WO1999010458A1 - Aqueous agents for cleaning hard surfaces - Google Patents

Aqueous agents for cleaning hard surfaces Download PDF

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Publication number
WO1999010458A1
WO1999010458A1 PCT/EP1998/005202 EP9805202W WO9910458A1 WO 1999010458 A1 WO1999010458 A1 WO 1999010458A1 EP 9805202 W EP9805202 W EP 9805202W WO 9910458 A1 WO9910458 A1 WO 9910458A1
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Prior art keywords
alkyl
carbon atoms
radical
composition according
contain
Prior art date
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PCT/EP1998/005202
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German (de)
French (fr)
Inventor
Hermann Hensen
Bernd Fabry
Karl Heinz Schmid
Michael Neuss
Hans-Christian Raths
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Cognis Deutschland Gmbh
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Publication date
Priority claimed from DE19736906A external-priority patent/DE19736906A1/en
Priority claimed from DE19741911A external-priority patent/DE19741911C1/en
Priority claimed from DE1998113059 external-priority patent/DE19813059C2/en
Application filed by Cognis Deutschland Gmbh filed Critical Cognis Deutschland Gmbh
Publication of WO1999010458A1 publication Critical patent/WO1999010458A1/en

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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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0008—Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
    • C11D17/003—Colloidal solutions, e.g. gels; Thixotropic solutions or pastes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/24—Preparation of carboxylic acid esters by reacting carboxylic acids or derivatives thereof with a carbon-to-oxygen ether bond, e.g. acetal, tetrahydrofuran
    • C07C67/26—Preparation of carboxylic acid esters by reacting carboxylic acids or derivatives thereof with a carbon-to-oxygen ether bond, e.g. acetal, tetrahydrofuran with an oxirane ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
    • C08G65/2603—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen
    • C08G65/2615—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen the other compounds containing carboxylic acid, ester or anhydride groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
    • C08G65/2642—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds characterised by the catalyst used
    • C08G65/2669—Non-metals or compounds thereof
    • C08G65/2672—Nitrogen or compounds 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/28—Sulfonation products derived from fatty acids or their derivatives, e.g. esters, amides
    • 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
    • C11D1/02—Anionic compounds
    • C11D1/37—Mixtures of compounds all of which are anionic
    • 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
    • C11D1/65—Mixtures of anionic 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
    • C11D1/66—Non-ionic compounds
    • C11D1/83—Mixtures of non-ionic with anionic 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
    • C11D1/86—Mixtures of anionic, cationic, and non-ionic 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
    • C11D1/88—Ampholytes; Electroneutral compounds
    • C11D1/94—Mixtures with anionic, cationic or non-ionic 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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/22—Carbohydrates or derivatives thereof
    • C11D3/222—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
    • 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
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/123—Sulfonic acids or sulfuric acid esters; Salts thereof derived from carboxylic acids, e.g. sulfosuccinates
    • 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
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
    • C11D1/146—Sulfuric acid esters
    • 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
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/16—Sulfonic acids or sulfuric acid esters; Salts thereof derived from divalent or polyvalent alcohols
    • 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
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/29—Sulfates of polyoxyalkylene ethers
    • 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
    • C11D1/52—Carboxylic amides, alkylolamides or imides or their condensation products with alkylene oxides
    • C11D1/523—Carboxylic alkylolamides, or dialkylolamides, or hydroxycarboxylic amides (R1-CO-NR2R3), where R1, R2 or R3 contain one hydroxy group per alkyl group
    • 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
    • C11D1/52—Carboxylic amides, alkylolamides or imides or their condensation products with alkylene oxides
    • C11D1/525—Carboxylic amides (R1-CO-NR2R3), where R1, R2 or R3 contain two or more hydroxy groups per alkyl group, e.g. R3 being a reducing sugar rest
    • 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
    • C11D1/662—Carbohydrates or derivatives
    • 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
    • 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
    • C11D1/721—End blocked ethers
    • 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
    • C11D1/88—Ampholytes; Electroneutral compounds
    • C11D1/90—Betaines

Definitions

  • the invention relates to aqueous compositions for cleaning hard surfaces containing fatty acid polyglycol ester sulfates and other surfactants, and to the use of these mixtures for the production of cleaning compositions for hard surfaces
  • AZR all-purpose cleaners
  • Low-foaming AZR are those that develop a small volume of foam when used manually, which significantly reduces within a few minutes. Means of this kind have been known for a long time and are established on the market. These are essentially aqueous surfactant solutions of different types with or without the addition of builders, hydrotropes or solvents. To demonstrate the effectiveness at the beginning of the cleaning process, the consumer also wants a certain amount of foam in the application solution, but the foam should collapse quickly so that once cleaned surfaces do not have to be wiped off.
  • agents of the type mentioned are usually formulated with low-foaming nonionic surfactants, for example mixed ethers or alcohol alkoxylates, in particular oxo alcohol ethoxylates.
  • agents of the prior art are often not sufficiently skin-compatible, so that despite a large number of products on the market, both the manufacturers of the products and the customers have a constant need for milder preparations which nevertheless have at least the same level in terms of foam and cleaning behavior known products. The object of the invention was then to take these needs into account. Description of the invention
  • the invention relates to aqueous compositions for cleaning hard surfaces, containing
  • the agents according to the invention are also highly concentrated, flowable and weakly foaming, have a low cloud point, are largely irrespective of the concentration and are not irritating to the skin and have excellent cleaning properties.
  • the invention includes the knowledge that mixtures of fatty acid polyglycol ester sulfate salts and mixed ethers together with alkali soaps, alkyl sulfates, alkylbenzenesulfonates, fatty alcohol ethoxylates, alkyl oligoglucosides and / or betaines leads to a further improvement in the desired properties.
  • Fatty acid polyglycol ester sulfates which may be present as component (a) preferably follow the formula (I),
  • R 1 CO is a linear or branched, saturated or unsaturated acyl radical having 6 to 22 carbon atoms
  • x is an average of 1 to 3
  • AO is a CH2CH2O-, CH 2 CH (CH 3 ) 0- and / or CH ( CH 3 ) CH 2 0 radical
  • X represents an alkali and / or alkaline earth metal, ammonium, alkylammonium, alkanolammonium or glucammonium, and are usually prepared by sulfating the corresponding fatty acid polyglycol esters.
  • ethylene oxide, propylene oxide or a mixture thereof - in random or block distribution - is added to the corresponding fatty acids, this reaction being acid-catalyzed, but preferably in the presence of bases such as sodium methylate or calcined hydrotalcite. If a degree of alkoxylation of 1 is desired, the intermediates can also be prepared by esterifying the fatty acids with an appropriate alkylene glycol.
  • the sulfation of the fatty acid polyglycol esters can be carried out in a manner known per se with chlorosulfonic acid or preferably gaseous sulfur trioxide, the molar ratio between fatty acid polyglycol ester and sulfating agent being in the range from 1: 0.95 to 1: 1, 2, preferably 1: 1 to 1: 1 , 1 and the reaction temperature can be 30 to 80 and preferably 50 to 60 ° C. It is also possible to undersulfate the fatty acid polyglycol esters, ie to use significantly fewer sulfating agents than would be stoichiometrically required for complete conversion.
  • Typical examples of suitable starting materials are the addition products of 1 to 3 mol of ethylene oxide and / or propylene oxide, but preferably the adducts with 1 mol of ethylene oxide or 1 mol of propylene oxide with caproic acid, caprylic acid, 2-ethylhexanoic acid, capric acid, lauric acid, isotridecanoic acid, myristic acid, palmitic acid, Palmoleic acid, stearic acid, isostearic acid, oleic acid, elaidic acid, petroselinic acid, linoleic acid, linolenic acid, elaeostearic acid, arachic acid, gadoleic acid, behenic acid and erucic acid and their technical mixtures, which are then sulfated and neutralized as described above.
  • Fatty acid polyglycol ester sulfates of the formula (I) are preferably used in which R 1 CO stands for an acyl radical having 12 to 18 carbon atoms, x for an average of 1 or 2, AO for a CH ⁇ CH ⁇ O group and X for sodium or ammonium, such as for example lauric acid + 1 EO sulfate sodium salt, lauric acid + 1 EO sulfate ammonium salt, coconut fatty acid + 1 EO sulfate sodium salt, coconut fatty acid + 1 EO sulfate ammonium salt, tallow fatty acid + 1 EO sulfate sodium salt, tallow fatty acid + 1 EO sulfate ammonium salt and mixtures thereof.
