EP2205711B1 - Cleaning composition for metal surfaces - Google Patents

Description

The invention relates to an aqueous alkaline cleaning composition containing at least one demulsifying nonionic surfactant according to the invention for metallic surfaces, which can be used to aqueous, alkaline, surfactant-containing bath solutions (= cleaning baths, baths), optionally with non-polar organic contaminants such eg Oil (s) or / and other predominantly or completely organic soils such as e.g. Fat (s), soap (s) or / and other metalworking aids (s) such as e.g. Pulling aids including anionic organic compounds and particulate soil are polluted to act demulcent with the addition of at least one cationic organic compound and the cleaner composition of these contaminants largely or completely free. 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.

Frequently, 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. Often, however, even after some time, the demulsifying state of the bath in an emulsifying state, and often the cleaning performance has dropped steadily. Depending on the throughput and degree of soiling, as well as high levels of oil and other contaminants, 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 here means: 1. optionally analysis of bath composition, pH and / or alkalinity, 2. optionally supplementing the bath in particular with surfactant (s) and / or builder (s), 3. removal of oil and other contaminants such as particle dirt from the bath and 4. if necessary supplementation of water. Because despite the addition of larger amounts of demulsifying surfactants then often the demulsifying state of the bath could no longer be adjusted.

In such cases, in particular, an increased content of emulsifiers, corrosion inhibitors, e.g. Petrolsulfonaten and / or drawing aids as pollution in the bathroom disturbing effect. 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.

Simple alternatives for solving, reducing or avoiding this problem are cleaning processes with a continuous overflow, in which corresponding amounts of bath solution are continuously discarded, or purification processes, in which relatively long is driven to an elevated or high degree of contamination and in which then the entire bath solution is replaced in the context of cleaning and bath care by new bath solution. Both alternatives are expensive.

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. For a total organic bath content of 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. In particular, anionic organic compounds such as u.a. anionic surfactants often occur in soiling. In addition, a scaffold with about 3 to 50 g / L of Builder (s) is often included.

In the automotive industry often often expensive and expensive to clean 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 ,

In the cleaning of especially metallic surfaces, e.g. of bodywork or bodywork elements prior to phosphating and before subsequent varnishing is attempted for many years, despite the entry of oil and other non-polar organic contaminants to set a long-term stable bath. All or many of these contaminants come from means of temporary (temporary) corrosion protection, from machining and / or from the treatment of metallic surfaces. Due to the often steady entry of oil and other nonpolar organic contaminants into the cleaner bath, bath maintenance is required from time to time or continuously to remove the oils and other non-polar organic contaminants and to maintain or restore high cleaning performance.

1. 1. Diskontinuierliche Badpflegeverfahren ohne höhere Investitionen für die Badpflege, insbesonders bei kleineren Anlagen;
2. 2. Kontinuierliche Badpflegeverfahren mit einem Ölabscheider wie z.B. einem Absetzbehälter, Entöler, Koaleszenzabscheider, Separator, einer Zentrifuge oder ähnlichen Vorrichtungen zur Ölabscheidung (insbesonders Membran-freie Verfahren mit der Schwerkraft und Dichteunterschieden als Trennprinzip) zur Abscheidung und Entfernung von Ölen und weiteren unpolaren organischen Verschmutzungen aus dem Reinigerbad und seinem Kreislauf, wobei sich die Verschmutzungen des Reinigerbades kontinuierlich im Ölabscheider ansammeln und dort bei Bedarf entfernt werden können;
3. 3. Kontinuierliche Badpflegeverfahren mit einem kostspieligen und in der Pflege aufwendigen Membranfiltrationsverfahren mit einer Membranfiltrationsanlage (z.B. Ultra- oder Mikrofiltrationsanlage). Die Membranen dieser Anlagen lassen die anorganischen Bestandteile, einen Teil der Tenside und Wasser passieren und halten die unpolaren organischen Bestandteile weitgehend zurück.

As a bath care process as part of cleaning processes are used industrially today:

1. 1. Discontinuous bath care procedures without higher investment for bathroom care, especially for smaller facilities;
2. 2. Continuous bath care procedures using an oil separator such as a settling tank, de-oiler, coalescer, separator, centrifuge or similar oil separation equipment (especially membrane-free gravity and density differential separation) for the separation and removal of oils and other non-polar organic contaminants from the detergent bath and its circulation, whereby the soiling of the detergent bath continuously accumulate in the oil separator and can be removed there if necessary;
3. 3. Continuous bath care procedures with a costly and in the care consuming membrane filtration process with a membrane filtration plant (eg ultra or microfiltration plant). Leave the membranes of these plants the inorganic constituents, some of the surfactants and water pass and largely retain the nonpolar organic constituents.

In a batch process without Badpflegemaßnahmen to improve or / and maintain the bath a plant is often approached in a clean state and used until an increased or high pollution with oils and other non-polar organic contaminants has occurred. Here, the cleaning performance of the cleaner bath drops steadily. Finally, the polluted bath is then usually discarded. It requires a fresh approach to the bathroom to use the bathroom again with high cleaning performance.

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. In this case, however, 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.

In particular, the cleaner bath is used as a precursor prior to the pretreatment of surfaces of substrates prior to painting or prior to treatment or passivation of the metallic surfaces or prior to use of an industrial washer or for intermediate cleaning. Typically, 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.

As surfactant (s), 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. Preferably, 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. Preferably, no anionic or / and amphoteric surfactants are added to the demulsifying detergent bath, because they can not be demulsified with these surfactants.

In addition, in addition to water, in particular, builders of the cleaner skeleton, pickling inhibitors, corrosion inhibitors and optionally further additives may occur in the cleaner bath. Usually, in the more industrialized countries, neither in the pollution nor in the fresh bath significant amounts of organic solvents are included.

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 25 56 527 A1 describes metal detergent with alkylpolyglycol tert-butyl ether of certain formula especially as a foam suppressant.

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.

DE 102006018216 A1, published on 31.10.2007 , teaches processes for demulsifying purification and lists a variety of surfactants and cationic organic polymers, which are basically possible for the design of a demulsifying purification process. As demulsifying surfactants certain classes of nonionic or cationic surfactants are listed with their basic composition.

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.

The object is achieved with 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. Preferably, water of city water quality or / and fully desalted water is used to dilute the concentrate. Preferably, 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.

It has now been found that the 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.

Even without the presence of at least one cationic organic compound, the at least one demulsifying nonionic surfactant according to the invention acts demulsifying. The stronger one of these surfactants has a demulsifying effect, the better it is suitable for the demulsifying detergent bath. But it is also advisable that it also has a high cleaning performance and a low foaming tendency.

In particular, 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.

Preferably, 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. In particular, 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. In particular, 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.

The demulsifying nonionic surfactants (alkyl alcohols) according to the invention may independently of one another have one or two branched or unbranched (= linear) alkyl groups, which are independently saturated or unsaturated, and two alkyl groups are gemini surfactants. 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. These can often be removed from the bathroom comparatively easily. 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. Preferably, 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. Preferably, in certain embodiments, 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.

Most preferably, 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.

wobei N^⊕ Stickstoff als quaternäre Ammonium-Verbindung darstellt,
wobei R₁ eine Alkylgruppe - gesättigt oder ungesättigt - mit einer durchschnittlichen Zahl an Kohlenstoffatomen im Bereich von 8 bis 18 Kohlenstoffatomen bei jeweils entweder linearer oder verzweigter Kettenausbildung ist,
wobei die Alkylgruppe R₁ gegebenenfalls eine oder mehrere aromatische oder/und phenolische Gruppen enthalten kann oder durch jene ersetzt sein kann, wobei R₂ Wasserstoff, (EO)_x (= Polyetherkette der Formel "- CH₂ - CH₂ - O -" mit x = 1 bis 50 Einheiten mit oder ohne Endgruppenverschluss insbesonders mit einer Methyl-, Ethyl-, Propyl-, Isopropyl-, n-Butyl-, Isobutyl-, Tertiärbutyl- oder Benzyl-Gruppe), (PO)_y (= Polyetherkette der Formel "- CHCH₃ - CH₂ - O -" mit y = 1 bis 10 Einheiten mit oder ohne Endgruppenverschluss insbesonders mit einer Methyl-, Ethyl-, Propyl-, Isopropyl-, n-Butyl-, Isobutyl-, Tertiärbutyl- oder Benzyl-Gruppe) oder eine Alkylgruppe - gesättigt oder ungesättigt - mit einer durchschnittlichen Zahl an Kohlenstoffatomen im Bereich von 1 bis 18 Kohlenstoffatomen bei entweder linearer oder verzweigter Kettenausbildung ist,
wobei die Alkylgruppe R² gegebenenfalls eine oder mehrere aromatische, oder/und phenolische Gruppen enthalten kann oder durch jene ersetzt sein kann, wobei R³ und R₄ unabhängig voneinander (EO)_x (= Polyetherkette der Formel "-CH₂ - CH₂ - O -" mit x = 1 bis 50 Einheiten mit oder ohne Endgruppenverschluss für jede Polyetherkette unabhängig voneinander insbesonders mit einer Methyl-, Ethyl-, Propyl-, Isopropyl-, n-Butyl-, Isobutyl-, Tertiärbutyl- oder Benzyl-Gruppe), (PO)_y (= Polyetherkette der Formel "- CHCH₃ - CH₂ - O -" mit y = 1 bis 10 Einheiten mit oder ohne Endgruppenverschluss für jede Polyetherkette unabhängig voneinander insbesonders mit einer Methyl-, Ethyl-, Propyl-, Isopropyl-, n-Butyl-, Isobutyl-, Tertiärbutyl- oder Benzyl-Gruppe) oder/und eine Alkylgruppe - gesättigt oder ungesättigt - mit einer durchschnittlichen Zahl an Kohlenstoffatomen im Bereich von 1 bis 10 bei jeweils entweder linearer oder verzweigter Kettenausbildung ist,
wobei R³ oder/und R₄ unabhängig voneinander mindestens eine oder mehrere aromatische oder/und phenolische Gruppen enthalten oder durch jene ersetzt sein können,
wobei gegebenenfalls R₂, R³ oder/und R₄ unabhängig voneinander eine oder mehrere Gruppen ausgewählt aus Amino-Gruppen, Carbonyl-Gruppen, Ester-Gruppen, Ether-Gruppen, OH-Gruppen und Nitro-Gruppen an mindestens einem der Kohlenstoffatome oder/und zwischen den Kohlenstoffatomen mindestens einer Alkylgruppe enthalten oder/und darstellen können.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. Preferably, the at least one cationic surfactant is selected from amphiphilic compounds of general formula (I)

where N ^{⊕ represents} nitrogen as a quaternary ammonium compound,
wherein 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 may} optionally contain or be replaced by one or more aromatic and / or phenolic groups, 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), (PO) _y (= polyether chain of the formula "- CHCH ₃ - CH ₂ - O -" where y = 1 to 10 units with or without end-capping, in particular with a methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl or benzyl Group) or an alkyl group - saturated or unsaturated - having an average number of carbon atoms in the range of 1 to 18 carbon atoms in either linear or branched chain formation,
where the alkyl group R ^{2 may} optionally contain or be replaced by one or more aromatic and / or phenolic groups, where R ³ and R _{4 are} independently (EO) _x (= polyether chain of the formula "-CH ₂ - CH ₂ - O - "where x = 1 to 50 units with or without end capping for each polyether chain, independently of one another, in particular with a methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl or benzyl group), (PO) _y (= polyether chain of the formula "-CHCH ₃ -CH ₂ -O-" where y = 1 to 10 units with or without end-capping for each polyether chain independently of one another, in particular with a methyl, ethyl, propyl, isopropyl , n-butyl, isobutyl, tert-butyl or benzyl group) or / and an alkyl group - saturated or unsaturated - having an average number of carbon atoms in the range of 1 to 10 in each case either linear or branched chain formation,
wherein R ³ or / and R ₄ independently of one another may contain or be replaced by at least one or more aromatic or / and phenolic groups,
where appropriate, R ₂ , R ³ or / and R ₄ independently of one another are selected from amino groups, carbonyl groups, ester groups, ether groups, OH groups and nitro groups on at least one of the carbon atoms or / and between the carbon atoms of at least one alkyl group or / and represent.

