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 metalworking aids (s)
• s e.g. Pulling
• 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 cleaning metallic objects which are intended to remove the contaminants, in particular from the metal processing and from the corrosion protection, from the metallic surfaces of metallic objects, are initially driven in a demulsifying state.
• the demulsifying state of the bath in an emulsifying state, and often the cleaning performance has dropped steadily.
• Bath care means: 1. optionally analysis of bath composition, pH and / or alkalinity, 2.
• the high contents of anionic organic compounds in the heavily soiled cleaner bath, especially on anionic surfactants prevent by their eponymous negative charges that are located on the surfaces of the oil droplets, the attraction of distributed in the bathroom oil droplets with each other. They thus prevent the coalescence of the oil droplets to larger oil droplets and thus the demulsifying effect of forming larger droplets and the separation of oil, which could then possibly even accumulate on the bath surface, where it could easily be removed.
• the heavily soiled cleaning baths often have an oil content in the range of 1 to 6 or even 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 phosphating zone to allow the most continuous cleaning of the cleaner bath and to ensure a consistently high cleaning performance ,
• a bath In a continuous bath care process, a bath is often approached once in a clean state and as long as possible continue to use the pollution with oils and other non-polar organic contaminants is continuously or repeatedly removed at short intervals to a certain extent and the substances required for cleaning be continuously or repeatedly added at short intervals to operate the cleaner bath with the highest possible cleaning performance and under uniform conditions as possible.
• the surfaces of the membranes of membrane filtration processes can easily occupy with grease, particulate soil and other contaminants and clog the pore channels of the membranes, so then this example. must be cleaned by rinsing. Every membrane filtration process is extremely labor-intensive and cost-intensive.
• 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 and / or optionally at least one additive such as at least one defoamer and optionally at least one entrained oil and optionally further contaminants.
• a surfactant for example, in each case at least one borate, carbonate, hydroxide, phosphate, silicate, optionally at least one organic solvent and / or optionally at least one additive such as at least one defoamer and optionally at least one entrained oil and optionally further contaminants.
• 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.
• EP 0 054 895 A1 teaches a surfactant mixture for mechanical cleaning hard surfaces such as bottles, which is a nonionic ethoxylated-propoxylated surfactant having an alkyl chain of 6 to 18 carbon atoms and optionally an end cap R 2 or R 3 in the form of an alkyl radical having 1 to 4 C. Atoms and quaternary ammonium salts.
• DE 40 14 859 A1 discloses the use of a combination of ionic and nonionic surfactants containing an alk (en) yl polyethylene glycol mixed ether having end cap R 5 or R 7 ; the addition of a cationic organic compound is not described.
• DE 33 15 951 A1 relates to the use of end-capped polyglycol ethers having alkyl groups of 4-8 carbon atoms as foam-suppressing additives in low-foaming detergents.
• WO 98/26034 A1 refers to aqueous surfactant mixtures for soil contaminated metallic workpieces based on certain nonionic surfactants and anionic-amphoteric substances and fluorine-containing substances and surfactants.
• DE 32 47 431 A1 describes processes for the regeneration or recycling of aqueous degreasing and cleaning solutions, without mentioning end-capped demulsifying nonionic surfactants, wherein due to the insufficient de-oiling a demulsification is to be made.
• An object of the invention is to propose an aqueous cleaner composition which makes a cleaner bath for soiled metallic surfaces easier or / and less expensive for oil (s), other non-polar organic contaminants, particulate soil, soap (s) and / or others Metalworking aids (n) such as Drawing aids can be cleaned.
• 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 and at least one cationic surfactant, wherein the at least one demulsifying nonionic surfactant based on ethoxylated alkyl alcohols having one or two alkyl groups with an average each having from 7.5 to 16.5 carbon atoms and having an average of from 5.5 to 18.5 EO groups per alkyl group and having one or two end group closures, at least one end capping compound being an isopropyl, isobutyl, tertiary butyl or / and benzyl group wherein the surfactant is not propoxylated, and wherein the at least one cationic surfactant is a quaternary ammonium compound having one or two aromatic and / or substituted aromatic groups.