  • R 1 CO stands for an acyl radical having 12 to 18 carbon atoms
  • x for an average of 1 or 2
  • AO for a CH ⁇ CH ⁇ O group
  • X for sodium or ammonium, such as for example lauric acid + 1
  • R 2 represents a linear or branched alkyl and / or alkenyi radical having 6 to 22 carbon atoms
  • R 3 represents hydrogen, an alkyl radical having 1 to 8 carbon atoms or a benzyl radical
  • n1 and n2 independently of one another for 0 or numbers of 1 to 20 and m1 and m2 independently of one another represent 0 or numbers from 1 to 3, with the proviso that at least one of the two parameters n1 and n2 is not equal to 0.
  • Typical examples are addition products of 1 to 10 mol of ethylene oxide or 1 to 2 mol of propylene oxide and 1 to 10 mol of ethylene oxide with octanol, CiM ⁇ coconut oil alcohol, Ci6-Guerbet alcohol and / or tallow fatty alcohol, which are then mixed with methyl chloride, dimethyl sulfate, butyl chloride or benzyl chloride end groups.
  • the agents according to the invention can contain components (a) and (b) in a weight ratio of 90:10 to 10:90, preferably 75:25 to 15:85 and in particular 60:40 to 25:75.
  • Anionic surfactants are examples of 1 to 10 mol of ethylene oxide or 1 to 2 mol of propylene oxide and 1 to 10 mol of ethylene oxide with octanol, CiM ⁇ coconut oil alcohol, Ci6-Guerbet alcohol and / or tallow fatty alcohol, which are then mixed with methyl chloride, dimethyl sulfate, butyl
  • anionic surfactants which can be considered as component (c) are soaps, alkylbenzenesulfonates, alkanesulfonates, olefinsulfonates, alkylethersulfonates, glycerinethersulfonates, ⁇ -methyl estersulfonates, sulfofatty acids, alkylsulfates, alkylethersulfates, glycerolethersulfate, mono-ether sulfate, monoglysulfate sulfates, , fatty acid amide (ether) sulfates, mono- and Dialkylsulfo- succinate, mono- and dialkyl sulfosuccinamates, sulfotriglycerides, amide soaps, ether carboxylic acids and salts thereof, fatty acid taurides, N-Acyiamino Acid such as acyl lactylates, acyl tartrates,
  • anionic surfactants contain polyglycol ether chains, they can have a conventional, but preferably a narrow, homolog distribution.
  • Alkali soaps, alkyl sulfates, alkyl benzene sulfonates, alkyl ether sulfates, monoglyceride sulfates and / or suifosuccinates are preferably used.
  • Typical examples of further nonionic surfactants which can be considered as component (c) are fatty alcohol polyglycol ethers, alkylphenol polyglycol ethers, fatty acid polyglycol esters, fatty acid amide polyglycol ethers, fatty amine polyglycol ethers, alkoxylated triglycerides, alk (en) yl oligoglycosides, especially fatty acid-N-alkyl-glycols-fatty acid-N-alkyl-glycols vegetable products based on wheat), polyol fatty acid esters, sugar esters, sorbitan esters, polysorbates and amine oxides.
  • nonionic surfactants contain polyglycol ether chains, they can have a conventional, but preferably a narrow, homolog distribution.
  • Typical examples of amphoteric or zwitterionic surfactants are alkyl betaines, alkyl amido betaines, aminopropionates, aminoglycinates, imidazolinium betaines and sulfobetaines.
  • Fatty alcohol polyglycol ethers, alkyl oligoglucosides, fatty acid N-alkyl glucamides and / or betaines are preferably used.
  • the agents according to the invention can contain components (a) and (c) in a weight ratio of 90:10 to 10:90, preferably 75:25 to 25:75 and in particular 60:40 to 40:60 and components (a), (b) and (c) in the weight ratio (10 to 90): (5 to 85): (5 to 85) and in particular (20 to 80): (10 to 50): (10 to 50), with the proviso that add the weight information to 100% by weight.
  • nonionic surfactants used are alkyl and alkenyl oligoglycosides which follow the formula (III) R 0- [G] P (III)
  • R 4 is an alkyl and / or alkenyl radical having 4 to 22 carbon atoms
  • G is a sugar radical having 5 or 6 carbon atoms
  • p is a number from 1 to 10.
  • the alkyl and / or alkenyl oligoglycosides can be derived from aldoses or ketoses with 5 or 6 carbon atoms, preferably glucose.
  • the preferred alkyl and / or alkenyl oligoglycosides are thus alkyl and / or alkenyl oligoglucosides.
  • the index number p in the general formula (III) indicates the degree of oligomerization (DP), ie the distribution of mono- and oligoglycosides, and stands for a number between 1 and 10.
  • Alkyl and / or alkenyl oligoglycosides with an average degree of oligomerization p of 1.1 to 3.0 are preferably used. From an application point of view, preference is given to those alkyl and / or alkenyl oligoglycosides whose degree of oligomerization is less than 1.7 and in particular between 1.2 and 1.4.
  • the alkyl or alkenyl radical R 4 can be derived from primary alcohols having 4 to 11, preferably 8 to 10, carbon atoms. Typical examples are butanol, capro alcohol, caprylic alcohol, capric alcohol and undecyl alcohol and their technical mixtures, such as are obtained, for example, in the hydrogenation of technical fatty acid methyl esters or in the course of the hydrogenation of aldehydes from Roelen's oxosynthesis.
  • the alkyl or alkenyl radical R 4 can also be derived from primary alcohols having 12 to 22, preferably 12 to 14, carbon atoms.
  • Typical examples are lauryl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, arachyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol, brassidyl alcohol and the technical mixtures described above, which can be obtained as well as their technical mixtures.
  • Alkyl oligoglucosides based on hardened Ci ⁇ coconut alcohol with a DP of 1 to 3 are preferred.
  • component (c) Another group of preferred nonionic surfactants which can form component (c) are fatty acid N-alkylpolyhydroxyalkylamides which follow the formula (IV)
  • R 5 CO for an aliphatic acyl radical with 6 to 22 carbon atoms
  • R 6 for an alkyl or hydroxyalkyl radical with 1 to 4 carbon atoms
  • [Z] for a linear or branched polyhydroxyalkyl radical with 3 to 12 carbon atoms and 3 to 10 hydroxyl groups stands.
  • the fatty acid N-alkyl polyhydroxyalkylamides are known substances which can usually be obtained by reductive amination of a reducing sugar with an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.
  • the fatty acid N-alkylpolyhydroxyalkylamides are preferably derived from reducing sugars having 5 or 6 carbon atoms, in particular from glucose.
  • the preferred fatty acid N-alkylpolyhydroxyalkylamides are therefore fatty acid N-alkylglucamides as represented by the formula (V):
  • the preferred fatty acid N-alkylpolyhydroxyalkylamides used are glucamides of the formula (V) in which R 6 represents an alkyl group and R 5 CO represents the acyl radical of caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, palmoleic acid, stearic acid, isostearic acid, Oleic acid, elaidic acid, petroselinic acid, linoleic acid, linolenic acid, arachic acid, gadoleic acid, behenic acid or erucic acid or their technical mixtures.
  • V glucamides of the formula (V) in which R 6 represents an alkyl group and R 5 CO represents the acyl radical of caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, palmoleic acid, stearic acid, isostearic acid, Oleic acid, elaidic
  • Fatty acid N-alkylglucamides of the formula (V) which are obtained by reductive amination of glucose with methylamine and subsequent acylation with lauric acid or Ci2 / 4 coconut fatty acid or a corresponding derivative are particularly preferred.
  • the polyhydroxyalkylamides can also be derived from maltose and palatinose.
  • surfactants of the betaine type can form component (c).
  • Betaines are known surfactants which are predominantly produced by carboxyalkylation, preferably carboxymethylation, of aminic compounds.
  • the starting materials are preferably condensed with halocarboxylic acids or their salts, in particular with sodium chloroacetate, one mol of salt being formed per mole of betaine.
  • unsaturated carboxylic acids such as, for example, acrylic acid, is also possible.
  • betaines and "real" amphoteric surfactants reference is made to the contribution by U.PIoog in Seifen- ⁇ le-Fette-Wwachs, 108, 373 (1982).
  • R 7 for alkyl and / or alkenyi radicals with 6 to 22 carbon atoms
  • R 8 for hydrogen or alkyl radicals with 1 to 4 carbon atoms
  • R 9 for alkyl radicals with 1 to 4 carbon atoms
  • n for numbers from 1 to 6
  • X for a Alkali and / or alkaline earth metal or ammonium.
