polymers stands for a selection from the group consisting of cationic polymers, cationic copolymers, cationic block copolymers and cationic graft copolymers in particular, the optionally weakly demulsifying, too weakly demulsifying or even missing demulsifying method and action of the bath containing at least one demulsifying, especially nonionic surfactant due to the demulsifying effect of at least one nonionic surfactant according to the invention and on the other hand optionally also of at least to produce and / or enhance a cationic surfactant and / or to maintain the demulsifying action and effect of the bath for as long as possible or even over a long period of time
  • At least one cationic organic compound is preferably selected from amphiphilic compounds which have at least one quaternary ammonium group or / and at least one ring group having at least one nitrogen atom as head group, where either the at least one nitrogen atom of the ring group or the ring group at least one has at least one alkyl group independently of one another - saturated or unsaturated - each having an average number of carbon atoms.
  • each having independently of one another - saturated or unsaturated, branched or unbranched - may each contain one or more aromatic groups or may be replaced by those, and optionally wherein at least one alkyl group may have a different average number of carbon atoms than at least one other alkyl group, and / or b) from cationic polymers, which in the case of water-soluble cationic polymers are often also cationic polyelectrolytes, where the cationic polymers have at least one quaternary ammonium group or / and at least one nitrogen-containing heterocyclic positively charged group having 5 or 6 ring atoms and at least five units of a Monomergrundbausteins or more - in particular one, two, three, four or five - different monomer backbones in mi At least one polymer chain included.
  • 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.
  • Basic building blocks in a molecule can be arranged in random, isotactic, syndiotactic, atactic and / or block wise, optionally in certain areas, for example as block copolymers or graft copolymers.
  • At least one cationic organic compound is preferably selected from amphiphilic compounds of the general formula (I)
  • N nitrogen as a quaternary ammonium compound
  • R 1 is an alkyl group - saturated or unsaturated - having an average number of carbon atoms in the range of 8 to 18 carbon atoms in each case either linear or branched chain formation, wherein the alkyl group R 1 optionally a or more or may be replaced by those wherein R 2 is hydrogen,
  • At least one cationic surfactant has one or two benzyl groups.
  • R 2 is particularly preferably selected for alkyl groups having 1 or 8 to 16 carbon atoms; most preferred is to select them from 1 or 10 to 14 carbon atoms.
  • R 3 particular preference is given to selecting alkyl groups having 1 or 6 carbon atoms in the case of R 3 , the latter in particular as the benzyl group.
  • At least one cationic organic compound is preferably selected from amphiphilic compounds of the general formula (II)
  • N ® represents nitrogen as a quaternary ammonium compound
  • R 1 is independently an alkyl group - saturated or unsaturated - having an average number of carbon atoms in the range of 4 to 22 carbon atoms in each case either linear or branched chain formation
  • optionally at least one of Alkyl groups R 1 independently may contain one or more aromatic and / or phenolic groups and / or be replaced by those
  • R 2 is an alkyl group - saturated or unsaturated - having an average number of carbon atoms in the range of 1 to 22 carbon atoms in either linear or branched chain formation
  • the alkyl group R 2 may optionally contain or be replaced by one or more aromatic and / or phenolic groups
  • R 3 independently of one another are hydrogen
  • At least one cationic organic compound is preferably selected from amphiphilic compounds of the general formula
  • N ® represents nitrogen as a quaternary ammonium compound, it being possible where appropriate for CH - CH to be replaced by CH - R 4 - CH, wherein R 4 is independently an alkyl group - saturated or unsaturated - having an average number of carbon atoms in the range of 1 to 14 carbon atoms in either linear or branched chain formation, optionally wherein at least one of the alkyl groups R 4 is independently one or more aromatic and / or and phenolic groups may contain and / or be replaced by those where optionally at least one of the alkyl groups R 4 independently also at least one amino group, carbonyl group, ester group, ether group, OH group and nitro group may contain at least one of the carbon atoms and / or between the carbon atoms of at least one alkyl group, wherein optionally N ® - CH may be replaced by N ⁇ - R 5 - CH, wherein R 5 is independently an alkyl group - saturated or unsaturated - with a average number of carbon
  • At least one of the groups R 3 is independently one or more groups selected from amino groups, carbonyl groups, ester groups, ether groups, OH groups and nitro groups on at least one of the carbon atoms and / or between the carbon atoms contain at least one alkyl group and / or can / can.
  • R 4 is selected from alkyl groups having 1 to 4 carbon atoms; most preferred is to select them from 2 or 3 carbon atoms.
  • R 4 particular preference is given to selecting alkyl groups having 1 to 6 carbon atoms in R 5 ; it is very particularly preferred to select these from 2 to 5 carbon atoms.
  • at least one cationic organic compound is preferably selected from amphiphilic compounds of general formula (IV) and their tautomers
  • N ⁇ represents nitrogen, it being possible for one, two, three, four, five, six, seven, eight or nine R 3 to be bonded to the ring of the general formula (IV), the nitrogen-bonded R 1 being obligatory and R 3 bound to the ring is optional, the ring having one, two or three double bonds, optionally one or more carbon atoms in the ring being independently replaced by at least one nitrogen atom, at least one sulfur atom and / or by at least one oxygen , where optionally to this at least one nitrogen atom, an R 3 may be bonded, wherein optionally one, two, three or four cyclic groups which are saturated, unsaturated or aromatic, may be independently fused with 5 or 6 ring atoms to the first ring If appropriate, one, two, three or four R 3 can / may be bound independently of one another in this at least one further ring where optionally in this at least one further ring independently one or more carbon atoms can be replaced by at least one nitrogen atom, at least one sulfur atom and / or by at
  • At least one cationic organic compound is preferably selected from amphiphilic compounds of general formula (V) and their tautomers
