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EP0189085B1 - Quaternary ammonium compounds containing cationic surfactants and their use in cleaning compositions - Google Patents

Quaternary ammonium compounds containing cationic surfactants and their use in cleaning compositions Download PDF

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Publication number
EP0189085B1
EP0189085B1 EP86100364A EP86100364A EP0189085B1 EP 0189085 B1 EP0189085 B1 EP 0189085B1 EP 86100364 A EP86100364 A EP 86100364A EP 86100364 A EP86100364 A EP 86100364A EP 0189085 B1 EP0189085 B1 EP 0189085B1
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Prior art keywords
cationic surfactants
carbon atoms
quaternary ammonium
ammonium compounds
acid
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EP86100364A
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German (de)
French (fr)
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EP0189085A2 (en
EP0189085A3 (en
Inventor
Jürgen Dr. Geke
Horst Dr. Rutzen
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/38—Cationic compounds
    • C11D1/62—Quaternary ammonium compounds

Definitions

  • the invention relates to new, improved cationic surfactants based on quaternary ammonium compounds and the use of such cationic surfactants in industrial cleaning solutions.
  • aqueous solutions which contain surfactants in addition to other auxiliaries, such as builder substances, complexing agents, organic or inorganic corrosion protection agents and optionally other substances.
  • surfactants in addition to other auxiliaries, such as builder substances, complexing agents, organic or inorganic corrosion protection agents and optionally other substances.
  • DE-A-27 12 900 and DE-A-32 47 431 propose processes in which, in addition to other detergent components, quaternary ammonium compounds are used as cationic surfactants in the alkaline pH range, in which organic ammonium nitrogen atoms are used Residues, especially alkyl residues of different chain lengths, are bound.
  • Counterions of the ammonium cations used are, for example, anions such as chloride, sulfate or methyl sulfate, which are known as anions which cause corrosion.
  • the necessary content of such anions undesirably promotes corrosion on system parts and treated metal surfaces. This is an extremely disadvantage, in particular when treating metal surfaces with aqueous products, in particular when higher application concentrations of cationic surfactants are desired. Corrosion occurs not only in the long term during the intermediate storage of treated parts, but also directly when treating corresponding surfaces with the aqueous application solutions.
  • DE-A-30 48 642 also discloses surfactant mixtures for cleaning bottles and other objects with hard surfaces (porcelain, plastic, metal) which contain cationic surfactants based on ammonium compounds.
  • cationic surfactants based on ammonium compounds.
  • a disadvantage of these surfactants is that they contain chloride, bromide or methyl sulfate as anions. In this case, too, the anions counteract the desired corrosion protection on system parts (e.g. dishwashers) and treated surfaces as a result of the treatment with such surfactant mixtures.
  • quaternary ammonium compounds which contain at least one long-chain hydroxyalkyl radical by reacting the salt of a tertiary amine and an inorganic or organic acid in water with an epoxy compound which has at least one terminal epoxy group and at least 6 C atoms, at atmospheric pressure and temperatures between 40 and 100 ° C and a pH of at least 7 are known from DE-A-33 21 608.
  • Suitable acids are: boric acid, carbonic acid, phosphoric acid, phenol, capric acid and acidic salts of carbonic acid, phosphoric acid and sulfuric acid.
  • the compounds prepared in this way are used as textile softeners or antistatic agents or as antimicrobials.
  • the resulting quaternary ammonium compounds were also unable to meet the high demands in terms of user-friendliness and corrosion protection that are placed on commercially available cationic surfactants.
  • the anions of numerous organic acids are not suitable for the formation of cationic surfactants because the resulting quaternary ammonium compounds are poorly water-soluble. They are produced in paste-like form and, due to their poor water solubility, cannot be assembled in industrial cleaners.
  • ammonium cations which contain numerous hydroxyalkyl groups, cause troublesome precipitates in water which is not completely demineralized, which likewise makes the use of such cationic surfactants impossible.
  • cationic surfactants are often expected to have a demulsifying and / or defoaming effect on emulsions and / or anionic surfactants or emulsifiers.
  • the quaternary ammonium compounds disclosed in the said application had no demulsifying effect on emulsions and / or anionic emulsifiers.
  • DE-A-26 31 733 also describes a process for promoting condensation and / or polymerization reactions of organic isocyanates, in which a catalytic amount of a quaternary hydroxyalkylammonium compound of the general formula used.
  • the radical R 4 can mean an alkyl group with 1 to 15 C atoms and the radicals R i , R 2 and R 3 independently of one another alkyl groups or hydroxyalkyl groups with 1 to 20 C atoms or a benzyl group.
  • the anion is preferably derived from the following acids: formic acid, acetic acid, hexanoic acid and the straight-chain or branched heptanoic acids, octanoic acids, decanoic acids and hexadecanoic acids; Neoacids such as 3,3-dimethylbutanoic acid, unsaturated aliphatic acids such as oleic acid, acrylic acid, methacrylic acid, undecenoic acid and aromatic acids such as benzoic acid, phenylacetic acid and salicylic acid.
  • other di- (hydroxyalkyl) compounds of the general formula have already been recommended as emulsifiers, wetting agents and the like.
  • the object of the present invention was to provide new, improved cationic surfactants based on quaternary ammonium compounds which do not have the disadvantages of the prior art.
  • cationic surfactants should be made available for industrially usable cleaning agents, the components of which inhibit the corrosion process, ensure a sufficient demulsifying effect with regard to anionic contamination and can be readily packaged in aqueous industrial cleaners, i.e. are easily water-soluble, do not cause troublesome precipitates and are compatible with other components commonly used in industrial cleaners.
  • the object is achieved by cationic surfactants based on quaternary ammonium compounds, the ammonium nitrogen atom of which contains at least two alkyl radicals, a 2-hydroxyalkyl radical originating from the reaction with a terminal epoxide carrying 10 to 24 carbon atoms and optionally an arylalkyl group and the anion of which carries the anion is an organic carboxylic acid with 5 to 16 carbon atoms.
  • cationic surfactants not only have good demulsifying properties with regard to anionic surfactants or emulsifiers, but also make the treated surfaces hydrophobic in corresponding industrial cleaners, and help prevent corrosion by ensuring that the application liquids run off the treated surfaces well and without running and even an antistatic effect can be achieved on plastic surfaces.
  • linear or branched alkyl radicals which R 1 and R 2 can represent are methyl, ethyl, propyl, isopropyl, n-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tetradecyl and hexadecyl.
  • Quaternary ammonium compounds in which R 2 is hydrogen and R 1 is a linear or branched alkyl radical having 8 to 22 carbon atoms for example n-octyl, n-decyl, n-dodecyl, n-tetradecyl or n-hexadecyl, are preferred.
  • the total number of carbon atoms in both substituents R 1 and R 2 must be in the range from 8 to 22 carbon atoms.
  • the R 5 radical bonded to the ammonium nitrogen atom represents alkyl radicals such as, for example, n-butyl, i-butyl, tert-butyl, n-pentyl, tert-butylmethyl or n-hexyl or phenalkyl radicals such as benzyl, phenylethyl or phenylpropyl.
  • the counter anion in the cationic surfactants according to the invention is the anion of an organic carboxylic acid having 5 to 16 carbon atoms
  • the radical R 6 in the general formula 1 represents alkyl radicals such as, for example, n-butyl, i-butyl, tert-butyl, pentyl, Hexyl, octyl, 2-ethyl-hexyl, n-nonyl, i-nonyl, decyl, dodecyl or pentadecyl.
  • the isononanoate anion is particularly preferred.
  • Benzyldimethyl-2-hydroxydodecylammonium isononanoate (BDHAI), the benzyldimethyl-2-hydroxydodecylammonium salt of 9/13 versatic acid R , benzyldimethyl-2-hydroxydodecylammonium isopalmitate, butyldimethyl-2-hydroxydodecylammonylononononanoanoidonanoononanoatonate.
  • benzyldimethyl 2-hydroxydodecylammonium isonanoanoate is particularly preferred.
  • the compounds of the general formula I according to the invention can be prepared by methods known per se by adding the salt of a tertiary amine of the general formula
  • reaction mixture before the start Implementation has a pH of at least 7.
  • the epoxides of the general formula IV used to prepare the quaternary ammonium compounds according to the invention can thus be epoxides having 10 to 24 carbon atoms in which the oxirane ring is located at any point in the molecule.
  • the amines used to prepare the quaternary ammonium compounds of the general formula I are preferably tertiary alkyl, hydroxyalkyl or alkylarylamines, with dimethylbutylamine and dimethylbenzylamine being particularly preferred.
  • the carboxylic acids used to prepare the quaternary ammonium compounds according to the invention are preferably monocarboxylic acids having 5 to 8 carbon atoms in the alkyl radical. Isononanoic acid is particularly preferably used.
  • the quaternary ammonium compounds according to the invention are used as cationic surfactants in industrial cleaning solutions. They have the advantage over other cationic surfactants as well as quaternary ammonium compounds already known from the prior art that they do not contain any corrosive counterions or lead to undesirable precipitations.
  • acids are even able to inhibit the corrosion process on cleaned metal surfaces.
  • the lack of accumulation of corrosive anions in the baths and the inhibitory effect of the carboxylic acid anions thus improve the corrosion protection properties in aqueous media. This applies equally to parts that have to be temporarily stored before the further processing process, as well as to parts that are to be processed immediately.
  • the improved corrosion protection is particularly noticeable in the case of parts which have been treated with industrial cleaners containing quaternary ammonium compounds and which, due to their geometry, have a creative effect.
  • the risk of corrosion on such parts was particularly high, since if the solvent, usually water, evaporated, there was a risk that the ingredients and thus the corrosive components would be heavily concentrated. This is prevented when using industrial cleaning solutions containing the quaternary ammonium compounds according to the invention as cationic surfactants.
  • the cationic surfactants according to the invention offer a further advantage in that an advantageous hydrophobization of the cleaned surfaces, in particular the cleaned metal surfaces, is observed. Furthermore, corrosion of the treated parts is avoided by a very good drainage behavior of the application liquid.
  • aqueous industrial cleaning solutions which contain the quaternary ammonium compounds according to the invention as cationic surfactants can also be used for cleaning plastics, since they have an antistatic effect. It is precisely this that will open up such products to a wide range of applications in the future, since plastic surfaces, similar to metal surfaces, are being cleaned with an increasing tendency in spray processes.
  • the quaternary ammonium compounds according to the invention are suitable for use in all cleaning agents which are important for industrial cleaning. They can be used in sprayable cleaners, e.g. neutral to weakly alkaline cleaners or acid cleaners may be present, especially in cleaning solutions that are sprayed onto the parts to be cleaned under high pressure. Equally, however, they can also be used with advantage in immersion cleaners based on nonionic surfactants.
  • Quaternary ammonium compounds according to the invention are also used as cationic surfactants which act as demulsifiers or antifoams in industrial cleaning solutions for spraying or dipping.
  • the new improved cationic surfactants based on quaternary ammonium compounds are made up with other components, which are conventional for industrial cleaning solutions, by processes known per se.
  • these solutions may also contain other additives, for example alkanolamines, phosphates, borates or contain nitrites.
  • inhibitors in particular for non-ferrous metals, or biocides such as, for example, hexahydrotriazine derivatives and / or phenols and / or chlorophenols can be added to the solutions to prevent bacterial and / or fungal attack in the spraying or immersion systems.
  • Detergent solutions with application concentrations in the range from 0.5 to 5% were produced, which were intended for detergents to be applied in spraying.
  • the solutions had the following compositions (data in% by weight):
  • the cleaning agents formulated as described above could easily be applied by spraying. They showed little or no tendency to foam. The cleaning baths were stable for a long time and their cleaning power did not deteriorate over this time. Due to the use of the quaternary ammonium compounds according to the invention, the metal surfaces treated with the cleaners in the spray did not corrode, but instead had increased corrosion protection in comparison with treatment with conventional cleaners.
  • the cleaning agents formulated as described above had a high cleaning power on treated metal surfaces over a long period of time and their baths were very stable. Metal surfaces that had been treated with the above-described cleaners in immersion had improved corrosion protection compared to metal surfaces treated with conventional cleaners.
  • the emulsion cleavage was carried out according to the following test:
  • the cleaning compositions composed as described above showed good cleaning action and a uniform, run-free drainage behavior on the treated parts.
  • BDHAI shows a significantly better corrosion protection behavior.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)