  • Typical examples are the carboxymethylation products of hexylmethylamine, hexyldimethylamine, octyldimethylamine, Removal cyldimethylamin, dodecylmethylamine, dodecyldimethylamine, Dodecylethylmethylamin, Ci2 / i4-Kokosal- kyldimethylamin, myristyldimethylamine, cetyldimethylamine, stearyldimethylamine, Stearylethylmethyl- amine, oleyl dimethyl amine, Ci6 / 18 tallow alkyl dimethyl amine, and their technical Mixtures.
  • Carboxyalkylation products of amidoamines which follow the formula (VII) are also suitable,
  • R 10 CO represents an aliphatic acyl radical having 6 to 22 carbon atoms and 0 or 1 to 3 double bonds
  • m represents numbers from 1 to 3
  • R 8 , R 9 , n and X have the meanings given above.
  • Typical examples are reaction products of fatty acids with 6 to 22 carbon atoms, namely caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmi tic acid, palmoleic acid, stearic acid, isostearic acid, oleic acid, elaidic acid, petroselinic acid, linoleic acid, linolenic acid, elaeostearic acid, arachic acid, gadoleic acid, behenic acid and erucic acid and their technical mixtures, with N, N-dimethylaminoethylamine, N, N-dimethylaminopropyl -Diethylaminoethylamine and N,
  • R 11 is an alkyl radical having 5 to 21 carbon atoms
  • R 12 is a hydroxyl group
  • an OCOR 11 or NHCOR 11 radical and m is 2 or 3.
  • These substances are also known substances which can be obtained, for example, by cyclizing condensation of 1 or 2 moles of fatty acid with polyhydric amines, such as, for example, aminoethylethanolamine (AEEA) or diethylenetriamine.
  • AEEA aminoethylethanolamine
  • the corresponding carboxyalkylation products are mixtures of different open-chain betaines.
  • Typical examples are condensation products of the above-mentioned fatty acids with AEEA, preferably imidazolines based on lauric acid or again Ci2 / 14 coconut fatty acid, which are subsequently betainized with sodium chloroacetate.
  • Another object of the invention relates to the use of the surfactant mixtures according to the invention for the production of aqueous agents for cleaning hard surfaces.
  • these agents are all-purpose cleaners, sanitary cleaners, machine dishwashing detergents, rinse aid, agents for cleaning-in-place (CIP cleaners) and agents for machine cleaning of bottles.
  • CIP cleaners cleaning-in-place
  • the mixtures can contain minor amounts of other customary auxiliaries and additives.
  • auxiliaries and additives include, for example, solubilizers such as ethanol, isopropyl alcohol, ethylene glycol, diethylene glycol or preferably butyl diglycol, foam regulators such as soap, soluble builders such as citric acid or sodium citrate, EDTA or NTA and abrasives.
  • solubilizers such as ethanol, isopropyl alcohol, ethylene glycol, diethylene glycol or preferably butyl diglycol
  • foam regulators such as soap
  • soluble builders such as citric acid or sodium citrate
  • EDTA or NTA EDTA
  • abrasives abrasives.
  • the agents can contain cationic surfactants or biocides, for example glucoprotamine.
  • bleaching agents such as sodium hypochlorite or hydrogen peroxide as well as a suitable coloring and fragrance is possible.
  • the proportion of these additives can make up 1 to 8, preferably 4 to 6% by weight, based on the composition.
  • the agents are preferably made alkaline by adding sodium hydroxide and / or soda, a pH in the range from 9 to 10 being preferred.
  • the active substance content of the agents can be between 4 and 80% by weight and depends on whether a concentrate is desired (40 to 80, preferably 50 to 70% by weight of active component) which the consumer dilutes to the application concentration before cleaning is or a correspondingly diluted agent (4 to 50, preferably 10 to 30 wt .-% active content) is to be marketed. In the latter case, the active substance content is typically around 4 to 20% by weight. To produce the agents, it is sufficient to mix the starting materials purely mechanically, if appropriate at elevated temperature; there is no chemical reaction.
  • 2 eggs (approx. 100 to 110 g) were diluted 1: 1 with water at 16 ° d in an electric mixer and stirred for 2 minutes.
  • 100 g of the resulting emulsion were then made up in a double-walled measuring cylinder from 2000 ml to 500 ml with water at 16 ° C. and the temperature was raised to 50 ° C. After reaching the test temperature, 20 g of the surfactant mixtures were added to this mixture. With the help of a laboratory peristaltic pump, the solution was sucked from the bottom of the measuring cylinder with a glass tube.

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Abstract

The invention relates to novel aqueous detergents for hard surfaces, containing a) fatty acid polyglycol ester sulphates, b) mixed ethers and optionally, c) anionic, non-anionic and/or amphoteric or zwiterrionic tensides.

Description

Wäßrige Mittel zur Reinigung harter OberflächenAqueous agents for cleaning hard surfaces
Gebiet der ErfindungField of the Invention
Die Erfindung betrifft wäßrige Mittel zur Reinigung harter Oberflachen mit einem Gehalt an Fettsaure- polyglycolestersulfaten und weiteren Tensiden sowie die Verwendung dieser Mischungen zur Herstellung von Reinigungsmitteln für harte OberflachenThe invention relates to aqueous compositions for cleaning hard surfaces containing fatty acid polyglycol ester sulfates and other surfactants, and to the use of these mixtures for the production of cleaning compositions for hard surfaces
Stand der TechnikState of the art
Mittel für die Reinigung harter, nichttextiler Oberflächen, die im Haushalt und Gewerbesektor vorkommen, ausgenommen Geschirr, werden üblicherweise als Allzweckreiniger (AZR) bezeichnet. Schwachschaumende AZR sind solche, die bei manueller Anwendung ein geringfügiges ScJfaum- volumen entwickeln, das sich innerhalb von wenigen Minuten signifikant weiter vemngert. Mittel dieser Art sind seit langem bekannt und im Markt etabliert. Es handelt sich dabei im wesentlichen um wäßπge Tensidlösungen unterschiedlicher Art mit oder ohne Zusatz von Buiidern, Hydrotropen oder Losungsmitteln. Zum Nachweis der Wirksamkeit bei Beginn der Reinigungsarneit wird vom Verbraucher ferner zwar ein gewisses Schäumen der Anwendungslosung gewünscht, der Schaum soll jedoch rasch zusammenfallen, damit einmal gereinigte Flächen nicht nachgewischt werden müssen. Zu diesem Zweck werden Mittel der genannten Art üblicherweise mit schwach schäumenden nichtionischen Tensiden, beispielsweise Mischethern oder Alkoholalkoxyiaten, insbesondere Oxoalkoholethoxylaten formuliert. Mittel des Stands der Technik sind jedoch häufig nicht ausreichend hautverträglich, so daß trotz einer Vielzahl von im Markt befindlichen Produkten sowohl beiden Herstellern der Produkte als auch bei den Kunden ein stetiges Bedürfnis nach milderen Zubereitungen besteht, die gleichwohl hinsichtlich Schaum- und Reinigungsverhalten mindestens das Niveau bekannter Produkte erreichen müssen. Die Aufgabe der Erfindung hat somit dann bestanden, diesen Bedurfnissen Rechnung zu tragen. Beschreibung der ErfindungAgents for cleaning hard, non-textile surfaces that occur in the household and commercial sector, with the exception of dishes, are commonly referred to as all-purpose cleaners (AZR). Low-foaming AZR are those that develop a small volume of foam when used manually, which significantly reduces within a few minutes. Means of this kind have been known for a long time and are established on the market. These are essentially aqueous surfactant solutions of different types with or without the addition of builders, hydrotropes or solvents. To demonstrate the effectiveness at the beginning of the cleaning process, the consumer also wants a certain amount of foam in the application solution, but the foam should collapse quickly so that once cleaned surfaces do not have to be wiped off. For this purpose, agents of the type mentioned are usually formulated with low-foaming nonionic surfactants, for example mixed ethers or alcohol alkoxylates, in particular oxo alcohol ethoxylates. However, agents of the prior art are often not sufficiently skin-compatible, so that despite a large number of products on the market, both the manufacturers of the products and the customers have a constant need for milder preparations which nevertheless have at least the same level in terms of foam and cleaning behavior known products. The object of the invention was then to take these needs into account. Description of the invention
Gegenstand der Erfindung sind wäßrige Mittel für die Reinigung harter Oberflächen, enthaltendThe invention relates to aqueous compositions for cleaning hard surfaces, containing
(a) Fettsäurepolyglycolestersulfate,(a) fatty acid polyglycol ester sulfates,
(b) Mischether und gegebenenfalls(b) mixed ether and optionally
(c) anionische, nichtionische und/oder amphotere bzw. zwitterionische Tenside.(c) anionic, nonionic and / or amphoteric or zwitterionic surfactants.