  • N ⁇ represents nitrogen, it being possible for one, two, three, four, five, six, seven or eight R 3 to be bonded to the ring of the general formula (V), where the nitrogen-bonded R 3 and the amine Ring-bound R 1 are obligatory and wherein the ring-bound R 3 is optional, wherein the ring has one, two or three double bonds, optionally in the ring independently one or more carbon atoms by at least one nitrogen atom, at least one sulfur atom and / or by at least one oxygen may / may be replaced, it being possible for this at least one nitrogen atom to be attached to an R 3 , where appropriate one, two, three or four cyclic groups which are saturated, unsaturated or aromatic, independently of one another with 5 or 6 Ring atoms can be fused to the first ring /, wherein optionally in this at least one further ring independently of one another ei n, two, three or four R 3 may be bonded, it being possible for one or more carbon atoms in this at least
  • At least one cationic organic compound is preferably selected from amphiphilic compounds of general formula (VI) and their tautomers
  • N ® represents nitrogen, it being possible where appropriate to attach one, two, three, four, five, six or seven R 3 to the ring, the ring having one or two double bonds, wherein the nitrogen-bonded R 1 is obligatory and the R 3 attached to the ring is optional, it being possible for one or more carbon atoms in the ring to be replaced independently of one another by at least one nitrogen atom, at least one sulfur atom and / or by at least one oxygen , where optionally to this at least one nitrogen atom, an R 3 may be bonded, wherein optionally one, two or three cyclic groups which are saturated, unsaturated or aromatic, may be independently fused with 5 or 6 ring atoms to the first ring in which at least one further ring can optionally be bonded independently of one another, one, two, three or four R 3 , where appropriate in this at least one further ring being independently one or more carbon atoms by at least one nitrogen atom, at least one sulfur atom or / and by at least one oxygen ers may be ow
  • At least one cationic organic compound is preferably selected from amphiphilic compounds of general formula (VII) and their tautomers
  • N ⁇ represents nitrogen, it being possible for one, two, three, four, five or six R 3 to be bonded to the ring, the ring having one or two double bonds, the nitrogen-bonded R 3 and the ring bonded to the nitrogen R 1 are obligatory and wherein the R 3 attached to the ring is optional, it being possible for one or more carbon atoms in the ring to be replaced independently of one another by at least one nitrogen atom, at least one sulfur atom and / or by at least one oxygen, optionally where an R 3 may be bonded to this at least one nitrogen atom, optionally one, two or three saturated, unsaturated aromatic and / or aromatic cyclic groups being able to be fused to the first ring independently of one another with 5 or 6 ring atoms, optionally in this at least one further ring independently, one, two, three or four R 3 may be bonded, optionally wherein in this at least one further ring independently one or more carbon atoms by at least one nitrogen atom, at least one sulfur atom and / or
  • At least one amphiphilic cationic organic compound of the general formulas (I), (II) and (III) has at least one hydroxyl, ethyl, methyl, isopropyl, propyl on the central nitrogen head group (s) - or / and benzyl group independently as R 2 o- / / and R 3 , wherein optionally also at least one longer alkyl chain and / or more alkyl chains can occur.
  • R 3 is independently of one another, saturated or unsaturated, branched or unbranched - optionally one or more aromatic or / and phenolic groups, wherein at least one of the alkyl groups independently of each other independently of one another in each case at least one methyl group, ethyl group, hydroxyl group, isopropyl group, propyl group or / and a Benzyl group can be.
  • x it is particularly preferable for the compounds of the general formulas (I), (II), (III), (IV), (V), (VI) and (VII) and their tautomers, x to select from 1 to 7 units; most preferably, x is selected from 4 or 5 units. It is particularly preferable for the compounds of the general formulas (I), (II), (III), (IV), (V), (VI) and (VII) and their tautomers, y to select from 1 to 4 units ; most preferably, y is selected from 2 or 3 units.
  • R 3 are alkyl groups having 1 or 6 carbon atoms the latter in particular as a benzyl group.
  • At least one cationic organic compound is preferably selected from cationic polymers, cationic copolymers, cationic block copolymers and cationic graft copolymers which contain at least one cationic group of the general formula (VIII):
  • the compound has 1 to 500,000 cationic groups independently of each other having the following chemical structures, wherein N ® represents nitrogen as a quaternary ammonium group wherein at least one quaternary ammonium group has at least one alkyl group R 1 , the independently of one another hydrogen, an AI kyl distr A - saturated or unsaturated, branched or unbranched - having a number of 1 to 200 carbon atoms and / or an oxygen-containing group such as an OH group or oxygen as a bridging atom to a next group such as an alkyl group B with a number from 1 to 200 carbon atoms, wherein the predominant number of quaternary ammonium groups has at least two alkyl groups R 1 independently of one another hydrogen, an alkyl group A - saturated or unsaturated, branched or unbranched - having a number from 1 to 200 carbon atoms or / and an oxygen-containing group such as an OH group or oxygen as a bridging atom to a next group
  • a combination of cationic groups from at least two different cationic groups from different general formulas VIII, IX and X or / and their tautomers can also occur in at least one compound.
  • the cationic group shown in these general formulas or / and their tautomeric cationic group can each independently be present at least once, but in some embodiments at least 2, preferably 3, 4, 5, 6, 7, 8 to 20, 21 to 30, 31 to 40, 41 to 50, 51 to 60, 61 to 100, 101 to 200, 201 to 500, 501 to 1,000, 1,001 to 2,000, 2,001 to 5,000, 5,001 to 10,000, 10,001 to 50,000, 50,001 to 100,000, 100,001 to 200,000, 200,001 to 500,000 cationic groups.
  • a mixture of compounds is selected from compounds of general formulas VIII, IX and X and their tautomers whose number of cationic groups ranges from 30 to 300,000, preferably from 100 to 100,000, sometimes from 100 to 50,000, from 800 to 120,000, or from 2,000 to 250,000. Frequently, a mixture of these compounds occurs with a smaller or larger bandwidth of the number of cationic groups or / and with a smaller or larger bandwidth of the number of polymer units n.
