EP0272574A2 - Mixtures of liquid non-ionic surfactants - Google Patents

Mixtures of liquid non-ionic surfactants Download PDF

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Publication number
EP0272574A2
EP0272574A2 EP87118480A EP87118480A EP0272574A2 EP 0272574 A2 EP0272574 A2 EP 0272574A2 EP 87118480 A EP87118480 A EP 87118480A EP 87118480 A EP87118480 A EP 87118480A EP 0272574 A2 EP0272574 A2 EP 0272574A2
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EP
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Prior art keywords
weight
mixtures
alcohols
surfactant
alkyl
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EP87118480A
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German (de)
French (fr)
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EP0272574B1 (en
EP0272574A3 (en
Inventor
Peter Dr. Jeschke
Eva Dr. Kiewert
Claus Nieendick
Hans Dr. Nüsslein
Peter Dr. Sandkühler
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Priority to AT87118480T priority Critical patent/ATE94897T1/en
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Publication of EP0272574A3 publication Critical patent/EP0272574A3/en
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/825—Mixtures of compounds all of which are non-ionic
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/825—Mixtures of compounds all of which are non-ionic
    • C11D1/8255—Mixtures of compounds all of which are non-ionic containing a combination of compounds differently alcoxylised or with differently alkylated chains
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/835—Mixtures of non-ionic with cationic compounds
    • C—CHEMISTRY; METALLURGY
    • 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
    • C11D1/42—Amino alcohols or amino ethers
    • C11D1/44—Ethers of polyoxyalkylenes with amino alcohols; Condensation products of epoxyalkanes with amines
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/722—Ethers of polyoxyalkylene glycols having mixed oxyalkylene groups; Polyalkoxylated fatty alcohols or polyalkoxylated alkylaryl alcohols with mixed oxyalkylele groups
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S516/00—Colloid systems and wetting agents; subcombinations thereof; processes of
    • Y10S516/01—Wetting, emulsifying, dispersing, or stabilizing agents

Definitions

  • the alkylphenol ethoxylates used to a large extent as nonionic surfactant components have a considerably better cold behavior (lower pour point and cold cloud point) than comparable ethoxylates based on linear fatty alcohols.
  • the nonylphenol-10 EO adduct (NP-10) in particular is characterized by such excellent application properties that it has a universally applicable surfactant for detergents and cleaning agents, but also an emulsifier for a large number of technical applications.
  • this surfactant has very good degreasing properties, both on metal and on textile fabric. Because of these favorable properties, NP-10 is by far the most important representative in terms of quantity from the class of alkylphenol ethoxylates.
  • alkylphenol ethoxylates give cause for concern, so that considerable efforts are being made to at least partially replace these technologically high-quality surfactant components by components with better environmental compatibility.
  • Alkoxylated fatty alcohols of natural and / or synthetic origin are particularly suitable for this.
  • ether alcohols of the latter type only have the hydrophilicity values desired in practice - cloud point, for example, in the range from about 50 to 60 ° C. - only in those embodiments in which the ether alcohols as such are solid at room temperature.
  • the invention is based on the object of providing surfactant mixtures based on alkoxylated straight-chain and / or branched primary alcohols, in particular corresponding linear fatty alcohols, which are still liquid at low temperatures, for example at temperatures down to 5 ° C., and a can provide high surfactant performance.
  • the invention has in particular the task of creating a surfactant mixture which is similar in its essential technological properties to the NP-10 and which are constructed exclusively on the basis of environmentally compatible components.
  • the mixture according to the invention is prepared in a manner known per se by two-stage alkoxylation of the alcohol mixture, propylene oxide being added in the first stage and ethylene oxide being added in the second stage.
  • the starting alcohols are primarily mixtures obtained from coconut fatty alcohols, from which the majority of C12-C16 alcohols have been removed by distillation. Mixtures obtained from synthetic fatty alcohols, for example oxo alcohols, can also be used as starting materials. Such alcohols generally contain a proportion of alcohols branched methyl in the 2-position. However, preference is given to using the mixtures obtained from native alcohols, in which the alkyl radicals differ in each case by 2 carbon atoms.
  • the alkoxylation can be carried out in the presence of acidic or alkaline catalysts.
  • Alkaline catalysts such as hydroxides or alcoholates of potassium or sodium, are preferably used. Examples include NaOH, KOH, sodium methylate, sodium ethylate, potassium methylate and potassium ethylate.
  • the hydroxides and alcoholates can be used in alcoholic solution, after which the solution alcohol is removed by distillation before the alkoxylation. Usually 0.5 to 5%, preferably 1 to 3% catalyst, based on the starting material, is used.
  • the alkoxylation can be carried out at normal pressure by introducing the alkylene oxides into the alcohol mixture.
  • an autoclave under an increased initial pressure, for example an initial pressure of 2 to 10 bar, preferably 3 to 6 bar.
  • the pressure then drops to normal pressure.
  • the temperature of the alcohol to be alkoxylated is generally 80 to 200 ° C, usually 100 to 180 ° C.
  • the alkoxylate can generally be used directly. If the small catalyst residues interfere, they can be neutralized, for example wise by adding organic acids such as acetic acid or citric acid.
  • carbon dioxide can also be pressed into the autoclave and the precipitated alkali carbonate can be filtered off.
  • Alkoxylated fatty alcohols in the production of which first propylene oxide and then ethylene oxide are added, are known per se. However, they differ considerably in the composition of the radical R from the mixtures according to the invention.
  • US Pat. No. 2,174,761 describes products which in some cases have considerably higher proportions of PO and are derived from cetyl or dodecyl alcohol. These have much higher solidification areas and are less biodegradable.
  • DE 27 24 349-A1 describes spray-dried detergents which contain nonionic surfactants of a similar constitution, the alkyl radicals preferably having 12 to 18 carbon atoms and not consisting of mixtures with a predominant content of C9 to C10 alkyl radicals.
  • DE 28 10 703-A1 describes nonionic surfactants in a different order of the PO and EO groups.
  • a comparative experiment in which a mixed alcohol reacted with 4 mol PO and 15 mol EO with 43% C12-alkyl residues and 57% C13-alkyl residues (78% linear, 22% methyl branched) was examined, shows a comparatively high freezing point and an unfavorable washing result , which is why it was not to be expected that the mixtures according to the invention would offer significant advantages in this regard.
  • DE 32 32 616 discloses liquid detergents which contain mixtures of nonionic surfactants with a comparable molecular structure. However, these alkoxylates are preferably derived from alcohols having 12 to 18 carbon atoms or mixtures of cetyl, oleyl and stearyl alcohol mixtures. Surfactant mixtures of the composition according to the invention are neither disclosed nor suggested.
  • the nonionic surfactant mixture according to the invention is equivalent to the highest quality alkylphenol ethoxylates. This applies both to the compounds alone and to their mixtures with other additives and auxiliaries, as are usually used in detergents, cleaners, emulsifiers and dispersants.
  • the invention therefore relates to the replacement of nonylphenol-9- or 10 EO by the surfactant mixture defined according to the invention in known solid and liquid preparations, in particular detergents, wetting agents and dispersants.
  • liquid nonionic surfactants can also be combined with other readily biodegradable nonionic compounds.
  • Suitable additives are, for example, ethoxylates derived from primary alcohols or alkylamines having 10 to 18, in particular 10 to 14, carbon atoms and having an average of 1 to 4, preferably 2 to 3, EO groups.
  • the mixing ratio with these additives can be 1: 2 to 10: 1.
  • the composite compositions can be in solid or granular or in liquid form.
  • liquid washing, rinsing and cleaning agents for which the alkoxylates according to the invention are particularly suitable on account of their low cloud temperatures and favorable solution properties.
  • Solid detergents can, for example, have the following composition (in% by weight of anhydrous substance): 0.5 to 25%, preferably 1 to 20%, of the nonionic surfactant mixture according to the invention, 0 to 25%, preferably 2 to 20%, of anionic surfactants from the class of alkali soaps and sulfonate surfactants, in particular C 9-13 alkylbenzenesulfonates, alphasulfofatty acid salts, alphasulfofatty acid alkyl ester salts and alkanesulfonates each having 12 to 18 carbon atoms in the aliphatic radical, 0 to 10% of non-ionic C 10-18 alcohol ethoxylates containing 2 to 15 EO groups, 10 to 70%, preferably 20 to 50%, of builder salts from the class of the phosphates, polyphosphates, carbonates, silicates of sodium, sodium nitrilotriacetate and finely divided zeolite of the NaA type, 0.1 to 5% of complexing
  • Liquid assets include, for example 5 to 30%, preferably 8 to 25%, of the nonionic surfactant mixture according to the invention, 0 to 20%, preferably 2 to 15% of the aforementioned anionic surfactants, 0 to 10% of the aforementioned nonionic alcohol ethoxylates, 0.1 to 4%, preferably 0.2 to 2% of the aforementioned polyphosphonates, 0 to 2% of optical brighteners, Balance water, organic solvents and hydrotropes.
  • nonylphenol-10 EO a surfactant mixture according to the invention “product A”.
  • product A a surfactant mixture according to the invention.
  • a detergent formulation of the following composition was used, which contains 3% nonylphenol + 10 EO (NP-10) and was replaced by product A.
  • the ethoxylated C12-C14 amine + 2 EO was a product made from coconut fatty acids.
  • washing machine with drum arranged horizontally (Miele U 433); Soaking program; 60 ° C; Concentration 5 g / l; Water hardness 16 ° dH; 3 rinsing and spinning cycles; Textile samples made of cotton (B), polyester (PE) and blended fabrics made of polyester-cotton (PE / B), each soiled with a dust-skin fat combination; 0.3 kg test fabric and 3 kg clean filling laundry; photometric evaluation
  • the agents according to the invention are able to replace the ethoxylated nonylphenol without any noticeable loss of activity.
  • the combination according to Examples 2 and 4 is superior to the comparative product.
  • product A according to the invention achieved a carbon breakdown of over 70% and are therefore considered to be easily biodegradable.
  • Nonylphenol with 9 EO or 10 EO does not reach this value.
  • the degradability was over 80% (value found over 96%).
  • TA-5/10 EO is a 1: 1 mixture of C 16-18 tallow alcohol with 5 EO and 10 EO
  • C12-ABS Na-dodecylbenzenesulfonate (C 11-13- alkyl)
  • the soaps are sodium soaps
  • STP is Sodium tripolyphosphate
  • the cleaning ability was determined according to the quality standards of the industrial association cleaning and care products, published in soaps, oils, fats, waxes. 108 , No. 16, p. 527 (1982).
  • the cleaning agent to be tested was placed in a 1% aqueous solution on an artificially soiled PVC plastic surface.
  • a mixture of carbon black, machine oil, triglyceride of saturated fatty acids and low-boiling aliphatic hydrocarbon was used as artificial soiling.
  • the test area of 26 ⁇ 28 cm was evenly coated with 2 g of the artificial soiling with the aid of a surface coater.
  • a plastic sponge was impregnated with 20 ml of the detergent solution to be tested and moved mechanically on the test surface. After 6 wiping movements, the cleaned test area was kept under running water and the loose dirt was removed. The cleaning effect, d. H. the whiteness of the plastic surface cleaned in this way was measured using an LF 90 photoelectric colorimeter (Dr. B. Lange). The clean white plastic surface served as the white standard.
  • NP10 is only slightly superior to the agents according to the invention in formulations with a high surfactant content, but only scarcely achieves their cleaning effect when used sparingly.
  • Liquid abrasives of the composition listed below were produced and tested for their cleaning effect. The test procedure was identical to that used for testing all-purpose cleaners. Since liquid abrasives are used, in addition to the above-mentioned test grease, which mainly contains fat, a test which is more difficult to remove and mainly contains pigments has become dirt used. The latter consisted of soot, kaolin, calcium carbonate, petroleum jelly and low-boiling aliphatic hydrocarbon.

