EP1323817B1 - Cationic composition for hard surface cleaning - Google Patents

Cationic composition for hard surface cleaning Download PDF

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Publication number
EP1323817B1
EP1323817B1 EP01130813A EP01130813A EP1323817B1 EP 1323817 B1 EP1323817 B1 EP 1323817B1 EP 01130813 A EP01130813 A EP 01130813A EP 01130813 A EP01130813 A EP 01130813A EP 1323817 B1 EP1323817 B1 EP 1323817B1
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Prior art keywords
preparations
carbon atoms
alkyl
acid
esterquats
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German (de)
French (fr)
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EP1323817A1 (en
Inventor
Gilabert Bonastre Nuria
Agustin Sanchez
Rafael Pi Subirana
Joaquim Dr. Llosas Bigorra
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Cognis IP Management GmbH
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Cognis IP Management GmbH
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Priority to EP01130813A priority Critical patent/EP1323817B1/en
Priority to ES01130813T priority patent/ES2258506T3/en
Priority to DE50109370T priority patent/DE50109370D1/en
Priority to AT01130813T priority patent/ATE321834T1/en
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/24—Cleaning or pickling metallic material with solutions or molten salts with neutral solutions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/38—Cationic compounds
    • C11D1/62—Quaternary ammonium compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/10—Objects to be cleaned
    • C11D2111/14—Hard surfaces
    • C11D2111/16—Metals

