EP0340704A2 - Aqueous acid detergent compositions - Google Patents

Aqueous acid detergent compositions Download PDF

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Publication number
EP0340704A2
EP0340704A2 EP89107879A EP89107879A EP0340704A2 EP 0340704 A2 EP0340704 A2 EP 0340704A2 EP 89107879 A EP89107879 A EP 89107879A EP 89107879 A EP89107879 A EP 89107879A EP 0340704 A2 EP0340704 A2 EP 0340704A2
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EP
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Prior art keywords
weight
fatty
atoms
alcohols
ethylene oxide
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EP89107879A
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German (de)
French (fr)
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EP0340704B1 (en
EP0340704A3 (en
Inventor
Richard Dr. Baur
Dieter Stoeckigt
Hans-Werner Neumann
Hans-Helmut Dr. Goertz
Norbert Dr. Wagner
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BASF SE
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BASF SE
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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/042—Acids
    • 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
    • C11D1/72—Ethers of polyoxyalkylene glycols
    • 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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2075—Carboxylic acids-salts thereof
    • 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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3707—Polyethers, e.g. polyalkyleneoxides

Definitions

  • Aqueous acidic cleaner formulations are known. They contain tensides and acids as essential components.
  • the known acidic technical cleaners are used, for example, in dairies to remove deposits of lactic acid. They are also used to clean pipelines in which deposits of calcium and magnesium carbonates have formed.
  • the cleaning agent formulations In order to extend the exposure time of these technical cleaning systems when cleaning hard surfaces and thus to ensure optimal cleaning performance, the cleaning agent formulations must have a minimum viscosity so that the formulation cannot run off too quickly from the surface to be cleaned.
  • the viscosity of the known cleaner formulations is adjusted by using mixtures of different alkylphenol ethoxylates with different degrees of ethoxylation.
  • nonionic surfactants based on alkoxylated fatty alcohols, fatty acids, fatty amines, fatty acid amides or alkanesulfonamides are now used. However, the viscosity of such aqueous acidic cleaning formulations is not yet sufficient.
  • the present invention has for its object to provide aqueous acidic cleaner formulations which have an increased viscosity compared to the known acidic technical cleaners.
  • the cleaner formulations should also be stable in storage.
  • the detergent formulations can optionally contain further, conventional constituents, such as solubilizers, corrosion inhibitors and builders.
  • the aqueous acidic cleaning formulations contain, as an essential component (a), at least one nonionic surfactant based on alkoxylated fatty alcohols, fatty acids, fatty amines, fatty acid amides or alkanesulfonamides. These compounds are addition products of 3 to 40 moles of ethylene oxide with 1 mole of fatty alcohols, fatty acids, fatty amines, fatty acid amides or alkanesulfonamides each containing at least 8 carbon atoms.
  • the adducts of 3 to 20 moles of ethylene oxide with 1 mole of at least one alcohol having 10 to 18 carbon atoms are particularly preferred for use in the preparation of the aqueous acidic cleaner formulations.
  • Suitable alcohols are preferably coconut oil or tallow fatty alcohols, oleyl alcohol or synthetically produced alcohols with 8 to 18 carbon atoms.
  • the synthetic alcohols are produced, for example, by the Oxo process or the Ziegler process.
  • Preferred alcohols are, for example, isodecanol, decanol, isotridekanol and mixtures of C13 / C15 fatty alcohol mixtures and C16 / C16 fatty alcohol mixtures.
  • the ethoxylated fatty alcohols used with particular preference contain 3 to 16 moles of ethylene oxide per mole of alcohol.
  • the amount of nonionic surfactants in the aqueous acidic cleaning formulations is 1 to 20, preferably 5 to 15% by weight.
  • the aqueous acidic cleaning formulations contain, as a further essential component, at least one polyether polyol which can be obtained by reacting 2 to 6-valent alcohols which have 2 to 10 C atoms with alkylene oxides containing 2 to 4 C atoms and reacting these reaction products with 8 up to 30 carbon atoms containing 1,2-alkylene oxides, alkyl or alkenyl glycidyl ethers.
  • polyether polyols of component (b) are prepared in an at least two-stage process.
  • ethylene oxide or first ethylene oxide and then an alkylene oxide with 3 or 4 carbon atoms are added to a polyfunctional alcohol with 2 to 10 carbon atoms and 2 to 6 hydroxyl groups.
  • at least 1 alkylene oxide having 8 to 30 carbon atoms or an alkyl or alkenyl glycidyl ether having 8 to 30 carbon atoms in the alkyl or alkylene radical is added to the reaction product thus obtained. If mixtures of alkylene oxides with 2 to 4 carbon atoms are used in the first reaction stage, either statistical copolymers can be used (ie the reaction is carried out with mixtures of alkylene oxides carried out) or block copolymers.
  • the block copolymers are formed by first reacting the compounds to be alkoxylated, for example, with ethylene oxide and then with propylene oxide or a butylene oxide.
  • the alkylene oxides are added in a known manner to 2- to 6-valent alcohols.
  • These polyfunctional alcohols can be alkane polyols, alkene polyols, alkyne polyols or oxialkylene polyols.
  • alkane polyols are ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, trimethylolpropane, pentaerythritol, glycerol, 2,3,4,5- Hexantetrol, glucose and similarly structured sugars.
  • alkene polyols are 2-butene-1,4-diol, 2-hexene-1,4,6-triol, 1,5-hexadiene-3,4-diol, 3-heptene-1,2,6,7- tetrol.
  • alkyne polyols examples include 2-butyne-1,4-diol, 2-hexyne-1,4,6-triol and 4-octyne-1,2,7,8-tetrol.
  • oxyalkylene glycols are said to include diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol and the like. Connections are understood.
  • trimethylolpropane, pentaerythritol, ethylene glycol and diethylene glycol are preferably suitable for the preparation of the polyether polyols according to (b).
  • At least one sufficient amount of an alkylene oxide with 2 to 4 carbon atoms is added to 1 mol of the polyhydric alcohol to produce products which contain up to 90% by weight of oxyalkylene units of alkylene oxides containing 2 to 4 carbon atoms.
  • the alkylene oxide addition product produced in the first stage of the reaction can also consist entirely of oxyethylene units.
  • those reaction products of the polyhydric alcohols with ethylene oxide and propylene oxide which contain ethylene oxide and propylene oxide in a weight ratio of 70:30 to 95: 5 added to a polyhydric alcohol are of interest. This can be either statistical polymers or block copolymers.
  • the polyhydric alcohols prepared in the first process stage and reacted with C2- to C4-alkylene oxides are reacted with 1,2-alkylene oxides containing 8 to 30 C atoms.
  • 1,2-alkylene oxides 1,2-alkyl or 1,2-alkenyl glycidyl ether can also be used.
  • the preparation of such glycidyl ethers is known, for example, from US Pat. No. 4,086,279.
  • Suitable long-chain alkylene oxides are, for example, 1,2-epoxyoctane, 1,2-epoxydodecane, 1,2-epoxyhexadecane, 1,2-epoxyoctacosane as well as mixtures of the epoxides mentioned and the commercially available mixtures of epoxides which have 10 to 20 carbon atoms.