  • such a compound has a number of polymer units n which is greater by a factor of 1 to 1000 than the number of cationic groups, including their optionally present tautomeric cationic groups, in particular by a factor in the range of 1, 5 to 100, most preferably by a factor in the range of 2 to 30, especially by a factor in the range of 3 to 12 or from 3.5 to 8.
  • At least one quaternary ammonium group is present independently of the nitrogen atom in the polymer chain and / or with the nitrogen atom on the polymer chain, sometimes at least 25% of all present at least 75% of all such groups present. They are most preferably predominantly, almost completely or completely independently of one another with the nitrogen atom in the polymer chain or / and with the
  • Nitrogen atom on the polymer chain is Nitrogen atom on the polymer chain.
  • the polymer units of at least one cationic group are particularly preferably predominantly, almost completely or completely selected from polyamides, polycarbonates, polyesters, polyethers, polyamines, polyimines, polyolefins , Polysaccharides, polyurethanes, their derivatives, their mixtures and combinations thereof.
  • such compounds are particularly so that the polymer units of at least 25% of all cationic groups, of more than 50% of all cationic groups, of at least 75% of all cationic groups, of almost all cationic groups or of all cationic groups are each independently at least 25%, predominantly ( ⁇ 50%), at least 75%, almost completely or wholly selected from polyamides, polycarbonates, polyesters, polyethers, polyamines, polyimines, polyolefins, polysaccharides, polyurethanes, their derivatives, their mixtures and combinations thereof.
  • the derivatives of the polymer units of the polyolefins may be, for example, at least one compound of the polyethylenes, polypropylenes, polystyrenes, polyvinyl alcohols, polyvinylamines, polyvinyl esters, e.g. Polyvinyl acetate, polyvinyl ethers, polyvinyl ketones and their derivatives, their mixtures and combinations thereof occur.
  • derivatives of the polymer units of the polyamides may be, for example, at least one compound of the polyamino acids, the polyaramides and their derivatives, their mixtures and combinations thereof, in particular those selected from diaminocarboxylic acids, diaminodicarboxylic acids and their derivatives, their mixtures and their combinations.
  • the derivatives of the polymer units of the polyester may be, for example, at least one compound of the hydroxycarboxylic acids, dihydroxy- carboxylic acids, polycarbonates and their derivatives, their mixtures and combinations thereof, in particular those selected from polyesterpolycarbonates and their derivatives, their mixtures and combinations thereof.
  • derivatives of the polymer units of the polyethers may be, for example, at least one compound of the polyether block amides, polyalkylene glycols, polyamides, polyether ether ketones, polyetherimides, polyethersulfones and their derivatives, mixtures thereof and their combinations occur.
  • the compounds of the general formulas VIII, IX and X and their tautomers may be derivatives of the polymer units of the polyamines, for example at least one compound of the alkylenediamines, polyethyleneimines, vinylamine polymers and derivatives thereof, mixtures and combinations thereof, in particular those selected from diethylenediamines, Dipropylenediamines, ethylenediamines, propylenediamines, triethylenediamines, tripropylenediamines, polyethylenediamines, polypropylenediamines, vinylamine polymers and their derivatives, their mixtures and combinations thereof.
  • the derivatives of the polymer units of the polysaccharides may be, for example, at least one compound of corresponding biopolymers such as those based on cellulose, glycogen, starch and derivatives thereof, their modifications, their mixtures and their combinations occur, in particular selected from polyglucosides, condensation products of fructose or glucose and their derivatives, their mixtures and their combinations.
  • At least one cationic organic compound is preferably selected from cationic polymers, cationic copolymers, cationic block copolymers and cationic graft copolymers which are at least a cationic group of the general formula (IX) or / and their tautomer (s) contain:
  • the compound has 1 to 500,000 cationic groups independently of one another having the following chemical structures, wherein N ® represents nitrogen, wherein on the ring of the cationic group independently zero, one, two, three, four, five, six, seven, eight or nine R 1 are bonded, wherein the nitrogen-bonded R 1 is obligatory and the ring-bound R 1 is optional, wherein the ring of the cationic group independently one, two or three double bonds, optionally in the ring independently of one another, one or more carbon atoms may be replaced by at least one nitrogen atom, at least one sulfur atom and / or by at least one oxygen, optionally with one, two, three or four saturated, unsaturated and / or aromatic cyclic Groups with 5 or 6 ring atoms independently of the first ring of the cationic group may optionally be fused in this at least one further ring independently of one another, one, two, three or four R 1 , optionally in this at least one further ring independently one or more carbon atoms by at least one
  • Bridging atom to a next alkyl group B - saturated or unsaturated, branched or unbranched - having a number of 1 to 200 carbon atoms which may optionally contain one or more aromatic and / or phenolic groups independently of one another or may be replaced by those, or / and optionally a group selected from amino groups, carbonyl groups, ester groups, ether groups, OH groups and nitro groups on at least one of the carbon atoms and / or between the carbon atoms in each case at least one of the alkyl groups A or / and B may contain and / or where optionally at least one of the groups R 1 independently of one another may be branched or unbranched with a number of polymer units n from 5 to 1,000,000 monomer building blocks independently of one another, wherein the polymer units of at least one cationic group are at least partially selected from polyamides, polycarbonates, polyesters, polyethers, polyamines, polyimines, polyolefins, polysaccharides, polyure
  • At least one cationic organic compound is preferably selected from cationic polymers, cationic copolymers, cationic block copolymers and cationic graft copolymers which contain at least one cationic group of the general formula (X) or / and their tautomer (s):