Definitions

  • the invention is in the field of detergents and relates to novel preparations in particular for the (spray) cleaning of sheets, body parts and vehicles containing special esterquats and the use of these cationic surfactants for cleaning hard surfaces.
  • An important step in the manufacture of motor vehicles is to clean the greased sheets or bodies towards the end of the manufacturing process.
  • the components are either drawn by immersion baths, more often, however, the cleaning is carried out under high pressure with specially developed surfactant compositions.
  • the preparations have a sufficient cleaning performance and, above all, have to quickly and thoroughly remove grease, there is a requirement for complete freedom from foaming in the case of spray cleaning in particular. Since the process is carried out under high pressure, the spray nozzles can lead to static charging of the sheets and body parts, which should definitely be prevented. This requirement must also be taken into account by industrial cleaning agents.
  • DMDSAC with an active substance content of 80 wt .-% is present as a cut-resistant paste and therefore can be processed only with some technical effort.
  • the invention relates to novel cationic preparations for cleaning hard surfaces, which are characterized in that they contain as cationic surfactants Esterquats whose acyl radical or acyl radicals of unsaturated fatty acids having 8 to 22 and preferably 16 to 22 carbon atoms and iodine numbers in the range in 100 to Derive 150. Another advantage of the new ester quats is that they are still transparent and liquid in very high concentrations and therefore easy to handle.
  • the quaternized fatty acid triethanolamine ester salts follow the formula (I), in the R 1 CO for an unsaturated acyl radical having 8 to 22, preferably 16 to 22 carbon atoms and an iodine value of 50 to 200, R 2 and R 3 are independently hydrogen or R 1 CO, R 4 is an alkyl radical having 1 to 4 Carbon atoms or a (CH 2 CH 2 O) q H group, m, n and p in total are 0 or numbers from 1 to 12, q is numbers from 1 to 12 and X is halide, alkyl sulfate or alkyl phosphate.
  • esterquats which can be used according to the invention are products based on unsaturated C 16 -C 22 -fatty acids with iodine numbers in the range from 100 to 150, such as palmitoleic acid, petroselinic acid, linoleic acid, linolenic acid, gadoleic acid and technical mixtures thereof, as they occur, for example, in the pressure splitting of natural fats and oils.
  • Technical C 16 / 18- sunflower or oilseed rape, in particular fatty acids are used, which substantially comprise a carbon chain length of 16 to 22 carbon atoms and shorter chain homologues in amounts less than 20, preferably less than 15 wt .-% have.
  • the fatty acids and the triethanolamine in a molar ratio of 1.1: 1 to 3: 1 can be used.
  • an employment ratio of 1.2: 1 to 2.2: 1, preferably 1.5: 1 to 1.9: 1 has proven to be particularly advantageous.
  • the preferred esterquats are technical mixtures of mono-, di- and triesters with an average degree of esterification of 1.5 to 1.9.
  • quaternized fatty acid triethanolamine ester salts of the formula (I) have proven to be particularly advantageous in which R 1 CO for the unsaturated acyl radical of rapeseed fatty acid, R 2 is R 1 CO, R 3 is hydrogen, R 4 is a methyl group, m, n and p is 0 and X is methyl sulfate.
  • suitable esterquats are, in addition, quaternized ester salts of fatty acids with diethanolalkylamines of the formula (II) , in the R 1 CO for an unsaturated acyl radical having 8 to 22, preferably 16 to 22 carbon atoms and an iodine value of 100 to 150, R 2 is hydrogen or R 1 CO, R 4 and R 5 are independently alkyl radicals having 1 to 4 carbon atoms or a (CH 2 CH 2 O) q H group, m, n and p in total are 0 or numbers from 1 to 12, q is numbers from 1 to 12 and X is halide, alkyl sulfate or alkyl phosphate.
  • R 1 CO for an unsaturated acyl radical having 8 to 22, preferably 16 to 22 carbon atoms and an iodine value of 100 to 150
  • R 2 is hydrogen or R 1 CO
  • R 4 and R 5 are independently alkyl radicals having 1 to 4 carbon atoms or a (CH 2 CH 2
  • R 1 CO for an unsaturated acyl radical having 8 to 22, preferably 16 to 22 carbon atoms and an iodine value of 100 to 150
  • R 2 is hydrogen or R 1 is CO
  • R 4 , R 6 and R 7 are independently alkyl radicals with 1 to 4 carbon atoms or a (CH 2 CH 2 O) q H group
  • m, n and p in total are 0 or numbers from 1 to 12
  • q is numbers from 1 to 12
  • X is halide, alkyl sulfate or alkyl phosphate.
  • Both the fatty acids and the corresponding triglycerides can be used to prepare the esterquats of the formulas (I) to (IV).
  • Such a method which is to be mentioned as representative of the corresponding prior art, is proposed in the European patent EP 0750606 B1 (Cognis). It is also possible to carry out the condensation of the alkanolamines with the fatty acids in the presence of defined amounts of dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, maleic acid, fumaric acid, glutaric acid, adipic acid, sorbic acid, pimelic acid, azelaic acid, sebacic acid and / or dodecanedioic acid.
  • dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, maleic acid, fumaric acid, glutaric acid, adipic acid, sorbic acid, pimelic acid, azelaic acid, sebacic acid and / or
  • the finished preparations usually contain the esterquats, based on the compositions, in amounts of from 1 to 10, and preferably from 2 to 8,% by weight.
  • these may also contain other customary auxiliaries and additives, but especially cosurfactants, the latter being nonionic compounds because of their particular compatibility with the cationic surfactants.
  • nonionic surfactants are fatty alcohol polyglycol ethers, alkylphenol polyglycol ethers, fatty acid polyglycol esters, fatty acid amide polyglycol ethers, fatty amine polyglycol ethers, alkoxylated triglycerides, mixed ethers, alk (en) yloligoglycosides, fatty acid N-alkylglucamides, Protein hydrolysates (especially wheat based vegetable products), polyol fatty acid esters, sugar esters, sorbitan esters, polysorbates and amine oxides. If the nonionic surfactants contain polyglycol ether chains, these may have a conventional, but preferably a narrow homolog distribution. Preference is given to using fatty alcohol polyglycol ethers, alkoxylated fatty acid lower alkyl esters or alkyl oligoglucosides.
  • the preferred fatty alcohol polyglycol ethers follow the formula (V), R 8 O (CH 2 CHR 9 O) n 1 H (V) in which R 8 is a linear or branched alkyl and / or alkenyl radical having 6 to 22, preferably 12 to 18 carbon atoms, R 9 is hydrogen or methyl and n 1 is a number from 1 to 20.
  • Typical examples are the addition products of on average 1 to 20 and preferably 5 to 10 moles of ethylene and / or propylene oxide to caproic alcohol, caprylic alcohol, 2-ethylhexyl alcohol, capric alcohol, lauryl alcohol, isotridecyl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol , Petroselinylalkohol, Linolylalkohol, Linolenylalkohol, Elaeostearylalkohol, Arachylalkohol, Gadoleylalkohol, Behenylalkohol, Erucylalkohol and Brassidylalkohol as well as their technical mixtures. Particularly preferred are addition products of 3, 5 or 7 moles of ethylene oxide to technical Kokosfettalkohole.
  • Suitable alkoxylated fatty acid lower alkyl esters are surfactants of the formula ( VI ), R 10 CO (OCH 2 CHR 11) n 2 OR 12 (VI) in the R 10 CO for a linear or branched, saturated and / or unsaturated acyl radical having 6 to 22 carbon atoms, R 11 for hydrogen or methyl, R 12 for linear or branched alkyl radicals having 1 to 4 carbon atoms and n 2 for numbers from 1 to 20
  • Typical examples are the formal charge products of an average of 1 to 20 and preferably 5 to 10 moles of ethylene and / or propylene oxide in the methyl, ethyl, propyl, isopropyl, butyl and tert-butyl esters of caproic acid, caprylic acid, 2-ethylhexanoic acid, capric acid, lauric acid, isotridecanoic acid, myristic acid, palmitic acid, palmitoleic acid, stearic acid,
  • Alkyl and alkenyl oligoglycosides which are also preferred nonionic surfactants, usually follow the formula ( VII ), R 13 O- [G] p (VII) in which R 13 is an alkyl and / or alkenyl radical having 4 to 22 carbon atoms, G is a sugar radical having 5 or 6 carbon atoms and p is a number from 1 to 10. They can be obtained by the relevant methods of preparative organic chemistry. Representative of the extensive literature reference is made here to the documents EP 0301298 A1 and WO 90/03977 .
  • the alkyl and / or alkenyl oligoglycosides can be derived from aldoses or ketoses having 5 or 6 carbon atoms, preferably glucose.
  • the preferred alkyl and / or Alkenyloligoglykoside are thus alkyl and / or Alkenyloligo glucoside .
  • alkyl and / or alkenyl oligoglycosides having an average degree of oligomerization p of from 1.1 to 3.0. From an application point of view, those alkyl and / or alkenyl oligoglycosides whose degree of oligomerization is less than 1.7 and in particular between 1.2 and 1.4 are preferred.
  • the alkyl or alkenyl radical R 13 can be derived from primary alcohols having 4 to 11, preferably 8 to 10 carbon atoms.
  • Typical examples are butanol, caproic alcohol, caprylic alcohol, capric alcohol and undecyl alcohol and technical mixtures thereof, as obtained, for example, in the hydrogenation of technical fatty acid methyl esters or in the hydrogenation of aldehydes from Roelen's oxo synthesis.
  • compositions have a surfactant content of 30 to 50, preferably 35 to 45 and a water content of 50 to 70, preferably 55 to 65 wt .-%.
  • the new ester quats are also highly concentrated liquid and transparent. They have excellent cleaning performance, high hydrophobicity and excellent antistatic properties. If the biodegradability of an inventive ben Dicolzaoylmethylethoxymonium Methosulfates according to storm test to 100%, then DSDMAC achieved under the same conditions, a value of 62%.
  • Another object of the invention therefore relates to the use of esterquats whose acyl radical or acyl radicals are derived from unsaturated fatty acids having 8 to 22, preferably 16 to 22 carbon atoms and iodine numbers in the range of 100 to 150, for the preparation of preparations for the cleaning of hard surfaces in which they may be present in amounts of 1 to 30, preferably 5 to 25 and in particular 10 to 15 wt .-% - based on the means.
  • Table 1 gives formulation examples: ⁇ b> ⁇ u> Table 1 ⁇ / u> Formulation examples for the final cleaning of body parts ⁇ / b> composition
  • Example 1 Ex. 2 Esterquat 1) 7.5 11.0 Kokosimidazolin - 2.0 Coconut fatty acid 2-ethylhexyl 7 12.0 Octanol + 4EO - 3.0 butyglycol 10 20.0 water ad 100 1) Dicolzaoylmethylethoxymonium Methosulfate

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Abstract

Cationic preparations for cleaning hard surfaces contain, as cationic surfactants, ester-quats (I) in which the acyl group(s) is/are derived from 8-22C fatty acids and have an iodine index of at least 50. An Independent claim is also included for the use of (I) for the production of preparations for cleaning hard surfaces.

Description

Gebiet der ErfindungField of the invention

Die Erfindung befindet sich auf dem Gebiet der Reinigungsmittel und betrifft neuartige Zubereitungen insbesondere für die (Spritz-)Reinigung von Blechen, Karosserieteilen und Fahrzeugen mit einem Gehalt an speziellen Esterquats sowie die Verwendung dieser Kationtenside zur Reinigung harter Oberflächen.The invention is in the field of detergents and relates to novel preparations in particular for the (spray) cleaning of sheets, body parts and vehicles containing special esterquats and the use of these cationic surfactants for cleaning hard surfaces.