Abstract

The invention relates to new cationic surfactants based on quaternary ammonium compounds corresponding to the general formula R1-CHOH-CHR2-N+R3R4R5 R6CO2-(1) wherein R1 is a linear or branched alkyl residue having from 1 to 22 carbon atoms; R2 is hydrogen or a linear or branched alkyl residue having from 1 to 21 carbon atoms, the total number of carbon atoms of the substituents R1 and R2 being in the range of from 8 to 22; R3 and R4 each represent methyl, ethyl, 2-hydroxyethyl or 2-hydroxypropyl; R5 represents an alkyl residue having from 4 to 6 carbon atoms or a phenalkyl residue having from 1 to 3 carbon atoms in the alkyl residue; and R6 represents a linear or branched alkyl residue having from 4 to 15 carbon atoms. The cationic surfactants have particular utility in cleaning agents.

Description

Die Erfindung betrifft neue, verbesserte Kationtenside auf der Basis von quartären Ammoniumverbindungen und die Verwendung derartiger Kationtenside in industriell angewendeten Reinigerlösungen.The invention relates to new, improved cationic surfactants based on quaternary ammonium compounds and the use of such cationic surfactants in industrial cleaning solutions.

Für die Reinigung von Halbfertigteilen oder Fertigteilen in der industriellen Produktion, beispielsweise von Kraftfahrzeugteilen aus Eisen oder Stahl, werden wässrige Lösungen verwendet, die Tenside neben weiteren Hilfsstoffen, wie Buildersubstanzen, Komplexbildnern, organischen oder anorganischen Korrosionsschutzmitteln und gegebenenfalls weiteren Substanzen enthalten. So werden in der DE-A-27 12 900 und der DE-A-32 47 431 Verfahren vorgeschlagen, in denen im alkalischen pH-Wert-Bereich neben weiteren Reinigerbestandteilen quartäre Ammoniumverbindungen als Kationtenside verwendet werden, in denen an das Ammonium-Stickstoffatom organische Reste, insbesondere Alkylreste unterschiedlicher Kettenlänge, gebunden sind.For the cleaning of semi-finished parts or finished parts in industrial production, for example motor vehicle parts made of iron or steel, aqueous solutions are used which contain surfactants in addition to other auxiliaries, such as builder substances, complexing agents, organic or inorganic corrosion protection agents and optionally other substances. For example, DE-A-27 12 900 and DE-A-32 47 431 propose processes in which, in addition to other detergent components, quaternary ammonium compounds are used as cationic surfactants in the alkaline pH range, in which organic ammonium nitrogen atoms are used Residues, especially alkyl residues of different chain lengths, are bound.

Gegenionen der verwendeten Ammonium-Kationen sind beispielsweise Anionen wie Chlorid, Sulfat oder Methylsulfat, die als Korrosion verursachende Anionen bekannt sind. Der notwendige Gehalt an derartigen Anionen fördert unerwünschterweise an Anlagenteilen und behandelten Metalloberflächen die Korrosion. Dies ist insbesondere bei der Behandlung von Metalloberflächen mit wässrigen Produkten von außerordentlichem Nachteil, insbesondere dann, wenn höhere Anwendungskonzentrationen an Kationtensiden gewünscht sind. Dabei tritt Korrosion nicht nur langfristig bei der Zwischenlagerung behandelter Teile ein, sondern auch unmittelbar bei der Behandlung entsprechender Flächen mit den wässrigen Anwendungslösungen.Counterions of the ammonium cations used are, for example, anions such as chloride, sulfate or methyl sulfate, which are known as anions which cause corrosion. The necessary content of such anions undesirably promotes corrosion on system parts and treated metal surfaces. This is an extremely disadvantage, in particular when treating metal surfaces with aqueous products, in particular when higher application concentrations of cationic surfactants are desired. Corrosion occurs not only in the long term during the intermediate storage of treated parts, but also directly when treating corresponding surfaces with the aqueous application solutions.

Auch in der DE-A-30 48 642 werden Tensidgemische zur Reinigung von Flaschen und sonstigen Gegenständen mit harten Oberflächen (Porzellan, Kunststoff, Metall) offenbart, die kationische Tenside auf der Basis von Ammoniumverbindungen enthalten. Ein Nachteil dieser Tenside ist jedoch auch, daß sie als Anionen Chlorid, Bromid oder Methylsulfat enthalten. Auch in diesem Fall wirken die Anionen einem als Folge der Behandlung mit derartigen Tensidgemischen erwünschten Korrosionsschutz auf Anlagenteilen (z.B. Spülmaschinen) und behandelten Oberflächen entgegen.DE-A-30 48 642 also discloses surfactant mixtures for cleaning bottles and other objects with hard surfaces (porcelain, plastic, metal) which contain cationic surfactants based on ammonium compounds. However, a disadvantage of these surfactants is that they contain chloride, bromide or methyl sulfate as anions. In this case, too, the anions counteract the desired corrosion protection on system parts (e.g. dishwashers) and treated surfaces as a result of the treatment with such surfactant mixtures.

Verfahren zur Herstellung von quartären Ammoniumverbindungen, die wenigstens einen langkettigen Hydroxyalkylrest enthalten, durch Umsetzung des Salzes eines tertiären Amins und einer anorganischen oder organischen Säure in Wasser mit einer Epoxidverbindung, die wenigstens eine endständige Epoxygruppe und wenigstens 6 C-Atome aufweist, bei Normaldruck, Temperaturen zwischen 40 und 100°C und einem pH-Wert von wenigstens 7 sind aus der DE-A-33 21 608 bekannt. Als geeignete Säuren werden hier genannt: Borsäure, Kohlensäure, Phosphorsäure, Phenol, Caprinsäure und saure Salze der Kohlensäure, Phosphorsäure und der schwefligen Säure. Die so hergestellten Verbindungen finden Verwendung als Textilweichmacher oder -antistatika beziehungsweise als Antimikrobika.Process for the preparation of quaternary ammonium compounds which contain at least one long-chain hydroxyalkyl radical by reacting the salt of a tertiary amine and an inorganic or organic acid in water with an epoxy compound which has at least one terminal epoxy group and at least 6 C atoms, at atmospheric pressure and temperatures between 40 and 100 ° C and a pH of at least 7 are known from DE-A-33 21 608. Suitable acids are: boric acid, carbonic acid, phosphoric acid, phenol, capric acid and acidic salts of carbonic acid, phosphoric acid and sulfuric acid. The compounds prepared in this way are used as textile softeners or antistatic agents or as antimicrobials.