More preferably, 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 ,

Preferably, 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.

This condition can be measured by a titration according to Epton. 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.

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. In addition, with regard to 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. This added amount of at least one cationic compound or the amount of at least one cationic compound subsequently achieved in the detergent composition may then preferably be of the order that the detergent composition operates in the weakly anionic region, at the charge neutral point or in the weakly cationic region (= demulsifying procedure ). This allows the non-polar organic. 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 removal of these nonpolar organic compounds and / or anionic organic compounds via the removal of their reaction products serves to keep the detergent bath ready for use in the long term despite further input of non-polar organic compounds and / or anionic organic compounds, without the need for special elaborate measures Cleaning or replacement of the cleaner bath for a long time or permanently comes.

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. In the meantime, that is to say before the first addition or from an addition to a subsequent addition of at least one cationic organic compound to the cleaner 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.

In the following, no distinction is made between bath, bath solution and detergent bath and therefore mostly spoken of the "bath". Here, for example, these terms also include a solution, e.g. is applied by spraying.

The aqueous alkaline, surfactant-containing bath used for the alkaline purification preferably has a pH in the range of pH 7 to 14, 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 ,

The oils used in practice are today very complicated composite mixtures, which have a variety of different substances in addition to the constituents of the base oil. An oil can therefore contain in many cases about 50 different substances. The term "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. On the other hand, the term "oil" in the context of this application also means at least one base oil from this oil-containing composition. In particular, 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. In particular, the at least one anionic organic compound acts on the state of the bath. As 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.

Although the content of 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, in the process with the inventive composition the content of either oil (s) (in narrow sense) or oil-containing composition (= oil (s) including other contaminants, which may come partly from the constituents of the oils, but sometimes also from chemical reactions of the constituents of the oil-containing composition ago) in the bath especially in continuous Operation is preferably maintained at not more than 3 g / L, especially at not more than 2.5, 2, 1.5, 1, 0.8, 0.6, 0.4, 0.2 or 0.1 g / L or preferably in the range of 0.01 to 3 g / L, more preferably in the range of 0.02 to 2.2 g / L or from 0.03 to 1.5 g / L, most preferably in the range of 0.05 to 1 g / L. In this case, 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. In the process with the composition according to the invention it is particularly preferred that 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 from 0.05 to 0.7 g / L or from 0.1 to 1.6 g / L, which depends in particular on the plant and the driving style. However, 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.

In particular, oil (s), fat (s), soap (s), metalworking aids such as, for example, drawing aids and / or, if appropriate, non-polar organic contaminants Also 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, Schweißschmauch 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.

The pollution usually contains at least one oil, often also at least one anionic organic compound. When using oil (s) with a lot of additives, in practice, 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.

In particular, the method with the composition according to the invention for cleaning processes and baths with contaminations is provided 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. In many cases, 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 be driven well demulsifying if the appropriate levels contained in the bath or / and appropriate additives are added to it.

In many cases, it is advantageous or even necessary to limit the content of anionic organic compounds in a bath to certain maximum levels, because otherwise the demulsification of oil is reduced or prevented, so that the content of oil and other contaminants in the bath increases and the Cleaning performance of the bath decreases. The content of anionic organic compounds is 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. In an industrial plant e.g. for heavily deformed parts before further treatment, in particular for the corrosion protection of metallic surfaces, before passivation, before pretreatment e.g. with a conversion treatment composition, e.g. 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.

Because the content of 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.

When cleaning the metallic surfaces of oil-containing compositions, 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. However, 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. However, it stops when the oil droplets reach a radius of curvature dictated by the geometry of the surfactant or surfactant mixtures used. In many embodiments, it is advisable, via the selection of surfactants, their contents and their mixture, to set a specific radius of curvature of the oil droplets as the predominant possible radius of curvature in baths via the coverage of the oil droplets. In this case, the method can be optimized in the fine range. This radius of curvature is preferably set in some embodiments, that the oil in a moving bath just not demulsified and that an oil-containing phase is therefore not or not yet accumulates more strongly on the surface of the bath, but in a dormant bath such as B. in a separating vessel (oil separator) spontaneously separates and accumulates on the surface of the bath as oil-containing, often other contaminants than oil-containing phase.

It has now been found that 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. In this case, 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. In this way 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. Preferably, 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 process of coalescence is diminished or even suppressed by the presence of anionic organic compounds in the bath, since the on the Oil droplets absorbed anionic organic compounds to charge the oil droplets of the same name, which in turn leads to a repulsion of the oil droplets with each other. Due to the addition of, for example, cationic organic compounds, this anionic charge can be partially or even completely neutralized, so that furthermore a demulsifying state is present and the coalescing of the oil droplets can proceed.

In practice this means for many embodiments that 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. Usually, all cationic surfactants can act as demulsifiers through interaction with at least one anionic organic compound. In addition, 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. That at least 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 Badumwälzung 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. In most cases, 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. In some embodiments, it is possible to keep the surfactant contents low so that 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. In some embodiments it is possible to keep these levels low so that 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. In many embodiments, 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.

In discontinuous operation, it may be worthwhile to replace the entire bath contents when cleaning the system when removing the dirt (bath replacement).

In the method according to the invention is at least one 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. Here, the term "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. In particular, 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 polymers at least one quaternary ammonium group and / or 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 - especially one, two, three, four or five - different monomer backbones in at least one Polymer chain included. Possible monomeric building blocks here are cationically charged polymers, in particular cationic polyelectrolytes, in particular those containing at least one quaternary nitrogen atom, at least one guanidinium group, at least one quaternized imidazoline group (= imidazolium group), at least one quaternized oxazolium group or / and at least one quaternized pyridyl group (= pyridinium group), such as those based on ethyleneimine (s), Hexamethylendiaminguanidium compounds, oxazolium, vinylimidazolium, vinylpyridinium compounds such as the corresponding chlorides. In particular, 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. In particular, 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. In the case of different types of 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.

wobei N^⊕ Stickstoff als quaternäre Ammonium-Verbindung darstellt,
wobei R₁ eine Alkylgruppe - gesättigt oder ungesättigt - mit einer durchschnittlichen Zahl an Kohlenstoffatomen im Bereich von 8 bis 18 Kohlenstoffatomen bei jeweils entweder linearer oder verzweigter Kettenausbildung ist,
wobei die Alkylgruppe R₁ gegebenenfalls eine oder mehrere aromatische oder/und phenolische Gruppen enthalten kann oder durch jene ersetzt sein kann,
wobei R² Wasserstoff, (EO)_x (= Polyetherkette der Formel "- CH₂ - CH₂ - O -" mit x = 1 bis 50 Einheiten mit oder ohne Endgruppenverschluss insbesonders mit einer Methyl-, Ethyl-, Propyl-, Isopropyl-, n-Butyl-, Isobutyl-, Tertiärbutyl- oder Benzyl-Gruppe), (PO)_y (= Polyetherkette der Formel "- CHCH₃ - CH₂ - O -" mit y = 1, bis 10 Einheiten mit oder ohne Endgruppenverschluss insbesonders mit einer Methyl-, Ethyl-, Propyl-, Isopropyl-, n-Butyl-, Isobutyl-, Tertiärbutyl- oder Benzyl-Gruppe) oder eine Alkylgruppe - gesättigt oder ungesättigt - mit einer durchschnittlichen Zahl an Kohlenstoffatomen im Bereich von 1 bis 18 Kohlenstoffatomen bei entweder linearer oder verzweigter Kettenausbildung ist,
wobei die Alkylgruppe R² gegebenenfalls eine oder mehrere aromatische, oder/und phenolische Gruppen enthalten kann oder durch jene ersetzt sein kann,
wobei R³ und R₄ unabhängig voneinander (EO)_x (= Polyetherkette der Formel "- CH₂ - CH₂ - O -" mit x = 1 bis 50 Einheiten mit oder ohne Endgruppenverschluss für jede Polyetherkette unabhängig voneinander insbesonders mit einer Methyl-, Ethyl-, Propyl-, Isopropyl-, n-Butyl-, Isobutyl-, Tertiärbutyl- oder Benzyl-Gruppe), (PO)_y (= Polyetherkette der Formel "- CHCH₃ - CH₂ - O -" mit y = 1 bis 10 Einheiten mit oder ohne Endgruppenverschluss für jede Polyetherkette unabhängig voneinander insbesonders mit einer Methyl-, Ethyl-, Propyl-, isopropyl, n-Butyl-, Isobutyl-, Tertiärbutyl- oder Benzyl-Gruppe) oder/und eine Alkylgruppe - gesättigt oder ungesättigt - mit einer durchschnittlichen Zahl an Kohlenstoffatomen im Bereich von 1 bis 10 bei jeweils entweder linearer oder verzweigter Kettenausbildung ist,
wobei R³ oder/und R₄ unabhängig voneinander mindestens eine oder mehrere aromatische oder/und phenolische Gruppen enthalten oder durch jene ersetzt sind,
wobei gegebenenfalls R₂, R³ oder/und R₄ unabhängig voneinander eine oder mehrere Gruppen ausgewählt aus Amino-Gruppen, Carbonyl-Gruppen, Ester-Gruppen, Ether-Gruppen, OH-Gruppen und Nitro-Gruppen an mindestens einem der Kohlenstoffatome oder/und zwischen den Kohlenstoffatomen mindestens einer Alkylgruppe enthalten oder/und darstellen können.Here, at least one cationic organic compound of the general formula (I)

