EP0189085A2 - 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 PDFInfo
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- EP0189085A2 EP0189085A2 EP86100364A EP86100364A EP0189085A2 EP 0189085 A2 EP0189085 A2 EP 0189085A2 EP 86100364 A EP86100364 A EP 86100364A EP 86100364 A EP86100364 A EP 86100364A EP 0189085 A2 EP0189085 A2 EP 0189085A2
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- cationic surfactants
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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.
- DE-OS 27 12 900 and DE-OS 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 ammonium is used. Nitrogen atom organic radicals, especially alkyl radicals 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-OS 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.
- the object of the present invention was therefore to provide new, improved cationic surfactants based on quaternary ammonium compounds, which Not have disadvantages from 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, ie are easily water-soluble, do not cause any troublesome precipitations and with others Components commonly used in industrial cleaners are compatible.
- the object is achieved by new, improved cationic surfactants based on quaternary ammonium compounds, the ammonium nitrogen atom of which carries 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 like
- Anion is the anion of 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, ie the radical R 6 in the general formula I 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.
- 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 in which R 3 , R 4 and R 5 have the meanings given above have, and an organic acid of the general formula in which R 6 has the meaning given above, in water with an epoxy compound of the general formula 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.
- 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.
- the anions of the organic acid used for the production of the ammonium compounds according to the invention 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 those parts - which have been treated with industrial cleaners containing quaternary ammonium compounds - and which have a creative effect due to their geometry.
- industrial cleaners containing quaternary ammonium compounds - Using conventional cleaners K was orrosionsgefahr particularly great, since evaporation of the solvent, was feared as a rule water, a strong enrichment of the ingredients and thus the corrosive constituents on such parts. This is when using the quaternary ammonium compounds according to the invention prevented as industrial cleaning solutions containing 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, using processes known per se.
- these solutions may also contain other additives, e.g. contain alkanolamines, phosphates, borates or nitrites.
- inhibitors in particular for non-ferrous metals, or biocides such as, for example, hexahydrotriazine derivatives and / or phenols and / or chlorophenols to prevent bacterial and / or fungal attack in the spraying or immersion systems can also be added to the solutions.
- 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 spraying 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: 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.
- the returned cleaning solution could be sprayed foam-free.
- 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%
- 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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Abstract
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-OS 27 12 900 und der DE-OS 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. Thus, DE-OS 27 12 900 and DE-OS 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 ammonium is used. Nitrogen atom organic radicals, especially alkyl radicals 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-OS 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-OS 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 organischen Säure in Wasser mit einer einen Hydroxyalkylrest einführenden endständigen Epoxidverbindung bei Normaldruck, Temperaturen zwischen 40 und 100°C und einem pH-Wert von wenigstens 7 sind aus der deutschen Patentanmeldung 33 21 608.8 bekannt. 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 KationTensiden 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.Process for the preparation of quaternary ammonium compounds containing at least one long-chain hydroxyalkyl radical by reacting the salt of a tertiary amine and an organic acid in water with a terminal introducing a hydroxyalkyl radical The epoxy compound at normal pressure, temperatures between 40 and 100 ° C and a pH of at least 7 are known from German patent application 33 21 608.8. 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. In addition, it was 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.
Aufgabe der vorliegenden Erfindung war es somit, 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.The object of the present invention was therefore to provide new, improved cationic surfactants based on quaternary ammonium compounds, which Not have disadvantages from 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, ie are easily water-soluble, do not cause any troublesome precipitations and with others Components commonly used in industrial cleaners are compatible.