Die resultierenden quartären Ammoniumverbindungen konnten jedoch ebenfalls die hohen Anforderungen hinsichtlich Anwendungsfreundlichkeit und Korrosionsschutz nicht erfüllen, die an handelsübliche kationische Tenside gestellt werden. So sind die Anionen zahlreicher organischer Säuren zur Kationtensid-Gegenionbildung nicht geeignet, da die resultierenden quartären Ammoniumverbindungen schlecht wasserlöslich sind. Sie fallen bei der Herstellung in pastöser Form an und lassen sich aufgrund ihrer schlechten Wasserlöslichkeit nicht in industriellen Reinigern konfektionieren. Außerdem zeigte sich, daß Ammonium-Kationen, die zahlreiche Hydroxyalkyl-Gruppen enthalten, in nicht vollentsalztem Wasser störende Ausfällungen verursachen, was den Einsatz von derartigen Kation-Tensiden ebenfalls unmöglich macht. Weiterhin wird von kationischen Tensiden häufig eine demulgierende und/oder entschäumende Wirkung auf Emulsionen und/oder anionische Tenside bzw. Emulgatoren erwartet. Die in der genannte Anmeldung offenbarten quartären Ammoniumverbindungen hatten jedoch keine demulgierende Wirkung auf Emulsionen und/oder anionische Emulgatoren. Diese Nachteile wurden auch nicht durch deutlich verbesserte Korrosionsschutz-Eigenschaften der hergestellten Kationtenside kompensiert; verglichen mit handelsüblichen kationischen Tensiden ergab sich ein nur annähernd gleich guter Korrosionsschutz.However, the resulting quaternary ammonium compounds were also unable to meet the high demands in terms of user-friendliness and corrosion protection that are placed on commercially available cationic surfactants. For example, the anions of numerous organic acids are not suitable for the formation of cationic surfactants because the resulting quaternary ammonium compounds are poorly water-soluble. They are produced in paste-like form and, due to their poor water solubility, cannot be assembled in industrial cleaners. It was also found that ammonium cations, which contain numerous hydroxyalkyl groups, cause troublesome precipitates in water which is not completely demineralized, which likewise makes the use of such cationic surfactants impossible. Furthermore, cationic surfactants are often expected to have a demulsifying and / or defoaming effect on emulsions and / or anionic surfactants or emulsifiers. However, the quaternary ammonium compounds disclosed in the said application had no demulsifying effect on emulsions and / or anionic emulsifiers. These disadvantages were also not compensated for by the significantly improved corrosion protection properties of the cationic surfactants produced; compared to commercially available cationic surfactants, corrosion protection was only approximately the same.

In der DE-A-26 31 733 wird ferner ein Verfahren zur Förderung von Kondensations- und/oder Polymerisationsreaktionen von organischen Isocyanaten beschrieben, bei welchem man eine katalytische Menge einer quartären Hydroxyalkylammoniumverbindung der allgemeinen Formel

Figure imgb0001
verwendet. Hierin kann beispielsweise der Rest R4 eine Alkylgruppe mit 1 bis 15 C-Atomen und die Reste Ri, R2 und R3 unabhängig voneinander Alkylgruppen oder Hydroxyalkylgruppen mit 1 bis 20 C-Atomen oder eine Benzylgruppe bedeuten. Das Anion leitet sich vorzugsweise von folgenden Säuren ab: Ameisensäure, Essigsäure, Hexansäure sowie die geradkettigen oder verzweigten Heptansäuren, Octansäuren, Decansäuren und Hexadecansäuren; Neosäuren, wie 3,3-Dimethyl-butansäure, ungesättigte aliphatische Säuren, wie Ölsäure, Acrylsäure, Methacrylsäure, Undecensäure und aromatische Säuren, wie Benzoesäure, Phenylessigsäure und Salicylsäure. Im Text dieser Patentanmeldung wird ausgeführt, daß "andere Di-(hydroxyalkyl)-Verbindungen der allgemeinen Formel bereits als Emulgatoren, Netzmittel und dergleichen empfohlen wurden".DE-A-26 31 733 also describes a process for promoting condensation and / or polymerization reactions of organic isocyanates, in which a catalytic amount of a quaternary hydroxyalkylammonium compound of the general formula
Figure imgb0001
 used. Herein, for example, the radical R 4 can mean an alkyl group with 1 to 15 C atoms and the radicals R i , R 2 and R 3 independently of one another alkyl groups or hydroxyalkyl groups with 1 to 20 C atoms or a benzyl group. The anion is preferably derived from the following acids: formic acid, acetic acid, hexanoic acid and the straight-chain or branched heptanoic acids, octanoic acids, decanoic acids and hexadecanoic acids; Neoacids such as 3,3-dimethylbutanoic acid, unsaturated aliphatic acids such as oleic acid, acrylic acid, methacrylic acid, undecenoic acid and aromatic acids such as benzoic acid, phenylacetic acid and salicylic acid. In the text of this patent application it is stated that "other di- (hydroxyalkyl) compounds of the general formula have already been recommended as emulsifiers, wetting agents and the like".

In der dieser deutschen Patentanmeldung entsprechenden US-A-4 040 992 wird an der besagten Stelle als Stand der Technik auf die US―A―2 759 975 verwiesen.In the US-A-4 040 992 corresponding to this German patent application, reference is made at the said point as prior art to US ― A als 2,759,975.

In der US―A―2 759 975 werden quaternäre Ammoniumsalz der allgemeinen Formel

Figure imgb0002
beschrieben, wobei Ar Phenyl, Naphthyl oder substituierte Phenylreste, R Alkylreste mit 7 bis 18 C-Atomen und R1 Wasserstoff, Methyl, Ethyl oder Hydroxymethyl bedeuten. Das Anion X steht für Chlorid, Bromid, Jodid, ein-, zwei- oder dreibasisches Phosphat, Acetat, Lactat, Gluconat, Sulfat, Nitrat, Nitrit, Alkylsulfate oder Alkyl- bzw. Arylsulfonate. Die Verbindungen können als Emulgatoren oder Netzmittel für sehr vielfältige Zwecke Verwendung finden, unter anderem für Metallreiniger-Formulierungen.In US ― A ― 2,759,975 quaternary ammonium salt of the general formula
Figure imgb0002
 described, wherein Ar is phenyl, naphthyl or substituted phenyl radicals, R alkyl radicals having 7 to 18 carbon atoms and R 1 is hydrogen, methyl, ethyl or hydroxymethyl. The anion X stands for chloride, bromide, iodide, mono-, di- or tri-basic phosphate, acetate, lactate, gluconate, sulfate, nitrate, nitrite, alkyl sulfates or alkyl or aryl sulfonates. The compounds can be used as emulsifiers or wetting agents for a very wide range of purposes, including metal cleaner formulations.

Die Aufgabe der vorliegenden Erfindung war es demgegenüber, neue, verbesserte Kationtenside auf der Basis von quartären Ammoniumverbindungen zur Verfügung zu stellen, die die Nachteile aus dem Stand der Technik nicht aufweisen. Insbesondere sollten Kationtenside für industriell verwendbare Reinigungsmittel zur Verfügung gestellt werden, deren Bestandteile den Korrosionsprozeß inhibieren, für eine ausreichende demulgierende Wirkung bezüglich anionischer Kontamination Sorge tragen und in wässrigen industriellen Reinigern gut konfektioniert werden können, d.h. leicht wasserlöslich sind, keine störenden Ausfällungen verursachen und mit anderen üblicherweise in Industriereinigern verwendeten Komponenten verträglich sind.In contrast, the object of the present invention was to provide new, improved cationic surfactants based on quaternary ammonium compounds which do not have the disadvantages of the prior art. In particular, cationic surfactants should be made available for industrially usable cleaning agents, the components of which inhibit the corrosion process, ensure a sufficient demulsifying effect with regard to anionic contamination and can be readily packaged in aqueous industrial cleaners, i.e. are easily water-soluble, do not cause troublesome precipitates and are compatible with other components commonly used in industrial cleaners.

Die Aufgabe wird gelöst durch Kationtenside auf der Basis von quartären Ammoniumverbindungen, deren Ammonium-Stickstoffatom mindestens zwei Alkylreste, einen aus der Umsetzung mit einem 10 bis 24 C-Atome tragenden endständigen Epoxid stammenden 2-Hydroxyalkylrest und gegebenenfalls eine Arylalkylgruppe trägt und dessen Anion das Anion einer organischen Carbonsäure mit 5 bis 16 C-Atomen ist. Es wurde nämlich überraschend gefunden, daß derartige Kationtenside nicht nur gute demulgierende Eigenschaften bezüglich anionischer Tenside bzw. Emulgatoren aufweisen, sondern auch in entsprechenden Industriereinigern die behandelten Oberflächen hydrophobieren, zur Vermeidung von Korrosion dadurch beitragen, daß die Anwendungsflüssigkeiten gut und läuferfrei von den behandelten Flächen ablaufen und auf Kunststoffoberflächen sogar ein Antistatik-Effekt erzielt werden kann.The object is achieved by cationic surfactants based on quaternary ammonium compounds, the ammonium nitrogen atom of which contains at least two alkyl radicals, a 2-hydroxyalkyl radical originating from the reaction with a terminal epoxide carrying 10 to 24 carbon atoms and optionally an arylalkyl group and the anion of which carries the anion is an organic carboxylic acid with 5 to 16 carbon atoms. Surprisingly, it was found that such cationic surfactants not only have good demulsifying properties with regard to anionic surfactants or emulsifiers, but also make the treated surfaces hydrophobic in corresponding industrial cleaners, and help prevent corrosion by ensuring that the application liquids run off the treated surfaces well and without running and even an antistatic effect can be achieved on plastic surfaces.