  • the compound has 1 to 500,000 cationic groups independently of each other having the following chemical structures, wherein N ⁇ represents nitrogen, wherein independently of the ring of the cationic group zero, one, two, three, four, five, six or seven R are bound 1, wherein the R 1 bound to the nitrogen required and the R 1 bound to the ring is optionally, wherein the ring of the cationic group independently has one or two double bonds, optionally in the ring of the cationic group independently one or more carbon atoms can be replaced by at least one nitrogen atom, at least one sulfur atom and / or by at least one oxygen, wherein optionally one, two or three saturated, unsaturated o- / / and aromatic cyclic groups having 5 or 6 ring atoms independently of one another may be fused to the first ring of the cationic group, it being possible for this at least one further ring to be independently bonded to one, two, three or four R 1 , where appropriate in this at least one further ring, independently of one another, one or more
  • 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 SuI ions - fonat.
  • ions based on halide such as e.g. Bromide and / or chloride and / or carboxylate-based ions in particular such as e.g.
  • 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, especially 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 discharge 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, 1: 1 to 10: 1 is maintained.
  • this ratio is in the range from 0.5: 1 to 5: 1, particularly preferably in the range from 0.7: 1 to 1.2: 1, very particularly preferably in the range from 0.9: 1 to 1: 1.
  • 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 in the bath is present in excess compared to the unreacted anionic organic compounds present, then the bath is emulsifying and contains little oil (s) and / or contaminants associated therewith, but has the cleaning performance usually already accepted. In a middle range of this ratio of cationic organic compounds to the present unreacted anionic organic compounds conditions 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 related 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 detergent additionally contains at least one scaffold, that is, at least one builder, and / or this is added to the bath.
  • the scaffold may help to suppress rusting on steel or white rust on zinc surfaces.
  • the scaffold may preferably comprise at least one borate-based builder such as orthoborate (s) and / or tetraborate (s), silicate (s) such as metasilicate (s), orthosilicate (s) or / and polysilicate (s) ), Phosphate (s) such as orthophosphate (s), tripolyphosphate (s) and / or pyrophosphate (s), at least one alkaline medium, for example based on potassium hydroxide, sodium hydroxide, sodium carbonate, sodium bicarbonate, KaIi- umcarbonat and / or potassium bicarbonate, at least an amine such as based on monoalkylamine (s), trialkylamine (s), monoalkanolamine (s) o- / and trialkano
  • 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 from 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 batch processes.
  • the bath contains at least one additive such as e.g. contains a corrosion inhibitor or / and at least one additive is optionally added to the bath again.
  • a corrosion inhibitor for example, those based on alkylamidocarboxylic acid (s), amino carboxylic 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 e.g. at least one biocide and / or at least one defoamer may be contained in the bath and / or added to the bath, in particular in the range from 0.01 to 0.5 g / l in each case.
  • 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 cleaner 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 in particular the anionic surfactants, which are optionally contained in the bath and are usually derived only from contaminants, 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 matter accumulates. chen compounds on the bath surface at least partially, especially in the oil-containing phase, and can then be removed if necessary from the bath.
  • 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 without soiling is in the range from 0.5 to 300 g / L or from 1.2 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 of 4 to 20 g / L, from 5 to 15 g / L or from 5.5 to 12 g / L. In particular, it may be in the range of 4 to 7 g / l for the cleaning of bodies, sheets and / or parts prior to phosphating by spraying, and in particular in the range of 7 to 30 g / l in the case of immersion methods.
  • not more than 10 g / L of anionic organic compounds accumulate in the bath until bath care, and it is particularly preferred that no 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 drain-off.
  • the amount of cationic organic compounds to be added in this case can either be determined by Epton titration, chromatographically or simply, accurately and effectively by multiple proportionate addition of cationic organic compounds to determine in the latter method, according to 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.
  • the bath it is particularly preferred in continuous operation to adjust the bath so that no or almost no unreacted cationic organic compounds are contained in the bath. Because as well as anionic organic compounds are absorbed by the bath, the unreacted cationic organic compounds in the bath will react with the anionic organic compounds.
  • anionic organic compounds and “cationic organic compounds” in the context of this application mean the corresponding unreacted compounds and not the adducts resulting therefrom. In some systems it may be sufficient to drive a cleaning zone (bath) or only a part of the various cleaning zones (cleaning baths) according to the invention, especially if in this way the other cleaning zones are not more heavily contaminated.
  • 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 many cases essentially at atmospheric pressure in the case of cleaning processes, if printing is not used in circulation processes, for example by injection flooding (possibly up to about 50 bar), while injection molding often uses injection pressures in the range from 0.1 to 5 bar.
  • the temperatures are in the purification process - depending on the chemical composition - preferably in the range of 5 to 99 0 C, more preferably in the range of 10 to 95 0 C, wherein spraying often in the range of 40 to 70 0 C and immersion often in Range of 40 to 95 0 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 those ⁇ 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.
  • the content of the detergent bath of oil (s), including other contaminants often in the range of 0.05 to 1 g / L or / and the content of surfactants often in the range of 0.05 to 0.5 g / L
  • the content of the cleaner bath of oil (s) including other contaminants is often in the range of 0.7 to 6 g / L and / or the content of surfactants in the range of 0.3 to 1, 5 g / L is.