where N ^{⊕ represents} nitrogen as a quaternary ammonium compound,
wherein 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 may} optionally contain or may be replaced by one or more aromatic and / or phenolic groups,
where R ^{2 is} hydrogen, (EO) _x (= polyether chain of the formula "- CH ₂ -CH ₂ -O-" where x = 1 to 50 units with or without end-capping, in particular with a methyl, ethyl, propyl, isopropyl , n-butyl, isobutyl, tert-butyl or benzyl group), (PO) _y (= polyether chain of the formula "- CHCH ₃ - CH ₂ -O-" with y = 1, up to 10 units with or without end-capping in particular with a methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl or benzyl group) or an alkyl group - saturated or unsaturated - having an average number of carbon atoms in the range of 1 to 18 carbon atoms with either linear or branched chain formation,
wherein the alkyl group R ^{2 may} optionally contain or may be replaced by one or more aromatic and / or phenolic groups,
where R ³ and R ₄ independently of one another (EO) _x (= polyether chain of the formula "- CH ₂ -CH ₂ -O-" where x = 1 to 50 units with or without end-capping for each polyether chain independently of one another, in particular with a methyl, Ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl or benzyl), (PO) _y (= polyether chain of the formula "-CHCH ₃ -CH ₂ -O-" where y = 1 to 10 units with or without end-capping for each polyether chain independently of one another, in particular with a methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl or benzyl group) or / and an alkyl group - saturated or unsaturated - with an average number of carbon atoms in the range of 1 to 10 for either linear or branched chain formation,
wherein R ³ or / and R ₄ independently of one another contain or are replaced by at least one or more aromatic or / and phenolic groups,
where appropriate, R ₂ , R ³ or / and R ₄ independently of one another are selected from amino groups, carbonyl groups, ester groups, ether groups, OH groups and nitro groups on at least one of the carbon atoms or / and between the carbon atoms of at least one alkyl group or / and represent.

More preferably, at least one cationic surfactant has one or two benzyl groups.

In the case of compounds of general formula (I), 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. With compounds of general formula (I), particular preference is given to selecting alkyl groups having 1 or 6 carbon atoms in R ³ , the latter in particular as benzyl group.

wobei N^⊕ Stickstoff als quaternäre Ammonium-Verbindung darstellt,
wobei R₁ unabhängig voneinander eine Alkylgruppe - gesättigt oder ungesättigt - mit einer durchschnittlichen Zahl an Kohlenstoffatomen im Bereich von 4 bis 22 Kohlenstoffatomen bei jeweils entweder linearer oder verzweigter Kettenausbildung ist,
wobei gegebenenfalls mindestens eine der Alkylgruppen R₁ unabhängig voneinander eine oder mehrere aromatische oder/und phenolische Gruppen enthalten kann oder/und durch jene ersetzt sein kann,
wobei R₂ eine Alkylgruppe - gesättigt oder ungesättigt - mit einer durchschnittlichen Zahl an Kohlenstoffatomen im Bereich von 1 bis 22 Kohlenstoffatomen bei entweder linearer oder verzweigter Kettenausbildung ist, wobei die Alkylgruppe R² gegebenenfalls eine oder mehrere aromatische oder/und phenolische Gruppen enthalten oder durch jene ersetzt sein kann,
wobei R³ unabhängig voneinander Wasserstoff, (EO)_x (= Polyetherkette der Formel "- CH₂ - CH₂ - O -" mit x = 1 bis 50 Einheiten insbesonders mit einer Methyl-, Ethyl-, Propyl-, Isopropyl-, n-Butyl-, Isobutyl-, Tertiärbutyl- oder Benzyl-Gruppe), (PO)_y (= Polyetherkette der Formel "- CHCH₃ - CH₂ - O -" mit y = 1 bis 10 Einheiten insbesonders mit einer Methyl-, Ethyl-, Propyl-, Isopropyl-, n-Butyl-, Isobutyl-, Tertiärbutyl- oder Benzyl-Gruppe) oder/und eine Alkylgruppe - gesättigt oder ungesättigt - mit einer durchschnittlichen Zahl an Kohlenstoffatomen im Bereich von 1 bis 10 bei jeweils entweder linearer oder verzweigter Kettenausbildung ist,
wobei mindestens eine der Alkylgruppen R³ unabhängig voneinander eine oder mehrere aromatische oder/und phenolische Gruppen enthält oder/und durch jene ersetzt ist, wobei gegebenenfalls R² unabhängig voneinander eine oder mehrere Gruppen ausgewählt aus Amino-Gruppen, Carbonyl-Gruppen, Ester-Gruppen, Ether-Gruppen, OH-Gruppen und Nitro-Gruppen an mindestens einem der Kohlenstoffatome oder/und zwischen den Kohlenstoffatomen mindestens einer Alkylgruppe enthalten kann,
wobei gegebenenfalls mindestens eine Gruppe R³ unabhängig voneinander eine oder mehrere Gruppen ausgewählt aus Amino-Gruppen, Carbonyl-Gruppen, Ester-Gruppen, Ether-Gruppen, OH-Gruppen und Nitro-Gruppen an mindestens einem der Kohlenstoffatome oder/und zwischen den Kohlenstoffatomen mindestens einer Alkylgruppe enthalten oder/und darstellen darstellen kann.In this case, at least one cationic organic compound is preferably selected from amphiphilic compounds of the general formula (II)

where N ^{⊕ represents} nitrogen as a quaternary ammonium compound,
wherein 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,
where appropriate, at least one of the alkyl groups R ₁ independently of one another may contain one or more aromatic and / or phenolic groups and / or be replaced by those
wherein 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 wherein the alkyl group R ² optionally contains or through one or more aromatic and / or phenolic groups can be replaced
where R ^{3 is} independently of one another hydrogen, (EO) _x (= polyether chain of the formula "- CH ₂ -CH ₂ -O-" where x = 1 to 50 units, in particular with a methyl, ethyl, propyl, isopropyl, n -butyl, isobutyl, tertiary butyl or benzyl group), (PO) _y (= polyether chain of the formula "- CHCH ₃ - CH ₂ - O -" with y = 1 to 10 units in particular with a methyl, ethyl , Propyl, isopropyl, n-butyl, isobutyl, tert-butyl or benzyl group) or / and an alkyl group - saturated or unsaturated - having an average number of carbon atoms in the range of 1 to 10 in each case either linear or branched Chain training is,
wherein at least one of the alkyl groups R ³ independently of one another contains or is replaced by one or more aromatic and / or phenolic groups, where appropriate, R ² independently of one another contain 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 of at least one alkyl group can
where appropriate, at least one group 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 or / and between the carbon atoms at least may contain or represent an alkyl group.

In the case of compounds of the general formula (II), particular preference is given to selecting alkyl groups having 1 or 8 to 16 carbon atoms in the case of R ² ; most preferred is to select them from 1 or 10 to 14 carbon atoms. In the case of compounds of the general formula (II), 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.

wobei N^⊕ Stickstoff als quaternäre Ammonium-Verbindung darstellt, wobei gegebenenfalls CH - CH durch CH - R₄ - CH ersetzt sein kann,
wobei R₄ unabhängig voneinander eine Alkylgruppe - gesättigt oder ungesättigt - mit einer durchschnittlichen Zahl an Kohlenstoffatomen im Bereich von 1 bis 14 Kohlenstoffatomen bei jeweils entweder linearer oder verzweigter Kettenausbildung ist
wobei mindestens eine der Alkylgruppen R₄ unabhängig voneinander eine oder mehrere aromatische oder/und phenolische Gruppen enthält oder/und durch jene ersetzt ist,
wobei gegebenenfalls mindestens eine der Alkylgruppen R₄ unabhängig voneinander auch mindestens eine Amino-Gruppe, Carbonyl-Gruppe, Ester-Gruppe, Ether-Gruppe, OH-Gruppe und Nitro-Gruppe an Mindestens einem der Kohlenstoffatome oder/und zwischen den Kohlenstoffatomen von mindestens einer Alkylgruppe enthalten kann,
wobei gegebenenfalls N^⊕ - CH durch N^⊕ - R₅ - CH ersetzt sein kann,
wobei R⁵ unabhängig voneinander eine Alkylgruppe - gesättigt oder ungesättigt - mit einer durchschnittlichen Zahl an Kohlenstoffatomen im Bereich von 1 bis 8 Kohlenstoffatomen bei jeweils entweder linearer oder verzweigter Kettenausbildung ist,
wobei gegebenenfalls mindestens eine der Alkylgruppen R⁵ unabhängig voneinander eine oder mehrere aromatische oder/und phenolische Gruppen enthalten kann oder/und durch jene ersetzt sein kann,
wobei gegebenenfalls mindestens eine der Alkylgruppen R⁵ unabhängig voneinander auch mindestens eine Amino-Gruppe, Carbonyl-Gruppe, Ester-Gruppe, Ether-Gruppe, OH-Gruppe und Nitro-Gruppe an mindestens einem der Kohlenstoffatome oder/und zwischen den Kohlenstoffatomen mildestens einer Alkylgruppe enthalten kann,
wobei R₁ unabhängig voneinander Wasserstoff oder eine Alkylgruppe - gesättigt oder ungesättigt - mit einer durchschnittlichen Zahl an Kohlenstoffatomen im Bereich von 4 bis 22 Kohlenstoffatomen bei jeweils entweder linearer oder verzwelgter Kettenausbildung ist,
wobei gegebenenfalls mindestens eine der Alkylgruppen R₁ unabhängig voneinander eine oder mehrere aromatische oder/und phenolische Gruppen enthalten kann oder/und durch jene ersetzt sein kann,
wobei R³ unabhängig voneinander Wasserstoff, (EO)_x (= Polyetherkette der Formel "- CH₂ - CH₂ - O -" mit x = 1 bis 50 Einheiten mit oder ohne Endgruppenverschluss für jede Polyetherkette unabhängig voneinander insbesonders mit einer Methyl-, Ethyl-, Propyl-, Isopropyl-, n-Butyl-, Isobutyl-, Tertiärbutyl- oder Benzyl-Gruppe), (PO)_y (= Polyetherkette der Formel "- CHCH₃ - CH₂ - O -" mit y = 1 bis 10 Einheiten mit oder ohne Endgruppenverschluss für jede Polyetherkette unabhängig voneinander insbesonders mit einer Methyl-, Ethyl-, Propyl-, Isopropyl-, n-Butyl-, Isobutyl-, Tertiärbutyl- oder Benzyl-Gruppe) oder/und eine Alkylgruppe - gesättigt oder ungesättigt - mit einer durchschnittlichen Zahl an Kohlenstoffatomen im Bereich von 1 bis 10 bei jeweils entweder linearer oder verzweigter Kettenausbildung ist,
wobei gegebenenfalls mindestens eine der Alkylgruppen R³ unabhängig voneinander eine oder mehrere aromatische oder/und phenolische Gruppen enthalten kann oder/und durch jene ersetzt sein kann,
wobei gegebenenfalls mindestens eine der Gruppen R³ unabhängig voneinander eine oder mehrere Gruppen ausgewählt aus Amino-Gruppen, Carbonyl-Gruppen, Ester-Gruppen, Ether-Gruppen, OH-Gruppen und Nitro-Gruppen an mindestens einem der Kohlenstoffatome oder/und zwischen den Kohlenstoffatomen mindestens einer Alkylgruppe enthalten oder/und darstellen kann/können.In this case, 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 - CH,
wherein R ^{5 is} independently an alkyl group - saturated or unsaturated - having an average number of carbon atoms in the range of 1 to 8 carbon atoms in each case either linear or branched chain formation,
where appropriate, at least one of the alkyl groups R ⁵ independently of one another may contain one or more aromatic and / or phenolic groups and / or be replaced by those
where appropriate, at least one of the alkyl groups R ^5, independently of one another, also has 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 alkyl group can contain
wherein R _{1 is} independently hydrogen or an alkyl group - saturated or unsaturated - having an average number of carbon atoms in the range of 4 to 22 carbon atoms, each with either linear or lame chain formation,
where appropriate, at least one of the alkyl groups R ₁ independently of one another may contain one or more aromatic and / or phenolic groups and / or be replaced by those
where R ³ independently of one another are hydrogen, (EO) _x (= polyether chain of the formula "- CH ₂ -CH ₂ -O-" where x = 1 to 50 units with or without end-capping for each polyether chain independently of one another, in particular with a methyl, ethyl -, propyl, isopropyl, n-butyl, isobutyl, tert-butyl or benzyl group), (PO) _y (= polyether chain of the formula "- CHCH ₃ - CH ₂ - O -" with y = 1 to 10 Units with or without end capping for each polyether chain independently of one another in particular with a methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl or benzyl group) or / and an alkyl group - saturated or unsaturated - with an average number of carbon atoms in the range of 1 to 10 for either linear or branched chain formation,
where appropriate, at least one of the alkyl groups R ³ independently of one another may contain one or more aromatic and / or phenolic groups and / or be replaced by those
where appropriate, 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 or / and between the carbon atoms contain at least one alkyl group and / or can / can.