Gegenstand der Erfindung sind somit neue, verbesserte Kationtenside auf der Basis von quartären Ammoniumverbindungen, die dadurch gekennzeichnet sind, daß sie die allgemeine Formel

Figure imgb0003
aufweisen, in der

  • R1 ein linearer oder verzweigter Alkylrest mit 1 bis 22 C-Atomen,
  • R2 Wasserstoff oder ein linearer oder verzweigter Alkylrest mit 1 bis 21 C-Atomen sein kann, wobei die Gesamtzahl der C-Atome der Substituenten R1 und R2 im Bereich von 8 bis 22 liegt, und
  • R3 und R4 für Methyl, Ethyl, 2-Hydroxyethyl oder 2-Hydroxypropyl,
  • R5 für Alkylreste mit 4 bis 6 C-Atomen oder Phenalkylreste mit 1 bis 3 C-Atomen im Alkylrest und
  • R6 für lineare oder verzweigte Alkylreste mit 4 bis 15 C-Atomen stehen.
The invention thus relates to new, improved cationic surfactants based on quaternary ammonium compounds, which are characterized in that they have the general formula
Figure imgb0003
 have in which
  • R 1 is a linear or branched alkyl radical having 1 to 22 carbon atoms,
  • R 2 can be hydrogen or a linear or branched alkyl radical having 1 to 21 C atoms, the total number of C atoms of the substituents R 1 and R 2 being in the range from 8 to 22, and
  • R 3 and R 4 are methyl, ethyl, 2-hydroxyethyl or 2-hydroxypropyl,
  • R 5 for alkyl radicals with 4 to 6 carbon atoms or phenalkyl radicals with 1 to 3 carbon atoms in the alkyl radical and
  • R 6 represents linear or branched alkyl radicals having 4 to 15 carbon atoms.

Beispiele für lineare oder verzweigte Alkylreste, für die R1 und R2 stehen können, sind Methyl, Ethyl, Propyl, Isopropyl, n-Butyl, tert.-Butyl, Pentyl, Hexyl, Heptyl, Octyl, Nonyl, Decyl, Dodecyl, Tetradecyl und Hexadecyl. Bevorzugt werden quartäre Ammoniumverbindungen, in denen R2 für Wasserstoff und R1 für einen linearen oder verzweigten Alkylrest mit 8 bis 22 C-Atomen, z.B. n-Octyl, n-Decyl, n-Dodecyl, n-Tetradecyl oder n-Hexadecyl stehen. In jedem Fall muß die Gesamtzahl der C-Atome beider Substituenten R1 und R2 im Bereich von 8 bis 22 C-Atomen liegen.Examples of linear or branched alkyl radicals which R 1 and R 2 can represent are methyl, ethyl, propyl, isopropyl, n-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tetradecyl and hexadecyl. Quaternary ammonium compounds in which R 2 is hydrogen and R 1 is a linear or branched alkyl radical having 8 to 22 carbon atoms, for example n-octyl, n-decyl, n-dodecyl, n-tetradecyl or n-hexadecyl, are preferred. In any case, the total number of carbon atoms in both substituents R 1 and R 2 must be in the range from 8 to 22 carbon atoms.

Der am Ammonium-Stickstoffatom gebundene Rest R5 steht für Alkylreste wie beispielsweise n-Butyl, i-Butyl, tert.-Butyl, n-Pentyl, tert.-Butylmethyl oder n-Hexyl oder für Phenalkylreste wie Benzyl, Phenylethyl oder Phenylpropyl.The R 5 radical bonded to the ammonium nitrogen atom represents alkyl radicals such as, for example, n-butyl, i-butyl, tert-butyl, n-pentyl, tert-butylmethyl or n-hexyl or phenalkyl radicals such as benzyl, phenylethyl or phenylpropyl.

Das Gegenanion in den erfindungsgemäßen Kationtensiden ist das Anion einer organischen Carbonsäure mit 5 bis 16 C-Atomen, d.h. der Rest R6 in der allgemeinen Formel 1 steht für Alkylreste wie z.B. n-Butyl, i-Butyl, tert.-Butyl, Pentyl, Hexyl, Octyl, 2-Ethyl-hexyl-, n-Nonyl, i-Nonyl, Decyl, Dodecyl oder Pentadecyl. Besonders bevorzugt wird das Isononanoat-Anion.The counter anion in the cationic surfactants according to the invention is the anion of an organic carboxylic acid having 5 to 16 carbon atoms, ie the radical R 6 in the general formula 1 represents alkyl radicals such as, for example, n-butyl, i-butyl, tert-butyl, pentyl, Hexyl, octyl, 2-ethyl-hexyl, n-nonyl, i-nonyl, decyl, dodecyl or pentadecyl. The isononanoate anion is particularly preferred.

Vorzugsweise werden in industriellen Reinigungsmitteln folgende Einzelverbindungen verwendet:The following individual compounds are preferably used in industrial cleaning agents:

Benzyldimethyl-2-hydroxydodecylammoniumisononanoat (BDHAI), das Benzyldimethyl-2-hydroxydodecylammonium-Salz der 9/13-VersaticsäureR, Benzyldimethyl-2-hydroxydodecylammoniumisopalmitat, Butyldimethyl-2-hydroxydodecylammoniumisononanoat und Benzyldimethyl-2-hydroxyhexadecylammoniumisononanoat. Von diesen wird Benzyldimethyl-2-hydroxydodecylammoniumisononanoat besonders bevorzugt.Benzyldimethyl-2-hydroxydodecylammonium isononanoate (BDHAI), the benzyldimethyl-2-hydroxydodecylammonium salt of 9/13 versatic acid R , benzyldimethyl-2-hydroxydodecylammonium isopalmitate, butyldimethyl-2-hydroxydodecylammonylononononanoanoidonanoononanoatonate. Of these, benzyldimethyl 2-hydroxydodecylammonium isonanoanoate is particularly preferred.

Die erfindungsgemäßen Verbindungen de allgemeinen Formel I lassen sich nach an sich bekannten Methoden dadurch herstellen, daß man das Salz eines tertiären Amins der allgemeinen FormelThe compounds of the general formula I according to the invention can be prepared by methods known per se by adding the salt of a tertiary amine of the general formula

Figure imgb0004
in der R3, R4 und R5 die oben angegebenen Bedeutungen haben, und einer organischen Säure der allgemeinen Formel
Figure imgb0005
in der R6 die oben angegebene Bedeutung hat, in Wasser mit einer Epoxidverbindung der allgemeinen Formel
Figure imgb0006
in der R1 und R2 die oben angegebenen Bedeutungen haben und zusammen eine Anzahl von C-Atomen im Bereich von 8 bis 22 aufweisen, in stöchiometrischem Verhältnis bei Normaldruck und einer Temperatur zwischen 40 und 100°C umsetzt, wobei das Reaktionsgemisch vor Beginn der Umsetzung einen pH-Wert von wenigstens 7 aufweist.
Figure imgb0004
 in which R 3 , R 4 and R 5 have the meanings given above, and an organic acid of the general formula
Figure imgb0005
 in which R 6 has the meaning given above, in water with an epoxy compound of the general formula
Figure imgb0006
 in which R 1 and R 2 have the meanings given above and together have a number of C atoms in the range from 8 to 22, in a stoichiometric ratio at normal pressure and a temperature between 40 and 100 ° C, the reaction mixture before the start Implementation has a pH of at least 7.

Die zur Herstellung der erfindungsgemäßen quartären Ammoniumverbindungen verwendeten Epoxide der allgemeinen Formel IV können also Epoxide mit 10 bis 24 C-Atomen sein, in denen sich der Oxiranring an jeder beliebigen Stelle des Moleküls befindet. Bevorzugt werden allerdings quartäre Ammoniumverbindungen, die durch Umsetzung des Amin-Salzes mit einem 1,2-Epoxid hergestellt wurden, d.h. Verbindungen der allgemeinen Formel 1, in der R1 ein Alkylrest mit 8 bis 22 C-Atomen und R2 ein Wasserstoffatom ist.The epoxides of the general formula IV used to prepare the quaternary ammonium compounds according to the invention can thus be epoxides having 10 to 24 carbon atoms in which the oxirane ring is located at any point in the molecule. However, preference is given to quaternary ammonium compounds which have been prepared by reacting the amine salt with a 1,2-epoxide, ie compounds of the general formula 1 in which R 1 is an alkyl radical having 8 to 22 C atoms and R 2 is a hydrogen atom.

Die zur Herstellung der quartären Ammoniumverbindungen der allgemeinen Formel I verwendeten Amine sind vorzugsweise tertiäre Alkyl-, Hydroxyalkyl- oder Alkylarylamine, wobei Dimethylbutylamin und Dimethylbenzylamin besonders bevorzugt werden.The amines used to prepare the quaternary ammonium compounds of the general formula I are preferably tertiary alkyl, hydroxyalkyl or alkylarylamines, with dimethylbutylamine and dimethylbenzylamine being particularly preferred.

Die zur Herstellung der erfindungsgemäßen quartären Ammoniumverbindungen eingesetzten Carbonsäuren sind bevorzugt Monocarbonsäuren mit 5 bis 8 C-Atomen im Alkylrest. Besonders bevorzugt wird Isononansäure eingesetzt.The carboxylic acids used to prepare the quaternary ammonium compounds according to the invention are preferably monocarboxylic acids having 5 to 8 carbon atoms in the alkyl radical. Isononanoic acid is particularly preferably used.