• the invention is also achieved with a soiled bath containing an aqueous alkaline cleaning composition which contains the at least one demulsifying nonionic surfactant according to the invention and the at least one cationic surfactant according to the invention and a soil.
• the invention is further achieved with an aqueous concentrate for an aqueous alkaline cleaning composition in which the at least a demulsifying non-ionic surfactant according to the invention and at least one cationic surfactant according to the invention is present in a concentration which is higher by a factor of 5 to 5,000 than in the aqueous alkaline cleaning 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 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 corresponding to the main claim may be present in the cleaner composition according to the invention.
• 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 is an isopropyl, isobutyl, tertiary butyl or / and benzyl group, in particular at least one benzyl group is an end group closure, 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 in each case on average 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, 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 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.
• Each alkyl group may, if desired, independently of one another have one or more aromatic, substituted aromatic, phenolic or / and substituted phenolic groups, with particular preference being given to amino, hydroxyl, carbonyl or / and nitro groups as substituents.
• An alkyl group of the at least one demulsifying surfactant of the present invention contains an average of 7.5 to 16.5 carbon atoms, more preferably 7.5 to 14.5 on average, 8.5 to 12.5 or 8.5 to 11.5 carbon atoms, and average 5.5 to 18.5 EO groups, especially on average 6.5 to 16.5, 7.5 to 14.5 or 9.5 to 12.5 EO groups (ethylene oxide groups), in particular on average 7.5 to 12.5, 8.5 to 11.5 or 9.5 to 10.5 EO groups.
• the end group cap may contain, for each alkyl group independently of one another, isopropyl, isobutyl, tert-butyl or benzyl, in particular benzyl or tert-butyl.
• the at least one demulsifying nonionic surfactant and the at least one cationic surfactant quaternary ammonium compound having one or two aromatic and / or substituted aromatic groups may be in an aqueous alkaline cleaner composition optionally contaminated with and without contact with at least one other cationic organic compound such as, for example, at least one cationic organic polymeric compound demulsifying.
• 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.
• the inventive demulsifying nonionic Surfactant acts 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 cleaner composition of the invention may preferably additionally at least one further nonionic surfactant, at least one amphiphilic surfactant, at least one cationic organic polymer, at least one scaffold, at least one corrosion inhibitor and / or at least one further additive and optionally corresponding counterions to the amphiphilic surfactants, cationic Surfactants and / or 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 of the invention does not contain 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 ° C.
• This nonionic surfactant can act as a defoamer.
• the detergent composition at least temporarily contains at least one cationic organic polymer, mandatory at least one quaternary ammonium compound having one or two aromatic and / or substituted aromatic groups preferably selected from amphiphilic compounds of the general formula (I), for the chemical reaction with non-polar organic compounds and / or anionic organic compounds, especially from contaminants.
• the at least one cationic surfactant in the detergent composition of the invention is a quaternary ammonium compound having one or two aromatic and / or substituted aromatic groups.
• 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 immediately before its chemical reaction contains a content of cationic organic compounds in the bath - especially in batch operation - in an amount in which the stoichiometric ratio of cationic organic compounds to anionic organic compounds in the bath 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 having end group closure and the contents of the at least one cationic organic compound in the cleaner composition according to the invention may preferably be approximately or at least selected such that the cleaner composition is weakly anionic, weak cationic region or charge neutral.
• the detergent composition according to the invention is preferably in a range from -0.005 g / L to +0.025 g / L, in particular, depending on its concentration of active ingredients, from -0.02 g / L to +0.08 g / L or -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.
• Epton's two-phase titration is conducted by undercoating the detergent composition to be tested after dilution with demineralized water and after neutralization under control with pH-paper with dichloromethane, and with a cationic substance solution as reagent and a cationic dye-anionic indicator mixture Dye is titrated with vigorous stirring. The stirring is interrupted again and again to await the separation of the two phases. With As 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 has completely disappeared from the dichloromethane phase and has 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 cleaning composition according to the invention can be carried out so that only in particular, even if a certain degree of contamination of nonpolar organic compounds and / or anionic organic compounds in the cleaning composition has set, ie has enriched some amount of nonpolar organic compounds and / or anionic organic compounds in the detergent composition, an amount of at least one cationic compound of the soiled cleaner composition is added.