Überraschenderweise wurde gefunden, daß die erfindungsgemäßen Mittel auch hochkonzentriert fließfähig und schwach schäumend sind, einen niedrigen Kältetrübungspunkt aufweisen, weitgehend unabhängig von der Konzentration nicht hautreizend sind und dabei über ein ausgezeichnetes Reinigungsvermögen verfügen. Die Erfindung schließt die Erkenntnis ein, daß Mischungen von Fettsäurepoly- glycolestersulfat-Salzen und Mischethem zusammen mit Alkaliseifen, Alkylsulfaten, Alkylbenzolsulfo- naten, Fettalkoholethoxylaten, Alkyloligoglucosiden und/oder Betainen zu einer weiteren Verbesserung der gewünschten Eigenschaften führt.Surprisingly, it has been found that the agents according to the invention are also highly concentrated, flowable and weakly foaming, have a low cloud point, are largely irrespective of the concentration and are not irritating to the skin and have excellent cleaning properties. The invention includes the knowledge that mixtures of fatty acid polyglycol ester sulfate salts and mixed ethers together with alkali soaps, alkyl sulfates, alkylbenzenesulfonates, fatty alcohol ethoxylates, alkyl oligoglucosides and / or betaines leads to a further improvement in the desired properties.
FettsäurepolyqlycolestersulfateFatty acid polyglycol ester sulfates
Fettsäurepolyglycolestersulfate, die als Komponente (a) enthalten sein können, folgen vorzugsweise der Formel (I),Fatty acid polyglycol ester sulfates which may be present as component (a) preferably follow the formula (I),
Figure imgf000004_0001
Figure imgf000004_0001
in der R1CO für einen linearen oder verzweigten, gesättigten oder ungesättigten Acylrest mit 6 bis 22 Kohlenstoffatomen, x für Zahlen von durchschnittlich 1 bis 3 und AO für einen CH2CH2O-, CH2CH(CH3)0- und/oder CH(CH3)CH20-Rest und X für ein Alkali- und/oder Erdalkalimetall, Ammonium, Alkylammonium, Alkanolammonium oder Glucammonium steht, und werden üblicherweise durch Sulfatierung der entsprechenden Fettsäurepolyglycolester hergestellt. Diese wiederum sind nach den einschlägigen präparativen Verfahren der organischen Chemie erhältlich. Hierzu wird Ethylenoxid, Propylenoxid oder deren Gemisch - in random- oder Blockverteiiung - an die entsprechenden Fettsäuren angelagert, wobei diese Reaktion säurekatalysiert, vorzugsweise aber in Gegenwart von Basen, wie z.B. Natriummethylat oder calciniertem Hydrotalcit erfolgt. Wird ein Alkoxylierungsgrad von 1 gewünscht, können die Zwischenprodukte auch durch Veresterung der Fettsäuren mit einem entsprechenden Alkylenglycol hergestellt werden. Die Sulfatierung der Fettsäurepolyglycolester kann in an sich bekannter Weise mit Chlorsulfonsäure oder vorzugsweise gasförmigem Schwefeltrioxid durchgeführt werden, wobei das molare Einsatzverhältnis zwischen Fettsäurepolyglycolester und Sulfatierungsmittel im Bereich von 1 : 0,95 bis 1 : 1 ,2, vorzugsweise 1 : 1 bis 1 : 1 ,1 und die Reaktions- temperatur 30 bis 80 und vorzugsweise 50 bis 60°C betragen kann. Es ist ferner möglich, die Fettsäurepolyglycolester zu untersulfatieren, d.h. deutlich weniger Sulfatierungsmittel einzusetzen, als dies für eine vollständige Umsetzung stochiometrisch erforderlich wäre. Wählt man beispielsweise molare Einsatzmengen von Fettsäurepolyglycolester zu Sulfatierungsmittel von 1 : 0,5 bis 1 : 0,95 werden Mischungen von Fettsäurepolyglycolestersulfaten und Fettsäurepolyglycolestem erhalten, die für eine ganze Reihe von Anwendungen ebenfalls vorteilhaft sind. Um eine Hydrolyse zu vermeiden ist es dabei sehr wichtig, die Neutralisation bei einem pH-Wert im Bereich von 5 bis 9, vorzugsweise 7 bis 8 durchzuführen. Typische Beispiele für geeignete Ausgangsstoffe sind die Anlagerungsprodukte von 1 bis 3 Mol Ethylenoxid und/oder Propyienoxid, vorzugsweise aber die Addukte mit 1 Mol Ethylenoxid oder 1 Mol Propyienoxid an Capronsäure, Caprylsäure, 2-Ethylhexansäure, Caprinsäure, Laurinsäure, Isotridecansäure, Myristinsäure, Palmitinsäure, Palmoleinsäure, Stearinsäure, Isostearinsäure, Ölsäure, Elaidinsäure, Petroselinsäure, Linolsäure, Linolensäure, Elaeostearinsäure, Arachinsäure, Gadolein- säure, Behensäure und Erucasäure sowie deren technische Mischungen, die dann wie oben beschrieben sulfatiert und neutralisiert werden. Vorzugsweise werden Fettsäurepolygiycolestersulfate der Formel (I) eingesetzt, in der R1CO für einen Acylrest mit 12 bis 18 Kohlenstoffatomen, x für durchschnittlich 1 oder 2, AO für eine CH∑CH∑O-Gruppe und X für Natrium oder Ammonium steht, wie beispielsweise Laurinsäure+1 EO-sulfat-Natriumsalz, Laurinsäure+1 EO-sulfat-Ammoniumsalz, Kokosfettsäure+1 EO- sulfat-Natriumsalz, Kokosfettsäure+1 EO-sulfat-Ammoniumsalz, Talgfettsäure+1 EO-sulfat-Natriumsatz, Talgfettsäure+1 EO-sulfat-Ammoniumsalz sowie deren Mischungen.in which R 1 CO is a linear or branched, saturated or unsaturated acyl radical having 6 to 22 carbon atoms, x is an average of 1 to 3 and AO is a CH2CH2O-, CH 2 CH (CH 3 ) 0- and / or CH ( CH 3 ) CH 2 0 radical and X represents an alkali and / or alkaline earth metal, ammonium, alkylammonium, alkanolammonium or glucammonium, and are usually prepared by sulfating the corresponding fatty acid polyglycol esters. These in turn can be obtained using the relevant preparative processes in organic chemistry. For this purpose, ethylene oxide, propylene oxide or a mixture thereof - in random or block distribution - is added to the corresponding fatty acids, this reaction being acid-catalyzed, but preferably in the presence of bases such as sodium methylate or calcined hydrotalcite. If a degree of alkoxylation of 1 is desired, the intermediates can also be prepared by esterifying the fatty acids with an appropriate alkylene glycol. The sulfation of the fatty acid polyglycol esters can be carried out in a manner known per se with chlorosulfonic acid or preferably gaseous sulfur trioxide, the molar ratio between fatty acid polyglycol ester and sulfating agent being in the range from 1: 0.95 to 1: 1, 2, preferably 1: 1 to 1: 1 , 1 and the reaction temperature can be 30 to 80 and preferably 50 to 60 ° C. It is also possible to undersulfate the fatty acid polyglycol esters, ie to use significantly fewer sulfating agents than would be stoichiometrically required for complete conversion. For example, if molar amounts of fatty acid polyglycol ester to sulfating agent of 1: 0.5 to 1: 0.95 are selected, mixtures of fatty acid polyglycol ester sulfates and fatty acid polyglycol esters are obtained, which are also advantageous for a whole range of applications. In order to avoid hydrolysis, it is very important to carry out the neutralization at a pH in the range from 5 to 9, preferably 7 to 8. Typical examples of suitable starting materials are the addition products of 1 to 3 mol of ethylene oxide and / or propylene oxide, but preferably the adducts with 1 mol of ethylene oxide or 1 mol of propylene oxide with caproic acid, caprylic acid, 2-ethylhexanoic acid, capric acid, lauric acid, isotridecanoic acid, myristic acid, palmitic acid, Palmoleic acid, stearic acid, isostearic acid, oleic acid, elaidic acid, petroselinic acid, linoleic acid, linolenic acid, elaeostearic acid, arachic acid, gadoleic acid, behenic acid and erucic acid and their technical mixtures, which are then sulfated and neutralized as described above. Fatty acid polyglycol ester sulfates of the formula (I) are preferably used in which R 1 CO stands for an acyl radical having 12 to 18 carbon atoms, x for an average of 1 or 2, AO for a CH∑CH∑O group and X for sodium or ammonium, such as for example lauric acid + 1 EO sulfate sodium salt, lauric acid + 1 EO sulfate ammonium salt, coconut fatty acid + 1 EO sulfate sodium salt, coconut fatty acid + 1 EO sulfate ammonium salt, tallow fatty acid + 1 EO sulfate sodium salt, tallow fatty acid + 1 EO sulfate ammonium salt and mixtures thereof.