Abstract

A liquid mixture of propylene oxide/ethylene oxide derivatives of alcohols of the formula R-O-(C3H5O)1-2-(C2H4O)6-8-H in which R is an alkyl or alkenyl radical which is linear or methyl-branched in position 2 and which has the following chain distribution: C8 = 0 to 5 %, C9-10 = 75 to 90 %, C11-12 = 5 to 15 %, C13-14 = 4 to 10 %, C15-16 = 0 to 3 %, is, by reason of its physical and washing properties, suitable as readily biodegradable substitute for alkylphenol ethoxylates.

Description

Die heute im großen Umfang als nichtionische Tensidkomponenten eingesetzten Alkylphenolethoxylate besitzen ein erheblich besseres Kälteverhalten (tieferer Stockpunkt und Kältetrübungspunkt) als vergleichbare Ethoxylate auf Basis linearer Fettalkohole. Im Be­reich der Alkylphenolethoxylate zeichnet sich insbesondere das Nonylphenol-10 EO-Addukt (NP-10) durch so hervorragende anwen­dungstechnische Eigenschaften aus, daß hier ein universell ein­setzbares Tensid für Wasch- und Reinigungsmittel, aber auch ein Emulgator für eine Vielzahl von technischen Anwendungszwecken vorliegt. Darüber hinaus verfügt dieses Tensid über sehr gute entfettende Eigenschaften, sowohl an Metall als auch an textilem Gewebe. Aufgrund dieser günstigen Eigenschaften ist heute NP-10 der mit Abstand mengenmäßig bedeutendste Vertreter aus der Sub­stanzklasse der Alkylphenolethoxylate.The alkylphenol ethoxylates used to a large extent as nonionic surfactant components have a considerably better cold behavior (lower pour point and cold cloud point) than comparable ethoxylates based on linear fatty alcohols. In the area of alkylphenol ethoxylates, the nonylphenol-10 EO adduct (NP-10) in particular is characterized by such excellent application properties that it has a universally applicable surfactant for detergents and cleaning agents, but also an emulsifier for a large number of technical applications. In addition, this surfactant has very good degreasing properties, both on metal and on textile fabric. Because of these favorable properties, NP-10 is by far the most important representative in terms of quantity from the class of alkylphenol ethoxylates.