• Compounds and / or the anionic organic compounds in the cleaning composition largely or completely chemically react with the at least one cationic compound and / or not readily soluble in water form water-soluble compounds. 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 temporarily 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 the metallic surfaces with an aqueous, surfactant-containing bath, b) before the so-called pretreatment of metallic surfaces of substrates eg before painting, for example with a pretreatment composition (Conversion treatment) such as by phosphating, before joining, before forming or / and before painting, c) before using an industrial Washer and / or d) used as an intermediate cleaning eg before a gear or engine production.
• a pretreatment composition Conversion treatment
• conversion treatment such as by phosphating, before joining, before forming or / and before painting
• an industrial Washer and / or d used as an intermediate cleaning eg before a gear or engine production.
• bath bath solution
• detergent bath e.g. is applied by spraying.
• the aqueous alkaline, surfactant-containing bath used for the alkaline purification preferably has a pH in the range of pH 7 to 14, 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 is intended herein to mean, on the one hand, an "oil-containing composition” which is a composition based on many compounds having a substantially oil-containing character, comprising at least one base oil and typically also at least one anionic organic compound such as at least contains a compound based on petroleum sulfonate.
• oil in the context of this application also means at least one base oil from this oil-containing composition.
• At least one base oil but also fat (s), soap (s), which at least one (further) anionic organic compound and / or some other substances added to the base oil and their reaction products, in particular with water, interfere with the soiling of the bath. because it reduces the cleaning performance of the bath or even brought to a standstill.
• the at least one anionic organic compound acts on the state of the bath.
• oils which may contribute to the pollution of the bath, are often naphthenic and / or aliphatic oils in question. These oils are most commonly called machining oils. Under certain circumstances, they are also referred to and / or used as quenching oils, hardening oils, scouring oils, anticorrosive oils, coolants emulsions, cooling lubricant oils, cutting oils and / or forming oils.
• oils in the bath according to the invention can in principle also be high, such as 1 g / L, 5 g / L or 10 g / L
• oil (s), fat (s), soap (s), metalworking aids such as, for example, drawing aids and / or, if appropriate, non-polar organic contaminants
• particulate matter occur, which come as the oil (s), especially from the metal processing and / or from means for corrosion protection.
• Particulate matter can occur as a mixture essentially on the basis of dust, abrasion of, for example, metallic material (s), rubber, plastic (s) and / or abrasive (s), metallic chips, Sch resolutionschmauch 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 based on caprylic acid, lauric acid, oleic acid, palmitic acid and / or stearic acid, especially based on Alkalicaprylaten, alkali laurates , Alkalioleaten, Alkalipalmitaten and / or alkali metal stearates such as sodium stearate or / and potassium stearate or in particular corresponding further carboxylates. Fats and fatty oils can hydrolyze in the water Form compounds (soaps) that often have surfactant-like properties that can be (side by side) polar and / or nonpolar.
• anionic organic compounds such as based on caprylic acid, lauric acid, oleic acid, palmitic acid and / or stearic acid, especially based on Alkalicaprylaten, alkali laurates ,
• 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 may 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 method with the composition according to the invention for cleaning processes and baths with contaminations which have contents of anionic organic compounds, in particular contents of anionic organic compounds in the range of 0.2 g / L to very high levels such as on 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
• anionic organic compounds in many embodiments to values of not more than e.g. 50 g / L as e.g. limited by the use of a centrifugal system to throw off the dirt from the surface of the bath.
• a centrifugal system to throw off the dirt from the surface of the bath.
• Phosphating before joining and / or before forming, it may be recommended, if possible not more than e.g. 5 g / L of anionic organic compounds in an aqueous, alkaline, surfactant-containing bath. In a body cleaning plant in the automotive industry, it may be necessary, not more than e.g. To allow 1 g / L of anionic organic compounds in the cleaner bath in order to drive the system continuously and without special bath care measures.
• anionic organic compounds in a cleaning bath can affect in some systems due to also contained certain types of oil (s) in the pollution even at very low levels on the demulsifying effect of the bath: ZB often already about 0.05 or about 0.1 g / L of anionic organic compounds in order to reduce or even completely prevent the demulsifying effect, which also depends, inter alia, on the nature of the substances present.