MischetherMixed ether
Mischether stellen bekannte schaumarme Niotenside dar, die der Formel (II) folgen,Mixed ethers are known low-foam nonionic surfactants which follow the formula (II)
CH3 CH3 CH 3 CH 3
I II I
R20(CH2CH2θ)nl(CH2CHO)ml(CH2CH2θ)n2(CH2CHO)m2R3 (II)R20 (CH2CH2θ) nl (CH2CHO) ml (CH2CH2θ) n2 (CH2CHO) m2R 3 (II)
in der R2 für einen linearen oder verzweigten Alkyl- und/oder Alkenyirest mit 6 bis 22 Kohlenstoffatomen, R3 für Wasserstoff, einen Alkylrest mit 1 bis 8 Kohlenstoffatomen oder einen Benzylrest, n1 und n2 unab-hängig voneinander für 0 oder Zahlen von 1 bis 20 und m1 und m2 unabhängig voneinander für 0 oder Zahlen von 1 bis 3 stehen, mit der Maßgabe, daß mindestens einer der beiden Parameter n1 und n2 ungleich 0 ist. Typische Beispiele sind Anlagerungsprodukte von 1 bis 10 mol Ethylenoxid bzw. 1 bis 2 Mol Propyienoxid und 1 bis 10 Mol Ethylenoxid an Octanol, CiMβ-Kokosfett- alkohol, Ci6-Guerbetalkohol und/oder Taigfettalkohol, die anschließend mit Methylchlorid, Dimethyl- sulfat, Butylchlorid oder Benzylchlorid endgruppenverschlossen werden. Die erfindungsgemäßen Mittel können die Komponenten (a) und (b) im Gewichtsverhältnis 90 : 10 bis 10 : 90, vorzugsweise 75 : 25 bis 15 : 85 und insbesondere 60 : 40 bis 25 : 75 enthalten. Aniontensidein which R 2 represents a linear or branched alkyl and / or alkenyi radical having 6 to 22 carbon atoms, R 3 represents hydrogen, an alkyl radical having 1 to 8 carbon atoms or a benzyl radical, n1 and n2 independently of one another for 0 or numbers of 1 to 20 and m1 and m2 independently of one another represent 0 or numbers from 1 to 3, with the proviso that at least one of the two parameters n1 and n2 is not equal to 0. Typical examples are addition products of 1 to 10 mol of ethylene oxide or 1 to 2 mol of propylene oxide and 1 to 10 mol of ethylene oxide with octanol, CiMβ coconut oil alcohol, Ci6-Guerbet alcohol and / or tallow fatty alcohol, which are then mixed with methyl chloride, dimethyl sulfate, butyl chloride or benzyl chloride end groups. The agents according to the invention can contain components (a) and (b) in a weight ratio of 90:10 to 10:90, preferably 75:25 to 15:85 and in particular 60:40 to 25:75. Anionic surfactants
Typische Beispiele für anionische Tenside, die als Komponente (c) in Betracht kommen, sind Seifen, Alkylbenzolsulfonate, Alkansulfonate, Olefinsulfonate, Alkylethersulfonate, Glycerinethersuifonate, α- Methylestersulfonate, Sulfofettsäuren, Alkylsulfate, Alkylethersulfate, Glycerinethersulfate, Monogly- cerid(ether)sulfate, Hydroxymischethersulfate, Fettsäureamid(ether)sulfate, Mono- und Dialkylsulfo- succinate, Mono- und Dialkylsulfosuccinamate, Sulfotriglyceride, Amidseifen, Ethercarbonsäuren und deren Salze, Fettsäureisethionate, Fettsäuresarcosinate, Fettsäuretauride, N-Acyiaminosäuren wie beispielsweise Acyllactylate, Acyltartrate, Acylglutamate und Acylaspartate, Alkyloligoglucosidsulfate, Proteinfettsäurekondensate (insbesondere pflanzliche Produkte auf Weizenbasis) und Alkyl(ether)phos- phate. Sofern die anionischen Tenside Polyglycoletherketten enthalten, können diese eine konventionelle, vorzugsweise jedoch eine eingeengte Homologenverteilung aufweisen. Vorzugsweise werden alkaliseifen, Alkylsulfate, Alkylbenzolsulfonate, Alkylethersulfate, Monoglyceridsulfate und/oder Suifo- succinate eingesetzt.Typical examples of anionic surfactants which can be considered as component (c) are soaps, alkylbenzenesulfonates, alkanesulfonates, olefinsulfonates, alkylethersulfonates, glycerinethersulfonates, α-methyl estersulfonates, sulfofatty acids, alkylsulfates, alkylethersulfates, glycerolethersulfate, mono-ether sulfate, monoglysulfate sulfates, , fatty acid amide (ether) sulfates, mono- and Dialkylsulfo- succinate, mono- and dialkyl sulfosuccinamates, sulfotriglycerides, amide soaps, ether carboxylic acids and salts thereof, fatty acid taurides, N-Acyiaminosäuren such as acyl lactylates, acyl tartrates, acyl glutamates and acyl aspartates, alkyl oligoglucoside sulfates, protein fatty acid condensates (especially vegetable products based on wheat) and alkyl (ether) phosphates. If the anionic surfactants contain polyglycol ether chains, they can have a conventional, but preferably a narrow, homolog distribution. Alkali soaps, alkyl sulfates, alkyl benzene sulfonates, alkyl ether sulfates, monoglyceride sulfates and / or suifosuccinates are preferably used.
Nichtionische und amphotere TensideNonionic and amphoteric surfactants
Typische Beispiele für weitere nichtionische Tenside, die als Komponente (c) in Betracht kommen, sind Fettalkoholpolyglycolether, Alkylphenolpolyglycolether, Fettsäurepolyglycolester, Fettsäureamidpolygly- colether, Fettaminpolyglycolether, alkoxylierte Triglyceride, Alk(en)yloligoglykoside, Fettsäure-N-alkyl- glucamide, Proteinhydrolysate (insbesondere pflanzliche Produkte auf Weizenbasis), Polyolfettsäure- ester, Zuckerester, Sorbitanester, Polysorbate und Aminoxide. Sofern die nichtionischen Tenside Polyglycoletherketten enthalten, können diese eine konventionelle, vorzugsweise jedoch eine eingeengte Homologenverteilung aufweisen. Typische Beispiele für amphotere bzw. zwitterionische Tenside sind Alkylbetaine, Alkylamidobetaine, Aminopropionate, Aminoglycinate, Imidazoliniumbetaine und Sulfo- betaine. Vorzugsweise werden Fettalkoholpolyglycolether, Alkyloligoglucoside, Fettsäure-N-alkylgluca- mide und/oder Betaine eingesetzt. Die erfindungsgemäßen Mittel können die Komponenten (a) und (c) im Gewichtsverhältnis 90 : 10 bis 10 : 90, vorzugsweise 75 : 25 bis 25 : 75 und insbesondere 60 : 40 bis 40 : 60 und die Komponenten (a), (b) und (c) im Gewichtsverhältnis (10 bis 90) : (5 bis 85) : (5 bis 85) und insbesondere (20 bis 80) : (10 bis 50) : (10 bis 50) enthalten, mit der Maßgabe, daß sich die Gewichtsangaben zu 100 Gew.-% ergänzen.Typical examples of further nonionic surfactants which can be considered as component (c) are fatty alcohol polyglycol ethers, alkylphenol polyglycol ethers, fatty acid polyglycol esters, fatty acid amide polyglycol ethers, fatty amine polyglycol ethers, alkoxylated triglycerides, alk (en) yl oligoglycosides, especially fatty acid-N-alkyl-glycols-fatty acid-N-alkyl-glycols vegetable products based on wheat), polyol fatty acid esters, sugar esters, sorbitan esters, polysorbates and amine oxides. If the nonionic surfactants contain polyglycol ether chains, they can have a conventional, but preferably a narrow, homolog distribution. Typical examples of amphoteric or zwitterionic surfactants are alkyl betaines, alkyl amido betaines, aminopropionates, aminoglycinates, imidazolinium betaines and sulfobetaines. Fatty alcohol polyglycol ethers, alkyl oligoglucosides, fatty acid N-alkyl glucamides and / or betaines are preferably used. The agents according to the invention can contain components (a) and (c) in a weight ratio of 90:10 to 10:90, preferably 75:25 to 25:75 and in particular 60:40 to 40:60 and components (a), (b) and (c) in the weight ratio (10 to 90): (5 to 85): (5 to 85) and in particular (20 to 80): (10 to 50): (10 to 50), with the proviso that add the weight information to 100% by weight.