Particularly preferred in the case of the compounds of the general formula (III), 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. In the case of the compounds of general formula (III), 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.

wobei N^⊕ Stickstoff darstellt,
wobei an dem Ring der Allgemeinen Formel (IV) ein, zwei, drei, vier, fünf, sechs, sieben, acht oder neun R₃ gebunden sein kann/können,
wobei das am Stickstoff gebundene R₁ obligatorisch und das am Ring gebundene R₃ optional ist,
wobei der Ring eine, zwei oder drei Doppelbindungen aufweist,
wobei gegebenenfalls im Ring unabhängig voneinander ein oder mehrere Kohlenstoffatome durch mindestens ein Stickstoffatom, mindestens ein Schwefelatom oder/und durch mindestens ein Sauerstoff ersetzt sein kann,
wobei gegebenenfalls an dieses mindestens eine Stickstoffatom ein R₃ gebunden sein kann,
wobei gegebenenfalls noch eine, zwei, drei oder vier zyklische Gruppen, die gesättigt, ungesättigt oder aromatisch sind, unabhängig voneinander mit 5 oder 6 Ringatomen an den ersten Ring ankondensiert sein kann/können, wobei gegebenenfalls in diesem mindestens einen weiteren Ring unabhängig voneinander ein, zwei, drei oder vier R₃ gebunden sein kann/können,wobei gegebenenfalls in diesem mindestens einen weiteren Ring unabhängig voneinander ein oder mehrere Kohlenstoffatome durch mindestens ein Stickstoffatom, mindestens ein Schwefelatom oder/und durch mindestens ein Sauerstoff ersetzt sein kann/können, wobei gegebenenfalls an dieses mindestens eine Stickstoffatom, ein R₃ gebunden sein kann,
wobei R₁ eine Alkylgruppe - gesättigt oder ungesättigt - mit einer durchschnittlichen Zahl an Kohlenstoffatomen im Bereich von 4 bis 22 Kohlenstoffatomen bei jeweils entweder linearer oder verzweigter Kettenausbildung ist, wobei gegebenenfalls die Alkylgruppe R₁ eine oder mehrere aromatische oder/und phenolische Gruppen enthalten kann oder durch jene ersetzt sein kann,
wobei R₃ unabhängig voneinander Wasserstoff, Amino-Gruppe, Carbonyl-Gruppe, Ester-Gruppe, Ether-Gruppe, Nitro-Gruppe, OH-Gruppe, (EO)_x (= Polyetherkette der Formel "- CH₂ - CH₂ - O -" mit x = 1 bis 50 Einheiten mit oder ohne Endgruppenverschluss für jede Polyetherkette unabhängig voneinander insbesonders mit einer Methyl-, Ethyl-, Propyl-, Isopropyl-, n-Butyl-, Isobutyl-, Tertiärbutyl- oder Benzyl-Gruppe), (PO)_y (= Polyetherkette der Formel "-CHCH₃ - CH₂ - O -" mit y = 1 bis 10 Einheiten mit oder ohne Endgruppenverschluss für jede Polyetherkette unabhängig voneinander insbesonders mit einer Methyl-, Ethyl-, Propyl-, Isopropyl-, n-Butyl-, Isobutyl-, Tertiärbutyl- oder Benzyl-Gruppe) oder/und eine Alkylgruppe - gesättigt oder ungesättigt - mit einer durchschnittlichen Zahl an Kohlenstoffatomen im Bereich von 1 bis 6 Kohlenstoffatomen bei jeweils entweder linearer oder verzweigter Kettenausbildung ist, wobei gegebenenfalls mindestens eine der Alkylgruppen R₃ unabhängig voneinander eine oder mehrere aromatische oder/und phenolische Gruppen enthalten kann oder durch jene ersetzt sein kann,
wobei gegebenenfalls mindestens eine Gruppe R₃ unabhängig voneinander eine oder mehrere Gruppen ausgewählt aus Amino-Gruppen, Carbonyl-Gruppen, Ester-Gruppen, Ether-Gruppen, OH-Gruppen und Nitro-Gruppen an mindestens einem der Kohlenstoffatome oder/und zwischen den Kohlenstoffatomen mindestens einer Alkylgruppe enthalten kann.Here, 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 further 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, where appropriate to this at least one nitrogen atom, an R ₃ may be bonded,
wherein R _{1 is} an alkyl group - saturated or unsaturated - having an average number of carbon atoms in the range of 4 to 22 carbon atoms each is either linear or branched chain formation, optionally wherein the alkyl group R ₁ may contain or may be replaced by one or more aromatic and / or phenolic groups,
where R _{3 is} independently of one another hydrogen, amino group, carbonyl group, ester group, ether group, nitro group, OH group, (EO) _x (= polyether chain of the formula "- CH ₂ -CH ₂ -O- "with x = 1 to 50 units with or without end capping for each polyether chain, independently of one another, especially with a methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl or benzyl group), (PO _y (= polyether chain of the formula "-CHCH ₃ -CH ₂ -O-" where y = 1 to 10 units with or without end-capping for each polyether chain independently of one another, in particular with a methyl, ethyl, propyl, isopropyl, n -Butyl, isobutyl, tert-butyl or benzyl group) or / and an alkyl group - saturated or unsaturated - having an average number of carbon atoms in the range of 1 to 6 carbon atoms in each case either linear or branched chain formation, where appropriate, at least one the alkyl groups R ₃ independently v may contain one or more aromatic and / or phenolic groups or may be replaced by those
where appropriate, at least one group 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 or / and between the carbon atoms at least may contain an alkyl group.

wobei N^⊕ Stickstoff darstellt,
wobei an dem Ring der Allgemeinen Formel (V) gegebenenfalls ein, zwei, drei, vier, fünf, sechs, sieben oder acht R₃ gebunden sein kann/können,
wobei das am Stickstoff gebundene R₃ und das am Ring gebundene R₁ obligatorisch sind und wobei das am Ring gebundene R₃ optional ist,
wobei der Ring eine, zwei oder drei Doppelbindungen aufweist, wobei gegebenenfalls im Ring unabhängig voneinander ein oder mehrere Kohlenstoffatome durch mindestens ein Stickstoffatom, mindestens ein Schwefelatom oder/und durch mindestens ein Sauerstoff ersetzt sein kann/können,
wobei gegebenenfalls an dieses mindestens eine Stickstoffatom ein R₃ gebunden sein kann,
wobei gegebenenfalls noch eine, zwei, drei oder vier zyklische Gruppen, die gesättigt, ungesättigt oder aromatisch sind, unabhängig voneinander mit 5 oder 6 Ringatomen an den ersten Ring ankondensiert sein kann/können, wobei gegebenenfalls in diesem mindestens einen weiteren Ring unab-hängig voneinander ein, zwei, drei oder vier R₃ gebunden sein können, wobei gegebenenfalls in diesem mindestens einen weiteren Ring unabhängig voneinander ein oder mehrere Kohlenstoffatome durch mindestens ein Stickstoffatom, mindestens ein Schwefelatom oder/und durch mindestens ein Sauerstoff ersetzt sein kann/können, wobei gegebenenfalls an dieses mindestens eine Stickstoffatom ein R₃ gebunden sein. kann,
wobei R₁ eine Alkylgruppe - gesättigt oder ungesättigt - mit einer durchschnittlichen Zahl an Kohlenstoffatomen im Bereich von 4 bis 22 Kohlenstoffatomen bei jeweils entweder linearer oder verzweigter Kettenausbildung ist, wobei die Alkylgruppe R₁ gegebenenfalls eine oder mehrere aromatische oder/und phenolische Gruppen enthalten kann oder durch jene ersetzt sein kann,
wobei R₁ an einem Köhtenstöffätöm ohne jede Doppelbindung oder an einem Kohlenstoffatom mit einer Doppelbindung angebunden ist,
wobei R₃ unabhängig voneinander Wasserstoff, Amino-Gruppe, Carbonyl-Gruppe, Ester-Gruppe, Ether-Gruppe, Nitro-Gruppe, OH-Gruppe, (EO)_x (= Polyetherkette der Formel "- CH₂ - CH₂ - O -" mit x = 1 bis 50 Einheiten mit oder ohne Endgruppenverschluss für jede Polyetherkette unabhängig voneinander insbesonders mit einer Methyl-, Ethyl-, Propyl-, Isopropyl-, n-Butyl-, Isobutyl-, Tertiärbutyl- oder Benzyl-Gruppe), (PO)_y (= Polyetherkette der Formel "-CHCH₃ - CH₂ - O -" mit y = 1 bis 10 Einheiten mit oder ohne Endgruppenverschluss für jede Polyetherkette unabhängig voneinander insbesonders mit einer Methyl-, Ethyl-, Propyl-, Isopropyl-, n-Butyl-, Isobutyl-, Tertiärbutyl- oder Benzyl-Gruppe) oder/und eine Alkylgruppe - gesättigt oder ungesättigt - mit einer durchschnittlichen Zahl an Kohlenstoffatomen im Bereich von 1 bis 6 Kohlenstoffatomen bei jeweils entweder linearer oder verzweigter Kettenausbildung ist, wobei gegebenenfalls mindestens eine der Alkylgruppen R₃ unabhängig voneinander eine oder mehrere aromatische oder/und phenolische Gruppen enthalten kann oder durch jene ersetzt sein kann,
wobei gegebenenfalls mindestens eine Gruppe R₃ unabhängig voneinander eine oder mehrere Gruppen ausgewählt aus Amino-Gruppen, Carbonyl-Gruppen, Ester-Gruppen, Ether-Gruppen, OH-Gruppen und Nitro-Gruppen an mindestens einem der Kohlenstoffatome oder/und zwischen den Kohlenstoffatomen mindestens einer Alkylgruppe enthalten kann.Here, 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 ₃ may be bonded, wherein optionally 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 replaced by at least one oxygen / may be, optionally be bound to this at least one nitrogen atom, an R ₃ . can
wherein R _{1 is} 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, wherein the alkyl group R _{1 may} optionally contain one or more aromatic and / or phenolic groups or can be replaced by those
wherein R _{1 is} attached to a Köhtenstöffätöm without any double bond or on a carbon atom with a double bond,
where R _{3 is} independently of one another hydrogen, amino group, carbonyl group, ester group, ether group, nitro group, OH group, (EO) _x (= polyether chain of the formula "-CH ₂ -CH ₂ -O-" where x = 1 to 50 units with or without end capping for each polyether chain, independently of one another, in particular with a methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl , Tert-butyl or benzyl group), (PO) _y (= polyether chain of the formula "-CHCH ₃ -CH ₂ -O-" where y = 1 to 10 units with or without end capping for each polyether independently of one another, in particular with a methyl -, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl or benzyl group) or / and an alkyl group - saturated or unsaturated - having an average number of carbon atoms in the range of 1 to 6 carbon atoms each is either linear or branched chain formation, where optionally at least one of the alkyl groups R ₃ independently of one another may contain or may be replaced by one or more aromatic and / or phenolic groups,
where appropriate, at least one group 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 or / and between the carbon atoms at least may contain an alkyl group.