Stand der TechnikState of the art

Ein wichtiger Schritt bei der Herstellung von Kraftfahrzeugen besteht darin, die gefetteten Bleche bzw. Karosserien gegen Ende des Fertigungsprozesses zu reinigen. Hierzu werden die Bauteile entweder durch Tauchbäder gezogen, häufiger erfolgt jedoch die Reinigung unter Hochdruck mit speziell dafür entwickelten Tensidzusammensetzungen. Abgesehen davon, dass die Zubereitungen über eine hinreichende Reinigungsleistung verfügen und vor allem Fett rasch und gründlich ablösen müssen, besteht gerade bei der Spritzreinigung die Anforderung vollständiger Schaumfreiheit. Da der Prozess unter Hochdruck erfolgt, kann es über die Spritzdüsen zu einer statischen Aufladung der Bleche und Karosserieteile kommen, die auf jeden Fall verhindert werden soll. Auch dieser Anforderung müssen die industriellen Reinigungsmittel Rechnung tragen. Ähnlichen Problemen begegnet man jedoch auch im Rahmen der individuellen Fahrzeugreinigung, sowohl in automatischen Waschstraßen als auch bei einer Reihe von Reinigungsketten, die dem Verbraucher anbieten, sein Fahrzeug selbst mit einem Hochdruckwasserstrahl zu reinigen und dabei ähnliche Tensidzusammensetzungen einsetzen, wie sie auch bei der Entfettung der Karosserien Verwendung finden.An important step in the manufacture of motor vehicles is to clean the greased sheets or bodies towards the end of the manufacturing process. For this purpose, the components are either drawn by immersion baths, more often, however, the cleaning is carried out under high pressure with specially developed surfactant compositions. Apart from the fact that the preparations have a sufficient cleaning performance and, above all, have to quickly and thoroughly remove grease, there is a requirement for complete freedom from foaming in the case of spray cleaning in particular. Since the process is carried out under high pressure, the spray nozzles can lead to static charging of the sheets and body parts, which should definitely be prevented. This requirement must also be taken into account by industrial cleaning agents. However, similar problems are also encountered in the context of individual vehicle cleaning, both in automatic car washes and in a number of cleaning chains that offer the consumer to clean his own vehicle with a high pressure water jet and use similar surfactant compositions, as in the degreasing of Find body use.

Eine besondere Bedeutung besitzen hier kationische Tenside, da diese nicht nur eine hohe Reinigungskraft - speziell in Kombination mit nichtionischen Tensiden - besitzen, sondern Karosserien und Fahrzeuge auch hydrophobieren und damit schützen. Gleichzeitig wirken sie antistatisch, d.h. auch bei der Spritzreinigung unter Hochdruck wird einer statischen Aufladung der Metallteile entgegengewirkt. In der Praxis haben sich bislang Tetraalkylammoniumsalze vom Typ des Dimethyldistearylammoniumchlorids (DMDSAC) als besonders wirksam erwiesen, während Kationtenside vom konventionellen Esterquattyp, die das DMDSAC ansonsten in vielen Anwendungen verdrängt haben, hier bislang wirkungslos waren. Von Nachteil ist jedoch, dass die Tetraalkylammoniumsalze des Handels über keine hinreichende biologische Abbaubarkeit verfügen, was deren Einsatz nach Detergentiengesetz in manchen Ländern Europas erschwert. Weiterhin von Nachteil ist, dass beispielsweise DMDSAC bei einem Aktivsubstanzgehalt von 80 Gew.-% als schnittfeste Paste vorliegt und daher nur mit einigem technischen Aufwand verarbeitet werden kann.Of particular importance here are cationic surfactants, since they not only have a high cleaning power - especially in combination with nonionic surfactants - but also hydrophobize bodies and vehicles and thus protect them. At the same time, they have an antistatic effect, that is to say even during spray cleaning under high pressure a static charge of the metal parts is counteracted. Tetraalkylammonium salts of the dimethyldistearylammonium chloride (DMDSAC) type have been found to be particularly effective in practice, whereas conventional esterquatype cationic surfactants, which have otherwise displaced the DMDSAC in many applications, have heretofore been ineffective. However, it is disadvantageous that the tetraalkylammonium salts of commerce have no adequate biodegradability, which complicates their use according to detergent law in some European countries. Another disadvantage is that, for example, DMDSAC with an active substance content of 80 wt .-% is present as a cut-resistant paste and therefore can be processed only with some technical effort.

Somit hat die Aufgabe der vorliegenden Erfindung darin bestanden, neue Zubereitungen fürdie Reinigung harter Oberfläche, speziell für die Spritzreinigung von Blechen und die Hochdruckreinigung von Fahrzeugen zur Verfügung zu stellen, die zwar kationische Tenside enthalten, sich jedoch durch eine bessere biologische Abbaubarkeit auszeichnen und dabei gleichzeitig hinsichtlich Hydrophobierung und antistatischer Ausrüstung wenigstens das Niveau des Stands der Technik erreichen.Thus, the object of the present invention has been to provide new compositions for hard surface cleaning, especially for spray cleaning sheet and high pressure cleaning of vehicles, which contain cationic surfactants, but are characterized by better biodegradability and at the same time in terms of hydrophobing and antistatic finish, at least the level of the prior art.

Beschreibung der ErfindungDescription of the invention

Gegenstand der Erfindung sind neue kationische Zubereitungen zur Reinigung harter Oberflächen, die sich dadurch auszeichnen, dass sie als Kationtenside Esterquats enthalten, deren Acylrest bzw. Acylreste sich von ungesättigten Fettsäuren mit 8 bis 22 und vorzugsweise 16 bis 22 Kohlenstoffatomen und Iodzahlen im Bereich im 100 bis 150 ableiten. Ein weiterer Vorteil der neuen Esterquats besteht darin, dass sie auch noch in sehr hohen Konzentrationen transparent und flüssig und daher leicht zu handhaben sind.The invention relates to novel cationic preparations for cleaning hard surfaces, which are characterized in that they contain as cationic surfactants Esterquats whose acyl radical or acyl radicals of unsaturated fatty acids having 8 to 22 and preferably 16 to 22 carbon atoms and iodine numbers in the range in 100 to Derive 150. Another advantage of the new ester quats is that they are still transparent and liquid in very high concentrations and therefore easy to handle.

Überraschenderweise wurde gefunden, dass durch genaue Auswahl der Fettsäuren spezielle Esterquats erhältlich sind, die gegenüber den Tetraalkylammoniumsalzen des Stands der Technik nicht nur über eine deutlich verbesserte biologische Abbaubarkeit verfügen, sondern die behandelten Oberflächen auch über einen längeren Zeitraum hydrophobieren und für eine geringere statische Aufladung sorgen. Dieser Befund ist um so unerwarteter, als konventionelle Esterquats auf Basis von Talg- oder Kokosfettsäure in der Anwendung völlig ungeeignet sind.Surprisingly, it has been found that by precise selection of the fatty acids special esterquats are available which not only have a significantly improved biodegradability compared with the tetraalkylammonium salts of the prior art, but also hydrophobicize the treated surfaces over a relatively long period of time and provide less static charge , This finding is all the more unexpected, as conventional esterquats based on tallow or coconut fatty acid in the application are completely unsuitable.