• the size of the primary-cleaned oil droplets is usually very small, i. H. often of a diameter approximately in the range of 0.5 to 5 or even to 50 microns.
• a large interface between oil and water is generally energetically unfavorable, so the chemical system tends to coalesce several small oil droplets into at least one larger one. This process is also called coalescence.
• this radius of curvature is preferably set in some embodiments, that the oil in a moving bath just not demulsified and that an oil-containing phase is therefore not or not yet accumulates more strongly on the surface of the bath, but in a dormant bath such as B. in a separating vessel (oil separator) spontaneously separates and accumulates on the surface of the bath as oil-containing, often other contaminants than oil-containing phase.
• 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, ie in particular oil (s) and anionic organic compound (s), separate off and, in particular, also on the bath surface as an oil-containing phase accumulate and remove.
• the bath can be cleaned 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 or in individual embodiments only a small amount of at least one emulsifier of up to 0.5 g / L is intentionally added to the bath, preferably up to 0.2 g / L, particularly preferably up to 0.05 g / L, especially if the bath has little or no bath movement.
• At least one emulsifier may also be introduced by the pollution.
• the demulsifying surfactants and the cationic organic compounds act as demulsifiers.
• the nonionic surfactants used for the purification also often act as demulsifiers. In particular, they act as 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.
• At least one demulsifying surfactant contained in the bath and / or added to the bath is selected from the nonionic demulsifying surfactants of the present invention.
• all cationic surfactants can act as demulsifiers through interaction with at least one anionic organic compound.
• many nonionic surfactants have a particular emulsifying effect due to their molecular geometry, polarity of the total molecule or / and the surfactant mixture.
• the at least one demulsifying surfactant serves to reduce the surface tension, to clean, to demulsify, to adjust the emulsifying or demulsifying properties or / and to reduce the foaming tendency.
• a demulsifying nonionic surfactant will also act as a demulsifying surfactant as long as the conditions of use are such that it is in a demulsifying state that is substantially dependent on the chemical composition, the type and amount of soil, salinity, and temperature the bath and the type and performance of Badummélzung or pumps depends.
• Both the contents of the total amount of demulsifying surfactants and the contents of the demulsifying nonionic surfactants of the present invention in the aqueous alkaline detergent composition are preferably in the range of 0.01 to 60 g / L or 0.03 to 30 g / L, particularly preferred in the range of 0.05 to 20 g / L, most preferably in the range of 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 irrespective of 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 of 0.05 to 2 g / L, most preferably in the range of 0.08 to 1.5 g / L, from 0.1 to 1 g / L or from 0.12 to 0.7 g / 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 from 0.01 to 6 g / L or from 0.03 to 3 g / L, more preferably in the range of 0.05 to 2 g / L, most preferably in the range of 0.08 to 1.5 g / L, from 0.1 to 1 g / L or from 0.12 to 0.7 g / 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 ,
• 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.
• cationic organic compound which is contained in the cleaning bath and / or it is added consisting of cationic surfactants and optionally of cationic organic polymers.
• cationic polymers as in the other places, where not the other polymeric variants are listed, for a selection from the group consisting of cationic polymers, cationic copolymers, cationic block copolymers and cationic graft copolymers.
• the cationic organic compounds serve the demulcent, possibly weakly demulsifying, too weakly demulsifying or even missing demulsifying procedure and effect of the bath containing at least one demulsifying nonionic surfactant, due to the demulsifying action of the at least one nonionic surfactant according to the invention and also of the at least one cationic Produce surfactants and / or to reinforce and / or to maintain the demulsifying driving style and effect of the bath as long as possible or even permanently. Due to the demulsifying procedure, oil is separated from the bath and extends the service life of the bath.
• At least one further 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 is at least one positive Charge, and the at least one alkyl group independently - saturated or unsaturated - each having an average number of carbon atoms in the range of 4 to 22 carbon atoms, each having either linear or branched chain formation, wherein the alkyl group may optionally independently of one another - saturated or unsaturated, branched or unbranched - each contain one or more aromatic groups or may be replaced by those, and optionally at least an alkyl group may have a different average number of carbon atoms than at least one other alkyl group, and / or b) cationic polymers, which are often also cationic polyelectrolytes in the case of water-soluble cationic polymers, wherein the cationic poly
• 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 base unit or of a plurality of different basic monomer units may 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.