Nachteilig ist, daß die Umweltverträglichkeit dieser Alkylphenol­ethoxylate Anlaß zu Bedenken gibt, sodaß beträchtliche Bemühun­gen bestehen, wenigstens anteilig diese technologisch an sich hochwertige Tensidkomponente durch Komponenten mit besserer Umweltverträglichkeit zu ersetzen. Hierfür bieten sich insbe­sondere alkoxylierte Fettalkohole natürlicher und/oder synthe­tischen Ursprungs an. Ihr Einsatz bietet jedoch die folgende Schwierigkeit: Etheralkohole der zuletzt genannten Art besitzen die in der Praxis gewünschten Hydrophiliewerte - Trübungspunkt beispielsweise im Bereich von etwa 50 bis 60 °C - erst in solchen Ausführungsformen, in denen die Etheralkohole als solche bei Raumtemperatur fest sind. Hier liegt für die Praxis eine ent­ scheidende Einschränkung in dem Versuch des Austausches der Alkylphenol-Addukte gegen Addukte primärer Fettalkohole.It is disadvantageous that the environmental compatibility of these alkylphenol ethoxylates gives cause for concern, so that considerable efforts are being made to at least partially replace these technologically high-quality surfactant components by components with better environmental compatibility. Alkoxylated fatty alcohols of natural and / or synthetic origin are particularly suitable for this. However, their use presents the following difficulty: ether alcohols of the latter type only have the hydrophilicity values desired in practice - cloud point, for example, in the range from about 50 to 60 ° C. - only in those embodiments in which the ether alcohols as such are solid at room temperature. In practice there is an ent Limiting restriction in the attempt to replace the alkylphenol adducts with adducts of primary fatty alcohols.

Die Erfindung geht von der Aufgabe aus, Tensidmischungen auf der Basis von alkoxylierten geradkettigen und/oder verzweigten primären Alkoholen, insbesondere entsprechenden linearen Fett­alkoholen, zur Verfügung stellen, die noch bei niedrigen Tempe­raturen, beispielsweise bei Temperaturen bis herunter zu 5 °C flüssig sind und eine hohe Tensidleistung zur Verfügung stellen können. Die Erfindung hat sich insbesondere die Aufgabe ge­stellt, ein Tensidgemisch zu schaffen, das in seinen wesentlichen technologischen Eigenschaften dem NP-10 gleicht und ausschließ­lich auf Basis umweltverträglicher Komponenten aufgebaut sind.The invention is based on the object of providing surfactant mixtures based on alkoxylated straight-chain and / or branched primary alcohols, in particular corresponding linear fatty alcohols, which are still liquid at low temperatures, for example at temperatures down to 5 ° C., and a can provide high surfactant performance. The invention has in particular the task of creating a surfactant mixture which is similar in its essential technological properties to the NP-10 and which are constructed exclusively on the basis of environmentally compatible components.

Gegenstand der Erfindung sind dementsprechend bei Raumtempera­tur flüssige Tensidmischungen auf Basis von polyalkoxylierten Alkoholen mit hoher Tensidleistung, bestehend aus einem gerad­kettigen oder in 2-Stellung methyl-verzweigten Etheralkohol der allgemeinen Formel

    R - O - (PO)1-2- (EO)6-8- H

in der PO den Rest des ringgeöffneten Propylenoxids und EO den Rest des ringgeöffneten Ethylenoxids bedeuten, dadurch gekenn­zeichnet, daß die Alkyl- bzw. Alkenylreste R wie folgt zusam­mengesetzt sind: C₈ = 0 bis 5 Gew.-%, C9-10= 75 bis 90 Gew.-%, C11-12= 5 bis 15 Gew.-%, C13-14= 4 bis 10 Gew.-% und C15-16= 0 bis 3 Gew.-%.The invention accordingly relates to surfactant mixtures which are liquid at room temperature and are based on polyalkoxylated alcohols with a high surfactant output, consisting of a straight-chain or ether alcohol of the general formula which is methyl-branched in the 2-position

R - O - (PO) 1-2 - (EO) 6-8 - H

in the PO the rest of the ring-opened propylene oxide and EO the rest of the ring-opened ethylene oxide, characterized in that the alkyl or alkenyl radicals R are composed as follows: C₈ = 0 to 5% by weight, C 9-10 = 75 to 90% by weight, C 11-12 = 5 to 15% by weight, C 13-14 = 4 to 10% by weight and C 15-16 = 0 to 3% by weight.

Vorzugsweise steht R für lineare Alkylreste folgender Zusammen­setzung:
C₈ = 0 bis 2 Gew.-%, C₁₀ = 80 bis 84 Gew.-%, C₁₂ = 7 bis 12 Gew.-%, C₁₄ = 6 bis 8 Gew.-% und C15-16= 0 bis 1 Gew.-%.R preferably represents linear alkyl radicals of the following composition:
C₈ = 0 to 2% by weight, C₁₀ = 80 to 84% by weight, C₁₂ = 7 to 12% by weight, C₁₄ = 6 to 8% by weight and C 15-16 = 0 to 1% by weight. -%.

Die Herstellung des erfindungsgemäßen Gemisches erfolgt in an sich bekannter Weise durch zweistufige Alkoxylierung des Alko­holgemisches, wobei in der 1. Stufe Propylenoxid und in der 2. Stufe Ethylenoxid angelagert wird. Als Ausgangsalkohole kommen in erster Linie aus Cocosfettalkoholen gewonnene Gemische, von denen der Hauptanteil an C₁₂-C₁₆-Alkoholen destillativ abgetrennt worden sind. Ferner können auch aus synthetischen Fettalkoholen gewonnene Gemische, beispielsweise Oxoalkohole, als Ausgangs­stoffe verwendet werden. Derartige Alkohole enthalten in der Regel einen Anteil an in 2-Stellung methylverzweigten Alkoholen. Vorzugsweise werden jedoch die aus nativen Alkoholen gewonne­nen Gemische verwendet, in denen sich die Alkylreste jeweils um 2 C-Atome unterscheiden.The mixture according to the invention is prepared in a manner known per se by two-stage alkoxylation of the alcohol mixture, propylene oxide being added in the first stage and ethylene oxide being added in the second stage. The starting alcohols are primarily mixtures obtained from coconut fatty alcohols, from which the majority of C₁₂-C₁₆ alcohols have been removed by distillation. Mixtures obtained from synthetic fatty alcohols, for example oxo alcohols, can also be used as starting materials. Such alcohols generally contain a proportion of alcohols branched methyl in the 2-position. However, preference is given to using the mixtures obtained from native alcohols, in which the alkyl radicals differ in each case by 2 carbon atoms.