Die erfindungsgemäßen quartären Ammoniumverbindungen werden als Kationtenside in industriellen Reinigerlösungen verwendet. Sie haben dabei gegenüber anderen Kationtensiden wie auch schon aus dem Stand der Technik bekannten quartären Ammoniumverbindungen den Vorteil, daß sie keine korrosiven oder zu unerwünschten Ausfällungen führenden Gegenanionen enthalten. Die Anionen der für die Herstellung der erfindungsgemäßen Ammoniumverbindungen verwendeten organischen. Säure sind im Gegensatz dazu sogar in der Lage, den Korrosionsprozeß auf gereinigten Metalloberflächen zu inhibieren. Durch die fehlende Anreicherung korrosiver Anionen in den Bädern und die inhibierende Wirkung der Carbonsäure-Anionen wird also eine Verbesserung der Korrosionsschutzeigenschaften in wässrigen Medien erzielt. Dies gilt gleichermaßen für Teile, die vor dem Weiterverarbeitungsprozeß zwischengelagert werden müssen, als auch für Teile, die unmittelbar weiterverarbeitet werden. Der verbesserte Korrosionsschutz macht sich insbesondere bei solchen-mit quartäre Ammoniumverbindungen enthaltenden Industriereinigern behandelten-Teilen bemerkbar, die aufgrund ihrer Geometrie schöpfend wirken. Bei Verwendung herkömmlicher Reiniger war die Korrosionsgefahr auf solchen Teilen besonders groß, da bei Verdunsten des Lösungsmittels, in der Regel Wasser, eine starke Anreicherung der Inhaltsstoffe und damit auch der korrosiven Bestandteile zu befürchten war. Dies wird bei Verwendung von die erfindungsgemäßen quartären Ammoniumverbindungen als Kationtenside enthaltenden industriellen Reinigerlösungen verhindert.The quaternary ammonium compounds according to the invention are used as cationic surfactants in industrial cleaning solutions. They have the advantage over other cationic surfactants as well as quaternary ammonium compounds already known from the prior art that they do not contain any corrosive counterions or lead to undesirable precipitations. The anions of the organic used for the preparation of the ammonium compounds according to the invention. In contrast, acids are even able to inhibit the corrosion process on cleaned metal surfaces. The lack of accumulation of corrosive anions in the baths and the inhibitory effect of the carboxylic acid anions thus improve the corrosion protection properties in aqueous media. This applies equally to parts that have to be temporarily stored before the further processing process, as well as to parts that are to be processed immediately. The improved corrosion protection is particularly noticeable in the case of parts which have been treated with industrial cleaners containing quaternary ammonium compounds and which, due to their geometry, have a creative effect. When using conventional cleaners, the risk of corrosion on such parts was particularly high, since if the solvent, usually water, evaporated, there was a risk that the ingredients and thus the corrosive components would be heavily concentrated. This is prevented when using industrial cleaning solutions containing the quaternary ammonium compounds according to the invention as cationic surfactants.

Einen weiteren Vorteil bieten die erfindungsgemäßen Kationtenside insofern, als eine vorteilhafte Hydrophobierung der gereinigten Oberflächen, insbesondere der gereinigten Metalloberflächen, beobachtet wird. Weiterhin wird durch ein sehr gutes Ablaufverhalten der Anwendungsflüssigkeit Korrosion der behandelten Teile vermieden.The cationic surfactants according to the invention offer a further advantage in that an advantageous hydrophobization of the cleaned surfaces, in particular the cleaned metal surfaces, is observed. Furthermore, corrosion of the treated parts is avoided by a very good drainage behavior of the application liquid.

Es wurde weiterhin beobachtet, daß sich wässrige Industriereiniger-Lösungen, die die erfindungsgemäßen quartären Ammoniumverbindungen als Kationtenside enthalten, auch zur Kunststoffreinigung einsetzen lassen, da sie eine antistatische Wirkung aufweisen. Gerade dies erschließt derartigen Produkten in der Zukunft einen weiten Anwendungsbereich, da auch Kunststoffflächen analog Metallflächen mit steigender Tendenz in Spritzverfahren gereinigt werden.It has also been observed that aqueous industrial cleaning solutions which contain the quaternary ammonium compounds according to the invention as cationic surfactants can also be used for cleaning plastics, since they have an antistatic effect. It is precisely this that will open up such products to a wide range of applications in the future, since plastic surfaces, similar to metal surfaces, are being cleaned with an increasing tendency in spray processes.

Die erfindungsgemäßen quartären Ammoniumverbindungen eignen sich zur Verwendung in allen für die Industrielle Reinigung wichtigen Reinigungsmitteln. So können sie in spritzfähigen Reinigern, z.B. neutralen bis schwach alkalischen Reinigern oder sauren Reinigern enthalten sein, insbesondere in solchen Reinigungslösungen, die unter hohem Druck auf die zu reinigenden Teile aufgespritzt werden. Gleichermaßen sind sie jedoch mit Vorteil auch in Tauchreinigern auf der Basis nichtionischer Tenside zu verwenden.The quaternary ammonium compounds according to the invention are suitable for use in all cleaning agents which are important for industrial cleaning. They can be used in sprayable cleaners, e.g. neutral to weakly alkaline cleaners or acid cleaners may be present, especially in cleaning solutions that are sprayed onto the parts to be cleaned under high pressure. Equally, however, they can also be used with advantage in immersion cleaners based on nonionic surfactants.

Quartäre Ammoniumverbindungen gemäß der Erfindung werden ebenfalls als kationische Tenside eingesetzt, die in Industriereinigerlösungen zum Spritzen oder Tauchen als Demulgatoren oder Antischaummittel wirken.Quaternary ammonium compounds according to the invention are also used as cationic surfactants which act as demulsifiers or antifoams in industrial cleaning solutions for spraying or dipping.

Die neuen verbesserten Kationtenside auf der Basis von quartären Ammoniumverbindungen werden nach an sich bekannten Verfahren mit-für industrielle Reinigungslösungen üblichen-weiteren Bestandteilen konfektioniert. Diese Lösungen können neben den quartären Ammoniumverbindungen und üblichen Inhaltsstoffen gegebenenfalls noch weitere Zusätze, z.B. an Alkanolaminen, Phosphaten, Boraten oder Nitriten enthalten. Erwünschtenfalls können den Lösungen auch Inhibitoren, insbesondere für Nichteisenmetalle, oder Biozide wie beispielsweise Hexahydrotriazinderivate und/oder Phenole und/oder Chlorphenole zur Verhinderung von Bakterien- und/oder Pilzbefall in den Spritz- oder Tauchanlagen zugesetzt werden.The new improved cationic surfactants based on quaternary ammonium compounds are made up with other components, which are conventional for industrial cleaning solutions, by processes known per se. In addition to the quaternary ammonium compounds and conventional ingredients, these solutions may also contain other additives, for example alkanolamines, phosphates, borates or contain nitrites. If desired, inhibitors, in particular for non-ferrous metals, or biocides such as, for example, hexahydrotriazine derivatives and / or phenols and / or chlorophenols can be added to the solutions to prevent bacterial and / or fungal attack in the spraying or immersion systems.

Die Erfindung wird durch die nachstehenden Beispiele weiter erläutert.The invention is further illustrated by the examples below.

Beispiel 1example 1 (Herstellung von Benzyldimethyl-2-hydroxydodecylammoniumisononanoat) (BDHAI)(Production of Benzyldimethyl-2-hydroxydodecylammonium Isononanoate) (BDHAI)

57,88 g Wasser wurden in einen 500 ml-Dreihalskolben mit Rührer, Rückflußkühler, Flüssigkeitsthermometer und Stickstoffabdeckung gegeben. Dem wurden der Reihe nach 67,6 g (0,5 mol) Dimethylbenzylamin, 79,12 g (0,5 mol) Isononansäure und 94,0 g (0,5 mol) 1,2-Epoxydodecan (Epoxidzahl 8,51) zugesetzt. Das Gemisch wurde unter Rühren auf 95°C aufgeheizt und 3 Stunden unter diesen Bedingungen belassen. Nach Ablauf dieser Zeitspanne war die Epoxidzahl auf einen Wert kleiner 0,05 gefallen, die Säurezahl betrug ca. 2,0 und die Aminzahl ca. 100. Das auf Raumtemperatur abgekühlte, ca. 80%ige Produkt schied etwas Wasser ab, das abgetrennt und verworfen wurde.57.88 g of water was placed in a 500 ml three-necked flask equipped with a stirrer, reflux condenser, liquid thermometer and nitrogen blanket. This was followed in turn by 67.6 g (0.5 mol) of dimethylbenzylamine, 79.12 g (0.5 mol) of isononanoic acid and 94.0 g (0.5 mol) of 1,2-epoxydodecane (epoxide number 8.51) added. The mixture was heated to 95 ° C. with stirring and left under these conditions for 3 hours. After this period, the epoxy number had dropped to a value less than 0.05, the acid number was approximately 2.0 and the amine number approximately 100. The approximately 80% product, cooled to room temperature, separated off some water, which separated and was discarded.

Ausbeute an 80%igem Benzyldimethyl-2-hydroxydodecylammoniumisononanoat: 290 g.Yield of 80% benzyldimethyl 2-hydroxydodecylammonium isononanoate: 290 g.