Esterquatsesterquats

Unter der Bezeichnung "Esterquats" werden im allgemeinen quaternierte Fettsäuretriethanolaminestersalze verstanden. Es handelt sich dabei um bekannte Stoffe, die man nach den einschlägigen Methoden der präparativen organischen Chemie erhalten kann. In diesem Zusammenhang sei auf die Internationale Patentanmeldung WO 91/01295 (Henkel) verwiesen, nach der man Triethanolamin in Gegenwart von unterphosphoriger Säure mit Fettsäuren partiell verestert, Luft durchleitet und anschließend mit Dimethylsulfat oder Ethylenoxid quaterniert. Aus der Deutschen Patentschrift DE 4308794 C1 (Henkel) ist überdies ein Verfahren zur Herstellung fester Esterquats bekannt, bei dem man die Quaternierung von Triethanolaminestern in Gegenwart. von geeigneten Dispergatoren, vorzugsweise Fettalkoholen, durchführt. Übersichten zu diesem Thema sind beispielsweise von R.Puchta et al. in Tens.Surf.Det, 30, 186 (1993), M.Brock in Tens.Surf.Det 30, 394 (1993), R.Lagerman et al. in J.Am. Oil.Chem.Soc., 71 , 97 (1994) sowie I.Shapiro in Cosm.Toil. 109, 77 (1994) erschienen.The term "esterquats" is generally understood to mean quaternized fatty acid triethanolamine ester salts. These are known substances that can be obtained by the relevant methods of preparative organic chemistry. In this context, reference is made to International Patent Application WO 91/01295 (Henkel), according to which triethanolamine in the presence of hypophosphorous acid with fatty acids partially esterified, passing air and then quaternized with dimethyl sulfate or ethylene oxide. German Patent DE 4308794 C1 (Henkel) moreover discloses a process for the preparation of solid ester quats , in which the quaternization of triethanolamine esters in the presence. of suitable dispersants, preferably fatty alcohols. Reviews on this topic are, for example, by R. Puchta et al. in Tens.Surf.Det, 30, 186 (1993), M.Brock in Tens.Surf.Det 30, 394 (1993), R. Lagerman et al. in J. Am. Oil.Chem.Soc., 71 , 97 (1994) and I.Shapiro in Cosm.Toil. 109, 77 (1994) .

Die quaternierten Fettsäuretriethanolaminestersalze folgen der Formel (I),

Figure imgb0001
in der R1CO für einen ungesättigten Acylrest mit 8 bis 22, vorzugsweise 16 bis 22 Kohlenstoffatomen und einer Iodzahl von 50 bis 200, R2 und R3 unabhängig voneinander für Wasserstoff oder R1CO, R4 für einen Alkylrest mit 1 bis 4 Kohlenstoffatomen oder eine (CH2CH2O)qH-Gruppe, m, n und p in Summe für 0 oder Zahlen von 1 bis 12, q für Zahlen von 1 bis 12 und X für Halogenid, Alkylsulfat oder Alkylphosphat steht. Typische Beispiele für Esterquats, die im Sinne der Erfindung Verwendung finden können, sind Produkte auf Basis von ungesättigten C16-C22-Fettsäuren mit Iodzahlen im Bereich von 100 bis 150 wie Palmoleinsäure, Petroselinsäure, Linolsäure, Linolensäure, Gadoleinsäure sowie deren technische Mischungen, wie sie beispielsweise bei der Druckspaltung natürlicher Fette und Öle anfallen. Vorzugsweise werden technische C16/18-Sonnenblumen- oder insbesondere Rapsfettsäuren eingesetzt, die im wesentlichen eine C-Kettenlänge von 16 bis 22 Kohlenstoffatomen aufweisen und kürzerkettige Homologe in Mengen kleiner 20, vorzugsweise kleiner 15 Gew.-% aufweisen. Zur Herstellung der quaternierten Ester können die Fettsäuren und das Triethanolamin im molaren Verhältnis von 1,1 : 1 bis 3 : 1 eingesetzt werden. Im Hinblick auf die anwendungstechnischen Eigenschaften der Esterquats hat sich ein Einsatzverhältnis von 1,2 : 1 bis 2,2 : 1, vorzugsweise 1,5 : 1 bis 1,9 : 1 als besonders vorteilhaft erwiesen. Die bevorzugten Esterquats stellen technische Mischungen von Mono-, Di- und Triestern mit einem durchschnittlichen Veresterungsgrad von 1,5 bis 1,9 dar. Aus anwendungstechnischer Sicht haben sich quaternierte Fettsäuretriethanolaminestersalze der Formel (I) als besonders vorteilhaft erwiesen, in der R1CO für den ungesättigten Acylrest der Rapsfettsäure, R2 für R1CO, R3 für Wasserstoff, R4 für eine Methylgruppe, m, n und p für 0 und X für Methylsulfat steht.The quaternized fatty acid triethanolamine ester salts follow the formula (I),
Figure imgb0001
 in the R 1 CO for an unsaturated acyl radical having 8 to 22, preferably 16 to 22 carbon atoms and an iodine value of 50 to 200, R 2 and R 3 are independently hydrogen or R 1 CO, R 4 is an alkyl radical having 1 to 4 Carbon atoms or a (CH 2 CH 2 O) q H group, m, n and p in total are 0 or numbers from 1 to 12, q is numbers from 1 to 12 and X is halide, alkyl sulfate or alkyl phosphate. Typical examples of esterquats which can be used according to the invention are products based on unsaturated C 16 -C 22 -fatty acids with iodine numbers in the range from 100 to 150, such as palmitoleic acid, petroselinic acid, linoleic acid, linolenic acid, gadoleic acid and technical mixtures thereof, as they occur, for example, in the pressure splitting of natural fats and oils. Technical C 16 / 18- sunflower or oilseed rape, in particular fatty acids are used, which substantially comprise a carbon chain length of 16 to 22 carbon atoms and shorter chain homologues in amounts less than 20, preferably less than 15 wt .-% have. To prepare the quaternized esters, the fatty acids and the triethanolamine in a molar ratio of 1.1: 1 to 3: 1 can be used. In view of the performance properties of the esterquats, an employment ratio of 1.2: 1 to 2.2: 1, preferably 1.5: 1 to 1.9: 1 has proven to be particularly advantageous. The preferred esterquats are technical mixtures of mono-, di- and triesters with an average degree of esterification of 1.5 to 1.9. From an application point of view, quaternized fatty acid triethanolamine ester salts of the formula (I) have proven to be particularly advantageous in which R 1 CO for the unsaturated acyl radical of rapeseed fatty acid, R 2 is R 1 CO, R 3 is hydrogen, R 4 is a methyl group, m, n and p is 0 and X is methyl sulfate.