wobei N^⊕ Stickstoff darstellt,
wobei an dem Ring gegebenehfalls ein, zwei, drei; vier, fünf, sechs oder sieben R₃ gebunden sein kann/können,
wobei der Ring eine oder zwei Doppelbindungen aufweist,
wobei das am Stickstoff gebundene R₁ obligatorisch und das am Ring gebundene R₃ optional ist,
wobei gegebenenfalls im Ring unabhängig voneinander ein oder mehrere Kohlenstoffatome durch mindestens ein Stickstoffatom, mindestens ein Schwefelatom oder/und durch mindestens ein Sauerstoff ersetzt sein kann/können, wobei gegebenenfalls an dieses mindestens eine Stickstoffatom ein R₃ gebunden sein kann,
wobei gegebenenfalls noch eine, zwei oder drei zyklische Gruppen, die gesättigt, ungesättigt oder aromatisch sind, unabhängig voneinander mit 5 oder 6 Ringatomen an den ersten Ring ankondensiert sein kann/können, wobei gegebenenfalls in diesem mindestens einen weiteren Ring unabhängig voneinander ein, zwei, drei oder vier R₃ gebunden sein kann/können, wobei gegebenenfalls in diesem mindestens einen weiteren Ring unabhängig voneinander ein oder mehrere Kohlenstoffatome durch mindestens ein Stickstoffatom, mindestens ein Schwefelatom oder/und durch mindestens ein Sauerstoff ersetzt sein kann/können, wobei gegebenenfalls an dieses mindestens eine Stickstoffatom ein R₃ gebunden sein kann,
wobei R₁ eine Alkylgruppe - gesättigt oder ungesättigt - mit einer durchschnittlichen Zahl an Kohlenstoffatomen im Bereich von 4 bis 22 Kohlenstoffatomen bei jeweils entweder linearer oder verzweigter Kettenausbildung ist, wobei die Alkylgruppe R₁ gegebenenfalls eine oder mehrere aromatische oder/und phenolische Gruppen enthalten kann oder durch jene ersetzt sein kann,
wobei R₃ unabhängig voneinander Wasserstoff, Amino-Gruppe, Carbonyl-Gruppe, Ester-Gruppe, Ether-Gruppe, Nitro-Gruppe, OH-Gruppe, (EO)_x (= Polyetherkette der Formel "- CH₂ - CH₂ - O -" mit x = 1 bis 50 Einheiten mit oder ohne Endgruppenverschluss für jede Polyetherkette unabhängig voneinander insbesonders mit einer Methyl-, Ethyl-, Propyl-, Isopropyl-, n-Butyl-, Isobutyl-, Tertiärbutyl- oder Benzyl-Gruppe), (PO)_y (= Polyetherkette der Formel "-CHCH₃ - CH₂ - O -" mit y = 1 bis 10 Einheiten mit für jede Polyetherkette unabhängig voneinander oder ohne Endgruppenverschluss für jede Polyetherkette unabhängig voneinander insbesonders mit einer Methyl-, Ethyl-, Propyl-, Isopropyl-, n-Butyl-, Isobutyl-, Tertiärbutyl- oder Benzyl-Gruppe) oder/und eine Alkylgruppe - gesättigt oder ungesättigt - mit einer durchschnittlichen Zahl an Kohlenstoffatomen im Bereich von 1 bis 6 Kohlenstoffatomen bei jeweils entweder linearer oder verzweigter Kettenausbildung ist, wobei gegebenenfalls mindestens eine der Alkylgruppen R₃ unabhängig voneinander eine oder mehrere aromatische oder/und phenolische Gruppen enthalten kann oder durch jene ersetzt sein kann,
wobei gegebenenfalls mindestens eine Gruppe R₃ unabhängig voneinander eine oder mehrere Gruppen ausgewählt aus Amino-Gruppen, Carbonyl-Gruppen, Ester-Gruppen, Ether-Gruppen, OH-Gruppen und Nitro-Gruppen an mindestens einem der Kohlenstoffatome oder/und zwischen den Kohlenstoffatomen mindestens einer Alkylgruppe enthalten kann.Here, 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 atoms are replaced by at least one nitrogen atom, at least one sulfur atom and / or may be replaced by at least one oxygen / can, where appropriate, at this at least one nitrogen atom may be bound to R ₃ ,
wherein R _{1 is} 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, wherein the alkyl group R _{1 may} optionally contain one or more aromatic and / or phenolic groups or can be replaced by those
where R _{3 is} independently of one another hydrogen, amino group, carbonyl group, ester group, ether group, nitro group, OH group, (EO) _x (= polyether chain of the formula "- CH ₂ -CH ₂ -O- "with x = 1 to 50 units with or without end capping for each polyether chain, independently of one another, especially with a methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl or benzyl group), (PO _y (= polyether chain of the formula "-CHCH ₃ -CH ₂ -O-" where y = 1 to 10 units with, independently of one another or without end-capping for each polyether chain, independently of each other in particular with a methyl, ethyl, propyl , Isopropyl, n-butyl, isobutyl, tert-butyl or benzyl) and / or an alkyl group - saturated or unsaturated - having an average number of carbon atoms in the range of 1 to 6 carbon atoms in either linear or branched chain formation, optionally wherein at least one of the alkyl groups R ₃ independently of one another may contain or may be replaced by one or more aromatic and / or phenolic groups,
where appropriate, at least one group 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 or / and between the carbon atoms at least may contain an alkyl group.

wobei N^⊕ Stickstoff darstellt,
wobei an dem Ring ein, zwei, drei, vier, fünf oder sechs R₃ gebunden sein kann/können,
wobei der Ring eine oder zwei Doppelbindungen aufweist,
wobei das am Stickstoff gebundene R₃ und das am Ring gebundene R₁ obligatorisch sind und wobei das am Ring gebundene R₃ optional ist,
wobei gegebenenfalls im Ring unabhängig voneinander ein oder mehrere Kohlenstoffatome durch mindestens ein Stickstoffatom, mindestens ein Schwefelatom oder/und durch mindestens ein Sauerstoff ersetzt sein kann/können,
wobei gegebenenfalls an dieses mindestens eine Stickstoffatom ein R₃ gebunden sein kann,
wobei gegebenenfalls noch eine, zwei oder drei gesättigte, ungesättigte oder/und aromatische zyklische Gruppen unabhängig voneinander mit 5 oder 6 Ringatomen an den ersten Ring ankondensiert sein kann/können, wobei gegebenenfalls in diesem mindestens einen weiteren Ring unabhängig voneinander ein, zwei, drei oder vier R₃ gebunden sein kann/können, wobei gegebenenfalls in diesem mindestens einen weiteren Ring unabhängig voneinander ein oder mehrere Kohlenstoffatome durch mindestens ein Stickstoffatom, mindestens ein Schwefelatom oder/und durch mindestens ein Sauerstoff ersetzt sein kann/können,
wobei gegebenenfalls an dieses mindestens eine Stickstoffatom ein R₃ gebunden sein kann,
wobei R₁ eine Alkylgruppe - gesättigt oder ungesättigt - mit einer durchschnittlichen Zahl an Kohlenstoffatomen im Bereich von 4 bis 22 Kohlenstoffatomen bei jeweils entweder linearer oder verzweigter Kettenausbildung ist, wobei gegebenenfalls die Alkylgruppe R₁ eine oder mehrere aromatische oder/und phenolische Gruppen enthalten kann oder durch jene ersetzt sein kann,
wobei R₃ unabhängig voneinander Wasserstoff, Amino-Gruppe, Carbonyl-Gruppe, Ester-Gruppe, Ether-Gruppe, Nitro-Gruppe, OH-Gruppe, (EO)_x (= Polyetherkette der Formel "- CH₂ - CH₂ - O -" mit x = 1 bis 50 Einheiten mit oder ohne Endgruppenverschluss für jede Polyetherkette unabhängig voneinander insbesonders mit einer Methyl-, Ethyl-, Propyl-, Isopropyl-, n-Butyl-, Isobutyl-, Tertiärbutyl- oder Benzyl-Gruppe), (PO)_y (= Polyetherkette der Formel "-CHCH₃ - CH₂ - O -" mit y = 1 bis 10 Einheiten mit oder ohne Endgruppenverschluss für jede Polyetherkette unabhängig voneinander insbesonders mit einer Methyl-, Ethyl-, Propyl-, Isopropyl-, n-Butyl-, Isobutyl-, Tertiärbutyl- oder Benzyl-Gruppe) oder/und" eine Alkylgruppe - gesättigt oder ungesättigt - mit einer durchschnittlichen Zahl an Kohlenstoffatomen im Bereich von 1 bis 6 Kohlenstoffatomen bei jeweils entweder linearer oder verzweigter Kettenausbildung ist,
wobei mindestens eine der Alkylgruppen R₃ unabhängig voneinander gegebenenfalls eine oder mehrere aromatische oder/und phenolische Gruppen enthalten kann oder durch jene ersetzt sein kann,
wobei gegebenenfalls mindestens eine Gruppe R₃ unabhängig voneinander eine oder mehrere Gruppen ausgewählt aus Amino-Gruppen, Carbonyl-Gruppen, Ester-Gruppen, Ether-Gruppen, OH-Gruppen und Nitro-Gruppen an mindestens einem der Kohlenstoffatome oder/und zwischen den Kohlenstoffatomen mindestens einer Alkylgruppe enthalten kann.Here, 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 this at least one further ring independently of one another one or more carbon atoms are replaced by at least one nitrogen atom, at least one sulfur atom and / or may be replaced by at least one oxygen / can
optionally where an R ₃ can be bound to this at least one nitrogen atom,
wherein R _{1 is} 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 wherein the alkyl group R ₁ may contain one or more aromatic and / or phenolic groups can be replaced by those
where R _{3 is} independently of one another hydrogen, amino group, carbonyl group, ester group, ether group, nitro group, OH group, (EO) _x (= polyether chain of the formula "- CH ₂ -CH ₂ -O- "with x = 1 to 50 units with or without end capping for each polyether chain, independently of one another, especially with a methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl or benzyl group), (PO _y (= polyether chain of the formula "-CHCH ₃ -CH ₂ -O-" where y = 1 to 10 units with or without end-capping for each polyether chain independently of one another, in particular with a methyl, ethyl, propyl, isopropyl, n -Butyl, isobutyl, tert-butyl or benzyl group) or / and "is an alkyl group - saturated or unsaturated - having an average number of carbon atoms in the range of 1 to 6 carbon atoms in each case either linear or branched chain formation,
wherein at least one of the alkyl groups R ₃ independently of one another may optionally contain one or more aromatic or / and phenolic groups or may be replaced by those
where appropriate, at least one group 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 or / and between the carbon atoms at least may contain an alkyl group.