  • alkyl glycidyl ethers examples include dodecyl, tetradecyl, hexadecyl, octadecyl, eicosyl, 2-methyldodecyl and 2-methyl tetradecyl, 2-methylpentadecyl, 2-hexyldecyl or 2-octyldodecylglycidyl ether.
  • Alkenyl glycidyl ether is preferably oleyl glycidyl ether.
  • the alkoxylations in the first and second reaction stages for the preparation of the polyether polyols are preferably carried out in the presence of bases such as sodium hydroxide solution or potassium hydroxide solution, at higher temperatures, e.g. up to temperatures of 160 ° C.
  • the reaction products obtained in the second stage contain the long-chain 1,2-alkylene oxide or the long-chain glycidyl ether in an amount of 0.5 to 75, preferably 1 to 20% by weight in the attached form.
  • Amounts of 1,2-alkylene oxides having 8 to 30 carbon atoms or the corresponding glycidyl ethers in the polyether polyol are particularly preferred such that the average molar ratio of longer-chain epoxide or glycidyl ether to each individual hydroxyl group of the polyhydric alcohol is preferably between 0.5 and 5 0.5 to 1.5.
  • the molecular weight of the polyether polyols of component (b) of the detergent formulations is 1000 to 75,000 and is preferably in the range from 5000 to 25,000.
  • the polyether polyols described are used in amounts of 0.1 to 15, preferably 0.15 to 10,% by weight in aqueous acidic cleaner formulations. In such formulations, together with the nonionic surfactants specified under (a), they produce a synergistic effect with regard to the increase in viscosity.
  • the viscosities of the aqueous acidic cleaning formulations are 100 to 19000 mPa.s.
  • inorganic or organic acids are suitable, e.g. Hydrochloric acid, sulfuric acid, phosphoric acid, formic acid, oxalic acid and citric acid or dicarboxylic acid mixtures (e.g. from succinic acid, glutaric acid and adipic acid). Acidic phosphoric acid esters as well as amidosulfonic acid and propanesulfonic acid are also suitable.
  • the cleaning formulations contain 1 to 40, preferably 5 to 20% by weight of at least one acid.
  • the acidic cleaning formulations contain water to make up to 100% by weight.
  • the cleaner formulations may also contain other constituents, such as solubilizers, corrosion inhibitors or builders.
  • Solubilizers are, for example, compounds such as isopropanol, glycol ether, cumene sulfonic acid or their alkali salts.
  • the solubilizers are used in an amount of up to 10% by weight, based on the overall formulation.
  • the cleaner formulations can also contain corrosion inhibitors, which may be used in amounts of up to 1% by weight. Suitable corrosion inhibitors are, for example, for HCl / H2SO4, 1,4-butynediol with application amounts of 0.1 to 0.2% for 10% effectively present acid or for H3PO4 methylphenylthiourea with 0.5%, based on 20% effectively present acid.
  • the cleaner formulations may also contain builders if necessary. These are, for example, compounds such as acidic salts of phosphoric acid, sulfuric acid etc. (sodium hydrophosphate, sodium bisulfate).
  • the amount of builders in the detergent formulation is up to 20% by weight.
  • aqueous acidic cleaner formulations described above are used to clean hard surfaces.
  • the removal of calcium and magnesium carbonate deposits from pipelines or heat exchangers which are operated with hard water may be mentioned as an example.
  • the acidic cleaner formulations are also used in dairies, for example to remove lactic acid deposits from objects made of metal, porcelain or ceramics.
  • the parts given in the following examples are parts by weight, the data in% relate to the weight of the substances.
  • the viscosities were measured in a Couette rotary viscometer at 20 ° C and a shear of 150 seconds ⁇ 1.
  • the molecular weights of the substances are average molecular weights after the number average.
  • polyether polyols were used as thickeners (component (b)):
  • Polyether polyol with a molecular weight of approx. 17,000 which can be obtained by reacting 1 mol of trimethylolpropane with a mixture of 102 mol of ethylene oxide and 19 mol of propylene oxide and then further reacting the alkoxylation product with 3 mol of a 1,2-alkylene oxide with 16 carbon atoms.
  • the proportion of long-chain alkylene oxide was 4.06% by weight.
  • the proportion of longer-chain bound alkylene oxide was 4.18% by weight.
  • the built-in C18 alkylene oxide content was 4.55% by weight.
  • surfactant I Addition product of 7 moles of ethylene oxide with 1 mole of isodecanol.
  • Surfactant II Addition product of 8 moles of ethylene oxide with 1 mole of isotridecanol.
  • Surfactant III Addition product of 7 moles of ethylene oxide with 1 mole of a C13 / C15 fatty alcohol mixture.
  • Surfactant IV Addition product of 3 moles of ethylene oxide with 1 mole of a C13 / C15 fatty alcohol mixture.
  • surfactant V Addition product of 5 moles of ethylene oxide with 1 mole of a C13 / C15 fatty alcohol mixture.
  • Surfactant VI Addition product of 11 moles of ethylene oxide with 1 mole of a C13 / C15 fatty alcohol mixture.
  • Surfactant VII Addition product of 11 moles of ethylene oxide with 1 mole of a C16 / C18 fatty alcohol mixture.
  • Surfactant VIII Addition product of 5 moles of ethylene oxide with 1 mole of isotridecanol.
  • Surfactant IX Addition product of 10 moles of ethylene oxide with 1 mole of C9-alkylphenol.
  • Surfactant X Addition product of 8 moles of ethylene oxide with 1 mole of a C13- / C15 fatty alcohol.
  • aqueous acidic cleaner formulations were prepared by mixing the surfactant, thickener, acid and water: 10% surfactant X% thickener 20% acid 70-X% water.
  • a thickener-free formulation of the following composition was examined as a comparison: 15% surfactant 20% acid and 65% water.
  • composition of the aqueous acidic cleaner formulations produced in each case and the viscosity of these formulations is given in Table 1.
  • aqueous acidic cleaner formulations are obtained according to the invention which have greatly increased viscosities compared to the corresponding thickener-free cleaner formulations.
  • Aqueous acidic cleaner formulations were prepared in accordance with the standard formulation given in Example 1. The table also provides information about the viscosity of the detergent formulations.
  • Table 2 No. Surfactant (a) Concentration of surfactant [%] Thickener (b) Concentration of thickener [%] Acid 20% (c) Viscosity of the detergent formulation [mPa.s] 1 (compare) IX 10th - - H3PO4 18th 2 (compare) IX 10th A 1 " 40 3 (compare) III 10th - - " 90 4th III 10th A 1 " 2598 5 (compare) X 10th - - " 15 6 X 10th A 1 " 1082 7 VII 10th - - " 12 8th VII 10th A 1 " 865
  • compositions given in Table 2 under Nos. 4, 6 and 8 are examples according to the invention, the other compositions are used for comparison.
  • Table 2 the selection of the surfactant plays a decisive role for the desired high viscosity of a detergent formulation.
  • An ethoxylated alkylphenol as a surfactant does not give the desired increase in viscosity, while the surfactants III, X and VII on the other hand lead to a surprisingly increased viscosity of the detergent formulation.

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Abstract

The compositions contain as essential components (a) 1 to 20% by weight of at least one non-ionic surfactant based on alkoxylated fatty alcohols, fatty acids, fatty amines, fatty acid amides or alkanesulphonamides, (b) 0.1 to 15% by weight of at least one polyether polyol which is obtainable by reaction of 2 to 6-hydric alcohols, which have 2 to 10 C atoms, with alkylene oxides containing 2 to 4 C atoms, and reaction of these reaction products with 1,2-alkylene oxides, alkyl or alkenyl glycidyl ethers containing 8 to 30 C atoms and (c) 1 to 40% by weight of at least one acid.