Die Alkoxylierung kann, wie bekannt, in Gegenwart saurer oder alkalischer Katalysatoren durchgeführt werden. Vorzugsweise wer­den alkalische Katalysatoren, wie Hydroxide oder Alkoholate des Kaliums oder Natriums eingesetzt. Beispiele hierfür sind NaOH, KOH, Natriummethylat, Natriumethylat, Kaliummethylat und Kali­umethylat. Zwecks schnellerer und homogenerer Verteilung im Substrat können die Hydroxide und Alkoholate in alkoholischer Lösung eingesetzt werden, worauf man den Lösungs-Alkohol vor der Alkoxylierung destillativ entfernt. Üblicherweise werden 0,5 bis 5 %, bevorzugt 1 bis 3 % Katalysator, auf Ausgangsmaterial bezogen, eingesetzt. Die Alkoxylierung kann bei Normaldruck durch Einleiten der Alkylenoxide in das Alkoholgemisch erfolgen. Bevorzugt wird sie jedoch im Autoklaven unter erhöhtem Anfangs­druck beispielsweise einem Anfangsdruck von 2 bis 10 bar, vor­zugsweise 3 bis 6 bar, durchgeführt. Mit fortschreitender Um­setzung sinkt dann der Druck bis auf Normaldruck ab. Die Tem­peratur des zu alkoxylierenden Alkohols beträgt im allgemeinen 80 bis 200 °C, meist 100 bis 180 °C. Das Alkoxylat kann in der Regel unmittelbar verwendet werden. Falls die geringen Kataly­sator-Reste stören, können sie neutralisiert werden, beispiels­ weise durch Zusatz organischer Säuren, wie Essigsäure oder Zi­tronensäure. Man kann auch nach Abschluß der Alkoxylierung Koh­lendioxid in den Autoklaven pressen und das sich abscheidende Alkalicarbonat abfiltrieren.As is known, the alkoxylation can be carried out in the presence of acidic or alkaline catalysts. Alkaline catalysts, such as hydroxides or alcoholates of potassium or sodium, are preferably used. Examples include NaOH, KOH, sodium methylate, sodium ethylate, potassium methylate and potassium ethylate. For faster and more homogeneous distribution in the substrate, the hydroxides and alcoholates can be used in alcoholic solution, after which the solution alcohol is removed by distillation before the alkoxylation. Usually 0.5 to 5%, preferably 1 to 3% catalyst, based on the starting material, is used. The alkoxylation can be carried out at normal pressure by introducing the alkylene oxides into the alcohol mixture. However, it is preferably carried out in an autoclave under an increased initial pressure, for example an initial pressure of 2 to 10 bar, preferably 3 to 6 bar. As the implementation progresses, the pressure then drops to normal pressure. The temperature of the alcohol to be alkoxylated is generally 80 to 200 ° C, usually 100 to 180 ° C. The alkoxylate can generally be used directly. If the small catalyst residues interfere, they can be neutralized, for example wise by adding organic acids such as acetic acid or citric acid. After the alkoxylation has ended, carbon dioxide can also be pressed into the autoclave and the precipitated alkali carbonate can be filtered off.

Alkoxylierte Fettalkohole, bei deren Herstellung zunächst Pro­pylenoxid und anschließend Ethylenoxid angelagert werden, sind an sich bekannt. Sie unterscheiden sich jedoch hinsichtlich der Zusammensetzung des Restes R ganz erheblich von den erfindungs­gemäßen Gemischen. So werden in US 2,174,761 Produkte beschrie­ben, die teilweise erheblich höhere Anteile an PO aufweisen und sich von Cetyl- bzw. Dodecylalkohol ableiten. Diese weisen we­sentlich höhere Erstarrungsbereiche auf und sind schlechter bio­logisch abbaubar. Die DE 27 24 349-A1 beschreibt sprühgetrock­nete Waschmittel, die nichtionische Tenside ähnlicher Konstitution enthalten, wobei die Alkylreste bevorzugt 12 bis 18 C-Atome auf­weisen und nicht aus Gemischen mit einem überwiegenden Gehalt an C₉- bis C₁₀-Alkylresten bestehen. Das gleiche gilt für die in DE 28 37 504-C2 beschriebenen Waschmittelgranulate. In der DE 28 10 703-A1 werden nichtionogene Tenside mit anderer Rei­henfolge der PO- und EO-Gruppen beschrieben. Ein Vergleichs­versuch, in dem ein mit 4 Mol PO und 15 Mol EO umgesetzter Mischalkohol mit 43 % C₁₂-Alkylresten und 57 % C₁₃-Alkylresten (78 % linear, 22 % methylverzweigt) untersucht wurde, läßt einen vergleichsweise hohen Erstarrungspunkt sowie ein ungünstigeres Waschergebnis erkennen, weshalb nicht zu erwarten war, daß die erfindungsgemäßen Gemische in dieser Hinsicht wesentliche Vor­teile bieten würden. Schließlich sind aus DE 32 32 616 flüssige Waschmittel bekannt, die Gemische von nichtionischen Tensiden mit vergleichbarem Molekülaufbau enthalten. Diese Alkoxylate leiten sich jedoch bevorzugt von Alkoholen mit 12 bis 18 C-Atomen bzw. Gemischen aus Cetyl-, Oleyl- und Stearylalkohol-Gemischen ab. Tensidgemische der erfindungsgemäßen Zusammensetzung sind weder offenbart noch nahegelegt.Alkoxylated fatty alcohols, in the production of which first propylene oxide and then ethylene oxide are added, are known per se. However, they differ considerably in the composition of the radical R from the mixtures according to the invention. For example, US Pat. No. 2,174,761 describes products which in some cases have considerably higher proportions of PO and are derived from cetyl or dodecyl alcohol. These have much higher solidification areas and are less biodegradable. DE 27 24 349-A1 describes spray-dried detergents which contain nonionic surfactants of a similar constitution, the alkyl radicals preferably having 12 to 18 carbon atoms and not consisting of mixtures with a predominant content of C₉ to C₁₀ alkyl radicals. The same applies to the detergent granules described in DE 28 37 504-C2. DE 28 10 703-A1 describes nonionic surfactants in a different order of the PO and EO groups. A comparative experiment, in which a mixed alcohol reacted with 4 mol PO and 15 mol EO with 43% C₁₂-alkyl residues and 57% C₁₃-alkyl residues (78% linear, 22% methyl branched) was examined, shows a comparatively high freezing point and an unfavorable washing result , which is why it was not to be expected that the mixtures according to the invention would offer significant advantages in this regard. Finally, DE 32 32 616 discloses liquid detergents which contain mixtures of nonionic surfactants with a comparable molecular structure. However, these alkoxylates are preferably derived from alcohols having 12 to 18 carbon atoms or mixtures of cetyl, oleyl and stearyl alcohol mixtures. Surfactant mixtures of the composition according to the invention are neither disclosed nor suggested.

Von besonderem Vorteil, insbesondere gegenüber alkoxylierten Al­kylphenolen ist die sehr gute biologische Abbaufähigkeit, die oberhalb 96 % liegt. Hinsichtlich der anwendungstechnischen Eigenschaften sind die erfindungsgemäßen nichtionischen Tensid­mischung der hochwertigsten Alkylphenolethoxylaten equivalent. Dies gilt sowohl für die Verbindungen allein als auch für ihre Gemische mit anderen Zusatz- und Hilfsstoffen, wie sie in Wasch-, Reinigungs-, Emulgier- und Dispergiermitteln üblicherweise ver­wendet werden.Of particular advantage, especially compared to alkoxylated alkylphenols, is the very good biodegradability, which is above 96%. With regard to the performance properties, the nonionic surfactant mixture according to the invention is equivalent to the highest quality alkylphenol ethoxylates. This applies both to the compounds alone and to their mixtures with other additives and auxiliaries, as are usually used in detergents, cleaners, emulsifiers and dispersants.