Beispiel 2Example 2 (Herstellung des Benzyldimethyl-2-hydroxydodecylammoniumsalzes der 9/13-VersaticR-Säure)(Preparation of the benzyldimethyl-2-hydroxydodecylammonium salt of 9/13 Versatic R acid)

In einen Dreihalskolben mit Rührer, Kontaktthermometer, Rückflußrührer und Stickstoffabdeckung wurden 59,0 g Wasser, 67,6 g (0,5 mol) Dimethylbenzylamin, 83,7 g (0,5 mol) 9/13-VersaticR-Säure (Säurezahl 335,3) und 94,0 g (0,5 mol) 1,2-Epoxydodecan (Epoxidzahl 8,51) in der genannten Reihenfolge unter Rühren gegeben und anschließend auf 95°C aufgeheizt. Nach 2 h war die Epoxidzahl auf 0 abgesunken und die Reaktion beendet. Bei Raumtemperatur schieden sich einige Wassertropfen am Boden des Kolbens ab, die abgetrennt und verworfen wurden. Die entstandene dunkle Lösung enthielt von der Herstellung her ca. 20% Wasser und besaß eine Säurezahl von 4,24 und einen Epton-Wert von 95,7 mval/ 100 g.59.0 g of water, 67.6 g (0.5 mol) of dimethylbenzylamine, 83.7 g (0.5 mol) of 9/13 Versatic R acid (acid number) were placed in a three-necked flask with stirrer, contact thermometer, reflux stirrer and nitrogen blanket 335.3) and 94.0 g (0.5 mol) of 1,2-epoxydodecane (epoxide number 8.51) are added in the order mentioned with stirring and then heated to 95.degree. After 2 h the epoxy number had dropped to 0 and the reaction had ended. At room temperature, some drops of water separated from the bottom of the flask, which were separated and discarded. The resulting dark solution contained approximately 20% water and had an acid number of 4.24 and an Epton value of 95.7 meq / 100 g.

Beispiel 3Example 3 (Herstellung von Benzyldimethyl-2-hydroxydodecylammoniumisopalmitat)(Production of Benzyldimethyl-2-hydroxydodecylammonium Isopalmitate)

In die in Beispiel 2 beschriebene Apparatur wurden der Reihe nach 68,1 g Wasser, 67,6 g (0,5 mol) Dimethylbenzylamin, 130 g (0,5 mol) Isopalmitinsäure (Säurezahl 215,3) und 94,0 g (0,5 mol) 1,2-Epoxydodecan gegeben. Nach zweistündigem Rühren bei 95°C und Abkühlen auf Raumtemperatur war eine zweiphasige Lösung entstanden. Die wässrige Phase wurde abgezogen, gewogen (35,1 g) und verworfen. Die Olphase enthielt ca. 10% Wasser. Das Produkt ist eine gelbe, klare Flüssigkeit (Epoxidzahl: 0,0; Säurezahl: 4,92; Epton-Wert: 84,8 mval/100 g).68.1 g of water, 67.6 g (0.5 mol) of dimethylbenzylamine, 130 g (0.5 mol) of isopalmitic acid (acid number 215.3) and 94.0 g ( 0.5 mol) of 1,2-epoxydodecane. After stirring for two hours at 95 ° C. and cooling to room temperature, a two-phase solution had formed. The aqueous phase was drawn off, weighed (35.1 g) and discarded. The oil phase contained approx. 10% water. The product is a yellow, clear liquid (epoxy number: 0.0; acid number: 4.92; Epton value: 84.8 meq / 100 g).

Beispiel 4Example 4 (Herstellung von n-Butyldimethyl-2-hydroxydodecylammoniumisononanoat)(Production of n-butyldimethyl-2-hydroxydodecylammonium isononanoate)

In der gleichen Apparatur und unter gleichen Bedingungen wie in Beispiel 2 wurden folgende Reaktionsteilnehmer umgesetzt: 45,7 g Wasser, 43,5 g (0,43 mol) Dimethylbutylamin, 68,0 g (0,43 mol) Isononansäure (Säurezahl 360,3) und 80,9 g (0,43 mol) 1,2-Epoxydodecan. Die Aufarbeitung des Reaktionsansatzes erfolgte wie in Beispiel 2 beschrieben. Es entstand eine gelbe, klare, 80%ige Lösung des Produktes (Epoxidzahl: 0,0; Säurezahl: 3,06; Epton-Wert: 125,1 mval/100 g).The following reactants were reacted in the same apparatus and under the same conditions as in Example 2: 45.7 g of water, 43.5 g (0.43 mol) of dimethylbutylamine, 68.0 g (0.43 mol) of isononanoic acid (acid number 360, 3) and 80.9 g (0.43 mol) of 1,2-epoxydodecane. The reaction mixture was worked up as described in Example 2. A yellow, clear, 80% solution of the product resulted (epoxy number: 0.0; acid number: 3.06; Epton value: 125.1 meq / 100 g).

Beispiel 5Example 5 (Herstellung von Benzyldimethyl-2-hydroxyhexadecylammoniumisononanoat)(Production of Benzyldimethyl-2-hydroxyhexadecylammoniumisononanoat)

In der gleichen Apparatur und unter gleichen Bedingungen wie in Beispiel 2 wurden folgende Reaktionsteilnehmer umgesetzt: 63,2 g Wasser, 67,6 g (0,5 mol) Dimethylbenzylamin, 79,1 g (0,5 mol) Isononansäure (Säurezahl 360,3) und 123,8 g (0,50 mol), 1,2-Epoxyhexadecan (Epoxidzahl 6,46). Nach Abkühlen auf Raumtemperatur schieden sich 3,1 g Wasser ab, die abgezogen und verworfen wurden. Die Ölphase war gelb und klar und enthielt das Produkt in einer Konzentration von 81% (Epoxidzahl: 0,06; Säuresahl: 10,9; Epton-Wert: 82,7 mval/100 g).The following reactants were reacted in the same apparatus and under the same conditions as in Example 2: 63.2 g of water, 67.6 g (0.5 mol) of dimethylbenzylamine, 79.1 g (0.5 mol) of isononanoic acid (acid number 360, 3) and 123.8 g (0.50 mol), 1,2-epoxyhexadecane (epoxy number 6.46). After cooling to room temperature, 3.1 g of water separated, which were drawn off and discarded. The oil phase was yellow and clear and contained the product in a concentration of 81% (epoxy number: 0.06; acid number: 10.9; Epton value: 82.7 meq / 100 g).

Beispiel 6Example 6

Es wurden Reinigerlösungen mit Anwendungskonzentrationen im Bereich von 0,5 bis 5% hergestellt, die für im Spritzen aufzubringende Reiniger vorgesehen waren. Die Lösungen hatten die folgenden Zusammensetzungen (Angaben in Gew.-%):Detergent solutions with application concentrations in the range from 0.5 to 5% were produced, which were intended for detergents to be applied in spraying. The solutions had the following compositions (data in% by weight):

a) Neutralreinigera) Neutral cleaner

  • 1. 30% Triethanolamin,
    • 10% Caprylsäure,
    • 5% Hexahydrotriazinderivat,
    • 0,5% Tolyltriazol,
    • 4% eines Anlagerungsproduktes von 2 EO und 4 PO an einen Alkohol mit 18 C-Atomen,
    • 1 % eines Anlagerungsproduktes von 5 EO und 30 PO an 1.2-Propylenglykol,
    • 1,5% Benzyldimethyl-2-hydroxydodecylammoniumisononanoat und
    • 48,0% vollentsalztes Wasser.
    1. 30% triethanolamine,
    • 10% caprylic acid,
    • 5% hexahydrotriazine derivative,
    • 0.5% tolyltriazole,
    • 4% of an adduct of 2 EO and 4 PO with an alcohol with 18 C atoms,
    • 1% of an adduct of 5 EO and 30 PO with 1,2-propylene glycol,
    • 1.5% benzyldimethyl 2-hydroxydodecylammonium isononanoate and
    • 48.0% demineralized water.
  • 2. 10% Natriumcaprylat,
    • 10% Triethanolamin,
    • 5% Borax,
    • 10% Natriumtriphosphat,
    • 4% eines Anlagerungsproduktes von 9 EO und 10 PO an Nonylphenol,
    • 2% Benzyldimethyl-2-hydroxydodecyl-ammoniumsalz der 9/13-VersaticR-Säure und
    • 59,0% vollentsalztes Wasser.
    2. 10% sodium caprylate,
    • 10% triethanolamine,
    • 5% borax,
    • 10% sodium triphosphate,
    • 4% of an adduct of 9 EO and 10 PO with nonylphenol,
    • 2% benzyldimethyl-2-hydroxydodecylammonium salt of 9/13 Versatic R acid and
    • 59.0% demineralized water.
b) Alkalischer Industriereinigerb) Alkaline industrial cleaner

  • 15% Kaliumtriphosphat,15% potassium triphosphate,
  • 6% Triethanolamin,6% triethanolamine,
  • 5% Kaliumhydroxid,5% potassium hydroxide,
  • 2% eines Anlagerungsproduktes von 3 EO und 6 PO an einen Alkohol mit 12 bis 18 C-Atomen,2% of an adduct of 3 EO and 6 PO with an alcohol having 12 to 18 carbon atoms,
  • 4% Isononansäure,4% isononanoic acid,
  • 2% Benzyldimethyl-2-hydroxydodecylammoniumisopalmitat und2% benzyldimethyl-2-hydroxydodecylammonium isopalmitate and
  • 66% vollentsalztes Wasser.66% demineralized water.
c) Saure Reinigerc) Acidic cleaners

  • 1. 25% Natriumdihydrogenphosphat,
    • 1% Benzoesäure,
    • 0,2% Natriumolybdat,
    • 1 % Butyldimethyl-2-hydroxydodecylammoniumisononanoat,
    • 3% nichtionogenes Tensid Triton DF16R und
    • 69,8% vollentsalztes Wasser.
    1. 25% sodium dihydrogen phosphate,
    • 1% benzoic acid,
    • 0.2% sodium polybdate,
    • 1% butyldimethyl-2-hydroxydodecylammonium isononanoate,
    • 3% non-ionic surfactant Triton DF16 R and
    • 69.8% demineralized water.
  • 2. 12% Diethanolamin,
    • 15% 2-Phosphonobutan-1.2.4-tricarbonsäure,
    • 5% Gluconsäure,
    • 3% nichtionogenes Tensid Triton DF16R,
    • 8% Fettalkoholsulfat in Form des Natriumsalzes,
    • 3% Phosphorsäure,
    • 2% Benzyldimethyl-2-hydroxydodecylammoniumisononanoat und
    • 52% vollentsalztes Wasser.
    2. 12% diethanolamine,
    • 15% 2-phosphonobutane-1.2.4-tricarboxylic acid,
    • 5% gluconic acid,
    • 3% non-ionic surfactant Triton DF16 R ,
    • 8% fatty alcohol sulfate in the form of the sodium salt,
    • 3% phosphoric acid,
    • 2% benzyldimethyl-2-hydroxydodecylammonium isononanoate and
    • 52% demineralized water.