Description

Wäßrige saure Reinigerformulierungen sind bekannt. Sie enthalten als wesentliche Bestandteile Tenside und Säuren. Die bekannten sauren technischen Reiniger werden beispielsweise in Molkereien eingesetzt, um Niederschläge der Milchsäure zu entfernen. Sie werden außerdem zur Reinigung von Rohrleitungen verwendet, in denen sich insbesondere Ab­lagerungen von Kalzium- und Magnesium-Carbonaten gebildet haben. Um eine Verlängerung der Einwirkungszeit dieser technischen Reinigersysteme bei der Reinigung harter Oberflächen zu erreichen und damit eine optimale Reinigungsleistung zu gewährleisten, müssen die Reinigerformulierungen eine Mindestviskosität aufweisen, damit ein zu schnelles Ablaufen der Formulierung von der zu reinigenden Oberfläche verhindert wird. Die Viskosität der bekannten Reinigerformulierungen wird dadurch eingestellt, daß man Mischungen verschiedener Alkylphenolethoxylate mit unter­schiedlichen Ethoxylierungsgraden einsetzt. Durch den ökologisch notwendig gewordenen Austausch der Alkylphenolethoxilate werden jetzt vor allem nichtionische Tenside auf der Basis von alkoxilierten Fettalkoholen, Fettsäuren, Fettaminen, Fettsäureamiden oder Alkansulfonamiden verwendet. Die Viskosität solcher wäßriger saurer Reingigungsformulierungen ist jedoch noch nicht ausreichend.Aqueous acidic cleaner formulations are known. They contain tensides and acids as essential components. The known acidic technical cleaners are used, for example, in dairies to remove deposits of lactic acid. They are also used to clean pipelines in which deposits of calcium and magnesium carbonates have formed. In order to extend the exposure time of these technical cleaning systems when cleaning hard surfaces and thus to ensure optimal cleaning performance, the cleaning agent formulations must have a minimum viscosity so that the formulation cannot run off too quickly from the surface to be cleaned. The viscosity of the known cleaner formulations is adjusted by using mixtures of different alkylphenol ethoxylates with different degrees of ethoxylation. Due to the ecologically necessary replacement of the alkylphenol ethoxylates, nonionic surfactants based on alkoxylated fatty alcohols, fatty acids, fatty amines, fatty acid amides or alkanesulfonamides are now used. However, the viscosity of such aqueous acidic cleaning formulations is not yet sufficient.

Der vorliegenden Erfindung liegt die Aufgabe zugrunde, wäßrige saure Reinigerformulierungen zur Verfügung zu stellen, die gegenüber den be­kannten sauren technischen Reinigern eine erhöhte Viskosität aufweisen. Die Reinigerformulierungen sollen außerdem lagerstabil sein.The present invention has for its object to provide aqueous acidic cleaner formulations which have an increased viscosity compared to the known acidic technical cleaners. The cleaner formulations should also be stable in storage.

Die Aufgabe wird erfindungsgemäß gelöst mit wäßrigen sauren Reiniger­formulierungen, die gekennzeichnet sind durch einen Gehalt an - jeweils bezogen auf das Gewicht der gesamten Formulierung -

  • (a) 1 bis 20 Gew.-% mindestens eines nichtionischen Tensids auf der Basis von alkoxylierten Fettalkoholen, Fettsäuren, Fettaminen, Fettsäure­amiden oder Alkansulfonamiden,
  • (b) 0,1 bis 15 Gew.-% mindestens eines Polyetherpolyols, das erhältlich ist durch Umsetzung von 2- bis 6-wertigen Alkoholen, die 2 bis 10 C-Atome aufweisen, mit 2 bis 4 C-Atome enthaltenden Alkylenoxiden und Reaktion dieser Umsetzungsprodukte mit 8 bis 30 C-Atome ent­haltenden 1,2-Alkylenoxiden, Alkyl- oder Alkenylglycidethern und
  • (c) 1 bis 40 Gew.-% mindestens einer Säure.
The object is achieved according to the invention with aqueous acidic cleaning formulations which are characterized by a content of - in each case based on the weight of the overall formulation -
  • (a) 1 to 20% by weight of at least one nonionic surfactant based on alkoxylated fatty alcohols, fatty acids, fatty amines, fatty acid amides or alkanesulfonamides,
  • (b) 0.1 to 15% by weight of at least one polyether polyol which can be obtained by reacting 2- to 6-valent alcohols which have 2 to 10 C atoms with alkylene oxides containing 2 to 4 C atoms and reaction of these reaction products with 1,2 to 8 alkylene oxides containing 8 to 30 C atoms, alkyl or alkenyl glycidyl ethers and
  • (c) 1 to 40% by weight of at least one acid.

Die Reinigerformulierungen können gegebenenfalls weitere, übliche Bestandteile, wie Lösungsvermittler, Korrosionsinhibitoren und Builder enthalten.The detergent formulations can optionally contain further, conventional constituents, such as solubilizers, corrosion inhibitors and builders.

Die wäßrigen sauren Reinigerformulierungen enthalten als eine wesentliche Komponente (a) mindestens ein nichtionisches Tensid auf der Basis von alkoxylierten Fettalkoholen, Fettsäuren, Fettaminen, Fettsäureamiden oder Alkansulfonamiden. Bei diesen Verbindungen handelt es sich um Anlagerungs­produkte von 3 bis 40 Mol Ethylenoxid an 1 Mol von jeweils mindestens 8 C-Atome enthaltenden Fettalkoholen, Fettsäuren, Fettaminen, Fettsäure­amiden oder Alkansulfonamiden. Besonders bevorzugt für den Einsatz zur Herstellung der wäßrigen sauren Reinigerformulierungen sind die An­lagerungsprodukte von 3 bis 20 Mol Ethylenoxid an 1 Mol mindestens eines Alkohols mit 10 bis 18 C-Atomen. Als Alkohole kommen vorzugsweise Kokos-oder Talgfettalkohole, Oleylalkohol oder synthetisch hergestellte Alkohole mit 8 bis 18 C-Atomen in Betracht. Die synthetischen Alkohole werden beispielsweise nach dem Oxo-Verfahren oder Ziegler-Verfahren her­gestellt. Bevorzugt zur Anwendung gelangende Alkohole sind beispielsweise Isodekanol, Dekanol, Isotridekanol sowie Mischungen aus C₁₃/C₁₅-Fett­alkoholgemischen und C₁₆/C₁₈-Fettalkoholgemischen. Die besonders bevorzugt zum Einsatz gelangenden ethoxylierten Fettalkohole enthalten 3 bis 16 Mol Ethylenoxid pro Mol Alkohol angelagert. Die Menge an nichtionischen Tensiden in den wäßrigen sauren Reinigerformulierungen beträgt 1 bis 20, vorzugsweise 5 bis 15 Gew.-%.The aqueous acidic cleaning formulations contain, as an essential component (a), at least one nonionic surfactant based on alkoxylated fatty alcohols, fatty acids, fatty amines, fatty acid amides or alkanesulfonamides. These compounds are addition products of 3 to 40 moles of ethylene oxide with 1 mole of fatty alcohols, fatty acids, fatty amines, fatty acid amides or alkanesulfonamides each containing at least 8 carbon atoms. The adducts of 3 to 20 moles of ethylene oxide with 1 mole of at least one alcohol having 10 to 18 carbon atoms are particularly preferred for use in the preparation of the aqueous acidic cleaner formulations. Suitable alcohols are preferably coconut oil or tallow fatty alcohols, oleyl alcohol or synthetically produced alcohols with 8 to 18 carbon atoms. The synthetic alcohols are produced, for example, by the Oxo process or the Ziegler process. Preferred alcohols are, for example, isodecanol, decanol, isotridekanol and mixtures of C₁₃ / C₁₅ fatty alcohol mixtures and C₁₆ / C₁₆ fatty alcohol mixtures. The ethoxylated fatty alcohols used with particular preference contain 3 to 16 moles of ethylene oxide per mole of alcohol. The amount of nonionic surfactants in the aqueous acidic cleaning formulations is 1 to 20, preferably 5 to 15% by weight.