Neben den quaternierten Fettsäuretriethanolaminestersalzen kommen als Esterquats ferner auch quaternierte Estersalze von Fettsäuren mit Diethanolalkylaminen der Formel (II) in Betracht,

Figure imgb0002
in der R1CO für einen ungesättigten Acylrest mit 8 bis 22, vorzugsweise 16 bis 22 Kohlenstoffatomen und einer Iodzahl von 100 bis 150, R2 für Wasserstoff oder R1CO, R4 und R5 unabhängig voneinander für Alkylreste mit 1 bis 4 Kohlenstoffatomen oder eine (CH2CH2O)qH-Gruppe, m, n und p in Summe für 0 oder Zahlen von 1 bis 12, q für Zahlen von 1 bis 12 und X für Halogenid, Alkylsulfat oder Alkylphosphat steht.In addition to the quaternized fatty acid triethanolamine ester salts, suitable esterquats are, in addition, quaternized ester salts of fatty acids with diethanolalkylamines of the formula (II) ,
Figure imgb0002
 in the R 1 CO for an unsaturated acyl radical having 8 to 22, preferably 16 to 22 carbon atoms and an iodine value of 100 to 150, R 2 is hydrogen or R 1 CO, R 4 and R 5 are independently alkyl radicals having 1 to 4 carbon atoms or a (CH 2 CH 2 O) q H group, m, n and p in total are 0 or numbers from 1 to 12, q is numbers from 1 to 12 and X is halide, alkyl sulfate or alkyl phosphate.

Als weitere Gruppe geeigneter Esterquats sind schließlich die quaternierten Estersalze von Fettsäuren mit 1,2-Dihydroxypropyldialkylaminen der Formel (III) zu nennen,

Figure imgb0003
in der R1CO für einen ungesättigten Acylrest mit 8 bis 22, vorzugsweise 16 bis 22 Kohlenstoffatomen und einer Iodzahl von 100 bis 150, R2 für Wasserstoff oder R1CO, R4, R6 und R7 unabhängig voneinander für Alkylreste mit 1 bis 4 Kohlenstoffatomen oder eine (CH2CH2O)qH-Gruppe, m, n und p in Summe für 0 oder Zahlen von 1 bis 12, q für Zahlen von 1 bis 12 und X für Halogenid, Alkylsulfat oder Alkylphosphat steht.Finally, the quaternized ester salts of fatty acids with 1,2-dihydroxypropyldialkylamines of the formula ( III ) should be mentioned as a further group of suitable esterquats.
Figure imgb0003
 in the R 1 CO for an unsaturated acyl radical having 8 to 22, preferably 16 to 22 carbon atoms and an iodine value of 100 to 150, R 2 is hydrogen or R 1 is CO, R 4 , R 6 and R 7 are independently alkyl radicals with 1 to 4 carbon atoms or a (CH 2 CH 2 O) q H group, m, n and p in total are 0 or numbers from 1 to 12, q is numbers from 1 to 12 and X is halide, alkyl sulfate or alkyl phosphate.

Des weiteren kommen als Esterquats noch Stoffe in Frage, bei denen die Ester- durch eine Amidbindung ersetzt ist und die vorzugsweise basierend auf Diethylentriamin der Formel (IV) folgen,

Figure imgb0004
in der R1CO für einen ungesättigten Acylrest mit 8 bis 22, vorzugsweise 16 bis 22 Kohlenstoffatomen und einer Iodzahl von 100 bis 150, R2 für Wasserstoff oder R1CO, R6 und R7 unabhängig voneinander für Alkylreste mit 1 bis 4 Kohlenstoffatomen oder eine (CH2CH2O)qH-Gruppe, q für Zahlen von 1 bis 12 und X für Halogenid, Alkylsulfat oder Alkylphosphat steht.In addition, other suitable esterquats are substances in which the ester is replaced by an amide bond and which preferably follow the formula ( IV ) based on diethylenetriamine,
Figure imgb0004
 in the R 1 CO for an unsaturated acyl radical having 8 to 22, preferably 16 to 22 carbon atoms and an iodine value of 100 to 150, R 2 is hydrogen or R 1 CO, R 6 and R 7 are independently alkyl radicals having 1 to 4 carbon atoms or a (CH 2 CH 2 O) q H group, q is a number of 1 to 12 and X is halide, alkyl sulfate or alkyl phosphate.

Hinsichtlich der Auswahl der bevorzugten Fettsäuren und des optimalen Veresterungsgrades gelten die für (I) genannten Beispiele auch für die Esterquats der Formeln (II) bis (IV). With regard to the selection of the preferred fatty acids and the optimal degree of esterification, the examples given for (I) also apply to the esterquats of the formulas (II) to (IV).

Zur Herstellung der Esterquats der Formeln (I) bis (IV) kann sowohl von Fettsäuren als auch den entsprechenden Triglyceriden ausgegangen werden. Ein solches Verfahren, das stellvertretend für den entsprechenden Stand der Technik genannt werden soll, wird in der europäischen Patentschrift EP 0750606 B1 (Cognis) vorgeschlagen. Ebenfalls ist es möglich, die Kondensation der Alkanolamine mit den Fettsäuren in Gegenwart definierter Mengen an Dicarbonsäuren, wie z.B. Oxalsäure, Malonsäure, Bernsteinsäure, Maleinsäure, Fumarsäure, Glutarsäure, Adipinsäure, Sorbinsäure, Pimelinsäure, Azelainsäure, Sebacinsäure und/oder Dodecandisäure durchzuführen. Auf diese Weise kommt es zur einer partiell oligomeren Struktur der Esterquats, was sich insbesondere bei Mitverwendung von Adipinsäure auf die Klarlöslichkeit der Produkte vorteilhaft auswirken kann. Üblicherweise gelangen die Esterquats in Form 80 bis 90 Gew.-%iger alkoholischer Lösungen in den Handel, die bei Bedarf problemlos mit Wasser verdünnt werden können.Both the fatty acids and the corresponding triglycerides can be used to prepare the esterquats of the formulas (I) to (IV). Such a method, which is to be mentioned as representative of the corresponding prior art, is proposed in the European patent EP 0750606 B1 (Cognis). It is also possible to carry out the condensation of the alkanolamines with the fatty acids in the presence of defined amounts of dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, maleic acid, fumaric acid, glutaric acid, adipic acid, sorbic acid, pimelic acid, azelaic acid, sebacic acid and / or dodecanedioic acid. In this way, a partially oligomeric structure of the esterquats occurs, which may have an advantageous effect on the clear solubility of the products, especially when adipic acid is used. Usually, the esterquats are marketed in the form of 80 to 90% by weight alcoholic solutions, which can easily be diluted with water if required.

Oberflächenaktive ZubereitungenSurface-active preparations

Üblicherweise enthalten die fertigen Zubereitungen die Esterquats - bezogen auf die Mittel - in Mengen von 1 bis 10 und vorzugsweise 2 bis 8 Gew.-%. Daneben können diese auch weitere übliche Hilfs- und Zusatzstoffe, speziell aber Cotenside enthalten, wobei es sich bei letzteren wegen ihrer besonderen Kompatibilität mit den Kationtensiden um nichtionische Verbindungen handelt.The finished preparations usually contain the esterquats, based on the compositions, in amounts of from 1 to 10, and preferably from 2 to 8,% by weight. In addition, these may also contain other customary auxiliaries and additives, but especially cosurfactants, the latter being nonionic compounds because of their particular compatibility with the cationic surfactants.