• monomer building blocks in a molecule these can be arranged, if appropriate in specific regions, randomly, isotactically, syndiotactically, atactically and / or in blocks, for example as block copolymers or graft copolymers.
• 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 R 3 , the latter in particular as benzyl group.
• At least one cationic organic compound is preferably selected from amphiphilic compounds of the general formula (III) where 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 each case either linear or branched chain formation wherein at least one of the alkyl groups R 4 independently of one another contains or is replaced by one or more aromatic and / or phenolic groups, where appropriate, at least one of the alkyl groups R 4 independently of one another and also at least one amino group, carbonyl group, ester group, ether group, OH group and nitro group on at least one of the carbon atoms or / and between the carbon atoms of at least one May contain alkyl group, where optionally N ⁇ - CH can be replaced by N ⁇ - R 5 -
• 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 where 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 general formula (IV), wherein the nitrogen-bonded R 1 is obligatory and the R 3 attached to the ring is optional, wherein the ring has one, two or three double bonds, optionally one or more carbon atoms in the ring may 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 can be bound to this at least one nitrogen atom, optionally one, two, three or four cyclic groups which are saturated, unsaturated or aromatic, independently of each other may be fused with 5 or 6 ring atoms to the first ring, optionally in this at least one further ring independently, two or three or four R 3 may be bonded, wherein optionally in this at least one at
• At least one cationic organic compound is preferably selected from amphiphilic compounds of general formula (V) and their tautomers where 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 general formula (V), wherein the nitrogen-bonded R 3 and the ring-attached R 1 are obligatory and wherein the ring-attached R 3 is optional, wherein the ring has one, two or three double bonds, optionally one or more carbon atoms in the ring being independently of one another replaced by at least one nitrogen atom, at least one sulfur atom and / or by at least one oxygen, optionally where an R 3 can be bound to this at least one nitrogen atom, optionally one, two, three or four cyclic groups which are saturated, unsaturated or aromatic, can be fused independently with 5 or 6 ring atoms to the first ring /, wherein optionally in this at least one further ring independently of one another one, two, three or four R
• At least one cationic organic compound is preferably selected from amphiphilic compounds of general formula (VI) and their tautomers where N ⁇ represents nitrogen, wherein, given on the ring, one, two, three; four, five, six or seven R 3 can be bound, wherein the ring has one or two double bonds, wherein the nitrogen-bonded R 1 is obligatory and the R 3 attached to the ring is optional, optionally one or more carbon atoms in the ring independently of one another can be replaced by at least one nitrogen atom, at least one sulfur atom and / or by at least one oxygen, it being possible for an R 3 to be bonded to this at least one nitrogen atom, optionally one, two or three cyclic groups which are saturated, unsaturated or aromatic, may be fused independently with 5 or 6 ring atoms to the first ring, optionally in this at least one further ring independently one, two, three or four R may be bonded 3 / can, where appropriate, in this at least one further ring independently of one another one or more carbon
• At least one cationic organic compound is preferably selected from amphiphilic compounds of general formula (VII) and their tautomers where N ⁇ represents nitrogen, it being possible for one, two, three, four, five or six R 3 to be bonded to the ring, wherein the ring has one or two double bonds, wherein the nitrogen-bonded R 3 and the ring-attached R 1 are obligatory and wherein the ring-attached R 3 is optional, optionally one or more carbon atoms in the ring independently of one another can be replaced by at least one nitrogen atom, at least one sulfur atom and / or by at least one oxygen, optionally where an R 3 can be bound to this at least one nitrogen atom, optionally one, two or three saturated, unsaturated or / and aromatic cyclic groups can be fused independently with 5 or 6 ring atoms to the first ring /, wherein optionally in this at least one further ring independently one, two, three or four R may / may be bonded to 3, wherein optionally in
• At least one amphiphilic cationic organic compound of the general formulas (I), (II) and (III) has at least one hydroxyl, ethyl, methyl, isopropyl, propyl or / and at the head group or groups with central nitrogen atom Benzyl group independently as R 2 or / and R 3 , wherein optionally also at least one longer alkyl chain and / or more alkyl chains can occur.