Die wäßrigen sauren Reinigerformulierungen enthalten als weitere wesent­liche Komponente mindestens ein Polyetherpolyol, das erhältlich ist durch Umsetzung von 2 bis 6-wertigen Alkoholen, die 2 bis 10 C-Atome aufweisen, mit 2 bis 4 C-Atome enthaltenden Alkylenoxiden und Reaktion dieser Um­setzungsprodukte mit 8 bis 30 C-Atome enthaltenden 1,2-Alkylenoxiden, Alkyl- oder Alkenylglycidethern. Verbindungen dieser Art werden beispiels­weise beschrieben in den US-Patentschriften 4 649 224, 4 655 239 und 4 709 099. Die Polyetherpolyole der Komponente (b) werden in einem minde­stens 2-stufigen Verfahren hergestellt. In der ersten Verfahrensstufe lagert man Ethylenoxid oder zunächst Ethylenoxid und dann ein Alkylenoxid mit 3 oder 4 Kohlenstoffatomen an einen polyfunktionellen Alkohol mit 2 bis 10 Kohlenstoffatomen und 2 bis 6 Hydroxygruppen an. In der zweiten Reaktionsstufe wird an das so erhaltene Umsetzungsprodukt mindestens 1 Alkylenoxid mit 8 bis 30 Kohlenstoffatomen oder ein Alkyl-oder Alkenyl­glycidether mit 8 bis 30 Kohlenstoffatomen im Alkyl- bzw. Alkylenrest angelagert. Sofern man in der ersten Reaktionsstufe Mischungen aus Alkylenoxiden mit 2 bis 4 C-Atomen einsetzt, kann man entweder statisti­sche Copolymerisate (d.h. die Umsetzung wird mit Mischungen aus Alkylen­ oxiden durchgeführt) oder Blockcopolymerisate herstellen. Die Block­copolymerisate entstehen, indem man die zu alkoxylierenden Verbindungen beispielsweise zunächst mit Ethylenoxid und dann anschließend mit Propylenoxid oder einem Butylenoxid umsetzt. Die Alkylenoxide werden in bekannter Weise an 2- bis 6-wertige Alkohole addiert. Bei diesen poly­funktionellen Alkoholen kann es sich um Alkanpolyole, Alkenpolyole, Alkin­polyole oder Oxialkylenpolyole handeln. Beispiele für Alkanpolyole sind Ethylenglykol, 1,2-Propylenglykol, 1,3-Propylenglykol, 1,2-Butandiol, 1,3-Butandiol, 1,4-Butandiol, Trimethylolpropan, Pentaerythrit, Glycerin, 2,3,4,5-Hexantetrol, Glucose u.a. ähnlich aufgebaute Zucker. Beispiele für Alkenpolyole sind 2-Buten-1,4-diol, 2-Hexen-1,4,6-triol, 1,5-Hexa­dien-3,4-diol, 3-Hepten-1,2,6,7-tetrol. Beispiele für Alkinpolyole sind 2-Butin-1,4-diol, 2-Hexin-1,4,6-triol und 4-Octin-1,2,7,8-tetrol. Unter Oxyalkylenglykolen sollen im vorliegenden Zusammenhang Diethylenglykol, Triethylenglykol, Tetraethylenglykol, Dipropylenglykol u.ä. Verbindungen verstanden werden. Von den genannten polyfunktionellen Alkoholen kommen vorzugsweise Trimethylolpropan, Pentaerythrit, Ethylenglykol und Diethylenglykol zur Herstellung der Polyetherpolyole gemäß (b) in Betracht. An 1 Mol des mehrwertigen Alkohols lagert man mindestens soviel eines Alkylenoxids mit 2 bis 4 C-Atomen an, daß Produkte entstehen, die bis zu 90 Gew.-% Oxyalkyleneinheiten von 2 bis 4 C-Atome enthaltenden Alkylenoxiden aufweisen. Das in der ersten Stufe der Umsetzung her­gestellte Alkylenoxidanlagerungsprodukt kann jedoch auch vollständig aus Oxyethyleneinheiten bestehen. Außer den reinen Ethylenoxidaddukten an die in Betracht kommenden mehrwertigen Alkohole sind solche Umsetzungsprodukte der mehrwertigen Alkohole mit Ethylenoxid und Propylenoxid von Interesse, die Ethylenoxid und Propylenoxid im Gewichtsverhältnis 70 : 30 bis 95 : 5 an einen mehrwertigen Alkohol addiert enthalten. Hierbei kann es sich entweder um statistische Polymerisate oder um Blockcopolymerisate handeln.The aqueous acidic cleaning formulations contain, as a further essential component, at least one polyether polyol which can be obtained by reacting 2 to 6-valent alcohols which have 2 to 10 C atoms with alkylene oxides containing 2 to 4 C atoms and reacting these reaction products with 8 up to 30 carbon atoms containing 1,2-alkylene oxides, alkyl or alkenyl glycidyl ethers. Compounds of this type are described, for example, in US Pat. Nos. 4,649,224, 4,655,239 and 4,709,099. The polyether polyols of component (b) are prepared in an at least two-stage process. In the first stage of the process, ethylene oxide or first ethylene oxide and then an alkylene oxide with 3 or 4 carbon atoms are added to a polyfunctional alcohol with 2 to 10 carbon atoms and 2 to 6 hydroxyl groups. In the second reaction stage, at least 1 alkylene oxide having 8 to 30 carbon atoms or an alkyl or alkenyl glycidyl ether having 8 to 30 carbon atoms in the alkyl or alkylene radical is added to the reaction product thus obtained. If mixtures of alkylene oxides with 2 to 4 carbon atoms are used in the first reaction stage, either statistical copolymers can be used (ie the reaction is carried out with mixtures of alkylene oxides carried out) or block copolymers. The block copolymers are formed by first reacting the compounds to be alkoxylated, for example, with ethylene oxide and then with propylene oxide or a butylene oxide. The alkylene oxides are added in a known manner to 2- to 6-valent alcohols. These polyfunctional alcohols can be alkane polyols, alkene polyols, alkyne polyols or oxialkylene polyols. Examples of alkane polyols are ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, trimethylolpropane, pentaerythritol, glycerol, 2,3,4,5- Hexantetrol, glucose and similarly structured sugars. Examples of alkene polyols are 2-butene-1,4-diol, 2-hexene-1,4,6-triol, 1,5-hexadiene-3,4-diol, 3-heptene-1,2,6,7- tetrol. Examples of alkyne polyols are 2-butyne-1,4-diol, 2-hexyne-1,4,6-triol and 4-octyne-1,2,7,8-tetrol. In the present context, oxyalkylene glycols are said to include diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol and the like. Connections are understood. Of the polyfunctional alcohols mentioned, trimethylolpropane, pentaerythritol, ethylene glycol and diethylene glycol are preferably suitable for the preparation of the polyether polyols according to (b). At least one sufficient amount of an alkylene oxide with 2 to 4 carbon atoms is added to 1 mol of the polyhydric alcohol to produce products which contain up to 90% by weight of oxyalkylene units of alkylene oxides containing 2 to 4 carbon atoms. However, the alkylene oxide addition product produced in the first stage of the reaction can also consist entirely of oxyethylene units. In addition to the pure ethylene oxide adducts to the polyhydric alcohols in question, those reaction products of the polyhydric alcohols with ethylene oxide and propylene oxide which contain ethylene oxide and propylene oxide in a weight ratio of 70:30 to 95: 5 added to a polyhydric alcohol are of interest. This can be either statistical polymers or block copolymers.