Die Erfindung betrifft daher in einer weiteren Ausführungsform den Ersatz von Nonylphenol-9- bzw. 10 EO durch das erfindungs­gemäß definierte Tensidgemisch in bekannten festen und flüssigen Zubereitungen insbesondere Waschmitteln, Netzmitteln und Disper­giermitteln.In a further embodiment, the invention therefore relates to the replacement of nonylphenol-9- or 10 EO by the surfactant mixture defined according to the invention in known solid and liquid preparations, in particular detergents, wetting agents and dispersants.

In einer weiteren Ausführungsform der Erfindung können die flüssigen nichtionischen Tenside auch mit weiteren biologisch gut abbaufähigen nichtionischen Verbindungen kombiniert werden. Mit solchen Kombinationen kann die Waschleistung noch weiter ge­steigert werden, ohne Nachteile hinsichtlich der sonstigen positiven Eigenschaften in Kauf nehmen zu müssen. Geeignete Zu­sätze sind beispielsweise von primären Alkoholen oder Alkylaminen mit 10 bis 18, insbesondere 10 bis 14 C-Atomen abgeleitete Ethoxylate mit durchschnittlich 1 bis 4, vorzugsweise 2 bis 3 EO-Gruppen. Das Mischungsverhältnis mit diesen Zusätzen kann 1 : 2 bis 10 : 1 betragen. Darüber hinaus können sie bei Einsatz in Wasch- und Reinigungsmittel mit bekannten anionischen, nicht­ionischen, ampholytischen zwitterionischen und kationischen Ten­siden, Gerüstsalzen, Sequestrierungsmitteln, Bleichmitteln, Ver­grauungsinhibitoren, Avivagewirkstoffen, Schauminhibitoren und sonstigen in solchen Mitteln üblicherweise eingesetzten Wirkstoffen kombiniert werden. Die zusammengesetzten Mittel können in fester bzw. körniger oder in flüssiger Form vorliegen. Von besonderem Interesse sind im vorliegenden Fall flüssige Wasch-, Spül- und Reinigungsmittel, für solche die erfindungsgemäßen Alkoxylate aufgrund ihrer niedrigen Trübungstemperaturen und günstigen Lösungseigenschaften besonders geeignet sind.In a further embodiment of the invention, the liquid nonionic surfactants can also be combined with other readily biodegradable nonionic compounds. With such combinations, the washing performance can be increased even further without having to accept disadvantages with regard to the other positive properties. Suitable additives are, for example, ethoxylates derived from primary alcohols or alkylamines having 10 to 18, in particular 10 to 14, carbon atoms and having an average of 1 to 4, preferably 2 to 3, EO groups. The mixing ratio with these additives can be 1: 2 to 10: 1. In addition, when used in detergents and cleaning agents, they can be combined with known anionic, nonionic, ampholytic zwitterionic and cationic surfactants, skeletal salts, sequestering agents, bleaching agents, graying inhibitors, anti-aging agents, foam inhibitors and other active ingredients conventionally used in such agents. The composite compositions can be in solid or granular or in liquid form. Of particular Of interest in the present case are liquid washing, rinsing and cleaning agents, for which the alkoxylates according to the invention are particularly suitable on account of their low cloud temperatures and favorable solution properties.

Feste Waschmittel können beispielsweise die folgende Zusammensetzung aufweisen (in Gew.-% wasserfreie Substanz):
0,5 bis 25 %, vorzugsweise 1 bis 20 % der erfindungsgemäßen nichtionischen Tensidmischung,
0 bis 25 %, vorzugsweise 2 bis 20 % an anionischen Tensiden aus der Klasse der Alkaliseifen und Sulfonat-Tenside, insbesondere der C9-13-Alkylbenzolsulfonate, Alphasulfofettsäuresalze, Alphasulfofettsäurealkylestersalze und Alkansulfonate mit je­weils 12 bis 18 C-Atomen im aliphatischen Rest,
0 bis 10 % an nichtionischen, 2 bis 15 EO-Gruppen aufweisenden C10-18-Alkoholethoxylaten,
10 bis 70 %, vorzugsweise 20 bis 50 % an Buildersalzen aus der Klasse der Phosphate, Polyphosphate, Carbonate, Silikate des Natriums, des Na-Nitrilotriacetats und des feinteiligen Zeoliths vom Typ NaA,
0,1 bis 5 % an Komplexierungsmitteln aus der Klasse der Na-Salze von Polyphosphonsäuren und der homo- oder copolymeren Poly­mercarbonsäuren, insbesondere des Hydroxyethandiphospho­nats, des Ethylendiamintetramethylenphosphonats und der Acrylsäure-Maleinsäurecopolymeren,
0 bis 30 %, vorzugsweise 5 bis 20 % an Perverbindungen und ihrer Kombination mit Aktivatoren, insbesondere Natriumper­borat-monohydrat und -tetrahydrat sowie Tetraacetylethylen­diamin,
0 bis 10 % an sonstigen Waschmittelbestandteilen aus der Klasse der Vergrauungsinhibitoren, Enzyme, optischen Aufheller, Farb- und Duftstoffe,
0 bis 30 % an Neutralsalzen, wie Natriumsulfat.Solid detergents can, for example, have the following composition (in% by weight of anhydrous substance):
0.5 to 25%, preferably 1 to 20%, of the nonionic surfactant mixture according to the invention,
0 to 25%, preferably 2 to 20%, of anionic surfactants from the class of alkali soaps and sulfonate surfactants, in particular C 9-13 alkylbenzenesulfonates, alphasulfofatty acid salts, alphasulfofatty acid alkyl ester salts and alkanesulfonates each having 12 to 18 carbon atoms in the aliphatic radical,
0 to 10% of non-ionic C 10-18 alcohol ethoxylates containing 2 to 15 EO groups,
10 to 70%, preferably 20 to 50%, of builder salts from the class of the phosphates, polyphosphates, carbonates, silicates of sodium, sodium nitrilotriacetate and finely divided zeolite of the NaA type,
0.1 to 5% of complexing agents from the class of the Na salts of polyphosphonic acids and of the homo- or copolymeric polymer carboxylic acids, in particular of hydroxyethane diphosphonate, of ethylenediaminetetramethylene phosphonate and of acrylic acid-maleic acid copolymers,
0 to 30%, preferably 5 to 20%, of per compounds and their combination with activators, in particular sodium perborate monohydrate and tetrahydrate and tetraacetylethylene diamine,
0 to 10% of other detergent components from the class of graying inhibitors, enzymes, optical brighteners, colors and fragrances,
0 to 30% of neutral salts such as sodium sulfate.

Flüssige Mittel enthalten beispielsweise
5 bis 30 %, vorzugsweise 8 bis 25 % der erfindungsgemäßen nicht­ionischen Tensidmischung,
0 bis 20 %, vorzugsweise 2 bis 15 % der vorgenannten anionischen Tenside,
0 bis 10 % der vorgenannten nichtionischen Alkoholethoxylate,
0,1 bis 4 %, vorzugsweise 0,2 bis 2 % der vorgenannten Polyphos­phonate,
0 bis 2 % an optischen Aufhellern,
Rest Wasser, organische Lösungsmittel und Hydrotrope.Liquid assets include, for example
5 to 30%, preferably 8 to 25%, of the nonionic surfactant mixture according to the invention,
0 to 20%, preferably 2 to 15% of the aforementioned anionic surfactants,
0 to 10% of the aforementioned nonionic alcohol ethoxylates,
0.1 to 4%, preferably 0.2 to 2% of the aforementioned polyphosphonates,
0 to 2% of optical brighteners,
Balance water, organic solvents and hydrotropes.