Alkyl- und/oder AlkenyloliqoqlykosideAlkyl and / or alkenyl olefin glycosides
In einer bevorzugten Ausführungsform der Erfindung werden als nichtionische Tenside Alkyl- und Alkenyloligoglykoside eingesetzt, die der Formel (III) folgen, R 0-[G]P (III)In a preferred embodiment of the invention, the nonionic surfactants used are alkyl and alkenyl oligoglycosides which follow the formula (III) R 0- [G] P (III)
in der R4 für einen Alkyl- und/oder Alkenylrest mit 4 bis 22 Kohlenstoffatomen, G für einen Zuckerrest mit 5 oder 6 Kohlenstoffatomen und p für Zahlen von 1 bis 10 steht. Sie können nach den einschlägigen Verfahren der präparativen organischen Chemie erhalten werden. Stellvertretend für das umfangreiche Schrifttum sei hier auf die Übersichtsarbeit von Biermann et al. in Starch/Stärke 45, 281 (1993), B.Salka in Cosm.Toil. 108, 89 (1993) sowie J.Kahre et al. in SÖFW-Journal Heft 8, 598 (1995) verwiesen.in which R 4 is an alkyl and / or alkenyl radical having 4 to 22 carbon atoms, G is a sugar radical having 5 or 6 carbon atoms and p is a number from 1 to 10. They can be obtained according to the relevant procedures in preparative organic chemistry. Representative of the extensive literature here is the review by Biermann et al. in Starch /force 45, 281 (1993), B.Salka in Cosm.Toil. 108, 89 (1993) and J.Kahre et al. in SÖFW-Journal Issue 8, 598 (1995).
Die Alkyl- und/oder Alkenyloligoglykoside können sich von Aldosen bzw. Ketosen mit 5 oder 6 Kohlenstoffatomen, vorzugsweise der Glucose ableiten. Die bevorzugten Alkyl- und/oder Alkenyloligoglykoside sind somit Alkyl- und/oder Alkenyloligoglucoside. Die Indexzahl p in der allgemeinen Formel (III) gibt den Oiigomerisierungsgrad (DP), d. h. die Verteilung von Mono- und Oligoglykosiden an und steht für eine Zahl zwischen 1 und 10. Während p in einer gegebenen Verbindung stets ganzzahlig sein muß und hier vor allem die Werte p = 1 bis 6 annehmen kann, ist der Wert p für ein bestimmtes Alkyloligo- glykosid eine analytisch ermittelte rechnerische Größe, die meistens eine gebrochene Zahl darstellt. Vorzugsweise werden Alkyl- und/oder Alkenyloligoglykoside mit einem mittleren Oiigomerisierungsgrad p von 1 ,1 bis 3,0 eingesetzt. Aus anwendungstechnischer Sicht sind solche Alkyl- und/oder Alkenyloligoglykoside bevorzugt, deren Oiigomerisierungsgrad kleiner als 1 ,7 ist und insbesondere zwischen 1 ,2 und 1 ,4 liegt. Der Alkyl- bzw. Alkenylrest R4 kann sich von primären Alkoholen mit 4 bis 11 , vorzugsweise 8 bis 10 Kohlenstoffatomen ableiten. Typische Beispiele sind Butanol, Capronalkohol, Caprylalkohol, Caprinalkohol und Undecylalkohol sowie deren technische Mischungen, wie sie beispielsweise bei der Hydrierung von technischen Fettsäuremethylestern oder im Verlauf der Hydrierung von Aldehyden aus der Roelen'schen Oxosynthese erhalten werden. Bevorzugt sind Alkyioligo- glucoside der Kettenlänge Cβ-Cio (DP = 1 bis 3), die als Vorlauf bei der destillativen Auftrennung von technischem Cβ-Cis-Kokosfettalkohol anfallen und mit einem Anteil von weniger als 6 Gew.-% C12- Alkohol verunreinigt sein können sowie Alkyloligoglucoside auf Basis technischer Cg/n-Oxoalkohole (DP = 1 bis 3). Der Alkyl- bzw. Alkenylrest R4 kann sich ferner auch von primären Alkoholen mit 12 bis 22, vorzugsweise 12 bis 14 Kohlenstoffatomen ableiten. Typische Beispiele sind Laurylalkohol, My- ristylalkohol, Cetylalkohol, Palmoleylalkohol, Stearylalkohol, Isostearylalkohol, Oleylalkohol, Elaidyl- alkohol, Petroselinylalkohol, Arachylalkohol, Gadoleylalkohol, Behenylalkohol, Erucylalkohol, Brassidyl- alkohol sowie deren technische Gemische, die wie oben beschrieben erhalten werden können. Bevorzugt sind Alkyloligoglucoside auf Basis von gehärtetem Ci∑ -Kokosalkohol mit einem DP von 1 bis 3. Fettsäure-N-alkylpolvhvdroxyalkylamideThe alkyl and / or alkenyl oligoglycosides can be derived from aldoses or ketoses with 5 or 6 carbon atoms, preferably glucose. The preferred alkyl and / or alkenyl oligoglycosides are thus alkyl and / or alkenyl oligoglucosides. The index number p in the general formula (III) indicates the degree of oligomerization (DP), ie the distribution of mono- and oligoglycosides, and stands for a number between 1 and 10. While p must always be an integer in a given compound and especially here can assume the values p = 1 to 6, the value p for a certain alkyl oligoglycoside is an analytically determined arithmetic parameter, which usually represents a fractional number. Alkyl and / or alkenyl oligoglycosides with an average degree of oligomerization p of 1.1 to 3.0 are preferably used. From an application point of view, preference is given to those alkyl and / or alkenyl oligoglycosides whose degree of oligomerization is less than 1.7 and in particular between 1.2 and 1.4. The alkyl or alkenyl radical R 4 can be derived from primary alcohols having 4 to 11, preferably 8 to 10, carbon atoms. Typical examples are butanol, capro alcohol, caprylic alcohol, capric alcohol and undecyl alcohol and their technical mixtures, such as are obtained, for example, in the hydrogenation of technical fatty acid methyl esters or in the course of the hydrogenation of aldehydes from Roelen's oxosynthesis. Preferred are alkioligoglucosides of chain length Cβ-Cio (DP = 1 to 3), which are obtained as a preliminary step in the separation of technical Cβ-Cis-coconut fatty alcohol by distillation and are contaminated with a proportion of less than 6% by weight of C12 alcohol can as well as alkyl oligoglucosides based on technical Cg / n-oxo alcohols (DP = 1 to 3). The alkyl or alkenyl radical R 4 can also be derived from primary alcohols having 12 to 22, preferably 12 to 14, carbon atoms. Typical examples are lauryl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, arachyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol, brassidyl alcohol and the technical mixtures described above, which can be obtained as well as their technical mixtures. Alkyl oligoglucosides based on hardened Ci∑ coconut alcohol with a DP of 1 to 3 are preferred. Fatty acid N-alkyl polydroxyalkylamides
Eine weitere Gruppe bevorzugter nichtionischer Tenside, die die Komponente (c) bilden können, stellen Fettsäure-N-alkylpolyhydroxyalkylamide dar, die der Formel (IV) folgen,Another group of preferred nonionic surfactants which can form component (c) are fatty acid N-alkylpolyhydroxyalkylamides which follow the formula (IV)
R6R6
Figure imgf000008_0001
Figure imgf000008_0001
in der R5CO für einen aliphatischen Acylrest mit 6 bis 22 Kohlenstoffatomen, R6 für einen Alkyl- oder Hydroxyalkylrest mit 1 bis 4 Kohlenstoffatomen und [Z] für einen linearen oder verzweigten Polyhy- droxyalkylrest mit 3 bis 12 Kohlenstoffatomen und 3 bis 10 Hydroxylgruppen steht. Bei den Fettsäure- N-alkylpolyhydroxyalkylamiden handelt es sich um bekannte Stoffe, die üblicherweise durch reduktive Aminierung eines reduzierenden Zuckers mit einem Alkyiamin oder einem Alkanolamin und nachfolgende Acylierung mit einer Fettsäure, einem Fettsäurealkylester oder einem Fettsäurechlorid erhalten werden können. Hinsichtlich der Verfahren zu ihrer Herstellung sei auf die US-Patentschriften US 1,985,424, US 2,016,962 und US 2,703,798 sowie die Internationale Patentanmeldung WO 92/06984 verwiesen. Eine Übersicht zu diesem Thema von H.Kelkenberg findet sich in Tens.Surf.Deterg. 25, 8 (1988).in the R 5 CO for an aliphatic acyl radical with 6 to 22 carbon atoms, R 6 for an alkyl or hydroxyalkyl radical with 1 to 4 carbon atoms and [Z] for a linear or branched polyhydroxyalkyl radical with 3 to 12 carbon atoms and 3 to 10 hydroxyl groups stands. The fatty acid N-alkyl polyhydroxyalkylamides are known substances which can usually be obtained by reductive amination of a reducing sugar with an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride. With regard to the processes for their production, reference is made to US Pat. Nos. 1,985,424, 2,016,962 and 2,703,798 and international patent application WO 92/06984. An overview of this topic by H.Kelkenberg can be found in Tens.Surf.Deterg. 25, 8 (1988).