In der zweiten Stufe zur Herstellung der Polyetherpolyole (b) werden die in der ersten Verfahrensstufe hergestellten, mit C₂- bis C₄-Alkylenoxiden umgesetzten mehrwertigen Alkohole mit 8 bis 30 C-Atome enthaltenden 1,2-Alkylenoxiden zur Reaktion gebracht. Anstelle der 1,2-Alkylenoxide kann man auch 1,2-Alkyl- oder 1,2-Alkenylglycidether einsetzen. Die Herstellung solcher Glycidylether ist beispielsweise aus der US-PS 4 086 279 bekannt. Geeignete langkettige Alkylenoxide sind beispielsweise 1,2-Epoxyoctan, 1,2-Epoxydodecan, 1,2-Epoxyhexadecan, 1,2-Epoxyoctacosan sowie Mischungen der genannten Epoxide sowie die im Handel erhältlichen Mischungen von Epoxiden, die 10 bis 20 Kohlen­stoffatome aufweisen. Beispiele für Alkylglycidylether sind Dodecyl-, Tetradecyl-, Hexadecyl-, Octadecyl-, Eicosyl-, 2-Methyldodecyl-, 2-Methyl­ tetradecyl-, 2-Methylpentadecyl-, 2-Hexyldecyl- oder 2-Octyldodecyl­glycidylether. Als Alkenylglycidylether kommt vorzugsweise Oleylglycidyl­ether in Betracht.In the second stage for the preparation of the polyether polyols (b), the polyhydric alcohols prepared in the first process stage and reacted with C₂- to C₄-alkylene oxides are reacted with 1,2-alkylene oxides containing 8 to 30 C atoms. Instead of the 1,2-alkylene oxides, 1,2-alkyl or 1,2-alkenyl glycidyl ether can also be used. The preparation of such glycidyl ethers is known, for example, from US Pat. No. 4,086,279. Suitable long-chain alkylene oxides are, for example, 1,2-epoxyoctane, 1,2-epoxydodecane, 1,2-epoxyhexadecane, 1,2-epoxyoctacosane as well as mixtures of the epoxides mentioned and the commercially available mixtures of epoxides which have 10 to 20 carbon atoms. Examples of alkyl glycidyl ethers are dodecyl, tetradecyl, hexadecyl, octadecyl, eicosyl, 2-methyldodecyl and 2-methyl tetradecyl, 2-methylpentadecyl, 2-hexyldecyl or 2-octyldodecylglycidyl ether. Alkenyl glycidyl ether is preferably oleyl glycidyl ether.

Die Alkoxylierungen in der ersten und zweiten Reaktionsstufe zur Herstellung der Polyetherpolyole wird bekanntlich vorzugsweise in Gegenwart von Basen wie Natronlauge oder Kalilauge, bei höheren Temperaturen, z.B. bis zu Temperaturen von 160°C vorgenommen. Die in der zweiten Stufe anfallenden Reaktionsprodukte enthalten das langkettige 1,2-Alkylenoxid bzw. den langkettigen Glycidylether in einer Menge von 0,5 bis 75, vorzugsweise 1 bis 20 Gew.-% in angelagerter Form. Besonders bevorzugt sind solche Mengen an 1,2-Alkylenoxiden mit 8 bis 30 Kohlen­stoffatomen bzw. den entsprechenden Glycidylethern im Polyetherpolyol, daß das durchschnittliche molare Verhältnis von längerkettigem Epoxid bzw. Glycidylether zu jeder einzelnen Hydroxylgruppe des mehrwertigen Alkohols zwischen 0,5 und 5, vorzugsweise 0,5 bis 1,5 liegt. Das Molekulargewicht der Polyetherpolyole der Komponente (b) der Reinigerformulierungen beträgt 1000 bis 75 000 und liegt vorzugsweise in dem Bereich von 5000 bis 25 000. Die 1,2-Alkylenoxide mit 8 bis 30 C-Atomen bzw. die an deren Stelle eingesetzten Glycidylether sind zu 0,5 bis 75, vorzugsweise 1 bis 20 Gew.-% am Aufbau der Polyetherpolyole beteiligt. Die beschriebenen Polyetherpolyole werden in Mengen von 0,1 bis 15, vorzugsweise 0,15 bis 10 Gew.-% in wäßrigen sauren Reinigerformulierungen eingesetzt. Sie ergeben in solchen Formulierungen zusammen mit den unter (a) angegebenen nichtionischen Tensiden bezüglich der Viskositätserhöhung einen synergi­stischen Effekt. Die Viskositäten der wäßrigen sauren Reiniger­formulierungen betragen 100 bis 19000 mPa.s.As is known, the alkoxylations in the first and second reaction stages for the preparation of the polyether polyols are preferably carried out in the presence of bases such as sodium hydroxide solution or potassium hydroxide solution, at higher temperatures, e.g. up to temperatures of 160 ° C. The reaction products obtained in the second stage contain the long-chain 1,2-alkylene oxide or the long-chain glycidyl ether in an amount of 0.5 to 75, preferably 1 to 20% by weight in the attached form. Amounts of 1,2-alkylene oxides having 8 to 30 carbon atoms or the corresponding glycidyl ethers in the polyether polyol are particularly preferred such that the average molar ratio of longer-chain epoxide or glycidyl ether to each individual hydroxyl group of the polyhydric alcohol is preferably between 0.5 and 5 0.5 to 1.5. The molecular weight of the polyether polyols of component (b) of the detergent formulations is 1000 to 75,000 and is preferably in the range from 5000 to 25,000. The 1,2-alkylene oxides with 8 to 30 C atoms or the glycidyl ethers used in their place 0.5 to 75, preferably 1 to 20 wt .-% involved in the structure of the polyether polyols. The polyether polyols described are used in amounts of 0.1 to 15, preferably 0.15 to 10,% by weight in aqueous acidic cleaner formulations. In such formulations, together with the nonionic surfactants specified under (a), they produce a synergistic effect with regard to the increase in viscosity. The viscosities of the aqueous acidic cleaning formulations are 100 to 19000 mPa.s.

Als Komponente (c) der Reinigerformulierungen kommen anorganische oder organische Säuren in Betracht, z.B. Salzsäure, Schwefelsäure, Phosphor­säure, Ameisensäure, Oxalsäure und Zitronensäure oder Dicarbonsäure­gemische (z.B. aus Bernsteinsäure, Glutarsäure und Adipinsäure). Außerdem eignen sich saure Phosphorsäureester sowie Amidosulfonsäure und Propansulfonsäure. Die Reinigerformulierungen enthalten 1 bis 40, vorzugsweise 5 bis 20 Gew.-% mindestens einer Säure.As component (c) of the cleaning formulations, inorganic or organic acids are suitable, e.g. Hydrochloric acid, sulfuric acid, phosphoric acid, formic acid, oxalic acid and citric acid or dicarboxylic acid mixtures (e.g. from succinic acid, glutaric acid and adipic acid). Acidic phosphoric acid esters as well as amidosulfonic acid and propanesulfonic acid are also suitable. The cleaning formulations contain 1 to 40, preferably 5 to 20% by weight of at least one acid.