B e i s p i e l eExample

Es werden die Eigenschaften von Nonylphenol-10 EO mit einer er­findungsgemäßen Tensidmischung "Produkt A" verglichen. Dieses erfindungsgemäße "Produkt A" weist die folgende Zusammenset­zung auf:
durchschnittliche Anzahl der PO-Gruppen 1,2
durchschnittliche Anzahl der EO-Gruppen 6,4
C₈ = 1 %
C₁₀ = 82 % C₁₂ = 10 %
C₁₄ = 7 %
C15-16= unter 0,1 %
(Alkylgruppen linear, gesättigt, primäre OH-Gruppe).The properties of nonylphenol-10 EO are compared with a surfactant mixture according to the invention “product A”. This "product A" according to the invention has the following composition:
average number of PO groups 1.2
average number of EO groups 6.4
C₈ = 1%
C₁₀ = 82% C₁₂ = 10%
C₁₄ = 7%
C 15-16 = less than 0.1%
(Alkyl groups linear, saturated, primary OH group).

Der Vergleich der Produkteigenschaften wurde dabei nach den fol­genden Kriterien geführt:
Kältetrübungspunkt (DIN 51 583)
Stockpunkt (DIN 51 583) (englisch: pour point)
Tauchnetzvermögen (DIN 53 901)
Bestimmung der Oberflächenspannung (DIN 53 914)
Trübungstemperatur (1%ig in deionisiertem Waser) (DIN 53 917)
Bestimmung des Waschvermögens

Figure imgb0001
The comparison of the product properties was carried out according to the following criteria:
Cold cloud point (DIN 51 583)
Pour point (DIN 51 583) (English: pour point)
Immersion network capacity (DIN 53 901)
Determination of the surface tension (DIN 53 914)
Turbidity temperature (1% in deionized water) (DIN 53 917)
Determination of washing power
Figure imgb0001

Bestimmung des WaschvermögensDetermination of washing power

Es wurde eine Waschmittelrezeptur folgender Zusammensetzung verwendet, in der 3 % Nonylphenol+10 EO (NP-10) enthalten sind und durch Produkt A ersetzt wurden. Das ethoxylierte C₁₂-C₁₄-­Amin+2 EO war ein aus Kokosfettsäuren hergestelltes Produkt.

Figure imgb0002
A detergent formulation of the following composition was used, which contains 3% nonylphenol + 10 EO (NP-10) and was replaced by product A. The ethoxylated C₁₂-C₁₄ amine + 2 EO was a product made from coconut fatty acids.
Figure imgb0002

PrüfbedingungenTest conditions

Waschmaschine mit horizontal angeordneter Trommel (Miele U 433); Einlaugen-Programm; 60 °C; Konzentration 5 g/l; Wasserhärte 16 °dH; 3maliges Nachspülen und Schleudern; Textilproben aus Baumwolle (B), Polyester (PE) und Mischgewebe aus Polyester-­Baumwolle (PE/B), jeweils angeschmutzt mit einer Staub-Hautfett-­Kombination; 0,3 kg Testgewebe und 3 kg saubere Füllwäsche; photometrische Auswertung

Figure imgb0003
Washing machine with drum arranged horizontally (Miele U 433); Soaking program; 60 ° C; Concentration 5 g / l; Water hardness 16 ° dH; 3 rinsing and spinning cycles; Textile samples made of cotton (B), polyester (PE) and blended fabrics made of polyester-cotton (PE / B), each soiled with a dust-skin fat combination; 0.3 kg test fabric and 3 kg clean filling laundry; photometric evaluation
Figure imgb0003

In einer zweiten Versuchsreihe wurden mit Staub und Hautfett angeschmutzte Wollsträngchen bei 30 °C und einer Waschmittel­konzentration von 1,8 g/l eines Waschmittels nachstehender Zusammensetzung gewaschen.

Figure imgb0004
In a second series of experiments, woolen strands soiled with dust and skin oil were washed at 30 ° C. and a detergent concentration of 1.8 g / l of a detergent of the composition below.
Figure imgb0004

Die erfindungsgemäßen Mittel vermögen hinsichtlich ihrer Waschkraft das ethoxylierte Nonylphenol ohne nennenswerte Wirkungseinbuße zu ersetzen. Die Kombination gemäß Beispiel 2 und 4 ist dem Vergleichsprodukt überlegen.With regard to their washing power, the agents according to the invention are able to replace the ethoxylated nonylphenol without any noticeable loss of activity. The combination according to Examples 2 and 4 is superior to the comparative product.

Biologische AbbaufähigkeitBiodegradability

Im modifizierten OECD-Screening-Test erreichten das erfindungs­gemäße Produkt A einen Kohlenstoff-Abbau von über 70 % und gelten daher als biologisch leicht abbaubar. Nonylphenol mit 9 EO bzw. 10 EO erreicht diesen Wert nicht. Nach den Kriterien der "Verordnung über die Abbaubarkeit anionischer und nichtioni­scher Stoffe in Wasch- und Reinigungsmitteln" vom 30.01.1977 lag die Abbaubarkeit bei über 80 % (gefundener Wert über 96 %).In the modified OECD screening test, product A according to the invention achieved a carbon breakdown of over 70% and are therefore considered to be easily biodegradable. Nonylphenol with 9 EO or 10 EO does not reach this value. According to the criteria of the "Ordinance on the Degradability of Anionic and Nonionic Substances in Washing and Cleaning Agents" of January 30, 1977, the degradability was over 80% (value found over 96%).

Beispiele 5 bis 7Examples 5 to 7

Die folgenden Versuche dokumentieren, daß bereits geringe Zu­sätze des erfindungsgemäßen Produktes als Zusatz zu an sich bekannten Waschmittelrezepturen eine deutliche Erhöhung der Waschkraft bewirken und in dieser Hinsicht bekannte Waschkraft­verstärker (alkoxylierte Alkylamine) übertreffen.The following experiments document that even small additions of the product according to the invention as an additive to detergent formulations known per se bring about a significant increase in washing power and outperform known washing power boosters (alkoxylated alkylamines) in this regard.