• R 1 is independently of one another, saturated or unsaturated, branched or unbranched - optionally one or more aromatic or / and phenolic groups.
• 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.
• R 1 are alkyl groups having 8 to 16 carbon atoms select; most preferred is to select them from 10 to 14 carbon atoms. 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.
• y is particularly preferably selected 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): wherein the compound has 1 to 500,000 cationic groups which independently of one another have the following chemical structures, where N ⁇ represents nitrogen as a quaternary ammonium group wherein at least one quaternary ammonium group has at least one alkyl group 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 and / or represents 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 having a number of 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 alky
• 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 may each be present at least once independently of each other, but in some embodiments at least 2, preferably with 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 greater 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 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 very particularly preferably occur predominantly, almost completely or completely independently of one another with the nitrogen atom in the polymer chain and / or with the 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 especially selected 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.
• derivatives of the polymer units of the polyolefins may be, for example, at least one compound of polyethylenes, polypropylenes, polystyrenes, polyvinyl alcohols, polyvinylamines, polyvinyl esters, e.g. Polyvinyl acetates, polyvinyl ethers, polyvinyl ketones and their derivatives, their mixtures and combinations thereof occur.
• the compounds of the general formulas VIII, IX. and. X. And their tautomers can / can be used as derivatives of the polymer units of the polyamides, for example, at least one compound of polyamino acids, polyaramides and their derivatives, mixtures and combinations thereof, especially selected from diaminocarboxylic acids, diaminodicarboxylic acids and derivatives thereof, their mixtures and combinations thereof.
• the derivatives of the polymer units of the polyesters may be, for example, at least one compound of the hydroxycarboxylic acids, dihydroxycarboxylic acids, Polycarbonates and their derivatives, their mixtures and combinations thereof, in particular selected from polyester polycarbonates 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 combinations thereof 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 can 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 derivatives Combinations occur, in particular selected from polyglucosides, condensation products of fructose or glucose and their derivatives, their mixtures and combinations thereof.
• 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 general formula (IX) or / and their tautomer (s) contain: wherein the compound has 1 to 500,000 cationic groups which independently of one another have the following chemical structures, where N ⁇ represents nitrogen, wherein zero, one, two, three, four, five, six, seven, eight, or nine R 1 are independently attached to the ring of the cationic group, wherein the nitrogen-bonded R 1 is obligatory and the R 1 attached to the ring is optional, wherein the ring of the cationic group independently of one another has one, two or three double bonds, optionally one or more carbon atoms in the ring of the cationic group being independently of one another replaced by at least one nitrogen atom, at least one sulfur atom and / or by at least one oxygen, optionally one, two, three or four saturated
• the groups R 1 independently of one another can branched or unbranched independently of one another with a number of the 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, polyurethanes, their derivatives, their mixtures and combinations thereof, where appropriate, at least one uncharged monomer or / and at least one corresponding uncharged group can occur independently of one another as the monomer base unit (e), where appropriate, at least one quaternary ammonium group can occur independently of one another with the nitrogen atom in the polymer chain and / or with the nitrogen atom on the polymer chain.
• the polymer units of at least one cationic group are at least partially selected from polyamides, polycarbonates, polyesters, polyethers, polyamines, polyimines, polyolefins, polys
• At least one cationic organic compound is preferably selected from cationic polymers, cationic copolymers, cationic block copolymers and cationic graft copolymers containing at least one cationic group of the general formula (X) or / and their tautomer (s): wherein the compound has 1 to 500,000 cationic groups which independently of one another have the following chemical structures, where N ⁇ represents nitrogen, wherein zero, one, two, three, four, five, six or seven R 1 are attached to the ring of the cationic group, wherein the nitrogen-bonded R 1 is obligatory and the R 1 attached to the ring is optional, wherein the ring of the cationic group independently of one another has one or two double bonds, optionally one or more carbon atoms in the ring of the cationic group being independently of one another replaced by at least one nitrogen atom, at least one sulfur atom and / or by at least one oxygen, optionally one, two or three saturated, unsaturated or / and aromatic cyclic
• this term is as at other points, where not the other polymeric variants are listed, for a selection from the group consisting of cationic polymers, cationic copolymers, cationic block copolymers and Rationischen graft copolymers - the at least one alkyl group - saturated or unsaturated, branched or unbranched - each independently 3 to 160 carbon atoms, more preferably 5 to 120 carbon atoms, completely more preferably 8 to 90 carbon atoms. It is particularly preferred to select x from 1 to 7 units; most preferably, x is selected from 4 or 5 units. It is particularly preferred to select y from 1 to 4 units; most preferably, y is selected from 2 or 3 units.