Außer den genannten Komponenten (a) bis (c) enthalten die sauren Reiniger­formulierungen zur Ergänzung auf 100 Gew.-% Wasser. Die Reinigerformulierungen können außerdem ggf. weitere Bestandteile ent­halten, wie Lösungsvermittler, Korrosionsinhibitoren oder Gerüstsubstanzen. Lösungsvermittler sind beispielsweise Verbindungen wie Isopropanol, Glykolether, Cumolsulfonsäure oder ihre Alkalisalze.In addition to the components (a) to (c) mentioned, the acidic cleaning formulations contain water to make up to 100% by weight. The cleaner formulations may also contain other constituents, such as solubilizers, corrosion inhibitors or builders. Solubilizers are, for example, compounds such as isopropanol, glycol ether, cumene sulfonic acid or their alkali salts.

Die Lösungsvermittler werden in einer Menge bis zu 10 Gew.-%, bezogen auf die gesamte Formulierung, angewendet. Die Reinigerformulierungen können außerdem Korrosionsinhibitoren enthalten, die ggf. in Mengen bis zu 1 Gew.-% eingesetzt werden. Gegeignete Korrosionsinhibitoren sind beispielsweise für HCl/H₂SO₄, Butindiol-1,4 mit Anwendungsmengen von 0,1 bis 0,2 % für 10 % effektiv vorhandene Säure oder für H₃PO₄ Methylphenylthioharnstoff mit 0,5 %,bezogen auf 20 % effektiv vorhandene Säure.The solubilizers are used in an amount of up to 10% by weight, based on the overall formulation. The cleaner formulations can also contain corrosion inhibitors, which may be used in amounts of up to 1% by weight. Suitable corrosion inhibitors are, for example, for HCl / H₂SO₄, 1,4-butynediol with application amounts of 0.1 to 0.2% for 10% effectively present acid or for H₃PO₄ methylphenylthiourea with 0.5%, based on 20% effectively present acid.

Die Reinigerformulierungen können außerdem ggf. noch Gerüstsubstanzen enthalten. Hierbei handelt es sich beispielsweise um Verbindungen wie saure Salze der Phosphorsäure, Schwefelsäure etc. (Natriumhydrophosphat, Natriumhydrogensulfat).The cleaner formulations may also contain builders if necessary. These are, for example, compounds such as acidic salts of phosphoric acid, sulfuric acid etc. (sodium hydrophosphate, sodium bisulfate).

Die Menge an Gerüstsubstanzen in der Reinigungsmittelformulierung beträgt bis zu 20 Gew.-%.The amount of builders in the detergent formulation is up to 20% by weight.

Die oben beschriebenen wäßrigen sauren Reinigerformulierungen werden zum Reinigen von harten Oberflächen verwendet. Beispielhaft genannt sei die Entfernung von Kalzium- und Magnesiumcarbonatniederschlägen aus Rohr­leitungen oder Wärmetauschern, die mit hartem Wasser betrieben werden. Die sauren Reinigerformulierungen werden auch in Molkereien verwendet, um beispielsweise Niederschläge der Milchsäure von Gegenständen aus Metall, Porzellan oder Keramik abzulösen.The aqueous acidic cleaner formulations described above are used to clean hard surfaces. The removal of calcium and magnesium carbonate deposits from pipelines or heat exchangers which are operated with hard water may be mentioned as an example. The acidic cleaner formulations are also used in dairies, for example to remove lactic acid deposits from objects made of metal, porcelain or ceramics.

Die in den folgenden Beispielen angegeben Teile sind Gewichtsteile, die Angaben in % beziehen sich auf das Gewicht der Stoffe.The parts given in the following examples are parts by weight, the data in% relate to the weight of the substances.

Die Viskositäten wurden in einem Couette-Rotationsviskosimeter bei 20°C und einer Scherung von 150 Sek⁻¹ gemessen. Die Molekulargewichte der Stoffe sind mittlere Molekulargewichte nach dem Zahlenmittel.The viscosities were measured in a Couette rotary viscometer at 20 ° C and a shear of 150 seconds⁻¹. The molecular weights of the substances are average molecular weights after the number average.

Als Verdicker wurden folgende Polyetherpolyole verwendet (Komponente (b)):The following polyether polyols were used as thickeners (component (b)):

Verdicker A:Thickener A:

Polyetherpolyol mit einem Molekulargewicht von ca. 17 000 das durch Umsetzung von 1 Mol Trimethylolpropan mit einer Mischung aus 102 Mol Ethylenoxid und 19 Mol Propylenoxid und anschließende weitere Umsetzung des Alkoxylierungsproduktes mit 3 Mol eines 1,2-Alkylenoxids mit 16 Kohlenstoffatomen erhältlich ist. Der Anteil an langkettigem Alkylenoxid betrug 4,06 Gew.-%.Polyether polyol with a molecular weight of approx. 17,000 which can be obtained by reacting 1 mol of trimethylolpropane with a mixture of 102 mol of ethylene oxide and 19 mol of propylene oxide and then further reacting the alkoxylation product with 3 mol of a 1,2-alkylene oxide with 16 carbon atoms. The proportion of long-chain alkylene oxide was 4.06% by weight.

Verdicker B:Thickener B:

Polyetherpolyol mit einem Molekulargewicht von ca. 17 000, das durch Umsetzung von 1 Mol Trimethylolpropan mit 85 Teilen Ethylenoxid und 15 Teilen Propylenoxid und anschließende weitere Umsetzung mit 3 Äquivalenten eine Gemisches von 1,2-Alkylenoxiden mit 15 bis 18 Kohlenstoff­atomen in der Alkylenkette erhältlich ist. Der Anteil an längerkettigem gebundenem Alkylenoxid betrug 4,18 Gew.-%.A polyether polyol with a molecular weight of approximately 17,000, which is obtainable by reacting 1 mol of trimethylolpropane with 85 parts of ethylene oxide and 15 parts of propylene oxide and subsequent further reaction with 3 equivalents, a mixture of 1,2-alkylene oxides with 15 to 18 carbon atoms in the alkylene chain . The proportion of longer-chain bound alkylene oxide was 4.18% by weight.

Verdicker C:Thickener C:

Polyetherpolyol mit einem Molekulargewicht von ca. 17 000, das durch Umsetzung von 1 Mol Trimethylolpropan mit 280 Mol Ethylenoxid und anschließende weitere Umsetzung mit 3 Äquivalenten eines 1,2-Alkylenoxids mit 12 Kohlenstoff­atomen erhalten wurde. Der Anteil des längerkettigen Alkylenoxids betrug 3,17 Gew.-%.Polyether polyol with a molecular weight of approximately 17,000, which was obtained by reacting 1 mol of trimethylolpropane with 280 mol of ethylene oxide and then further reacting with 3 equivalents of a 1,2-alkylene oxide having 12 carbon atoms. The proportion of the longer-chain alkylene oxide was 3.17% by weight.