  • cleaning methods and cleaning compositions were found that are relatively easy to use and their consumption costs are slightly higher depending on the initial conditions by the addition of cationic organic compounds previously not required or due to decreasing consumption of chemical substances due to increased cleaning power consumption costs of about the same or even lower levels than previously required. Nevertheless, some larger installations may save around 100,000 € per annum.
  • the bath is often not exchanged with heavy soiling (no expensive bath waste), but the appropriate amount of cationic organic compounds is added to the at least one nonionic surfactant-containing aqueous alkaline cleaning composition so that Demulsify oil and other contaminants and skim off as the oil-containing phase.
  • the quality of the oil thus obtained is often so high that in many cases it can even be thermally utilized (incinerated), especially if the water content is less than about 20% by weight instead of about 30 to 50% by weight.
  • the substrates purified by the process with the detergent compositions according to the invention may 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 / pretreatment composition based on silane / siloxane / polysiloxane, titanium / zirconium compound, iron oxide / cobalt oxide, chromate, oxalate, phosphonate / phosphate and / or 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 an anodization, with a CVD coating, with a PVD coating or / and with a temporary corrosion protection coating.
  • alkali phosphating e.g. for iron phosphating, for manganese phosphating or for zinc phosphating and / or
  • demulsifying surfactants mainly nonionic surfactants based on ethoxylated alkyl alcohols having one end-capping per alkyl group
  • various demulsifying cationic surfactants were tested in the laboratory for their demulsifying effect and foaming tendency.
  • All tested demulsifying nonionic surfactants based on ethoxylated alkyl alcohols having one end-capping per alkyl group proved to have a slightly more or less pronounced demulsifying effect but also in the cleaning performance and foaming tendency low, but significant differences from molecule to molecule. Nevertheless, all these preselected and tested demulsifying nonionic surfactants based on ethoxylated alkyl alcohols having one end-capping per alkyl group were particularly well suited to the large number of other potentially usable surfactants.
  • the most suitable demulsifying nonionic surfactant based on ethoxylated alkyl alcohols having end capping was used together with the most suitable demulsifying cationic surfactant in an industrial phosphating plant in continuous operation.
  • the former belongs to the demulsifying nonionic surfactants according to the invention.
  • the cleaning zones consist of two zones before phosphating: 1. Alkaline dip degreasing and 2. Alkaline spray degreasing. In both degreasing baths, substantially the same aqueous detergent composition is used.
  • levels of oil (s) including further soiling of more than 3 g / l were established in these baths during continuous operation over three to seven weeks. L per bath, especially in the bath of Tauchentfettung, where these levels could reach up to 10 g / L.
  • the baths were dosed with a scaffold and with a nonionic demulgierend acting surfactant and without the addition of other surfactants and postdosed, but not completely renewed. But there were also other surfactants registered by the cleaning of the components to be cleaned.
  • the re-dosing was required because of the discharge of cleaner components from the baths.
  • oil contents of the order of about 5 g / L Oil (s), including further soiling, gradually decreased in cleaner performance and resulted in insufficient defatting and uneven formation of the subsequently applied phosphate coating. Therefore, the required high paint quality could no longer be achieved with the required safety.
  • the cleaning baths contained no additives to demulsifying cationic surfactants, which were intentionally added and may not originate from the contamination of the baths.
  • the cleaning bath based on a neutral detergent formulation inter alia, a demulsifying nonionic surfactant according to the invention based on ethoxylated non-propoxylated alkyl alcohols having an average of 9.5 to 12.5 carbon atoms, with an average of 7.5 to 14.5 EO groups and added with an end group closure.
  • the demulsifying nonionic surfactant used according to the invention proved to be outstandingly suitable for its strong cleaning performance, its high demulsifying effect and its low foaming tendency.
  • the respective bath life could be doubled depending on the driving behavior, sometimes even at least be quadrupled until the entire bathroom has been replaced and thereby renewed.
  • the oil including the other contaminants, had largely accumulated on the bath surface as an oil-rich phase, including fats and other non-polar organic contaminants.
  • the oil-rich phase contained only 2 to 30 wt .-% aqueous phase including Builder and surfactants and even 70 to 98 wt .-% essentially of 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 demulsifying nonionic surfactant according to the invention which was basically contained in the bath composition, had to be replenished, since these surfactants were partially removed with the oil-rich phase.
  • the demulsifying cationic surfactant was not immediately added, but only when the levels of oil (s) including further contaminants in the bath had re-adjusted to 2.5 to 4 g / L after several weeks.
  • This cationic surfactant was specifically selected according to the conditions for the demulsifying procedure and was a quaternary ammonium compound of the general formula (I) having a benzyl group.
  • the surfactant concentration of the cleaning baths no longer had to be increased at very high levels of oil (s) and / or other contaminations and the consumption of chemicals dropped slightly, but above all due to the renewal of the baths at significantly longer intervals. Since the conversion of the operating mode of the cleaning baths tra- There are no longer any problems with phosphating and varnishing, which can be attributed to cleaning. The disposal costs of the cleaning baths have fallen drastically because the disposal cycles have been significantly extended and because no heavily polluted cleaning baths had to be disposed of more. The proportion of rework required after at least one coating, for example, by grinding by hand and often then by re-phosphating and painting, has been significantly reduced, which also helps to save high process costs.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Detergent Compositions (AREA)
  • Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)