Die Aufgabe wird gelöst durch neue, verbesserte 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 new, improved cationic surfactants based on quaternary ammonium compounds, the ammonium nitrogen atom of which carries 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 like Anion is the anion of 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
- R 1 ein linearer oder verzweigter Alkylrest mit 1 bis 22 C-Atomen,
- R 2 Wasserstoff oder ein linearer oder verzweigter Alkylrest mit 1 bis 21 C-Atomen sein kann, wobei die Gesamtzahl der C-Atome der Subsitutenten R1 und R2 im Bereich von 8 bis 22 liegt, und
- R 3 und R 4 für Methyl, Ethyl, 2-Hydroxyethyl oder 2-Hydroxypropyl,
- R für Alkylreste mit 4 bis 6 C-Atomen oder Phenalkylreste mit 1 bis 3 C-Atomen im Alkylrest und
- R 6 für lineare oder verzweigte Alkylreste mit 4 bis 15 C-Atomen stehen.
- 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 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 R 1 und R 2 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 I 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 I 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:
- Benzyldimethyl-2-hydroxydodecylammoniumisononanoat, das Benzyldimethyl-2-hydroxydodecylammonium-Salz der 9/13-VersaticsäureR, Benzyldimethyl-2-hydroxydodecyl- ammoniumisopalmitat, Butyldimethyl-2-hydroxydodecyl- ammoniumisononanoat und Benzyldimethyl-2-hydroxyhexa- decylammoniumisononanoat. Von diesen wird Benzyldime- thyl-2-hydroxydodecylammoniumisononanoat besonders bevorzugt.
- Benzyldimethyl-2-hydroxydodecylammonium isononanoate, the benzyldimethyl-2-hydroxydodecylammonium salt of 9/13 versatic acid R , benzyldimethyl-2-hydroxydodecylammonium isopalmitate, butyldimethyl-2-hydroxydodecylammoniumisononanoanoate and 2-hydroxyldimoniumdimoniumateonate. Of these, benzyldimethyl 2-hydroxydodecylammonium isononanoate is particularly preferred.
Die erfindungsgemäßen Verbindungen der allgemeinen Formel I lassen sich nach an sich bekannten Methoden dadurch herstellen, daß man das Salz eines tertiären Amins der allgemeinen Formel
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 I, 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 I 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. In contrast, the anions of the organic acid used for the production of the ammonium compounds according to the invention 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 those parts - which have been treated with industrial cleaners containing quaternary ammonium compounds - and which have a creative effect due to their geometry. Using conventional cleaners K was orrosionsgefahr particularly great, since evaporation of the solvent, was feared as a rule water, a strong enrichment of the ingredients and thus the corrosive constituents on such parts. This is when using the quaternary ammonium compounds according to the invention prevented as industrial cleaning solutions containing 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, using processes known per se. In addition to the quaternary ammonium compounds and conventional ingredients, these solutions may also contain other additives, e.g. contain alkanolamines, phosphates, borates or nitrites. If desired, inhibitors, in particular for non-ferrous metals, or biocides such as, for example, hexahydrotriazine derivatives and / or phenols and / or chlorophenols to prevent bacterial and / or fungal attack in the spraying or immersion systems can also be added to the solutions.
Die Erfindung wird durch die nachstehenden Beispiele weiter erläutert.The invention is further illustrated by the examples below.
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) isononanoic acid and 94.0 g (0.5 mol) 1,2-epoxydodecane (epoxide number 8.51) were 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-hydroxydodecyl- ammoniumisononanoat: 290 g.Yield of 80% benzyldimethyl-2-hydroxydodecylammoniumisononanoat: 290 g.
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-Versatic R_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 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.
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 ölphase 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 were added in succession to the apparatus described in Example 2. 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).
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).
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; Säurezahl: 10,9; Epton-Wert:
82,7 mval/100 g).In the same equipment and under the same conditions The following reactants were reacted 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).
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.-%):
- a) Neutralreiniger
- b) Alkalischer Industriereiniger
- c) Saure Reiniger
- a) Neutral cleaner
- b) Alkaline industrial cleaner
- c) Acidic cleaners
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 spraying did not corrode, but instead had increased corrosion protection in comparison with treatment with conventional cleaners.
Alkalische, industrielle Tauchreiniger; Anwendungskonzentrationen im Bereich von 1 bis 7 %.Alkaline industrial dip cleaners; Application concentrations in the range of 1 to 7%.