Verdicker D:Thickener D:

Polyetherpolyol mit einem Molekulargewicht von ca. 17 000, das durch Umsetzung von 1 Mol Trimethylolpropan mit 380 Mol Ethylenoxid und anschließende weitere Umsetzung mit 3 Äquivalenten eines 1,2-Alkylenoxids mit 18 Kohlenstoff­atomen erhalten wurde. Der Gehalt an eingebautem C₁₈-Alkylenoxid betrug 4,55 Gew.-%.Polyether polyol with a molecular weight of approximately 17,000, which was obtained by reacting 1 mol of trimethylolpropane with 380 mol of ethylene oxide and then further reacting with 3 equivalents of a 1,2-alkylene oxide with 18 carbon atoms. The built-in C₁₈ alkylene oxide content was 4.55% by weight.

In den Reinigerformulierungen wurden folgende Tenside verwendet: Tensid I: Anlagerungsprodukt von 7 Mol Ethylenoxid an 1 Mol Isodecanol. Tensid II: Anlagerungsprodukt von 8 Mol Ethylenoxid an 1 Mol Isotridecanol. Tensid III: Anlagerungsprodukt von 7 Mol Ethylenoxid an 1 Mol eines C₁₃/C₁₅-Fettalkohol-Gemisches. Tensid IV: Anlagerungsprodukt von 3 Mol Ethylenoxid an 1 Mol eines C₁₃/C₁₅-Fettalkohol-Gemisches. Tensid V: Anlagerungsprodukt von 5 Mol Ethylenoxid an 1 Mol eines C₁₃/C₁₅-Fettalkohol-Gemisches. Tensid VI: Anlagerungsprodukt von 11 Mol Ethylenoxid an 1 Mol eines C₁₃/C₁₅-Fettalkohol-Gemisches. Tensid VII: Anlagerungsprodukt von 11 Mol Ethylenoxid an 1 Mol eines C₁₆/C₁₈-Fettalkohol-Gemisches. Tensid VIII: Anlagerungsprodukt von 5 Mol Ethylenoxid an 1 Mol Isotridecanol. Tensid IX: Anlagerungsprodukt von 10 Mol Ethylenoxid an 1 Mol C₉-Alkylphenol. Tensid X: Anlagerungsprodukt von 8 Mol Ethylenoxid an 1 Mol eines C₁₃-/C₁₅-Fettalkohols. The following surfactants were used in the cleaner formulations: Surfactant I: Addition product of 7 moles of ethylene oxide with 1 mole of isodecanol. Surfactant II: Addition product of 8 moles of ethylene oxide with 1 mole of isotridecanol. Surfactant III: Addition product of 7 moles of ethylene oxide with 1 mole of a C₁₃ / C₁₅ fatty alcohol mixture. Surfactant IV: Addition product of 3 moles of ethylene oxide with 1 mole of a C₁₃ / C₁₅ fatty alcohol mixture. Surfactant V: Addition product of 5 moles of ethylene oxide with 1 mole of a C₁₃ / C₁₅ fatty alcohol mixture. Surfactant VI: Addition product of 11 moles of ethylene oxide with 1 mole of a C₁₃ / C₁₅ fatty alcohol mixture. Surfactant VII: Addition product of 11 moles of ethylene oxide with 1 mole of a C₁₆ / C₁₈ fatty alcohol mixture. Surfactant VIII: Addition product of 5 moles of ethylene oxide with 1 mole of isotridecanol. Surfactant IX: Addition product of 10 moles of ethylene oxide with 1 mole of C₉-alkylphenol. Surfactant X: Addition product of 8 moles of ethylene oxide with 1 mole of a C₁₃- / C₁₅ fatty alcohol.

Durch Mischen von Tensid, Verdicker, Säure und Wasser wurden folgende wäßrige saure Reinigerformulierungen gemäß den Beispielen hergestellt:
10 % Tensid
X % Verdicker
20 % Säure
70-X % Wasser.The following aqueous acidic cleaner formulations according to the examples were prepared by mixing the surfactant, thickener, acid and water:
10% surfactant
X% thickener
20% acid
70-X% water.

Als Vergleich wurde jeweils eine verdickerfreie Formulierung folgender Zusammensetzung untersucht:
15 % Tensid
20 % Säure und
65 % Wasser.A thickener-free formulation of the following composition was examined as a comparison:
15% surfactant
20% acid and
65% water.

Die Zusammensetzung der jeweils hergestellten wäßrigen sauren Reiniger­formulierungen und die Viskosität dieser Formulierungen ist in Tabelle 1 angegeben. Die Versuche wurde fortlaufend numeriert, soweit es sich um Vergleichsbeispiele handelt ist dies in der Tabelle mit dem Zusatz (Vergleich) kenntlich gemacht worden.

Figure imgb0001
Figure imgb0002
 The composition of the aqueous acidic cleaner formulations produced in each case and the viscosity of these formulations is given in Table 1. The experiments were numbered consecutively; as far as comparative examples are concerned, this has been indicated in the table with the addition (comparison).
Figure imgb0001
Figure imgb0002

Wie den Beispielen der Tabelle 1 zu entnehmen ist, erhält man erfindungsgemäß wäßrige saure Reinigerformulierungen, die im Vergleich zu den entsprechenden verdickerfreien Reinigerformulierungen stark erhöhte Viskositäten aufweisen.As can be seen from the examples in Table 1, aqueous acidic cleaner formulations are obtained according to the invention which have greatly increased viscosities compared to the corresponding thickener-free cleaner formulations.

Beispiel 2Example 2

Nach der im Beispiel 1 angegebenen Standardrezeptur wurden wäßrige saure Reinigerformulierungen hergestellt, deren Zusammensetzung in Tabelle 2 jeweils angegeben ist. Die Tabelle gibt außerdem Auskunft über die Viskosität der Reinigerformulierungen. Tabelle 2 Nr. Tensid (a) Konzentration des Tensids [%] Verdicker (b) Konzentration des Verdickers [%] Säure 20 % (c) Viskosität der Reinigerformulierung [mPa.s] 1 (Vergl.) IX 10 - - H₃PO₄ 18 2 (Vergl.) IX 10 A 1 " 40 3 (Vergl.) III 10 - - " 90 4 III 10 A 1 " 2598 5 (Vergl.) X 10 - - " 15 6 X 10 A 1 " 1082 7 VII 10 - - " 12 8 VII 10 A 1 " 865 Aqueous acidic cleaner formulations, the composition of which is shown in Table 2, were prepared in accordance with the standard formulation given in Example 1. The table also provides information about the viscosity of the detergent formulations. Table 2 No. Surfactant (a) Concentration of surfactant [%] Thickener (b) Concentration of thickener [%] Acid 20% (c) Viscosity of the detergent formulation [mPa.s] 1 (compare) IX 10th - - H₃PO₄ 18th 2 (compare) IX 10th A 1 " 40 3 (compare) III 10th - - " 90 4th III 10th A 1 " 2598 5 (compare) X 10th - - " 15 6 X 10th A 1 " 1082 7 VII 10th - - " 12 8th VII 10th A 1 " 865

Die in Tabelle 2 unter Nr. 4, 6 und 8 angegebenen Zusammensetzungen sind Beispiele gemäß Erfindung, die übrigen Zusammensetzungen dienen zum Vergleich. Wie aus Tabelle 2 ersichtlich ist, spielt die Auswahl des Tensids eine entscheidende Rolle für die gewünschte hohe Viskosität einer Reinigerformulierung. Ein ethoxyliertes Alkylphenol als Tensid (Vergleich Nr. 2 aus Tabelle 2) gibt nicht die gewünschte Viskositätserhöhung, während die Tenside III, X und VII demgegenüber zu einer überraschend erhöhten Viskosität der Reinigerformulierung führen.The compositions given in Table 2 under Nos. 4, 6 and 8 are examples according to the invention, the other compositions are used for comparison. As can be seen from Table 2, the selection of the surfactant plays a decisive role for the desired high viscosity of a detergent formulation. An ethoxylated alkylphenol as a surfactant (comparison No. 2 from Table 2) does not give the desired increase in viscosity, while the surfactants III, X and VII on the other hand lead to a surprisingly increased viscosity of the detergent formulation.