Abstract

La présente invention concerne une composition nettoyante alcaline aqueuse destinée à nettoyer les surfaces métalliques, qui contient au moins un tensioactif non ionique désémulsifiant à base d'alcools alkyliques éthoxylés ayant un ou deux groupes alkyles avec en moyenne respectivement 7,5 à 16,5 atomes de carbone et avec en moyenne 5,5 à 18,5 groupes EO par groupe alkyle ainsi qu'un groupe terminal coiffant ou deux groupes terminaux coiffants parmi lesquels au moins un groupe terminal coiffant est un groupe isopropyle, isobutyle, butyle tertiaire et/ou benzyle, le tensioactif n'étant pas propoxylé.
EP08839358.2A 2007-10-15 2008-09-30 Composition nettoyante pour surfaces métalliques Active EP2205711B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PL08839358T PL2205711T3 (pl) 2007-10-15 2008-09-30 Kompozycja środka czyszczącego do powierzchni metalicznych

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102007000501A DE102007000501A1 (de) 2007-10-15 2007-10-15 Reinigerzusammensetzung für metallische Oberflächen
PCT/EP2008/063089 WO2009050035A1 (fr) 2007-10-15 2008-09-30 Composition nettoyante pour surfaces métalliques

Publications (2)

Publication Number Publication Date
EP2205711A1 true EP2205711A1 (fr) 2010-07-14
EP2205711B1 EP2205711B1 (fr) 2013-05-15

Family

ID=40243874

Family Applications (1)

Application Number Title Priority Date Filing Date
EP08839358.2A Active EP2205711B1 (fr) 2007-10-15 2008-09-30 Composition nettoyante pour surfaces métalliques

Country Status (12)

Country Link
US (1) US9464259B2 (fr)
EP (1) EP2205711B1 (fr)
CN (1) CN101896591B (fr)
AU (1) AU2008313901B2 (fr)
CA (1) CA2702414C (fr)
DE (1) DE102007000501A1 (fr)
ES (1) ES2425144T3 (fr)
MX (1) MX2010004057A (fr)
PL (1) PL2205711T3 (fr)
PT (1) PT2205711E (fr)
WO (1) WO2009050035A1 (fr)
ZA (1) ZA201002430B (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021074544A1 (fr) 2019-10-18 2021-04-22 Arkema France Alcools alcoxylés et coiffés
WO2021074547A1 (fr) 2019-10-18 2021-04-22 Arkema France Alcoxylats à pouvoir hydrotrope amélioré
WO2021074545A1 (fr) 2019-10-18 2021-04-22 Arkema France Tensio-actifs à faible pouvoir moussant

Families Citing this family (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9090855B2 (en) 2010-06-17 2015-07-28 S.C. Johnson & Son, Inc. Anti-bacterial cleaning composition
DE102010052577B4 (de) 2010-11-25 2018-03-01 Volkswagen Ag Verfahren zur Pflege eines in einem Becken angeordneten Reinigungsfluids zur Reinigung eines Werkstücks und ein Becken gefüllt mit einem Reinigungsfluid
CN102277583B (zh) * 2011-08-22 2013-01-30 络力螯（昆山）生物科技研发中心有限公司 制备生物转化膜金属板的前处理方法
DE102015206812A1 (de) * 2015-04-15 2016-10-20 Henkel Ag & Co. Kgaa Polymerhaltige Vorspüle vor einer Konversionsbehandlung
DE102015209909A1 (de) * 2015-05-29 2016-12-01 Henkel Ag & Co. Kgaa Konditionierung vor einer Konversionsbehandlung von Metalloberflächen
DE102015209910A1 (de) * 2015-05-29 2016-12-01 Henkel Ag & Co. Kgaa Vorspüle enthaltend ein quartäres Amin zur Konditionierung vor einer Konversionsbehandlung
DE102016210289A1 (de) * 2016-06-10 2017-12-14 Henkel Ag & Co. Kgaa Verfahren zur reinigenden Vorbehandlung von durch Schweißen zusammengefügten eisenhaltigen Bauteilen
NZ749264A (en) * 2016-07-31 2020-08-28 Sterilex LLC Aluminum-compatible compositions for 2-part alkaline disinfectants and sanitizers
CN108624891A (zh) * 2018-05-15 2018-10-09 沈阳化工大学 一种高耐碱性水基金属清洗剂
CN109898078B (zh) * 2019-03-27 2021-10-29 佛山市利朗科环保科技有限公司 一种天然植酸金属螯合成膜剂及其制备方法
JP2025540919A (ja) 2022-11-04 2025-12-17 ケメタル ゲゼルシャフト ミット ベシュレンクテル ハフツング アルカリ性組成物、及び亜鉛－マグネシウム表面の洗浄方法