Die wie oben beschrieben formulierten Reinigungsmittel konnten gut im Spritzen aufgetragen werden. Sie zeigten geringe bzw. gar keine Neigung zum Schäumen. Die Reinigungsbäder waren über längere Zeit stabil und ließen über diese Zeit in ihrer Reinigungskraft nicht nach. Aufgrund der Verwendung der erfindungsgemäßen quartären Ammoniumverbindungen korrodierten die mit den Reinigern im Spritzen behandelten Metalloberflächen nicht, sondern wiesen im Vergleich zu einer Behandlung mit herkömmlichen Reinigern erhöhten Korrosionsschutz auf.The cleaning agents formulated as described above could easily be applied by spraying. They showed little or no tendency to foam. The cleaning baths were stable for a long time and their cleaning power did not deteriorate over this time. Due to the use of the quaternary ammonium compounds according to the invention, the metal surfaces treated with the cleaners in the spray did not corrode, but instead had increased corrosion protection in comparison with treatment with conventional cleaners.

Beispiel 7Example 7

Alkalische, industrielle Tauchreiniger; Anwendungskonzentrationen im Bereich von 1 bis 7%.

  • 1. 15% Kaliumtriphosphat,
    • 6% Triethanolamin,
    • 6% Isononansäure,
    • 1,5% Benzyldimethyl-2-hexadecylammoniumisononanoat,
    • 10% Diethanolamin,
    • 5% eines Anlagerungsproduktes von 10 EO an Nonylphenol und
    • 56,5% vollentsalztes Wasser.
  • 2. 40% Natriumdiphosphat,
    • 30% Natriumorthophosphat,
    • 10% Natriumtriphosphat,
    • 10% Natriummetasilicat,
    • 1% Benzyldimethyl-2-hydroxydodecyl-Ammoniumsalz der 9/13 VersaticR-Säure und
    • 9% eines Anlagerungsproduktes von 10 EO an Nonylphenol.
Alkaline industrial dip cleaners; Application concentrations in the range of 1 to 7%.
  • 1. 15% potassium triphosphate,
    • 6% triethanolamine,
    • 6% isononanoic acid,
    • 1.5% benzyldimethyl-2-hexadecylammonium isononanoate,
    • 10% diethanolamine,
    • 5% of an adduct of 10 EO with nonylphenol and
    • 56.5% demineralized water.
  • 2. 40% sodium diphosphate,
    • 30% sodium orthophosphate,
    • 10% sodium triphosphate,
    • 10% sodium metasilicate,
    • 1% benzyldimethyl-2-hydroxydodecyl ammonium salt of 9/13 Versatic R acid and
    • 9% of an adduct of 10 EO with nonylphenol.

Die wie oben beschrieben formulierten Reinigungsmittel hatten eine über längere Zeit hohe Reinigungskraft auf behandelten Metalloberflächen, und ihre Bäder wiesen eine hohe Stabilität auf. Metalloberflächen, die mit den oben beschriebenen Reinigern im Tauchen behandelt worden waren, wiesen einen verbesserten Korrosionsschutz im Vergleich zu mit herkömmlichen Reinigern behandelten Meta!Ioberflächen auf.The cleaning agents formulated as described above had a high cleaning power on treated metal surfaces over a long period of time and their baths were very stable. Metal surfaces that had been treated with the above-described cleaners in immersion had improved corrosion protection compared to metal surfaces treated with conventional cleaners.

Beispiel 8Example 8 Demulgierende WirkungDemulsifying effect A NeutralreinigerA neutral cleaner

Beschrieben wird die demulgierende Wirkung eines Neutralreinigers auf folgender Basis:

  • 35% Alkanoiamin-Cg-C12-Carboxylat
  • 2% 1-Hydroxyethan-1,1-diphosphonsäure
  • 0,5% Mercaptobenzthiazol
  • 3% Blockpolymerisat aus Ethylendiamin+30 mol Ethylenoxid sowie 60 mol Propylenoxid
  • 1% Anlagerungsprodukt von 10 mol Ethylenoxid an C12-C16-Fettamin
  • 58,5% Wasser.
The demulsifying effect of a neutral cleaner is described on the following basis:
  • 35% alkanoiamine Cg-C 12 carboxylate
  • 2% 1-hydroxyethane-1,1-diphosphonic acid
  • 0.5% mercaptobenzthiazole
  • 3% block polymer made from ethylenediamine + 30 mol ethylene oxide and 60 mol propylene oxide
  • 1% adduct of 10 mol ethylene oxide with C 12 -C 16 fatty amine
  • 58.5% water.

a. Emulsionsspaltunga. Emulsion splitting

Die Emulsionsspaltung wurde nach folgendem Test durchgeführt:The emulsion cleavage was carried out according to the following test:

10 g Bohröl wurden bei Raumtemperatur mit 40 g einer 2%igen wässrigen Neutralreinigerlösung in einem 270 ml Ölabscheidungskolben emulgiert. Eine äquivalente Menge BDHAI wurde zugegeben. Unter Schütteln wurde mit 2%iger heißer Neutralreinigerlösung aufgefüllt. Die Demulgation setzte spontan ein. Zur vollständigen Ölseparierung aus der sich zunächst abscheidenden "emulsionsartigen Phase" temperte man die Flüssigkeit zwei Stunden bei 80°C.10 g of drilling oil were emulsified at room temperature with 40 g of a 2% aqueous neutral cleaning solution in a 270 ml oil separation flask. An equivalent amount of BDHAI was added. The mixture was filled with 2% hot neutral cleaning solution while shaking. Demulsification started spontaneously. For complete oil separation from the initially "emulsion-like phase", the liquid was tempered at 80 ° C. for two hours.

Ergebnis:

  • Das Öl wurde praktisch quantitativ abgetrennt
  • b. Zusatz von Antischaummittel:
Result:
  • The oil was separated practically quantitatively
  • b. Addition of antifoam:

10 g Bohröl wurden bei Raumtemperatur mit 40 g einer 2%igen wässrigen Neutralreinigerlösung in einem 270 ml Ölabscheidungskolben emulgiert.10 g of drilling oil were emulsified at room temperature with 40 g of a 2% aqueous neutral cleaning solution in a 270 ml oil separation flask.

BDHAI wurde dieser Emulsion in stöchiometrischem Überschuß (Verhältnis Demulgator zu anionischem Emulgator=1,2:1) zugegeben. Ferner wurde das Anlagerungsprodukt von 30 Mol Ethylenoxid und 60 mol Propylenoxid an Ethylendiamin als Antischaummittel zugegeben (Verhältnis Demulgator: Antischaummittel=1:1). Unter Schütteln wurde mit 2%iger wässriger Neutralreinigerlösung aufgefüllt. Die Spaltung setzte spontan ein. Die rückgeführte Reinigungslösung konnte schaumfrei gespritzt werden.BDHAI was added to this emulsion in a stoichiometric excess (ratio of demulsifier to anionic emulsifier = 1.2: 1). Furthermore, the adduct of 30 moles of ethylene oxide and 60 moles of propylene oxide and ethylenediamine was added as an antifoam (ratio of demulsifier: antifoam = 1: 1). The mixture was filled with 2% aqueous neutral cleaning solution while shaking. The split started spontaneously. The returned cleaning solution could be sprayed foam-free.

B. Alkalische ReinigungsmittelB. Alkaline detergents

Beschrieben wird die Spaltung von Emulsionen in Gegenwart alkalischer Reinigungsmittel, die die jeweils einleitend angegebene Zusammensetzung hatten:

  • a) 63% Natriummetasilikat
    • 14% Natriumhydroxid
    • 15% Soda
    • 2% Fettalkohol+14 Ethylenoxid
    • 3% Alkylbenzolsulfonat.
Describing the cleavage of emulsions in the presence of alkaline cleaning agents, which each had the composition specified above:
  • a) 63% sodium metasilicate
    • 14% sodium hydroxide
    • 15% soda
    • 2% fatty alcohol + 14 ethylene oxide
    • 3% alkyl benzene sulfonate.