Vorzugsweise leiten sich die Fettsäure-N-alkylpolyhydroxyalkylamide von reduzierenden Zuckern mit 5 oder 6 Kohlenstoffatomen, insbesondere von der Glucose ab. Die bevorzugten Fettsäure-N-alkylpoly- hydroxyalkylamide stellen daher Fettsäure-N-alkylglucamide dar, wie sie durch die Formel (V) wiedergegeben werden:The fatty acid N-alkylpolyhydroxyalkylamides are preferably derived from reducing sugars having 5 or 6 carbon atoms, in particular from glucose. The preferred fatty acid N-alkylpolyhydroxyalkylamides are therefore fatty acid N-alkylglucamides as represented by the formula (V):
R6 OH OH OHR 6 OH OH OH
I I I II I I I
R5CO-N-CH .CH-CH-CH-CH-CH2OH (V)R5CO-N-CH .CH-CH-CH-CH-CH 2 OH (V)
II.
OHOH
Vorzugsweise werden als Fettsäure-N-alkylpolyhydroxyalkylamide Glucamide der Formel (V) eingesetzt, in der R6 für eine Alkylgruppe steht und R5CO für den Acylrest der Capronsäure, Caprylsäure, Caprinsäure, Laurinsäure, Myristinsäure, Palmitinsäure, Palmoleinsäure, Stearinsäure, Isostearinsäure, Ölsäure, Elaidinsäure, Petroselinsäure, Linolsäure, Linolensäure, Arachinsäure, Gadoleinsäure, Behensäure oder Erucasäure bzw. derer technischer Mischungen steht. Besonders bevorzugt sind Fettsäure-N-alkylglucamide der Formel (V), die durch reduktive Aminierung von Glucose mit Methylamin und anschließende Acylierung mit Laurinsäure oder Ci2/ 4-Kokosfettsäure bzw. einem entsprechenden Derivat erhalten werden. Weiterhin können sich die Polyhydroxyalkylamide auch von Maltose und Palatinose ableiten. BetaineThe preferred fatty acid N-alkylpolyhydroxyalkylamides used are glucamides of the formula (V) in which R 6 represents an alkyl group and R 5 CO represents the acyl radical of caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, palmoleic acid, stearic acid, isostearic acid, Oleic acid, elaidic acid, petroselinic acid, linoleic acid, linolenic acid, arachic acid, gadoleic acid, behenic acid or erucic acid or their technical mixtures. Fatty acid N-alkylglucamides of the formula (V) which are obtained by reductive amination of glucose with methylamine and subsequent acylation with lauric acid or Ci2 / 4 coconut fatty acid or a corresponding derivative are particularly preferred. Furthermore, the polyhydroxyalkylamides can also be derived from maltose and palatinose. Betaine
In einer weiteren bevorzugten Ausführungsform der Erfindung können Tenside vom Betaintyp die Komponente (c) bilden. Betaine stellen bekannte Tenside dar, die überwiegend durch Carboxyalkylie- rung, vorzugsweise Carboxymethylierung von aminischen Verbindungen hergestellt werden. Vorzugsweise werden die Ausgangsstoffe mit Halogencarbonsäuren oder deren Salzen, insbesondere mit Natriumchloracetat kondensiert, wobei pro Mol Betain ein Mol Salz gebildet wird. Ferner ist auch die Anlagerung von ungesättigten Carbonsäuren, wie beispielsweise Acryisäure möglich. Zur Nomenklatur und insbesondere zur Unterscheidung zwischen Betainen und "echten" Amphotensiden sei auf den Beitrag von U.PIoog in Seifen-Öle-Fette-Wachse, 108, 373 (1982) verwiesen. Weitere Übersichten zu diesem Thema finden sich beispielsweise von A.O'Lennick et al. in HAPPI, Nov. 70 (1986), S.Holzman et al. in Tens. Surf.Det. 23, 309 (1986), R.Bilbo et al. in Soap Cosm.Chem.Spec, Apr. 46 (1990) und P.EIIis et al. in Euro Cosm. 1, 14 (1994). Beispiele für geeignete Betaine stellen die Carboxyalkylie- rungsprodukte von sekundären und insbesondere tertiären Aminen dar, die der Formel (VI) folgen,In a further preferred embodiment of the invention, surfactants of the betaine type can form component (c). Betaines are known surfactants which are predominantly produced by carboxyalkylation, preferably carboxymethylation, of aminic compounds. The starting materials are preferably condensed with halocarboxylic acids or their salts, in particular with sodium chloroacetate, one mol of salt being formed per mole of betaine. The addition of unsaturated carboxylic acids, such as, for example, acrylic acid, is also possible. Regarding the nomenclature and in particular the distinction between betaines and "real" amphoteric surfactants, reference is made to the contribution by U.PIoog in Seifen-Öle-Fette-Wwachs, 108, 373 (1982). Further overviews on this topic can be found for example by A. O'Lennick et al. in HAPPI, Nov. 70 (1986), S. Holzman et al. in tens. Surf.Det. 23, 309 (1986), R.Bilbo et al. in Soap Cosm. Chem. Spec, Apr. 46 (1990) and P.EIIis et al. in Euro Cosm. 1, 14 (1994). Examples of suitable betaines are the carboxyalkylation products of secondary and in particular tertiary amines which follow the formula (VI)
R8 R 8
II.
R7-N-(CH2)nCOOX (VI)R7-N- (CH 2 ) nCOOX (VI)
I R9 IR 9
in der R7 für Alkyl- und/oder Alkenyireste mit 6 bis 22 Kohlenstoffatomen, R8 für Wasserstoff oder Alkylreste mit 1 bis 4 Kohlenstoffatomen, R9 für Alkylreste mit 1 bis 4 Kohlenstoffatomen, n für Zahlen von 1 bis 6 und X für ein Alkali- und/oder Erdalkalimetall oder Ammonium steht. Typische Beispiele sind die Carboxymethylierungsprodukte von Hexylmethylamin, Hexyldimethylamin, Octyldimethylamin, De- cyldimethylamin, Dodecylmethylamin, Dodecyldimethylamin, Dodecylethylmethylamin, Ci2/i4-Kokosal- kyldimethylamin, Myristyldimethylamin, Cetyldimethylamin, Stearyldimethylamin, Stearylethylmethyl- amin, Oleyldimethylamin, Ci6/18-Talgalkyldimethylamin sowie deren technische Gemische. Weiterhin kommen auch Carboxyalkylierungsprodukte von Amidoaminen in Betracht, die der Formel (VII) folgen,in which R 7 for alkyl and / or alkenyi radicals with 6 to 22 carbon atoms, R 8 for hydrogen or alkyl radicals with 1 to 4 carbon atoms, R 9 for alkyl radicals with 1 to 4 carbon atoms, n for numbers from 1 to 6 and X for a Alkali and / or alkaline earth metal or ammonium. Typical examples are the carboxymethylation products of hexylmethylamine, hexyldimethylamine, octyldimethylamine, Removal cyldimethylamin, dodecylmethylamine, dodecyldimethylamine, Dodecylethylmethylamin, Ci2 / i4-Kokosal- kyldimethylamin, myristyldimethylamine, cetyldimethylamine, stearyldimethylamine, Stearylethylmethyl- amine, oleyl dimethyl amine, Ci6 / 18 tallow alkyl dimethyl amine, and their technical Mixtures. Carboxyalkylation products of amidoamines which follow the formula (VII) are also suitable,
R8 R 8
I Ri0CO-NH-(CH2)m-N-(CH2)nCOOX (VII)I Ri0CO-NH- (CH 2 ) mN- (CH 2 ) nCOOX (VII)
II.