• the counterions to the amphiphilic compounds and to the cationic polymers are preferably anions selected from the group consisting of alkyl sulfate, carbonate, carboxylate, halide, nitrate, phosphate, phosphonate, sulfate or / and sulfonate ions.
• ions based on halide such as e.g. Bromide and / or chloride and / or carboxylate-based ions in particular such as e.g.
• monovalent ions preferably occur as counterions.
• Both the cationic organic compounds and the anionic organic compounds are usually polar and water-soluble.
• the ions neutralize.
• the cations in particular the alkalis and / or alkaline earths, in particular ammonium, sodium and / or potassium ions and the anions, in particular chloride ions, enter the aqueous solution and can remain there. Due to the removal, losses such as by 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, especially in discontinuous operation, in an amount in which the stoichiometric ratio of cationic organic compounds to anionic organic compounds in the range from 0.1: 1 to 10: 1.
• this ratio is in the range of 0.5: 1 to 5: 1, more preferably in the range of 0.7: 1 to 1.2: 1, most preferably in the range of 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 is present in excess in the bath compared to the unreacted anionic organic compounds present, then the bath is emulsifying and contains little oil (s) and / or contaminants associated therewith, but the cleaning performance is usually already accepted. In a middle range of this ratio of cationic organic compounds to the present unreacted anionic organic compounds In the bathroom, usually both the demulsifying effect of the bath, as well as its cleaning performance is high and at the same time the content of oil (s) and / or associated pollution low or very low. Therefore, it is advisable to work in many variants, such as the limit of cationic behavior to anionic behavior. Higher cleaning performance is also associated with a better cleaning result.
• the 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, potassium carbonate and / or potassium bicarbonate, at least one amine such as based on monoalkylamine (s), trialkylamine (s), monoalkanolamine (s) and / or trialkanolamine (s) such
• 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), aminocarboxylic acid (s), alkylhexanoic acid (s) and / or boric acid ester (s), in particular their amine salt (s), may be present in the bath and / or added to the bath.
• the content of corrosion inhibitor (s) is in particular 0 or in the range of 0.01 to 10 g / L, preferably 0 or in the range of 0.1 to 3 g / L, particularly preferably 0 or in the range of 0, 3 to 1 g / L.
• at least one additive such as 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.
• the bath content of the pickling inhibitors is preferably 0 or in the range of 0.01 to 10 g / L, particularly preferably in the range of 0.1 to 8 g / L.
• Boric acid (s), silicate (s) and / or phosphonate (s) can be used as the pickling inhibitor (s), among others.
• the anionic organic compounds which are optionally present in the bath and are usually derived only from soils are preferably obtained by a chemical reaction with at least one cationic organic compound or / and made less soluble in water with polyvalent cations.
• the resulting insoluble Compounds on the bath surface at least partially, especially in the oil-containing phase, and can then be removed from the bath as needed.
• These surfactants are usually derived mainly from the contaminants.
• the amphoteric surfactants and phosphate esters which usually also originate only from the contaminants, generally do not react chemically in this manner and generally remain dissolved in the bath solution as they are. All of these surfactants are preferably not intentionally added to the bath as they may interfere with demulsification and excessive foam tendency, especially.
• the total content of all active ingredients in the bath 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 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.
• the method with the composition according to the invention it is particularly preferred in discontinuous operation of a purification process in many embodiments that accumulate not more than 10 g / L of anionic organic compounds in the bath until bath care, and it is particularly preferred not more than 5 g / L or not more than 3.5 g / L, most preferably not more than 2 g / L of anionic organic compounds in the bath.
• Bath care is added.