Family Cites Families (31)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3444242A (en) * 1968-03-04 1969-05-13 Economics Lab Surface active agents
US4093663A (en) * 1973-11-15 1978-06-06 The Dow Chemical Company Novel onium surfactants
DE2556527A1 (de) * 1975-12-16 1977-06-30 Hoechst Ag Metallreinigungsmittel
US4069066A (en) * 1976-11-10 1978-01-17 The Procter & Gamble Company Method and composition for cleaning polished surfaces
GB1601360A (en) * 1977-07-12 1981-10-28 Procter & Gamble Textile treatment composition
DE3048642A1 (de) * 1980-12-23 1982-07-15 Hoechst Ag, 6000 Frankfurt "tensidgemisch zur reinigung harter oberlaechen"
DE3247431A1 (de) * 1982-12-22 1984-06-28 Henkel KGaA, 4000 Düsseldorf Verfahren zur regenerierung bzw. zum recycling von waessrigen entfettungs- und reinigungsloesungen
DE3315951A1 (de) * 1983-05-02 1984-11-08 Henkel KGaA, 4000 Düsseldorf Verwendung von polyglykolethern als schaumdrueckende zusaetze in schaumarmen reinigungsmitteln
DE4014859A1 (de) * 1990-05-09 1991-11-14 Henkel Kgaa Verwendung einer kombination ionischer und nichtionischer tenside
DE4324396A1 (de) * 1993-07-21 1995-01-26 Henkel Kgaa Reinigungsmittel mit hohem Benetzungsvermögen
US6489278B1 (en) * 1993-12-30 2002-12-03 Ecolab Inc. Combination of a nonionic silicone surfactant and a nonionic surfactant in a solid block detergent
WO1996009368A1 (fr) * 1994-09-23 1996-03-28 Church & Dwight Company, Inc. Agent de nettoyage aqueux pour surfaces metalliques
US5614027A (en) * 1994-09-23 1997-03-25 Church & Dwight Co., Inc. Metal cleaner with novel anti-corrosion system
DE19513391A1 (de) * 1995-04-08 1996-10-10 Henkel Kgaa Bi- und multifunktionelle Mischether
DE19517814A1 (de) * 1995-05-18 1996-11-21 Henkel Ecolab Gmbh & Co Ohg Hochkonzentrierter wasserhaltiger Grundreiniger
US5712236A (en) * 1995-08-02 1998-01-27 Church & Dwight Co., Inc. Alkali metal cleaner with zinc phosphate anti-corrosion system
US6211132B1 (en) 1996-12-13 2001-04-03 Henkel Corporation Composition and method for deburring/degreasing/cleaning metal surfaces
US6124253A (en) * 1997-09-16 2000-09-26 Church & Dwight Co., Inc. Aqueous composition for low-temperature metal-cleaning and method of use
US5863881A (en) * 1998-02-02 1999-01-26 Citra Science Ltd. Heavy oil remover
GB2335661A (en) * 1998-03-26 1999-09-29 Reckitt & Colman Inc Hard surface cleaners comprising amphoteric surfactant
US5998352A (en) * 1998-06-23 1999-12-07 Dotolo Research Ltd. Heavy oil remover
DE19856529A1 (de) * 1998-12-08 2000-06-15 Henkel Kgaa Reinigungsmittel für harte Oberflächen
US6310263B1 (en) * 1999-11-08 2001-10-30 Dotolo Research Ltd. Heavy oil remover
US6462014B1 (en) 2001-04-09 2002-10-08 Akzo Nobel N.V. Low foaming/defoaming compositions containing alkoxylated quaternary ammonium compounds
DE10121723A1 (de) * 2001-05-04 2002-11-07 Cognis Deutschland Gmbh Geminitenside
DE10137925A1 (de) * 2001-08-07 2003-02-20 Cognis Deutschland Gmbh Geminitenside und Polyethylenglycol
CA2530075C (fr) * 2003-06-27 2012-08-21 Harvey Pollard Composes de pyridinium amphiphiles, leurs procedes de fabrication et d'utilisation
US20050079992A1 (en) * 2003-10-10 2005-04-14 Ecolab Inc. Cleaning composition and methods
DE102004057623A1 (de) * 2004-11-29 2006-06-01 Henkel Kgaa Metallreiniger mit Polyethylenimin
US20070068392A1 (en) * 2005-09-27 2007-03-29 Kim Sung S Durable coffee pot system
DE102006018216B4 (de) 2006-04-18 2008-09-25 Chemetall Gmbh Verfahren zum demulgierenden Reinigen von metallischen Oberflächen

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2009050035A1 *

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021074544A1 (fr) 2019-10-18 2021-04-22 Arkema France Alcools alcoxylés et coiffés
WO2021074547A1 (fr) 2019-10-18 2021-04-22 Arkema France Alcoxylats à pouvoir hydrotrope amélioré
WO2021074545A1 (fr) 2019-10-18 2021-04-22 Arkema France Tensio-actifs à faible pouvoir moussant
FR3102173A1 (fr) 2019-10-18 2021-04-23 Arkema France Tensio-actifs à faible pouvoir moussant
FR3102174A1 (fr) 2019-10-18 2021-04-23 Arkema France Alcoxylats à pouvoir hydrotrope amélioré
FR3102177A1 (fr) 2019-10-18 2021-04-23 Arkema France Alcools alcoxylés et coiffés