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 Metalloberflächen 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.
Beschrieben wird die demulgierende Wirkung eines Neutralreinigers auf folgender Basis:
Die Emulsionsspaltung wurde nach folgendem Test durchgeführt: 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 "emul- - sionsartigen Phase" temperte man die Flüssigkeit zwei Stunden bei 80°C.The emulsion cleavage was carried out according to the following test: 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.
Das Öl wurde praktisch quantitativ abgetrennt.The oil was separated practically quantitatively.
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 Uberschuß (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.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.
Die rückgeführte Reinigungslösung konnte schaumfrei gespritzt werden.The returned cleaning solution could be sprayed foam-free.
Beschrieben wird die Spaltung von Emulsionen in Gegenwart alkalischer Reinigungsmittel, die die jeweils einleitend angegebene Zusammensetzung hatten:
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.
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.
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.
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 %)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%)
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 der 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.
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 Dehyquart R 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 Konzentraten der Rezepturen I und II:The test is carried out according to the chip test DIN 51360/2 with 1 to 3% solutions in fully deionized and 20 ° d water of concentrates of recipes I and II:
Die Ergebnisse sind der nachfolgenden Tabelle zu entnehmen.The results are shown in the table below.
Wie Spalten 4 und 5 zu entnehmen ist, zeigt BDHAI ein deutlich besseres Korrosionsschutzverhalten.As can be seen in columns 4 and 5, BDHAI shows a significantly better corrosion protection behavior.
Claims (12)
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AT86100364T ATE56698T1 (en) | 1985-01-21 | 1986-01-13 | NEW CATION SURFACETS BASED ON QUARTERIC AMMONIUM COMPOUNDS AND THEIR USE IN DETERGENTS. |
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DE19853501775 DE3501775A1 (en) | 1985-01-21 | 1985-01-21 | NEW QUARTAINE AMMONIUM COMPOUNDS AND THEIR USE IN CLEANING AGENTS |
DE3501775 | 1985-01-21 |
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EP (1) | EP0189085B1 (en) |
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AT (1) | ATE56698T1 (en) |
AU (1) | AU579443B2 (en) |
BR (1) | BR8600200A (en) |
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US3636114A (en) * | 1968-07-16 | 1972-01-18 | Union Carbide Corp | Novel quaternary ammonium compounds and method for preparation thereof |
BE793339A (en) * | 1970-10-20 | 1973-06-27 | Henkel & Cie Gmbh | ADDITIONAL LAUNDRY TREATMENT AGENT AND ITS PREPARATION PROCESS |
DE2712900C2 (en) * | 1977-03-24 | 1986-04-10 | Henkel KGaA, 4000 Düsseldorf | Process for cleaning metals by spraying |
DE3048642A1 (en) * | 1980-12-23 | 1982-07-15 | Hoechst Ag, 6000 Frankfurt | "TENSIDE MIXTURE FOR CLEANING HARD SURFACES" |
DE3246124A1 (en) * | 1982-12-13 | 1984-06-14 | Henkel KGaA, 4000 Düsseldorf | CLEANING PROCEDURE |
DE3247431A1 (en) * | 1982-12-22 | 1984-06-28 | Henkel KGaA, 4000 Düsseldorf | METHOD FOR REGENERATION OR FOR RECYCLING AQUEOUS DEGREASING AND CLEANING SOLUTIONS |