Die Versuche wurden in der in Beispiel 1 verwendeten Maschine durchgeführt und an der folgenden Reihe von Anschmutzungen getestet:

  • A I: Staub/Hautfett auf Baumwolle (Standardgewebe des Wä­scherei-Forschungsinstituts, Krefeld)
  • A II: Staub/Hautfett auf veredelter Baumwolle
  • A III: Staub/Hautfett auf 1:1 Mischgewebe aus veredelter Baum­wolle und Polyester
  • A IV: Staub/Hautfett auf Polyester
  • A V: Staub/Hautfett auf Wolle
  • A VI: Lippenstift auf A III-Gewebe
The tests were carried out in the machine used in Example 1 and tested on the following series of soiling:
  • AI: Dust / skin fat on cotton (standard fabric of the laundry research institute, Krefeld)
  • A II: Dust / skin fat on refined cotton
  • A III: Dust / skin fat on 1: 1 blended fabric made from refined cotton and polyester
  • A IV: Dust / skin fat on polyester
  • AV: Dust / skin fat on wool
  • A VI: Lipstick on A III fabric

Waschbedingungen(Einlaugen-Programm ohne Vorwäsche) Washing conditions (soaking program without prewash)

  • Beispiel 5: Normal-Programm, 60 °C, Flottenverhältnis (kg Wäsche zu Liter Wasser) = 1 : 5,6, Dosierung 4,4 g/lExample 5: Normal program, 60 ° C, liquor ratio (kg of laundry to liter of water) = 1: 5.6, dosage 4.4 g / l
  • Beispiel 6: Pflegeleicht-Programm, 40 °C, Flottenverhältnis 1 : 25, Dosierung 4,4 g/lExample 6: Easy care program, 40 ° C, liquor ratio 1:25, dosage 4.4 g / l
  • Beispiel 7: Feinwasch-Programm, 40 °C, Flottenverhältnis 1 : 25, Dosierung 4,4 g/lExample 7: Delicates program, 40 ° C, liquor ratio 1:25, dosage 4.4 g / l

In den Vergleichsversuchen (Index a, b) wurde NP10 = Nonyl­phenol und KA-2 EO = Kokosamin + 2 EO (Kokosalkyl = 2 % C₁₀, 56 % C₁₂, 22 C₁₄, 9 % C₁₆, 11 % C₁₈) eingesetzt. TA-5/10 EO ist ein 1 : 1 Gemisch aus C16-18-Talgalkohol mit jeweils 5 EO und 10 EO, C₁₂-ABS ist Na-Dodecylbenzolsulfonat (C11-13-Alkyl), die Seifen sind Natriumseifen, STP ist Natrium-tripolyphosphat, Aa-Ma-Cop ist ein 2 : 1 Acrylsäure-Maleinsäure-Copolymer-Na-Salz (MG = 70 000).In the comparative experiments (index a, b) NP10 = nonylphenol and KA-2 EO = coconut amine + 2 EO (coconut alkyl = 2% C₁₀, 56% C₁₂, 22 C₁₄, 9% C₁₆, 11% C₁₈) were used. TA-5/10 EO is a 1: 1 mixture of C 16-18 tallow alcohol with 5 EO and 10 EO, C₁₂-ABS is Na-dodecylbenzenesulfonate (C 11-13- alkyl), the soaps are sodium soaps, STP is Sodium tripolyphosphate, Aa-Ma-Cop is a 2: 1 acrylic acid-maleic acid copolymer Na salt (MW = 70,000).

Die Ergebnisse sind in Tabelle 1 zusammengestellt. Sie dokumen­tieren die verbesserte Waschkraft der Produkte gegenüber NP10 bzw. die erhöhte Waschkraftverstärkung gegenüber Kokosamin + 2 EO.

Figure imgb0005
The results are summarized in Table 1. They document the improved washing power of the products compared to NP10 and the increased washing power boost compared to coconut amine + 2 EO.
Figure imgb0005

Beispiele 8 und 9Examples 8 and 9

Es wurden Allzweckreiniger folgender Zusammensetzung hergestellt und deren Reinigungswirkung in der für diese Produktkategorie üblichen Anwendungskonzentration geprüft.

Figure imgb0006
All-purpose cleaners of the following composition were manufactured and their cleaning effect was tested in the usual concentration for this product category.
Figure imgb0006

PrüfbedingungenTest conditions

Die Bestimmung des Reinigungsvermögens erfolgte nach den Quali­tätsnormen des Industrieverbandes Putz- und Pflegemittel, ver­öffentlicht in Seifen, Öle, Fette, Wachse. 108, Nr. 16, S. 527 (1982).The cleaning ability was determined according to the quality standards of the industrial association cleaning and care products, published in soaps, oils, fats, waxes. 108 , No. 16, p. 527 (1982).

Zur Prüfung der Reinigungswirkung wurde das zu prüfende Reini­gungsmittel in 1 %iger wäßriger Lösung auf eine künstlich an­geschmutzte PVC-Kunststoffoberfläche gegeben. Als künstliche Anschmutzung wurde ein Gemisch aus Ruß, Maschinenöl, Trigly­cerid gesättigter Fettsäuren und niedersiedendem aliphatischen Kohlenwasserstoff verwendet. Die Testfläche von 26 × 28 cm wurde mit Hilfe eines Flächenstreichers gleichmäßig mit 2 g der künstlichen Anschmutzung beschichtet.To test the cleaning effect, the cleaning agent to be tested was placed in a 1% aqueous solution on an artificially soiled PVC plastic surface. A mixture of carbon black, machine oil, triglyceride of saturated fatty acids and low-boiling aliphatic hydrocarbon was used as artificial soiling. The test area of 26 × 28 cm was evenly coated with 2 g of the artificial soiling with the aid of a surface coater.

Ein Kunststoffschwamm wurde jeweils mit 20 ml der zu prüfenden Reinigungsmittellösung getränkt und maschinell auf der Testfläche bewegt. Nach 6 Wischbewegungen wurde die gereinigte Testfläche unter fließendes Wasser gehalten und der lose sitzende Schmutz entfernt. Die Reinigungswirkung, d. h. der Weißgrad der so ge­reinigten Kunststoffoberläche wurde mit einem photoelektrischen Farbmeßgerät LF 90 (Dr. B. Lange) gemessen. Als Weißstandard diente die saubere weiße Kunststoffoberfläche.A plastic sponge was impregnated with 20 ml of the detergent solution to be tested and moved mechanically on the test surface. After 6 wiping movements, the cleaned test area was kept under running water and the loose dirt was removed. The cleaning effect, d. H. the whiteness of the plastic surface cleaned in this way was measured using an LF 90 photoelectric colorimeter (Dr. B. Lange). The clean white plastic surface served as the white standard.

Da bei der Messung der sauberen Oberfläche auf 100 % eingestellt und die angeschmutzte Fläche mit 0 angezeigt wurde, waren die abgelesenen Werte bei den gereinigten Kunststoff-Flächen mit dem Prozentgehalt Reinigungsvermögen (% RV) gleichzusetzen.

Figure imgb0007
Since the measurement of the clean surface was set to 100% and the soiled area was displayed with 0, the read values for the cleaned plastic areas were to be equated with the percentage cleaning ability (% RV).
Figure imgb0007

Die Ergebnisse zeigen, daß NP10 nur in Rezepturen mit hohem Tensidanteil den erfindungsgemäßen Mitteln geringfügig überlegen ist, bei sparsamer Anwendung aber deren Reinigungswirkung nur knapp erreicht.The results show that NP10 is only slightly superior to the agents according to the invention in formulations with a high surfactant content, but only scarcely achieves their cleaning effect when used sparingly.

Beispiele 10 und 11Examples 10 and 11

Es wurden flüssige Scheuermittel der unten angeführten Zusam­mensetzung hergestellt und auf ihre Reinigungswirkung geprüft. Das Prüfverfahren war identisch mit dem bei der Prüfung von Allzweckreinigern verwendeten Verfahren. Da flüssige Scheuer­mittel angewendet werden, wurde zusätzlich zu dem bereits ge­nannten, vorwiegend Fett enthaltenden Testschmutz ein schwie­riger zu entfernender, vorwiegend Pigmente enthaltender Test­ schmutz eingesetzt. Letzterer bestand aus Ruß, Kaolin, Calci­umcarbonat, Vaseline und niedrig siedendem aliphatischen Koh­lenwasserstoff.