Also Published As

Publication number Publication date
PL2205711T3 (pl) 2013-12-31
ES2425144T3 (es) 2013-10-11
CN101896591B (zh) 2015-04-22
ZA201002430B (en) 2011-06-29
MX2010004057A (es) 2010-04-30
CA2702414C (fr) 2015-12-15
AU2008313901A1 (en) 2009-04-23
PT2205711E (pt) 2013-08-27
WO2009050035A1 (fr) 2009-04-23
EP2205711B1 (fr) 2013-05-15
AU2008313901B2 (en) 2013-08-15
US20100222248A1 (en) 2010-09-02
DE102007000501A1 (de) 2009-04-16
BRPI0818035A2 (pt) 2015-03-24
CA2702414A1 (fr) 2009-04-23
CN101896591A (zh) 2010-11-24
US9464259B2 (en) 2016-10-11

Similar Documents

Publication Publication Date Title
EP2205711B1 (fr) Composition nettoyante pour surfaces métalliques
EP2253741B1 (fr) Procédé de nettoyage désémulsifiant de surfaces métalliques
EP0213554B1 (fr) Produit de nettoyage désémulsifiant à effet de rétention d'humidité superficielle
EP3158049B1 (fr) Agent de nettoyage pour une élimination douce d'encres et de marqueurs
WO2006058570A1 (fr) Produit nettoyant pour metaux contenant un polyethylene imine
DE2125965C3 (de) Reinigungsmittel, insbesondere für Metall, Glas und feuerfeste Stoffe
DE4102709C1 (en) Degreasing metal surfaces using aq. prepn. - contg. biologically degradable adducts of lower alkylene oxide(s), fatty alcohol(s) and cationic surfactants
DE4001851A1 (de) Verfahren und vorrichtung zur reinigung, rueckgewinnung und wiederverwendung heisser, waessriger entfettungsbaeder und spritzreiniger
BRPI0818035B1 (pt) Composição limpadora alcalina aquosa para superfícies metálicas, banho contaminado e concentrado aquoso

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20100517

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MT NL NO PL PT RO SE SI SK TR

AX Request for extension of the european patent

Extension state: AL BA MK RS

DAX Request for extension of the european patent (deleted)
17Q First examination report despatched

Effective date: 20120615

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MT NL NO PL PT RO SE SI SK TR

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

Ref country code: GB

Ref legal event code: FG4D

Free format text: NOT ENGLISH

REG Reference to a national code

Ref country code: AT

Ref legal event code: REF

Ref document number: 612172

Country of ref document: AT

Kind code of ref document: T

Effective date: 20130615

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

Free format text: LANGUAGE OF EP DOCUMENT: GERMAN

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 502008009942

Country of ref document: DE

Effective date: 20130711

REG Reference to a national code

Ref country code: PT

Ref legal event code: SC4A

Free format text: AVAILABILITY OF NATIONAL TRANSLATION

Effective date: 20130814

REG Reference to a national code

Ref country code: SE

Ref legal event code: TRGR

REG Reference to a national code

Ref country code: SE

Ref legal event code: RPOT

REG Reference to a national code

Ref country code: NL

Ref legal event code: T3

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2425144

Country of ref document: ES

Kind code of ref document: T3

Effective date: 20131011

REG Reference to a national code

Ref country code: LT

Ref legal event code: MG4D

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20130515

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20130515

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20130816

Ref country code: LT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20130515

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20130915

Ref country code: NO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20130815

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20130815

Ref country code: HR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20130515

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LV

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20130515

REG Reference to a national code

Ref country code: PL

Ref legal event code: T3

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20130515

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20130515

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20130515

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: RO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20130515

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed

Effective date: 20140218

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MC

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20130515

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 502008009942

Country of ref document: DE

Effective date: 20140218

REG Reference to a national code

Ref country code: IE

Ref legal event code: MM4A

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20130930

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20130930

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20130930

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20130515

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20130515

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: HU

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT; INVALID AB INITIO

Effective date: 20080930

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20130930

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 9

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 10

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 11

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: AT

Payment date: 20190926

Year of fee payment: 12

REG Reference to a national code

Ref country code: AT

Ref legal event code: MM01

Ref document number: 612172

Country of ref document: AT

Kind code of ref document: T

Effective date: 20200930

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: AT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20200930

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: PT

Payment date: 20250909

Year of fee payment: 18

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20250926

Year of fee payment: 18

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: PL

Payment date: 20250903

Year of fee payment: 18

Ref country code: TR

Payment date: 20250910

Year of fee payment: 18

Ref country code: NL

Payment date: 20250925

Year of fee payment: 18

Ref country code: IT

Payment date: 20250922

Year of fee payment: 18

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: BE

Payment date: 20250925

Year of fee payment: 18

Ref country code: GB

Payment date: 20250923

Year of fee payment: 18

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20250925

Year of fee payment: 18

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: SE

Payment date: 20250924

Year of fee payment: 18

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: CZ

Payment date: 20250916

Year of fee payment: 18

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: ES

Payment date: 20251015

Year of fee payment: 18