DE3321608A1 (en) * | 1983-06-15 | 1984-12-20 | Henkel KGaA, 4000 Düsseldorf | METHOD FOR PRODUCING QUARTAINE AMMONIUM COMPOUNDS |
US4595526A (en) * | 1984-09-28 | 1986-06-17 | Colgate-Palmolive Company | High foaming nonionic surfacant based liquid detergent |
-
1985
- 1985-01-21 DE DE19853501775 patent/DE3501775A1/en not_active Withdrawn
-
1986
- 1986-01-13 DE DE8686100364T patent/DE3674216D1/en not_active Expired - Fee Related
- 1986-01-13 AT AT86100364T patent/ATE56698T1/en active
- 1986-01-13 EP EP86100364A patent/EP0189085B1/en not_active Expired - Lifetime
- 1986-01-17 US US06/820,281 patent/US4678605A/en not_active Expired - Fee Related
- 1986-01-17 BR BR8600200A patent/BR8600200A/en unknown
- 1986-01-20 ZA ZA86412A patent/ZA86412B/en unknown
- 1986-01-20 CA CA000499900A patent/CA1259011A/en not_active Expired
- 1986-01-20 AU AU52473/86A patent/AU579443B2/en not_active Ceased
- 1986-01-21 JP JP61011828A patent/JPS61192330A/en active Pending
Patent Citations (4)
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US2759975A (en) * | 1952-05-28 | 1956-08-21 | Gen Aniline & Film Corp | Mixed alkyl-benzyl-alkylol quaternary ammonium salts |
DE2631733A1 (en) * | 1975-07-29 | 1977-02-10 | Air Prod & Chem | METHOD FOR PROMOTING CONDENSATION AND / OR POLYMERIZATION REACTIONS OF ORGANIC ISOCYANATES |
US4040992A (en) * | 1975-07-29 | 1977-08-09 | Air Products And Chemicals, Inc. | Catalysis of organic isocyanate reactions |
EP0012215A1 (en) * | 1978-11-11 | 1980-06-25 | BASF Aktiengesellschaft | 2-Hydroxybutanesulfonic acid choline and its use as conducting salt |
Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0249164A1 (en) * | 1986-06-13 | 1987-12-16 | Henkel Kommanditgesellschaft auf Aktien | Cationic surfactants based on quaternary ammonium compounds and their use in detergents |
US4814108A (en) * | 1986-06-13 | 1989-03-21 | Henkel Kommanditgesellschaft Auf Aktien | Cationic surfactants based on quaternary ammonium compounds and use thereof in cleaning agents |
WO1989009204A1 (en) * | 1988-04-02 | 1989-10-05 | Henkel Kommanditgesellschaft Auf Aktien | Quaternary ammonium compounds |
EP0336267A2 (en) * | 1988-04-02 | 1989-10-11 | Henkel Kommanditgesellschaft auf Aktien | Quaternary ammonium compounds |
EP0336267A3 (en) * | 1988-04-02 | 1989-10-25 | Henkel Kommanditgesellschaft auf Aktien | Quaternary ammonium compounds |
EP0345475A1 (en) * | 1988-05-13 | 1989-12-13 | Hoechst Aktiengesellschaft | Process for the production of quaternary ammonium salts of long-chain aliphatic carboxylic acids |
EP2604674A1 (en) * | 2011-12-12 | 2013-06-19 | Basf Se | Use of quaternised alkylamine as additive in fuels and lubricants |
WO2013087701A1 (en) * | 2011-12-12 | 2013-06-20 | Basf Se | Use of quaternised alkyl amines as additives in fuels and lubricants |
EP4219667A3 (en) * | 2011-12-12 | 2023-08-16 | Basf Se | Use of quaternised alkylamine as additives in fuels and lubricants |
Also Published As
Publication number | Publication date |
---|---|
AU5247386A (en) | 1986-07-24 |
DE3501775A1 (en) | 1986-07-24 |
CA1259011A (en) | 1989-09-05 |
BR8600200A (en) | 1986-09-30 |
US4678605A (en) | 1987-07-07 |
ATE56698T1 (en) | 1990-10-15 |
DE3674216D1 (en) | 1990-10-25 |
ZA86412B (en) | 1986-09-24 |
JPS61192330A (en) | 1986-08-26 |
EP0189085A3 (en) | 1987-02-25 |
EP0189085B1 (en) | 1990-09-19 |
AU579443B2 (en) | 1988-11-24 |
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