Typische Beispiele für nichtionische Tenside sind Fettalkoholpolyglycolether, Alkylphenolpolyglycolether, Fettsäurepolyglycolester, Fettsäureamidpolyglycolether, Fettaminpolyglycolether, alkoxylierte Triglyceride, Mischether bzw. Mischformale, Alk(en)yloligoglykoside, Fettsäure-N-alkylglucamide, Proteinhydrolysate (insbesondere pflanzliche Produkte auf Weizenbasis), Polyolfettsäureester, Zuckerester, Sorbitanester, Polysorbate und Aminoxide. Sofern die nichtionischen Tenside Polyglycoletherketten enthalten, können diese eine konventionelle, vorzugsweise jedoch eine eingeengte Homologenverteilung aufweisen. Vorzugsweise werden Fettalkoholpolyglycolether, alkoxylierte Fettsäureniedrigalkylester oder Alkyloligoglucoside eingesetzt.Typical examples of nonionic surfactants are fatty alcohol polyglycol ethers, alkylphenol polyglycol ethers, fatty acid polyglycol esters, fatty acid amide polyglycol ethers, fatty amine polyglycol ethers, alkoxylated triglycerides, mixed ethers, alk (en) yloligoglycosides, fatty acid N-alkylglucamides, Protein hydrolysates (especially wheat based vegetable products), polyol fatty acid esters, sugar esters, sorbitan esters, polysorbates and amine oxides. If the nonionic surfactants contain polyglycol ether chains, these may have a conventional, but preferably a narrow homolog distribution. Preference is given to using fatty alcohol polyglycol ethers, alkoxylated fatty acid lower alkyl esters or alkyl oligoglucosides.

Die bevorzugten Fettalkoholpolyglycolether folgen der Formel (V),

        R 8 O(CH 2 CHR 9 O) n1 H     (V)

in der R8 für einen linearen oder verzweigten Alkyl- und/oder Alkenylrest mit 6 bis 22, vorzugsweise 12 bis 18 Kohlenstoffatomen, R9 für Wasserstoff oder Methyl und n1 für Zahlen von 1 bis 20 steht. Typische Beispiele sind die Anlagerungsprodukte von durchschnittlich 1 bis 20 und vorzugsweise 5 bis 10 Mol Ethylen- und/oder Propylenoxid an Capronalkohol, Caprylalkohol, 2-Ethylhexylalkohol, Caprinalkohol, Laurylalkohol, Isotridecylalkohol, Myristylalkohol, Cetylalkohol, Palmoleylalkohol, Stearylalkohol, Isostearylalkohol, Oleylalkohol, Elaidylalkohol, Petroselinylalkohol, Linolylalkohol, Linolenylalkohol, Elaeostearylalkohol, Arachylalkohol, Gadoleylalkohol, Behenylalkohol, Erucylalkohol und Brassidylalkohol sowie deren technische Mischungen. Besonders bevorzugt sind Anlagerungsprodukte von 3, 5 oder 7 Mol Ethylenoxid an technische Kokosfettalkohole.The preferred fatty alcohol polyglycol ethers follow the formula (V),

R 8 O (CH 2 CHR 9 O) n 1 H (V)

in which R 8 is a linear or branched alkyl and / or alkenyl radical having 6 to 22, preferably 12 to 18 carbon atoms, R 9 is hydrogen or methyl and n 1 is a number from 1 to 20. Typical examples are the addition products of on average 1 to 20 and preferably 5 to 10 moles of ethylene and / or propylene oxide to caproic alcohol, caprylic alcohol, 2-ethylhexyl alcohol, capric alcohol, lauryl alcohol, isotridecyl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol , Petroselinylalkohol, Linolylalkohol, Linolenylalkohol, Elaeostearylalkohol, Arachylalkohol, Gadoleylalkohol, Behenylalkohol, Erucylalkohol and Brassidylalkohol as well as their technical mixtures. Particularly preferred are addition products of 3, 5 or 7 moles of ethylene oxide to technical Kokosfettalkohole.

Als alkoxylierte Fettsäureniedrigalkylester kommen Tenside der Formel (VI) in Betracht,

        R 10 CO-(OCH 2 CHR 11 ) n2 OR 12      (VI)

in der R10CO für einen linearen oder verzweigten, gesättigten und/oder ungesättigten Acylrest mit 6 bis 22 Kohlenstoffatomen, R11 für Wasserstoff oder Methyl, R12 für lineare oder verzweigte Alkylreste mit 1 bis 4 Kohlenstoffatomen und n2 für Zahlen von 1 bis 20 steht Typische Beispiele sind die formalen Einschubprodukte von durchschnittlich 1 bis 20 und vorzugsweise 5 bis 10 Mol Ethylen- und/oder Propylenoxid in die Methyl-, Ethyl-, Propyl-, Isopropyl-, Butyl- und tert.-Butylester von Capronsäure, Caprylsäure, 2-Ethylhexansäure, Caprinsäure, Laurinsäure, Isotridecansäure, Myristinsäure, Palmitinsäure, Palmoleinsäure, Stearinsäure, Isostearinsäure, Ölsäure, Elaidinsäure, Petroselinsäure, Linolsäure, Linolensäure, Elaeostearinsäure, Arachinsäure, Gadoleinsäure, Behensäure und Erucasäure sowie deren technische Mischungen. Üblicherweise erfolgt die Herstellung der Produkte durch Insertion der Alkylenoxide in die Carbonylesterbindung in Gegenwart spezieller Katalysatoren, wie z.B. calcinierter Hydrotalcit. Besonders bevorzugt sind Umsetzungsprodukte von durchschnittlich 5 bis 10 Mol Ethylenoxid in die Esterbindung von technischen Kokosfettsäuremethylestern.Suitable alkoxylated fatty acid lower alkyl esters are surfactants of the formula ( VI ),

R 10 CO (OCH 2 CHR 11) n 2 OR 12 (VI)

in the R 10 CO for a linear or branched, saturated and / or unsaturated acyl radical having 6 to 22 carbon atoms, R 11 for hydrogen or methyl, R 12 for linear or branched alkyl radicals having 1 to 4 carbon atoms and n 2 for numbers from 1 to 20 Typical examples are the formal charge products of an average of 1 to 20 and preferably 5 to 10 moles of ethylene and / or propylene oxide in the methyl, ethyl, propyl, isopropyl, butyl and tert-butyl esters of caproic acid, caprylic acid, 2-ethylhexanoic acid, capric acid, lauric acid, isotridecanoic acid, myristic acid, palmitic acid, palmitoleic acid, stearic acid, isostearic acid, oleic acid, elaidic acid, petroselinic acid, linoleic acid, linolenic acid, elaeostearic acid, arachic acid, gadoleic acid, behenic acid and erucic acid, and technical mixtures thereof. Usually, the products are prepared by insertion of the alkylene oxides into the carbonyl ester bond in the presence of special catalysts, such as, for example, calcined hydrotalcite. Particularly preferred are reaction products of average 5 to 10 moles of ethylene oxide in the ester bond of technical Kokosfettsäuremethylestern.