Preferably 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. In the cationic organic compounds of the general formulas (I), (II), (III), (IV), (V), (VI) and (VII) and in their tautomers, R _{1 is} independently of one another, saturated or unsaturated, branched or unbranched - optionally one or more aromatic or / and phenolic groups. In the cationic organic compounds of the general formulas (I), (II), (III), (IV), (V), (VI) and (VII) and in their tautomers, 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. Preferably, in the case of compounds of the general formulas (I), (II), (III), (IV), (V), (VI) and (VII) and in their. Tautomers in which (PO) _{y is} included, also from (EO) _x , but it is optionally also preferred that (EO) _{x is contained} alone without (PO) _y .

Particularly preferred in the compounds of the general formulas (I), (II), (III), (IV), (V), (VI) and (VII) and in their tautomers, in 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. In the compounds of the general formulas (I), (II), (III), (IV), (V), (VI) and (VII) and in their tautomers, y is particularly preferably selected from 1 to 4 units; most preferably, y is selected from 2 or 3 units. Particularly preferred in the compounds of the general formulas (I), (II), (III), (IV), (V), (VI) and (VII) and in their tautomers, in R _{3 are} alkyl groups having 1 or 6 carbon atoms the latter in particular as a benzyl group.

wobei die Verbindung 1 bis 500.000 kationische Gruppen aufweist, die unabhängig voneinander die im Folgenden genannten chemischen Strukturen aufweisen,
wobei N^⊕ Stickstoff als quaternäre Ammonium-Gruppe darstellt
wobei mindestens eine quaternäre Ammonium-Gruppe mindestens eine Alkylgruppe R₁ aufweist, die unabhängig voneinander Wasserstoff, eine Alkylgruppe A - gesättigt oder ungesättigt, verzweigt oder unverzweigt - mit einer Zahl von 1 bis 200 Kohlenstoffatomen aufweist oder/und
eine Sauerstoff enthaltende Gruppe wie z.B. eine OH-Gruppe oder Sauerstoff als ein Brückenatom zu einer nächsten Gruppe wie z.B. einer Alkylgruppe B mit einer Zahl von 1 bis 200 Kohlenstoffatomen darstellt,
wobei die vorwiegende Zahl der quaternären Ammonium-Gruppen mindestens zwei Alkylgruppen R₁ aufweist, die unabhängig voneinander Wasserstoff, eine Alkylgruppe A - gesättigt oder ungesättigt, verzweigt oder unverzweigt - mit einer Zahl von 1 bis 200 Kohlenstoffatomen aufweist oder/und eine Sauerstoff enthaltende Gruppe wie z.B. eine OH-Gruppe oder Sauerstoff als ein Brückenatom zu einer nächsten Gruppe wie z.B. einer Alkylgruppe B mit einer Zahl von 1 bis 200 Kohlenstoffatomen darstellen,
wobei gegebenenfalls mindestens eine Alkylgruppe A oder/und mindestens eine Alkylgruppe B unabhängig voneinander eine oder mehrere aromatische oder/und phenolische Gruppen enthalten kann/können oder durch jene ersetzt sein kann/können,
wobei gegebenenfalls mindestens eine Alkylgruppe A oder/und mindestens eine Alkylgruppe B unabhängig voneinander eine oder mehrere Gruppen ausgewählt aus Wasserstoff, Amino-Gruppe, Carbonyl-Gruppe, Ester-Gruppe, Ether-Gruppe, Nitro-Gruppe, OH-Gruppe, (EO)_x (= Polyetherkette der Formel "- CH₂ - CH₂ - O -" mit x = 1 bis 50 Einheiten mit oder ohne Endgruppenverschluss für jede Polyetherkette unabhängig voneinander insbesonders mit.einer Methyl-, Ethyl-, Propyl-, Isopropyl-, n-Butyl-, Isobutyl-, Tertiärbutyl- oder Benzyl-Gruppe) und (PO)_y (= Polyetherkette der Formel "- CHCH₃ - CH₂ - O -" mit y = 1 bis 10 Einheiten mit oder ohne Endgruppenverschluss für jede Polyetherkette unabhängig voneinander insbesonders mit einer Methyl-, Ethyl-, Propyl-, Isopropyl- , n-Butyl-, Isobutyl-, Tertiärbutyl- oder Benzyl-Gruppe) an mindestens einem der Köhlenstoffatome oder/und zwischen den Kohlenstoffatomen der Alkylgruppe A oder/und der Alkylgruppe B sein kann/können oder/und durch diese ersetzt sein kann/können,
wobei gegebenenfalls an mindestens einer Alkylgruppe R₁ unabhängig voneinander mindestens eine Polymerkette unabhängig voneinander verzweigt oder unverzweigt mit einer Zahl der Polymereinheiten n aus 5 bis 1.000.000 Monomergrundbausteinen gebunden sein kann,
wobei die Polymereinheiten von mindestens einer kationischen Gruppe zumindest teilweise ausgewählt sind aus Polyamiden, Polycarbonaten, Polyestern, Polyethern, Polyaminen, Polyiminen, Polyolefinen, Polysacchariden, Polyurethanen, deren Derivaten, deren Mischungen und deren Kombinationen,
wobei gegebenenfalls als Monomergrundbaustein(e) unabhängig voneinander mindestens ein ungeladenes Monomer oder/und mindestens eine entsprechende ungeladene Gruppe auftreten kann/können, wobei gegebenenfalls mindestens eine quaternäre Ammonium-Gruppe unabhängig voneinander mit dem Stickstoffatom in der Polymerkette oder/und mit dem Stickstoffatom an der Polymerkette vorkommen kann.Here, 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 alkyl group A - saturated or unsaturated, branched or unbranched - having a number from 1 to 200 carbon atoms and / or an oxygen-containing group such as for example, an OH group or oxygen as a bridging atom to a next group such as an alkyl group B having a number from 1 to 200 carbon atoms,
where appropriate, at least one alkyl group A or / and at least one alkyl group B may independently contain one or more aromatic and / or phenolic groups or may be replaced by those
where appropriate, at least one alkyl group A or / and at least one alkyl group B independently of one another selected from one or more groups selected from hydrogen, amino group, carbonyl group, ester group, ether group, nitro group, OH group, (EO) _x (= polyether chain of the formula "- CH ₂ - CH ₂ - O -") with x = 1 to 50 units with or without end capping for each polyether chain independently of one another especially with a methyl, ethyl, propyl, isopropyl, n Butyl, isobutyl, tertiary butyl or benzyl group) and (PO) _y (= polyether chain of the formula "- CHCH ₃ - CH ₂ -O-" with y = 1 to 10 units with or without end capping for each polyether chain independently in particular with a methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl or benzyl group) on at least one of the Köhlenstoffatome or / and between the carbon atoms of the alkyl group A or / and the alkyl group B can / can and / or through this he can be / can
where optionally at least one alkyl group R _{1 can} independently of one another 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, polyurethanes, their derivatives, their mixtures and combinations thereof,
optionally as the monomer base unit (s) independently of one another at least one uncharged monomer or / and at least one corresponding uncharged group may occur, optionally wherein at least one quaternary ammonium group independently of one another with the nitrogen atom in the polymer chain and / or with the nitrogen atom on the Polymer chain may occur.

In the compounds selected from compounds of general formulas VIII, IX and X and their tautomers, 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.

In the compounds of general formulas VIII, IX and X and their tautomers, 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. In some embodiments, 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. It is particularly preferred in this case that 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.

In the compounds selected from compounds of the general formulas VIII, IX and X and their tautomers preferably 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.

In the compounds selected from compounds of the general formulas VIII, IX and X and their tautomers, 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. In some embodiments, 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.

In the case of the compounds selected from compounds of the general formulas VIII, IX and X and their tautomers, particularly preferably, almost completely or completely independently of one another, uncharged monomers or / and corresponding uncharged groups are present as monomer base constituent (s).

In the compounds of general formulas VIII, IX and X and their tautomers, 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.

In the case of 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.

In the case of the compounds of the general formulas VIII, IX and X and their tautomers, 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.

In the case of the compounds of the general formulas VIII, IX and X and their tautomers, 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.