• such plants e.g. have been driven over 3 days to 8 weeks and in which the cleaning performance is only low or very low and in which the bath hardly or no longer demulsifies, but possibly already emulsified, all these contaminants are still largely distributed in the bath solution.
• 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.
• anionic organic compounds and cationic organic compounds in the context of this application mean the corresponding unreacted compounds and not the adducts resulting therefrom.
• the bath solution can also be applied in at least one cleaning zone, for example by spraying or / and by spraying and brushing.
• the at least one substrate may optionally also be treated electrolytically, ie by electrolytic cleaning.
• these, but also other variants of the method are also suitable for tapes.
• the applied pressure in the cleaning processes is often substantially at atmospheric pressure when, for example, in printing in circulating processes.
• injection flood u.U. up to about 50 bar
• injection molding often with injection pressures in the range of 0.1 to 5 bar is used.
• the temperatures are in the cleaning process - depending partially on the chemical composition - preferably in the range of 5 to 99 ° C, more preferably in the range of 10 to 95 ° C, wherein spraying often in the range of 40 to 70 ° C and dipping often in Range of 40 to 95 ° C are applied.
• the nonionic surfactants typically have an HLB in the range of 5 to 12, often in the range of 6 to 12. Surfactants are preferably effective at HLB values ⁇ 10, especially those ⁇ 9 demulsifying.
• substrates in the form of sheets, coils (strips), wires, parts or / and composite components are preferably 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 cleaning baths containing oil (s) including other contaminants in heavy soiling in the range of 0.05 to 1 g / L or from 0.1 to 2 g / L depending on the type of installation and use and often in the order of about 0.5 g / L, for example, in automotive systems with bath care or in the order of about 8 g / L Oil (s) including other contaminants used eg in general industrial plants without bath care become.
• the content of the cleaner bath of oil (s), including other contaminants often ranges from 0.05 to 1 g / L or / and the content of surfactants, often ranges from 0.05 to 0.5 g / L
• the content of the detergent bath of oil (s) including other contaminants is often in the range of 0.7 to 6 g / L or / and the content of surfactants in the range of 0.3 to 1, 5 g / L lies.
• cleaning processes and cleaning compositions have been found in which continuous operation of the use of complex membrane filtration processes for bathroom care with costly ultrafiltration or microfiltration systems, which may require investment costs of 1 to 2 M €, can be dispensed with. This may possibly be switched to the use of oil separators, which usually incurs only investment costs in the order of about 10 to 80 T €.
• 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. hereby Significant cost savings and simplifications compared to prior art cleaning methods are possible.
• 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 or pretreatment composition based on silane / siloxane / polysiloxane, titanium / zirconium compound, iron oxide / cobalt oxide, chromate, oxalate, phosphonate / phosphate or / and organic polymer / copolymer or / and for coating with at least one composition based on a substantially organic polymeric composition, with a welding primer, with a galvanic coating, with an enamel coating, with an anodization, with a CVD Coating can be used with a PVD coating and / or with a temporary anti-corrosion coating.
• alkali phosphating e.g. for iron phosphating, for manganese phosphating or for zinc phosphating
• demulsifying surfactants mainly nonionic surfactants based on ethoxylated alkyl alcohols having one end-capping per alkyl group
• various demulsifying cationic surfactants were tested for their demulsifying effect and foaming tendency in these preliminary experiments in the laboratory.
• 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.
• the most suitable demulsifying nonionic surfactant based on ethoxylated alkyl alcohols having end capping was used along 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 pro were found in these baths during continuous operation over three to seven weeks Bath, especially in the bath of Tauchentfettung, where these levels could reach up to 10 g / L.
• the baths were dosed and replenished with a detergent scaffold and with a nonionic demulsifying surfactant and without the addition of other surfactants, but not completely renewed.
• Other surfactants were also introduced by the cleaning of the components to be cleaned. The replenishment was required because of the discharge of cleaner components from the baths.
• 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 cap.
• 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 quadrupled until the entire bathroom was 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 inclusive Builders and surfactants and even 70 to 98 wt .-% substantially 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. After draining the oil-rich phase, 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 After removal of the oil-rich phase, 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 driving style of the cleaning baths occurred There are no longer any problems with phosphating and painting, 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.

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

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• 2007
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