Claims (3)

1. Wäßrige saure Reinigerformulierungen, gekennzeichnet durch einen Gehalt an - jeweils bezogen auf das Gewicht der gesamten Formulierungen - (a) 1 bis 20 Gew.-% mindestens eines nichtionischen Tensids auf der Basis von alkoxylierten Fettalkoholen, Fettsäuren, Fettaminen, Fettsäureamiden oder Alkansulfonamiden, (b) 0,1 bis 15 Gew.-% mindestens eines Polyetherpolyols, das er­hältlich ist durch Umsetzung von 2 bis 6-wertigen Alkoholen, die 2 bis 10 C-Atome aufweisen, mit 2 bis 4 C-Atome enthaltenden Alkylenoxiden und Reaktion dieser Umsetzungsprodukte mit 8 bis 30 C-Atome enthaltenden 1,2-Alkylenoxiden, Alkyl- oder Alkenyl­glycidethern und (c) 1 bis 40 Gew.-% mindestens einer Säure. 1. Aqueous acidic cleaning formulations, characterized by a content of - in each case based on the weight of the total formulations - (a) 1 to 20% by weight of at least one nonionic surfactant based on alkoxylated fatty alcohols, fatty acids, fatty amines, fatty acid amides or alkanesulfonamides, (b) 0.1 to 15% by weight of at least one polyether polyol which can be obtained by reacting 2 to 6-valent alcohols which have 2 to 10 C atoms with alkylene oxides containing 2 to 4 C atoms and reacting them Reaction products with 8 to 30 carbon atoms containing 1,2-alkylene oxides, alkyl or alkenyl glycidyl ethers and (c) 1 to 40% by weight of at least one acid. 2. Wäßrige saure Reinigerformulierungen nach Anspruch 1, dadurch gekenn­zeichnet, daß sie als Bestandteil (a) Anlagerungsprodukte von 3 bis 40 Mol Ethylenoxid an 1 Mol von jeweils mindestens 8 C-Atome enthaltenden Fettalkoholen, Fett­säuren, Fettaminen, Fettsäureamiden oder Alkansulfonamiden enthalten. 2. Aqueous acidic cleaner formulations according to claim 1, characterized in that they are a component (a) Addition products of 3 to 40 moles of ethylene oxide with 1 mole of fatty alcohols, fatty acids, fatty amines, fatty acid amides or alkanesulfonamides each containing at least 8 carbon atoms. 3. Wäßrige saure Reinigerformulierungen nach Anspruch 1, dadurch gekenn­zeichnet, daß sie (a) Anlagerungsprodukte von 3 bis 20 Mol Ethylenoxid an 1 Mol minde­stens eines Alkohols mit 8 bis 18 C-Atomen und (b) Polyetherpolyole enthalten, die durch Umsetzung von 2 bis 6-wertigen Alkoholen, die 2 bis 6 C-Atome aufweisen, mit Ethylenoxid und/oder Propylenoxid und anschließende Reaktion dieser Umsetzungsprodukte mit 8 bis 30 C-Atome enthaltenden 1,2-Alkylenoxiden erhältlich sind, Molekulargewichte von 1000 bis 75 000 haben und 0,5 bis 75 Gew.-% des langkettigen Alkylenoxids eingebaut enthalten. 3. Aqueous acidic cleaner formulations according to claim 1, characterized in that they (a) adducts of 3 to 20 moles of ethylene oxide with 1 mole of at least one alcohol having 8 to 18 carbon atoms and (b) contain polyether polyols which are obtained by reacting 2 to 6-valent alcohols which have 2 to 6 C atoms with ethylene oxide and / or propylene oxide and then reacting these reaction products with 1,2-alkylene oxides containing 8 to 30 C atoms are available, have molecular weights of 1000 to 75,000 and contain 0.5 to 75 wt .-% of the long-chain alkylene oxide incorporated.
EP89107879A 1988-05-05 1989-04-29 Aqueous acid detergent compositions Expired - Lifetime EP0340704B1 (en)

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EP0598692A1 (en) * 1992-11-16 1994-05-25 The Procter & Gamble Company Pseudoplastic and thixotropic cleaning compositions
EP0616028A1 (en) * 1993-03-19 1994-09-21 The Procter & Gamble Company Cleaning compositions with short chain nonionic surfactants
TR26294A (en) * 1991-11-20 1995-03-15 Alsthom Gec AUTOMATIC CUTTER WITH MEDIUM VOLTAGE SALTER AND USE IN MEDIUM TENSIONED DEVICES WITH A CELL.
WO1998003243A1 (en) * 1996-07-19 1998-01-29 Henkel Kommanditgesellschaft Auf Aktien Use as antifoaming agents of ethylene oxide - propylene oxide addition compounds of glycerol or polyglycerol reacted with alpha-olefin epoxides
EP0875554A1 (en) * 1997-04-30 1998-11-04 The Procter & Gamble Company Acidic limescale removal compositions
EP0894849A1 (en) * 1997-07-29 1999-02-03 Basf Corporation Aqueous based solvent free cleaner compositions containing two nonionic surfactants

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* Cited by examiner, † Cited by third party
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EP0523681A2 (en) * 1991-07-17 1993-01-20 Johannes Dr. Behrensdorf Automatic dishwashing detergent composition and method for producing the same
EP0523681A3 (en) * 1991-07-17 1993-05-05 Johannes Dr. Behrensdorf Automatic dishwashing detergent composition and method for producing the same
TR26294A (en) * 1991-11-20 1995-03-15 Alsthom Gec AUTOMATIC CUTTER WITH MEDIUM VOLTAGE SALTER AND USE IN MEDIUM TENSIONED DEVICES WITH A CELL.
EP0598692A1 (en) * 1992-11-16 1994-05-25 The Procter & Gamble Company Pseudoplastic and thixotropic cleaning compositions
EP0616028A1 (en) * 1993-03-19 1994-09-21 The Procter & Gamble Company Cleaning compositions with short chain nonionic surfactants
WO1998003243A1 (en) * 1996-07-19 1998-01-29 Henkel Kommanditgesellschaft Auf Aktien Use as antifoaming agents of ethylene oxide - propylene oxide addition compounds of glycerol or polyglycerol reacted with alpha-olefin epoxides
EP0875554A1 (en) * 1997-04-30 1998-11-04 The Procter & Gamble Company Acidic limescale removal compositions
EP0894849A1 (en) * 1997-07-29 1999-02-03 Basf Corporation Aqueous based solvent free cleaner compositions containing two nonionic surfactants

Also Published As

Publication number Publication date
EP0340704B1 (en) 1993-12-08
DE3815291A1 (en) 1989-11-23
DE58906336D1 (en) 1994-01-20
EP0340704A3 (en) 1990-05-02
US4965009A (en) 1990-10-23
ATE98293T1 (en) 1993-12-15

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