Zu einer 4%igen Reinigerlösung in Leitungswasser wurden bei Raumtemperatur 2% Bohröl-Konzentrat emulgiert, eine mehr als äquivalente Menge (1:1,1) BDHAI zugegeben und ca. 3 min. gut gerührt. Man ließ die Mischung stehen, die Separierung des Öls begann sofort.

  • b) 60% Natriummetasilikat
    • 10% Natriumhydroxid
    • 15% Soda
    • 10% Natriumdiphosphat
    • 2,5% Fettalkohol+14 Ethylenoxid
    • 2,5% Kokosamin+12 Ethylenoxid.
2% drilling oil concentrate was emulsified at room temperature to a 4% cleaning solution in tap water, a more than equivalent amount (1: 1.1) of BDHAI was added and about 3 min. well stirred. The mixture was allowed to stand, and the separation of the oil began immediately.
  • b) 60% sodium metasilicate
    • 10% sodium hydroxide
    • 15% soda
    • 10% sodium diphosphate
    • 2.5% fatty alcohol + 14 ethylene oxide
    • 2.5% coconut amine + 12 ethylene oxide.

Wie unter a) beschrieben, wurde zu einer 3%igen Reinigerlösung eine doppelt äquivalente Menge BDHAI zur Emulsionsspaltung gegeben. Die Separierung begann sofort, wobei die wässrige Phase nahezu klar war.

  • c) 50% Natriumdiphosphat
    • 15% Natriumtriphosphat
    • 15% Trinatriumphosphat
    • 10% Soda
    • 7,7% Nonylphenol+14 Ethylenoxid
    • 2,3% Kokosfettsäuremonoethanolamid+4 Ethylenoxid.
As described under a), a double equivalent amount of BDHAI was added to a 3% detergent solution to split the emulsion. The separation started immediately, the aqueous phase being almost clear.
  • c) 50% sodium diphosphate
    • 15% sodium triphosphate
    • 15% trisodium phosphate
    • 10% soda
    • 7.7% nonylphenol + 14 ethylene oxide
    • 2.3% coconut fatty acid monoethanolamide + 4 ethylene oxide.

Wie unter a) und b) beschrieben, wurde einer belasteten 2%igen Reinigerlösung eine doppelt äquivalente Menge BDHAI zugegeben. Die Separierung erfolgte spontan, wobei die wässrige Phase nahezu klar wurde.As described under a) and b), a double equivalent amount of BDHAI was added to a contaminated 2% cleaning solution. The separation took place spontaneously, the aqueous phase becoming almost clear.

Die Anwesenheit von Pyro- oder Polymerphosphaten und/oder anionischen Tensiden bedingte eine höhere Zugabe an Demulgator zur vollständigen und raschen Demulgierung.The presence of pyro- or polymer phosphates and / or anionic surfactants necessitated a higher addition of demulsifier for complete and rapid demulsification.

Beispiel 9Example 9

Allgemeine.Reinigungsmittel (z.B. Reiniger für Fahrzeuge, Reiniger für Wände und Fußböden von Industriebetrieben und Produkte für die Dampfstrahlreinigung; Anwendungskonzentrationen im Bereich von 2 bis 30%)

  • 1. 8% eines Anlagerungsproduktes von 14 EO an einen Alkohol mit 12 bis 14 C-Atomen,
    • 7% Fettalkoholsulfat,
    • 3% Butyldimethyl-2-hydroxydodecylammoniumisononanoat,
    • 5% Kaliumhydroxid,
    • 10% Diethanolamin,
    • 6% Phosphorsäure und
    • 61% vollentsalztes Wasser.
  • 2. 8% Natriumtriphosphat,
    • 5% Isononansäure,
    • 5% Borsäure,
    • 8% Monoethanolamin,
    • 1 % Kaliumhydroxid,
    • 5% eines Anlagerungsproduktes von 12 EO an ein Amin mit 12 C-Atomen,
    • 3% Benzyldimethyl-2-hydroxydodecylammoniumisopalmitat und
    • 65% vollentsalztes Wasser.
General cleaning agents (e.g. cleaning agents for vehicles, cleaning agents for walls and floors of industrial companies and products for steam jet cleaning; application concentrations in the range from 2 to 30%)
  • 1. 8% of an adduct of 14 EO with an alcohol having 12 to 14 carbon atoms,
    • 7% fatty alcohol sulfate,
    • 3% butyldimethyl-2-hydroxydodecylammonium isononanoate,
    • 5% potassium hydroxide,
    • 10% diethanolamine,
    • 6% phosphoric acid and
    • 61% demineralized water.
  • 2.8% sodium triphosphate,
    • 5% isononanoic acid,
    • 5% boric acid,
    • 8% monoethanolamine,
    • 1% potassium hydroxide,
    • 5% of an adduct of 12 EO with an amine with 12 C atoms,
    • 3% benzyldimethyl-2-hydroxydodecylammonium isopalmitate and
    • 65% demineralized water.

Die wie oben beschrieben zusammengesetzten Reinigungsmittel zeigten gute Reinigungswirkung und ein gleichmäßiges, läuferfreies Ablaufverhalten auf den behandelten Teilen.The cleaning compositions composed as described above showed good cleaning action and a uniform, run-free drainage behavior on the treated parts.

Aufgrund ver Verwendung der erfindungsgemäßen quartären Ammoniumverbindungen war der Korrosionsschutz für mit den Reinigungslösungen behandelte Metallflächen und -gegenstände im Vergleich zu der Behandlung mit herkömmlichen Reinigungsmitteln deutlich verbessert.Due to the use of the quaternary ammonium compounds according to the invention, the corrosion protection for metal surfaces and objects treated with the cleaning solutions was significantly improved compared to the treatment with conventional cleaning agents.

Beispiel 10Example 10 Vergleichender KorrosionstestComparative corrosion test

Hinsichtlich ihrer korrosionsinhibierenden Eigenschaften wurden Lösungen vergleichend getestet, die als quartäre Ammoniumverbindung das aus dem Stand der Technik bekannte Produkt DehyquartR LDB (Fa. Henkel) und BDHAI gemäß der vorliegenden Erfindung enthielten.With regard to their corrosion-inhibiting properties, solutions were tested which contained the product DehyquartR LDB (from Henkel) and BDHAI according to the present invention as a quaternary ammonium compound.

Die Prüfung erfolgt gemäß dem Spänetest DIN 51360/2 mit 1 bis 3%igen Lösungen in vollentsalztem und 20° d-Wasser von Konzentration der Rezepturen I und II:

  • I: 12,5% DehyquartR LDB (35% Aktivgehalt) 37,5% Diethanolamin Rest Wasser
  • II: 5,5% BDHAI (80% Aktivgehalt) 37,5% Diethanolamin Rest Wasser.
The test is carried out according to the chip test DIN 51360/2 with 1 to 3% solutions in deionized and 20 ° d water with a concentration of recipes I and II:
  • I: 12.5% DehyquartR LDB (35% active content) 37.5% diethanolamine rest water
  • II: 5.5% BDHAI (80% active content) 37.5% diethanolamine rest water.

Die Ergebnisse sind der nachfolgenden Tabelle zu entnehmen.The results are shown in the table below.

Korrosionsgrad gemäß DIN 51360/2 bei Verwendung vonDegree of corrosion according to DIN 51360/2 when using

Figure imgb0007
Wie Spalten 4 und 5 zu entnehmen ist, zeigt BDHAI ein deutlich besseres Korrosionsschutzverhalten.
Figure imgb0007
 As can be seen in columns 4 and 5, BDHAI shows a significantly better corrosion protection behavior.

Claims (12)

1. Cationic surfactants based on quaternary ammonium compounds, characterized in that they correspond to the following general formula
Figure imgb0010
in which
R1 represents a linear or branched CI-22 alkyl group,
R2 represents hydrogen or a linear or branched C1-21 alkyl group, the total number of carbon atoms in the substituents R' and R2 being in the range from 8 to 22,
R3 and R4 represent methyl, ethyl, 2-hydroxyethyl or 2-hydroxypropyl,
R5 represents alkyl groups containing from 4 to 6 carbon atoms or phenalkyl groups containing from 1 to 3 carbon atoms in the alkyl group and
R6 represents linear or branched C4-15 alkyl groups.
2. Cationic surfactants as claimed in Claim 1, characterized in that, in general formula I, R1 is a C8-22 alkyl group and R2 is a hydrogen atom.
3. Cationic surfactants as claimed in Claim 2, characterized in that, in general formula I, R1 is a decyl or tetradecyl radical.
4. Cationic surfactants as claimed in Claim 1, characterized in that R and R4 are methyl groups.
5. Cationic surfactants as claimed in Claim 1, characterized in that, in general formula I, R5 is a benzyl or n-butyl group.
6. Cationic surfactants as claimed in Claim 1, characterized in that, in general formula I, R6 is an isooctyl group.
7. Benzyldimethyl-2-hydroxydodecylammonium isononanoate.
8. Benzyldimethyl-2-hydroxydodecylammonium salt of 9/13-Versatic acid.
9. Benzyldimethyl-2-hydroxydodecylammonium isopalmitate.
10. Butyldimethyl-2-hydroxydodecylammonium isononanoate.
11. Benzyldimethyl-2-hydroxyhexadecylammonium isononanoate.
12. The use of the cationic surfactants based on quaternary ammonium compounds claimed in Claims 1 to 11 in sprayable cleaning preparations, immersion cleaning preparations, demulsifying additives for industrial cleaning solutions or other cleaning preparations.
EP86100364A 1985-01-21 1986-01-13 Quaternary ammonium compounds containing cationic surfactants and their use in cleaning compositions Expired - Lifetime EP0189085B1 (en)

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