Alkyl- und Alkenyloligoglykoside, die ebenfalls bevorzugte nichtionische Tenside darstellen, folgen üblicherweise der Formel (VII),

        R 13 O-[G] p      (VII)

in der R13 für einen Alkyl- und/oder Alkenylrest mit 4 bis 22 Kohlenstoffatomen, G für einen Zuckerrest mit 5 oder 6 Kohlenstoffatomen und p für Zahlen von 1 bis 10 steht. Sie können nach den einschlägigen Verfahren der präparativen organischen Chemie erhalten werden. Stellvertretend für das umfangreiche Schrifttum sei hier auf die Schriften EP 0301298 A1 und WO 90/03977 verwiesen. Die Alkyl- und/oder Alkenyloligoglykoside können sich von Aldosen bzw. Ketosen mit 5 oder 6 Kohlenstoffatomen, vorzugsweise der Glucose ableiten. Die bevorzugten Alkyl- und/oder Alkenyloligoglykoside sind somit Alkyl- und/oder Alkenyloligoglucoside. Die Indexzahl p in der allgemeinen Formel (VII) gibt den Oligomerisierungsgrad (DP), d. h. die Verteilung von Mono- und Oligoglykosiden an und steht für eine Zahl zwischen 1 und 10. Während p in einer gegebenen Verbindung stets ganzzahlig sein muß und hier vor allem die Werte p = 1 bis 6 annehmen kann, ist der Wert p für ein bestimmtes Alkyloligo-glykosid eine analytisch ermittelte rechnerische Größe, die meistens eine gebrochene Zahl darstellt. Vorzugsweise werden Alkyl- und/oder Alkenyloligoglykoside mit einem mittleren Oligomerisierungsgrad p von 1,1 bis 3,0 eingesetzt. Aus anwendungstechnischer Sicht sind solche Alkyl- und/oder Alkenyloligoglykoside bevorzugt, deren Oligomerisierungsgrad kleiner als 1,7 ist und insbesondere zwischen 1,2 und 1,4 liegt. Der Alkyl- bzw. Alkenylrest R13 kann sich von primären Alkoholen mit 4 bis 11, vorzugsweise 8 bis 10 Kohlenstoffatomen ableiten. Typische Beispiele sind Butanol, Capronalkohol, Caprylalkohol, Caprinalkohol und Undecylalkohol sowie deren technische Mischungen, wie sie beispielsweise bei der Hydrierung von technischen Fettsäuremethylestern oder im Verlauf der Hydrierung von Aldehyden aus der Roelen'schen Oxosynthese erhalten werden. Bevorzugt sind Alkyloligoglucoside der Kettenlänge C8-C10 (DP = 1 bis 3), die als Vorlauf bei der destillativen Auftrennung von technischem C8-C18-Kokosfettalkohol anfallen und mit einem Anteil von weniger als 6 Gew.-% C12-Alkohol verunreinigt sein können sowie Alkyloligoglucoside auf Basis technischer C9/11-Oxoalkohole (DP = 1 bis 3). Der Alkyl- bzw. Alkenylrest R13 kann sich ferner auch von primären Alkoholen mit 12 bis 22, vorzugsweise 12 bis 14 Kohlenstoffatomen ableiten. Typische Beispiele sind Laurylalkohol, Myristylalkohol, Cetylalkohol, Palmoleylalkohol, Stearylalkohol, Isostearylalkohol, Oleylalkohol, Elaidylalkohol, Petroselinylalkohol, Arachylalkohol, Gadoleylalkohol, Behenylalkohol, Erucylalkohol, Brassidylalkohol sowie deren technische Gemische, die wie oben beschrieben erhalten werden können. Bevorzugt sind Alkyloligoglucoside auf Basis von gehärtetem C12/14-Kokosalkohol mit einem DP von 1 bis 3.Alkyl and alkenyl oligoglycosides, which are also preferred nonionic surfactants, usually follow the formula ( VII ),

R 13 O- [G] p (VII)

in which R 13 is an alkyl and / or alkenyl radical having 4 to 22 carbon atoms, G is a sugar radical having 5 or 6 carbon atoms and p is a number from 1 to 10. They can be obtained by the relevant methods of preparative organic chemistry. Representative of the extensive literature reference is made here to the documents EP 0301298 A1 and WO 90/03977 . The alkyl and / or alkenyl oligoglycosides can be derived from aldoses or ketoses having 5 or 6 carbon atoms, preferably glucose. The preferred alkyl and / or Alkenyloligoglykoside are thus alkyl and / or Alkenyloligo glucoside . The index number p in the general formula ( VII ) indicates the degree of oligomerization (DP), ie the distribution of monoglycerides and oligoglycosides, and stands for a number between 1 and 10. While p in a given compound must always be an integer, and here especially If the values p = 1 to 6 can be assumed, the value p for a given alkyloligo-glycoside is an analytically determined arithmetic variable, which usually represents a fractional number. Preference is given to using alkyl and / or alkenyl oligoglycosides having an average degree of oligomerization p of from 1.1 to 3.0. From an application point of view, those alkyl and / or alkenyl oligoglycosides whose degree of oligomerization is less than 1.7 and in particular between 1.2 and 1.4 are preferred. The alkyl or alkenyl radical R 13 can be derived from primary alcohols having 4 to 11, preferably 8 to 10 carbon atoms. Typical examples are butanol, caproic alcohol, caprylic alcohol, capric alcohol and undecyl alcohol and technical mixtures thereof, as obtained, for example, in the hydrogenation of technical fatty acid methyl esters or in the hydrogenation of aldehydes from Roelen's oxo synthesis. Preference is given to alkyl oligoglucosides of the chain length C 8 -C 10 (DP = 1 to 3) which are obtained as a feedstock in the distillative separation of technical C 8 -C 18 coconut fatty alcohol and in a proportion of less than 6% by weight C 12 - Alcohol may be contaminated as well as alkyl oligoglucosides based on technical C 9/11 oxo alcohols (DP = 1 to 3). The alkyl or alkenyl radical R 13 can furthermore also be derived from primary alcohols having 12 to 22, preferably 12 to 14, carbon atoms. Typical examples are lauryl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, arachyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol, brassidyl alcohol, and technical mixtures thereof which can be obtained as described above. Prefers are alkyl oligoglucosides based on hydrogenated C 12/14 cocoalcohol having a DP of 1 to 3.