In the case of the compounds of the general formulas VIII, IX and X and their tautomers, 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.

wobei die Verbindung 1 bis 500.000 kationische Gruppen aufweist, die unabhängig voneinander die im Folgenden genannten chemischen Strukturen aufweisen,
wobei N^⊕ Stickstoff darstellt,
wobei an dem Ring der kationischen Gruppe unabhängig voneinander null, ein, zwei, drei, vier, fünf, sechs, sieben, acht oder neun R₁ gebunden sind,
wobei das am Stickstoff gebundene R₁ obligatorisch und das am Ring gebundene R₁ optional ist,
wobei der Ring der kationischen Gruppe unabhängig voneinander eine, zwei oder drei Doppelbindungen aufweist,
wobei gegebenenfalls im Ring der kationischen Gruppe unabhängig voneinander ein oder mehrere Kohlenstoffatome durch mindestens ein Stickstoffatom, mindestens ein Schwefelatom oder/und durch mindestens ein Sauerstoff ersetzt sein kann/können,
wobei gegebenenfalls noch eine, zwei, drei oder vier gesättigte, ungesättigte oder/und aromatische zyklische Gruppen mit 5 oder 6 Ringatomen unabhängig voneinander an den ersten Ring der kationischen Gruppe ankondensiert sein kann/können,
wobei gegebenenfalls in diesem mindestens einen weiteren Ring unabhängig voneinander ein, zwei, drei oder vier R₁ gebunden sein kann/können,
wobei gegebenenfalls in diesem mindestens einen weiteren Ring unabhängig voneinander ein oder mehrere Kohlenstoffatome durch mindestens ein Stickstoffatom, mindestens ein Schwefelatom oder/und mindestens ein Sauerstoff ersetzt sein kann/können,
wobei gegebenenfalls R₁ unabhängig voneinander eine Alkylgruppe A - gesättigt oder ungesättigt, verzweigt oder unverzweigt - mit einer Zahl von 1 bis 200 Kohlenstoffatomen, die gegebenenfalls eine oder mehrere aromatische oder/und phenolische Gruppen unabhängig voneinander enthalten kann oder durch jene ersetzt sein kann, oder/und
eine Gruppe ausgewählt aus Amino-Gruppen, Carbonyl-Gruppen, Ester-Gruppen, Ether-Gruppen, OH-Gruppen, Nitro-Gruppen, Gruppen (EO)_x (= Polyetherkette der Formel "- CH₂ - CH₂ - O -" mit x = 1 bis 50 Einheiten mit oder ohne Endgruppenverschluss für jede Polyetherkette unabhängig voneinander insbesonders mit einer Methyl-, Ethyl-, Propyl-, Isopropyl-, n-Butyl-, Isobutyl-, Tertiärbutyl- oder Benzyl-Gruppe) oder/und Gruppen (PO)_y (= Polyetherkette der Formel "- CHCH₃ - CH₂ - O -" mit y = 1 bis 10 Einheiten mit oder ohne Endgruppenverschluss für jede Polyetherkette unabhängig voneinander insbesonders mit einer Methyl-, Ethyl-, Propyl-, Isopropyl-, n-Butyl-, Isobutyl-, Tertiärbutyl - oder Benzyl-Gruppe) unabhängig voneinander darstellen kann oder/und eine Sauerstoff enthaltende Gruppe, die Sauerstoff als ein
Brückenatom zu einer nächsten Alkylgruppe B - gesättigt oder ungesättigt, verzweigt oder unverzweigt - mit einer Zahl von 1 bis 200 Kohlenstoffatomen aufweist, die gegebenenfalls eine oder mehrere aromatische oder/und phenolische Gruppen unabhängig voneinander enthalten kann oder durch jene ersetzt sein kann, darstellen kann oder/und
gegebenenfalls eine Gruppe ausgewählt aus Amino-Gruppen, Carbonyl-Gruppen, Ester-Gruppen, Ether-Gruppen, OH-Gruppen und Nitro-Gruppen an mindestens einem der Kohlenstoffatome oder/und zwischen den Kohlenstoffatomen jeweils mindestens einer der Alkylgruppen A oder/und B enthalten kann oder/und
wobei gegebenenfalls an mindestens einer der Gruppen R₁ unabhängig voneinander mindestens eine Polymerkette unabhängig voneinander verzweigt oder unverzweigt mit einer Zahl der Polymereinheiten n aus 5 bis 1.000.000 Monomergrundbausteinen gebunden sein kann,
wobei die Polymereinheiten von mindestens einer kationischen Gruppe zumindest teilweise ausgewählt sind aus Polyamiden, Polycarbonaten, Polyestern, Polyethern, Polyaminen, Polyiminen, Polyolefinen, Polysacchariden, Polyurethanen, deren Derivaten, deren Mischungen und deren Kombinationen,
wobei gegebenenfalls als Monomergrundbaustein(e) unabhängig voneinander mindestens ein ungeladenes Monomer oder/und mindestens eine entsprechende ungeladene Gruppe auftreten kann/können,
wobei gegebenenfalls mindestens eine quaternäre Ammonium-Gruppe unabhängig voneinander mit dem Stickstoffatom in der Polymerkette oder/und mit dem Stickstoffatom an der Polymerkette vorkommen kann.Here, 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, unsaturated or / and aromatic cyclic groups having 5 or 6 ring atoms being able to be fused to the first ring of the cationic group independently of one another,
optionally one, two, three or four R ₁ can be bound independently in this at least one further ring,
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 at least one oxygen,
optionally wherein R _{1 is} independently an alkyl group A - saturated or unsaturated, branched or unbranched - having a number from 1 to 200 carbon atoms, which may optionally contain one or more aromatic and / or phenolic groups independently or may be replaced by those, or /and
a group selected from amino groups, carbonyl groups, ester groups, ether groups, OH groups, nitro groups, groups (EO) _x (= polyether chain of the formula "- CH ₂ - CH ₂ - O -" with x = 1 to 50 units with or without end capping for each polyether chain, independently of one another, in particular with a methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl or benzyl group) or / and groups ( PO) _y (= polyether chain of the formula "-CHCH ₃ -CH ₂ -O-" where y = 1 to 10 units with or without end-capping for each polyether chain independently of one another, in particular with a methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl or benzyl) may independently represent or / and an oxygen-containing group containing oxygen as a
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 and / or B. can and / or
wherein optionally at least one of 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.

wobei die Verbindung 1 bis 500.000 kationische Gruppen aufweist, die unabhängig voneinander die im Folgenden genannten chemischen Strukturen aufweisen,
wobei N^⊕ Stickstoff darstellt,
wobei an dem Ring der kationischen Gruppe unabhängig voneinander null, ein, zwei, drei, vier, fünf, sechs oder sieben R₁ gebunden sind,
wobei das am Stickstoff gebundene R₁ obligatorisch und das am Ring gebundene R₁ optional ist,
wobei der Ring der kationischen Gruppe unabhängig voneinander eine oder zwei Doppelbindungen aufweist,
wobei gegebenenfalls im Ring der kationischen Gruppe unabhängig voneinander ein oder mehrere Kohlenstoffatome durch mindestens ein Stickstoffatom, mindestens ein Schwefelatom oder/und durch mindestens ein Sauerstoff ersetzt sein kann/können,
wobei gegebenenfalls noch eine, zwei oder drei gesättigte, ungesättigte oder/und aromatische zyklische Gruppen mit 5 oder 6 Ringatomen unabhängig voneinander an den ersten Ring der kationischen Gruppe ankondensiert sein kann/können,
wobei gegebenenfalls in diesem mindestens einen weiteren Ring unabhängig voneinander ein, zwei, drei oder vier R₁ gebunden sein kann/können, wobei gegebenenfalls in diesem mindestens einen weiteren Ring unabhängig voneinander ein oder mehrere Kohlenstoffatome durch mindestens ein Stickstoffatom, mindestens ein Schwefelatom oder/und mindestens ein Sauerstoff ersetzt sein kann/können,
wobei gegebenenfalls R₁ unabhängig voneinander
eine Alkylgruppe A - gesättigt oder ungesättigt, verzweigt oder unverzweigt - mit einer Zahl von 1 bis 200 Kohlenstoffatomen ist, die gegebenenfalls eine oder mehrere aromatische oder/und phenolische Gruppen unabhängig voneinander enthalten kann oder durch jene ersetzt sein kann, oder/und
eine Gruppe ausgewählt aus Amino-Gruppen, Carbonyl-Gruppen, Ester-Gruppen, Ether-Gruppen, OH-Gruppen, Nitro-Gruppen, Gruppen (EO)_x (= Polyetherkette der Formel. - CH₂ - CH₂ - O -" mit x.= 1. bis 50 Einheiten mit oder ohne Endgruppenverschluss für jede Polyetherkette unabhängig voneinander insbesonders mit einer Methyl-, Ethyl-, Propyl-, Isopropyl-, n-Butyl-, Isobutyl-, Tertiärbutyl- oder Benzyl-Gruppe) oder/und Gruppen (PO)_y (= Polyetherkette der Formel "- CHCH₃ - CH₂ - O -" mit y = 1 bis 10 Einheiten mit oder ohne Endgruppenverschluss für jede Polyetherkette unabhängig voneinander insbesonders mit einer Methyl-, Ethyl-, Propyl- Isopropyl-, n-Bütyl-, Isobutyl-, Tertiärbutyl - oder Benzyl-Gruppe) unabhängig voneinander darstellen kann oder/und eine Sauerstoff enthaltende Gruppe, die Sauerstoff als ein Brückenatom zu einer nächsten Alkylgruppe B - gesättigt oder ungesättigt, verzweigt oder unverzweigt - mit einer Zahl von 1 bis 200 Kohlenstoffatomen, die gegebenenfalls eine oder mehrere aromatische oder/und phenolische Gruppen unabhängig voneinander enthalten kann oder durch jene ersetzt sein kann, darstellen kann oder/und gegebenenfalls eine Gruppe ausgewählt aus Amino-Gruppen, Carbonyl-Gruppen, Ester-Gruppen, Ether-Gruppen, OH-Gruppen und Nitro-Gruppen an mindestens einem der Kohlenstoffatome oder/und zwischen den Kohlenstoffatomen jeweils mindestens einer der Alkylgruppen A oder/und B enthalten kann oder/und
wobei gegebenenfalls an mindestens einer Alkylgruppe R₁ unabhängig voneinander mindestens eine Polymerkette unabhängig voneinander verzweigt oder unverzweigt mit einer Zahl der Polymereinheiten n aus 5 bis 1.000.000 Monomergrundbausteinen gebunden sein kann,
wobei die Polymereinheiten von mindestens einer kationischen Gruppe zumindest teilweise ausgewählt sind aus Polyamiden, Polycarbonaten, Polyestern, Polyethern, Polyaminen, Polyiminen, Polyolefinen, Polysacchariden, Polyurethanen, deren Derivaten, deren Mischungen und deren Kombinationen,
wobei gegebenenfalls als Monomergrundbaustein(e) unabhängig voneinander mindestens ein ungeladenes Monomer oder/und mindestens eine entsprechende ungeladene Gruppe auftreten kann/können,
wobei gegebenenfalls mindestens eine quaternäre Ammonium-Gruppe unabhängig voneinander mit dem Stickstoffatom in der Polymerkette oder/und mit dem Stickstoffatom an der Polymerkette vorkommen kann.Here, 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 groups having 5 or 6 ring atoms can be fused independently of one another to the first ring of the cationic group,
optionally in this at least one further ring independently, one, two, three or four R ₁ can be bound, 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 oxygen can be replaced,
where appropriate, R ₁ independently
an alkyl group A - saturated or unsaturated, branched or unbranched - having a number from 1 to 200 carbon atoms, which may optionally contain or may be replaced by one or more aromatic and / or phenolic groups, or / and
a group selected from amino groups, carbonyl groups, ester groups, ether groups, OH groups, nitro groups, groups (EO) _x (= polyether chain of the formula: -CH ₂ -CH ₂ -O- "with x = 1 to 50 units with or without end capping for each polyether chain, independently of one another, especially with a methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl or benzyl group) or / and Groups (PO) _y (= polyether chain of the formula "-CHCH ₃ -CH ₂ -O-" where y = 1 to 10 units with or without end-capping for each polyether chain independently of one another, especially with a methyl, ethyl, propyl-isopropyl , n-butyl, isobutyl, tert-butyl or benzyl) may independently represent or / and an oxygen-containing group, the oxygen as a bridging atom to a next alkyl group B - saturated or unsaturated, branched or unbranched - may be a number from 1 to 200 carbon atoms, which may optionally contain or may be replaced by one or more aromatic and / or phenolic groups independently of one another, or / and, where appropriate, 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 may each contain at least one of the alkyl groups A and / or B and / or
where optionally at least one alkyl group R _{1 can} independently of one another 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, 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.