Figure imgb0008
Liquid abrasives of the composition listed below were produced and tested for their cleaning effect. The test procedure was identical to that used for testing all-purpose cleaners. Since liquid abrasives are used, in addition to the above-mentioned test grease, which mainly contains fat, a test which is more difficult to remove and mainly contains pigments has become dirt used. The latter consisted of soot, kaolin, calcium carbonate, petroleum jelly and low-boiling aliphatic hydrocarbon.
Figure imgb0008

Die Ergebnisse zeigen, daß die erfindungsgemäßen Mittel gegen­über Fettschmutz dem Vergleichsprodukt nahezu gleichwertig, ge­genüber Pigmentschmutz jedoch überlegen sind.The results show that the agents according to the invention are almost equivalent to the comparison product compared to grease soiling, but are superior to pigment soiling.

Claims (5)

1. Bei Raumtemperatur flüssige Tensidmischungen auf der Basis polyalkoxylierter Alkohole, bestehend aus einem geradketti­gen oder in 2-Stellung methylverzweigten Etheralkohol der allgemeinen Formel

      R - O - (PO)1-2- (EO)6-8- H

in der PO den Rest des ringgeöffneten Propylenoxids und EO den Rest des ringgeöffneten Ethylenoxids bedeuten, dadurch gekennzeichnet, daß die Alkyl- bzw. Alkenylreste R wie folgt zusammengesetzt sind: C₈ = 0 bis 5 Gew.-%, C9-10= 75 bis 90 Gew.-%, C11-12= 5 bis 15 Gew.-%, C13-14= 4 bis 10 Gew.-% und C15-16= 0 bis 3 Gew.-%.1. Surfactant mixtures which are liquid at room temperature and are based on polyalkoxylated alcohols, consisting of a straight-chain or ether alcohol of the general formula which is methyl-branched in the 2-position

R - O - (PO) 1-2 - (EO) 6-8 - H

in the PO the rest of the ring-opened propylene oxide and EO the rest of the ring-opened ethylene oxide, characterized in that the alkyl or alkenyl radicals R are composed as follows: C₈ = 0 to 5% by weight, C 9-10 = 75 to 90% by weight, C 11-12 = 5 to 15% by weight, C 13-14 = 4 to 10% by weight and C 15-16 = 0 to 3% by weight. 2. Tensidmischung nach Anspruch 1, dadurch gekennzeichnet, daß R für einen linearen Alkylrest folgender Zusammenset­zung steht:
C₈ = 0 bis 2 Gew.-%, C₁₀ = 80 bis 84 Gew.-%, C₁₂ = 7 bis 12 Gew.-%, C₁₄ = 6 bis 8 Gew.-% und C15-16= 0 bis 1 Gew.-%.2. Surfactant mixture according to claim 1, characterized in that R represents a linear alkyl radical of the following composition:
C₈ = 0 to 2% by weight, C₁₀ = 80 to 84% by weight, C₁₂ = 7 to 12% by weight, C₁₄ = 6 to 8% by weight and C 15-16 = 0 to 1% by weight. -%. 3. Wasch- und Reinigungsmittel, enthaltend eine Tensidmischung gemäß Anspruch 1 und 2, wobei die Mittel frei von alkoxy­lierten Alkylphenolen sind.3. washing and cleaning agents containing a surfactant mixture according to claim 1 and 2, wherein the agents are free from alkoxylated alkylphenols. 4. Mittel nach Anspruch 3, worin die Tensidmischung in Kombi­nation mit ethoxylierten Alkylaminen mit 10 bis 18 C-Atomen in der Alkylkette vorliegt.4. Composition according to claim 3, wherein the surfactant mixture is present in combination with ethoxylated alkylamines having 10 to 18 carbon atoms in the alkyl chain. 5. Mittel nach Anspruch 4, worin das alkoxylierte Alkylamin 2 bis 3 EO-Gruppen aufweist.5. A composition according to claim 4, wherein the alkoxylated alkylamine has 2 to 3 EO groups.
EP87118480A 1986-12-22 1987-12-14 Mixtures of liquid non-ionic surfactants Expired - Lifetime EP0272574B1 (en)

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DE19863643895 DE3643895A1 (en) 1986-12-22 1986-12-22 LIQUID NON-ionic surfactant blends

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WO1991009925A2 (en) * 1989-12-22 1991-07-11 Henkel Kommanditgesellschaft Auf Aktien Use of a combination of non-ionic surface-active agents
GB2245262A (en) * 1990-06-22 1992-01-02 Unilever Plc Aluminosilicate slurries l
WO1994010278A1 (en) * 1992-11-04 1994-05-11 Henkel Kommanditgesellschaft Auf Aktien Aqueous surfactant concentrate
EP0652281A1 (en) * 1993-11-05 1995-05-10 The Dow Chemical Company Aqueous alkaline composition
EP0694606A3 (en) * 1994-07-29 1997-05-21 Hoechst Ag Mixtures of alkoxylates as foam depressing agent and use thereof
WO1999009121A1 (en) * 1997-08-20 1999-02-25 Colgate-Palmolive Company Microemulsion all purpose liquid cleaning compositions
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WO1991003536A1 (en) * 1989-08-30 1991-03-21 Henkel Kommanditgesellschaft Auf Aktien Use of polyalkylenediol ether mixtures as anti-foaming agents
WO1991009925A2 (en) * 1989-12-22 1991-07-11 Henkel Kommanditgesellschaft Auf Aktien Use of a combination of non-ionic surface-active agents
WO1991009925A3 (en) * 1989-12-22 1992-01-09 Henkel Kgaa Use of a combination of non-ionic surface-active agents
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GB2245262A (en) * 1990-06-22 1992-01-02 Unilever Plc Aluminosilicate slurries l
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EP0652281A1 (en) * 1993-11-05 1995-05-10 The Dow Chemical Company Aqueous alkaline composition
EP0694606A3 (en) * 1994-07-29 1997-05-21 Hoechst Ag Mixtures of alkoxylates as foam depressing agent and use thereof
WO1999009121A1 (en) * 1997-08-20 1999-02-25 Colgate-Palmolive Company Microemulsion all purpose liquid cleaning compositions
CN101584973A (en) * 2008-05-20 2009-11-25 考格尼斯知识产权管理有限责任公司 Aqueous tenside compounds with low pour point
EP2123350A1 (en) * 2008-05-20 2009-11-25 Cognis IP Management GmbH Aqueous tenside compounds with low pour point
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WO2011003904A1 (en) * 2009-07-10 2011-01-13 Basf Se Surfactant mixture having short- and long-chained components

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ATE94897T1 (en) 1993-10-15
US4965014A (en) 1990-10-23
DE3787516D1 (en) 1993-10-28
EP0272574A3 (en) 1989-09-06
ES2059351T3 (en) 1994-11-16
DE3643895A1 (en) 1988-06-30

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