In der Regel weisen die Mittel einen Tensidgehalt von 30 bis 50, vorzugsweise 35 bis 45 und einen Wassergehalt von 50 bis 70, vorzugsweise 55 bis 65 Gew.-% auf.In general, the compositions have a surfactant content of 30 to 50, preferably 35 to 45 and a water content of 50 to 70, preferably 55 to 65 wt .-%.

Gewerbliche AnwendbarkeitIndustrial Applicability

Die neuen Esterquats sind auch hochkonzentriert flüssig und transparent. Sie besitzen eine vorzügliche Reinigungsleistung, ein hohes Hydrophobierungsvermögen und ausgezeichnete antistatische Eigenschaften. Setzt man die biologische Abbaubarkeit eines erfindungsgemä-Ben Dicolzaoylmethylethoxymonium Methosulfates gemäß Sturm-Test zu 100 %, dann erreicht DSDMAC unter gleichen Bedingungen einen Wert von 62 %. Ein weiterer Gegenstand der Erfindung betrifft daher die Verwendung von Esterquats, deren Acylrest bzw. Acylreste sich von ungesättigten Fettsäuren mit 8 bis 22, vorzugsweise 16 bis 22 Kohlenstoffatomen und Iodzahlen im Bereich von 100 bis 150 ableiten, zur Herstellung von Zubereitungen für die Reinigung harter Oberflächen, in denen sie in Mengen von 1 bis 30, vorzugsweise 5 bis 25 und insbesondere 10 bis 15 Gew.-% - bezogen auf die Mittel - enthalten sein können.The new ester quats are also highly concentrated liquid and transparent. They have excellent cleaning performance, high hydrophobicity and excellent antistatic properties. If the biodegradability of an inventive ben Dicolzaoylmethylethoxymonium Methosulfates according to storm test to 100%, then DSDMAC achieved under the same conditions, a value of 62%. Another object of the invention therefore relates to the use of esterquats whose acyl radical or acyl radicals are derived from unsaturated fatty acids having 8 to 22, preferably 16 to 22 carbon atoms and iodine numbers in the range of 100 to 150, for the preparation of preparations for the cleaning of hard surfaces in which they may be present in amounts of 1 to 30, preferably 5 to 25 and in particular 10 to 15 wt .-% - based on the means.

BeispieleExamples

In Tabelle 1 sind Formulierungsbeispiele angegeben: Tabelle 1 Formulierungsbeispiele für die Endreinigung von Karosserieteilen Zusammensetzung Bsp. 1 Bsp. 2 Esterquat 1) 7,5 11,0 Kokosimidazolin - 2,0 Kokosfettsäure-2-ethylhexylester 7 12,0 Octanol+4EO - 3,0 Butylglycol 10 20,0 Wasser ad 100 1) Dicolzaoylmethylethoxymonium Methosulfate Table 1 gives formulation examples: <b><u> Table 1 </ u> Formulation examples for the final cleaning of body parts </ b> composition Example 1 Ex. 2 Esterquat 1) 7.5 11.0 Kokosimidazolin - 2.0 Coconut fatty acid 2-ethylhexyl 7 12.0 Octanol + 4EO - 3.0 butyglycol 10 20.0 water ad 100 1) Dicolzaoylmethylethoxymonium Methosulfate

Claims (10)

  1. Cationic preparations for cleaning hard surfaces, characterized in that they contain esterquats of which the acyl group(s) is/are derived from unsaturated C8-22 fatty acids with iodine values of 100 to 150 as cationic surfactants.
  2. Preparations as claimed in claim 1, characterized in that they contain esterquats corresponding to formula (I):
    Figure imgb0009
     in which R1CO is an unsaturated acyl group with 8 to 22 carbon atoms and an iodine value of 100 to 150, R2 and R3 independently of one another represent hydrogen or have the same meaning as R1CO, R4 is an alkyl group containing 1 to 4 carbon atoms or a (CH2CH2O)qH group, m, n and p together stand for 0 or numbers of 1 to 12, q is a number of 1 to 12 and X is halide, alkyl sulfate or alkyl phosphate.
  3. Preparations as claimed in claim 1, characterized in that they contain esterquats corresponding to formula (II):
    Figure imgb0010
     in which R1CO is an unsaturated acyl group with 8 to 22 carbon atoms and an iodine value of 100 to 150, R2 is hydrogen or has the same meaning as R1CO, R4 and R5 independently of one another are alkyl groups containing 1 to 4 carbon atoms, m and n together stand for 0 or numbers of 1 to 12 and X stands for halide, alkyl sulfate or alkyl phosphate.
  4. Preparations as claimed in claim 1, characterized in that they contain esterquats corresponding to formula (III):
    Figure imgb0011
     in which R1CO is an unsaturated acyl group with 8 to 22 carbon atoms and an iodine value of 100 to 150, R2 is hydrogen or has the same meaning as R1CO, R4, R6 and R7 independently of one another are alkyl groups containing 1 to 4 carbon atoms, m and n together stand for 0 or numbers of 1 to 12 and X stands for halide, alkyl sulfate or alkyl phosphate.
  5. Preparations as claimed in claim 1, characterized in that they contain esterquats corresponding to formula (IV):
    Figure imgb0012
     in which R1CO is an unsaturated acyl group with 8 to 22 carbon atoms and an iodine value of 100 to 150, R2 is hydrogen or has the same meaning as R1CO, R6 and R7 independently of one another are alkyl groups containing 1 to 4 carbon atoms and X is halide, alkyl sulfate or alkyl phosphate.
  6. Preparations as claimed in at least one of claims 1 to 5, characterized in that they contain esterquats in quantities of 1 to 10% by weight, based on the preparation.
  7. Preparations as claimed in at least one of claims 1 to 6, characterized in that they additionally contains co-surfactants.
  8. Preparations as claimed in claim 7, characterized in that they contain nonionic surfactants.
  9. Preparations as claimed in at least one of claims 1 to 8, characterized in that they have a surfactant content of 30 to 50 and a water content of 50 to 70% by weight.
  10. The use of esterquats of which the acyl group(s) is/are derived from unsaturated C8-22 fatty acids with iodine values of 100 to 150 for the production of preparations for cleaning hard surfaces.
EP01130813A 2001-12-24 2001-12-24 Cationic composition for hard surface cleaning Revoked EP1323817B1 (en)

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ES01130813T ES2258506T3 (en) 2001-12-24 2001-12-24 CATION COMPOSITIONS FOR CLEANING HARD SURFACES.
DE50109370T DE50109370D1 (en) 2001-12-24 2001-12-24 Cationic preparations for the cleaning of hard surfaces
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DE50109370D1 (en) 2006-05-18
ES2258506T3 (en) 2006-09-01
ATE321834T1 (en) 2006-04-15

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