Preferably, in the cationic polymers - 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.

In the process with the composition according to the invention, 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. In particular, 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. In the case of 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. When the cationic organic compounds come into contact with the anionic organic compounds, especially those from pollution, the ions neutralize. In this case, 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.

In contrast, 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.

In the process with the composition according to the invention, it is advantageous in many embodiments if 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. In particular, 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.

In this case, in particular in the case of discontinuous operation, in many embodiments it is preferred to add 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.

If the at least one cationic organic compound is contained in the bath in comparison to the present unreacted anionic organic compounds in the deficit, then 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.

In many embodiments, it is advantageous if 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 as monoethanolamine, triethanolamine, methyldiethanolamine and / or at least one complexing agent such as based on carboxylate (s) such as Gluconate or / and heptonate, sodium nitrilotriacetic acid (NTA) or / and phosphonate (s) such as HEDP. 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. In most cases, 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.

In many embodiments it is advantageous if 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. As 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. In addition, 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. Furthermore, 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.

In the process with the composition according to the invention, the anionic organic compounds which are optionally present in the bath and are usually derived only from soils, in particular the anionic surfactants, are preferably obtained by a chemical reaction with at least one cationic organic compound or / and made less soluble in water with polyvalent cations. Preferably, 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. However, 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.

In most cases, 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.

In 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.

In particular, in the case of discontinuous purification processes, it may be advantageous to determine the content of oil (s) or / and other contaminants, in particular of oil (s) or / and other nonpolar organic compounds, in the bath before a suitable amount of cationic organic Compounds and other bath components such as in particular to builders

Bath care is added. In 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. Only through the addition of 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 on simple Way eg can be removed mechanically and / or by lifting the bath level and draining. The amount of cationic organic compounds to be added in this case can 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.

In the case of continuous cleaning baths, on the other hand, it is usually sufficient to determine the amount of cationic organic compounds which is regularly required during the metering once the system is run in.

In some embodiments, 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. The terms "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. In diving, the at least one substrate may optionally also be treated electrolytically, ie by electrolytic cleaning. In particular, 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. by injection flood (u.U. up to about 50 bar) is waived, while in 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.

In the process with the composition according to the invention, substrates in the form of sheets, coils (strips), wires, parts or / and composite components are preferably cleaned. In general, 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.

Surprisingly, despite many decades of experience of many companies in the field of cleaning, it has been possible to find a new basic principle for cleaning processes.

Surprisingly, cleaning methods and cleaning compositions were found in which even with a very high level of contamination, a demulsifying procedure could be set without problems and in a simple way.

Surprisingly, cleaning processes and cleaning compositions have been found which can be run over or substantially in the long term with significantly lower levels of oil (s), including further soiling than has hitherto been possible in the prior art, and in which the initial high cleaning performance can be maintained over the long term. While it often decreases continuously in the methods of the prior art, if no membrane filtration methods are used: For so far, it is state of the art that the currently used for cleaning, inter alia, with (s) contaminated metallic surfaces cleaning baths a content of oil ( (e) including further pollution contaminants of at least 0,7 g / L and often in the range of 0,8 to 1,2 g / L eg in car-care plants with bath care and at least 1,5 g / l and often up to approx. 6 g / L to oil (s) including further contamination eg at Autom have obilanlagen without bath care, but even have levels up to about 20 g / L, for example, in general industrial plants without bath care. In contrast, it is readily possible in the methods with inventive composition in many embodiments, 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. In these processes, it is often possible to use them at as low surfactant levels as in the range of 0.1 to 0.3 g / L or from 0.1 to 0.7 g / L. In these processes, the content of the cleaner bath of oil (s), including other contaminants, often ranging from 0.05 to 1 g / L or / and the content of surfactants, often ranges from 0.05 to 0.5 g / L While in typical prior art cleaning processes, 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.

Therefore, it is often possible to drive the bath in processes with inventive composition with significantly lower consumption of surfactants and other bath components than previously possible, with an extension of the bath life often times by a multiple or even by several years. Here, the chemical oxygen demand of the wastewater (COD value) is often significantly reduced from the rinse zones, which is why the wastewater treatment can be significantly simplified and made more cost-effective. Often, the entry of oils, fats, soaps and other polluting substances into the pretreatment zone such as e.g. into the phosphating zone e.g. significantly reduced and thus the quality of the pretreatment process and the pretreatment layer significantly improved and evened.

Surprisingly, 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 €.

The replacement or the task of a membrane filtration system can be saved to a considerable extent personnel.

Surprisingly, 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.

In continuous systems with oil separators when using the cleaning process with a cleaner composition according to the invention is often in the long term, a low content of oil (s) including other contaminants achieved without special expenses than in the prior art, especially because this content is often about the Factor 2 can be lowered by using the addition of cationic organic compounds.

In the case of discontinuous systems, when using the cleaning process with a cleaner composition according to the invention, 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.

Inventive Examples and Comparative Examples:

In the following, the invention will be explained in more detail with reference to selected embodiments, without being limited thereto.

In preliminary experiments in the laboratory, a number of different types of demulsifying surfactants, mainly nonionic surfactants based on ethoxylated alkyl alcohols having one end-capping per alkyl group, were tested for their cleaning performance, for their demulsifying action and for their foaming tendency. At the same time, 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. Nevertheless, all of 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.

Thereafter, 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.

In this industrial phosphating line with subsequent painting for large-sized components, 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.

Before switching to an optimized process with a demulsifying nonionic surfactant according to the invention and with a cationic surfactant according to the invention, 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. Over this time, although 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. At 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 not 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.

Then, 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. Also, by changing the operating mode of the cleaning zones to bath compositions which, after the occurrence of a content of oil (s) including other contaminants such as fats, other non-polar organic pollutants or / and anionic organic compounds in the bath in the range of 2.5 to 4 g / L oil (s) including the further contamination with an addition of a cationic, demulsifying surfactant according to the invention as a quaternary ammonium compound according to the general formula (I) with a benzyl group, 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. Also, by the addition of this demulsifying cationic surfactant, 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. 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. In contrast, 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 combination of the two demulsifying surfactants according to the invention has proved to be outstanding: In this plant, neither the process parameters of the cleaning zones, nor the concentrations of the cleaning compositions have essentially been changed so far changed.

It also became possible to renew the second degreasing bath only after a longer period of use (for example after 6 months) than the first degreasing bath (for example after 4 months), which absorbs the soils much more strongly than the second degreasing bath.

Due to the procedure according to the invention, 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.

Claims (9)

1. An aqueous alkaline cleaner-composition for cleaning metallic surfaces that contains at least one non-ionic surfactant that acts in a demulsifying manner and at least one cationic surfactant, characterised in that the at least one non-ionic surfactant that acts in a demulsifying manner is based on ethoxylated alkyl alcohols with one or two alkyl groups with on average in each case 7.5 to 16.5 carbon atoms and with on average 5.5 to 18.5 EO groups per alkyl group and also with one or two end-group closures, of which at least one end-group closure is an isopropyl, isobutyl, tertiary butyl and/or benzyl group, the surfactant not being propoxylated, and in that the at least one cationic surfactant is a quaternary ammonium compound with one or two aromatic and/or substituted aromatic groups.
2. A cleaner-composition according to claim 1, characterised in that it additionally contains at least one further non-ionic surfactant, at least one amphiphilic surfactant, at least one cationic polymer, at least one cleaner-framework (builder), at least one corrosion-inhibitor and/or at least one further additive and also, if applicable, corresponding counter-ions to the amphiphilic surfactants, cationic surfactants and/or cationic polymeric compounds.
3. A cleaner-composition according to claim 1 or 2, characterised in that it additionally also contains at least one ethoxylated-propoxylated non-ionic surfactant with a cloud point below 20°C.
4. A cleaner-composition according to one of the preceding claims, characterised in that the at least one cationic organic compound is present in the cleaner-composition in roughly or at least such a content as is necessary for extensive or complete chemical reaction thereof with the non-polar organic compounds and/or anionic organic compounds present in the cleaner-composition.
5. A cleaner-composition according to one of the preceding claims, characterised in that the contents of the at least one surfactant that acts in a demulsifying manner and is based on ethoxylated alkyl alcohols with end-group closure and the contents of the at least one cationic organic compound are selected roughly or at least in such a way that the cleaner-composition operates in the weakly anionic, weakly cationic or charge-neutral range.
6. A cleaner-composition according to one of the preceding claims, characterised in that it has a content of cationic organic compounds in the bath - in particular in the case of discontinuous operation - in a quantity directly prior to the chemical reaction thereof at which the stoichiometric ratio of cationic organic compounds to anionic organic compounds in the bath is kept in the range from 0.1 : 1 to 10 : 1.
7. A cleaner-composition according to one of the preceding claims, characterised in that the total content of all the active ingredients in the bath without contaminants lies in the range from 0.5 to 300 g/l.
8. A contaminated bath containing an aqueous alkaline cleaner-composition, characterised in that it contains the at least one non-ionic surfactant that acts in a demulsifying manner and also the at least one cationic surfactant according to claim 1 and a contaminant.
9. An aqueous concentrate for an aqueous alkaline cleaner-composition, characterised in that it contains the at least one non-ionic surfactant that acts in a demulsifying manner and also the at least one cationic surfactant according to claim 1 in a concentration higher by a factor of 5 to 5000 than in the aqueous alkaline cleaner-composition that can be produced therefrom.