R9R9
in der R10CO für einen aliphatischen Acylrest mit 6 bis 22 Kohlenstoffatomen und 0 oder 1 bis 3 Doppelbindungen, m für Zahlen von 1 bis 3 steht und R8, R9, n und X die oben angegebenen Bedeutungen haben. Typische Beispiele sind Umsetzungsprodukte von Fettsäuren mit 6 bis 22 Kohlenstoffatomen, namentlich Capronsäure, Caprylsäure, Caprinsäure, Laurinsäure, Myristinsäure, Palmi- tinsäure, Palmoleinsäure, Stearinsäure, Isostearinsäure, Ölsäure, Elaidinsäure, Petroselinsäure, Linol- säure, Linolensäure, Elaeostearinsäure, Arachinsäure, Gadoleinsäure, Behensäure und Erucasäure sowie deren technische Gemische, mit N,N-Dimethylaminoethylamin, N,N-Dimethylaminopropylamin, N,N-Diethylaminoethylamin und N,N-Diethylaminopropylamin, die mit Natriumchloracetat kondensiert werden. Bevorzugt ist der Einsatz eines Kondensationsproduktes von Cδ -Kokosfettsäure-N.N-dime- thylaminopropylamid mit Natriumchloracetat. Weiterhin kommen als geeignete Ausgangsstoffe für die im Sinne der Erfindung einzusetzenden Betaine auch Imidazoline in Betracht, die der Formel (VIII) folgen,in which R 10 CO represents an aliphatic acyl radical having 6 to 22 carbon atoms and 0 or 1 to 3 double bonds, m represents numbers from 1 to 3 and R 8 , R 9 , n and X have the meanings given above. Typical examples are reaction products of fatty acids with 6 to 22 carbon atoms, namely caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmi tic acid, palmoleic acid, stearic acid, isostearic acid, oleic acid, elaidic acid, petroselinic acid, linoleic acid, linolenic acid, elaeostearic acid, arachic acid, gadoleic acid, behenic acid and erucic acid and their technical mixtures, with N, N-dimethylaminoethylamine, N, N-dimethylaminopropyl -Diethylaminoethylamine and N, N-diethylaminopropylamine, which are condensed with sodium chloroacetate. Preference is given to using a condensation product of C δ coconut fatty acid-NN-dimethylaminopropylamide with sodium chloroacetate. Furthermore, suitable starting materials for the betaines to be used in accordance with the invention are also imidazolines which follow the formula (VIII)
Figure imgf000010_0001
Figure imgf000010_0001
in der R11 für einen Alkylrest mit 5 bis 21 Kohlenstoffatomen, R12 für eine Hydroxylgruppe, einen OCOR11- oder NHCOR11-Rest und m für 2 oder 3 steht. Auch bei diesen Substanzen handelt es sich um bekannte Stoffe, die beispielsweise durch cyclisierende Kondensation von 1 oder 2 Mol Fettsäure mit mehrwertigen Aminen, wie beispielsweise Aminoethylethanolamin (AEEA) oder Diethylentriamin erhalten werden können. Die entsprechenden Carboxyalkylierungsprodukte stellen Gemische unterschiedlicher offenkettiger Betaine dar. Typische Beispiele sind Kondensationsprodukte der oben genannten Fettsäuren mit AEEA, vorzugsweise Imidazoline auf Basis von Laurinsäure oder wiederum Ci2/i4-Kokosfettsäure, die anschließend mit Natriumchloracetat betainisiert werden.in which R 11 is an alkyl radical having 5 to 21 carbon atoms, R 12 is a hydroxyl group, an OCOR 11 or NHCOR 11 radical and m is 2 or 3. These substances are also known substances which can be obtained, for example, by cyclizing condensation of 1 or 2 moles of fatty acid with polyhydric amines, such as, for example, aminoethylethanolamine (AEEA) or diethylenetriamine. The corresponding carboxyalkylation products are mixtures of different open-chain betaines. Typical examples are condensation products of the above-mentioned fatty acids with AEEA, preferably imidazolines based on lauric acid or again Ci2 / 14 coconut fatty acid, which are subsequently betainized with sodium chloroacetate.
Gewerbliche AnwendbarkeitIndustrial applicability
Ein weiterer Gegenstand der Erfindung betrifft die Verwendung der erfindungsgemäßen Tensid- mischungen zur Herstellung von wäßrigen Mitteln für die Reinigung harter Oberflächen. Typische Beispiele für diese Mittel sind Allzweckreiniger, Sanitärreiniger, Maschineller Geschirrspülmittel, Klarspülmittel, Mittel für die „Cleaning-in-place" (CIP-Reiniger) sowie Mittel für die maschinelle Reinigung von Flaschen.Another object of the invention relates to the use of the surfactant mixtures according to the invention for the production of aqueous agents for cleaning hard surfaces. Typical examples of these agents are all-purpose cleaners, sanitary cleaners, machine dishwashing detergents, rinse aid, agents for cleaning-in-place (CIP cleaners) and agents for machine cleaning of bottles.
Die Mischungen können in diesem Zusammenhang in untergeordneten Mengen weitere übliche Hilfsund Zusatzstoffe enthalten. Hierzu zählen beispielsweise Lösungsvermittler, wie Ethanol, Isopropyl- alkohol, Ethylenglycol, Diethylenglycol oder vorzugsweise Butyldiglycol, Schaumregulatoren, wie beispielsweise Seife, lösliche Builder, wie beispielsweise Citronensäure bzw. Natriumeitrat, EDTA oder NTA und Abrasivstoffe. In vielen Fällen ist eine zusätzliche bakterizide Wirkung erwünscht, weswegen die Mittel kationische Tenside oder Biozide, beispielsweise Glucoprotamin, enthalten können. Auch die Mitverwendung von Bleichmitteln wie Natriumhypochlorit oder Wasserstoffperoxid sowie geeigneter Färb- und Duftstoff ist möglich. Der Anteil dieser Zusatzstoffe kann 1 bis 8, vorzugsweise 4 bis 6 Gew.- % - bezogen auf die Mittel - ausmachen. Vorzugsweise werden die Mittel durch Zugabe von Natriumhydroxid und/oder Soda alkalisch eingestellt, wobei ein pH-Wert im Bereich von 9 bis 10 bevorzugt ist. Der Aktivsubstanzgehalt der Mittel kann zwischen 4 und 80 Gew.-% liegen und ist davon abhängig, ob ein Konzentrat erwünscht ist (40 bis 80, vorzugsweise 50 bis 70 Gew.-% Aktivanteil), das vom Verbraucher vor der Reinigung auf die Anwendungskonzentration verdünnt wird oder ein entsprechend verdünntes Mittel (4 bis 50, vorzugsweise 10 bis 30 Gew.-% Aktivanteil) vermarktet werden soll. In letzterem Fall liegt der Aktivsubstanzgehalt typischerweise bei etwa 4 bis 20 Gew.-%. Zur Herstellung der Mittel ist es ausreichend, die Einsatzstoffe gegebenenfalls bei erhöhter Temperatur rein mechanisch zu vermischen; eine chemische Reaktion findet dabei nicht statt. In this connection, the mixtures can contain minor amounts of other customary auxiliaries and additives. These include, for example, solubilizers such as ethanol, isopropyl alcohol, ethylene glycol, diethylene glycol or preferably butyl diglycol, foam regulators such as soap, soluble builders such as citric acid or sodium citrate, EDTA or NTA and abrasives. In many cases an additional bactericidal action is desired, which is why the agents can contain cationic surfactants or biocides, for example glucoprotamine. Also the The use of bleaching agents such as sodium hypochlorite or hydrogen peroxide as well as a suitable coloring and fragrance is possible. The proportion of these additives can make up 1 to 8, preferably 4 to 6% by weight, based on the composition. The agents are preferably made alkaline by adding sodium hydroxide and / or soda, a pH in the range from 9 to 10 being preferred. The active substance content of the agents can be between 4 and 80% by weight and depends on whether a concentrate is desired (40 to 80, preferably 50 to 70% by weight of active component) which the consumer dilutes to the application concentration before cleaning is or a correspondingly diluted agent (4 to 50, preferably 10 to 30 wt .-% active content) is to be marketed. In the latter case, the active substance content is typically around 4 to 20% by weight. To produce the agents, it is sufficient to mix the starting materials purely mechanically, if appropriate at elevated temperature; there is no chemical reaction.
BeispieleExamples
Das Reinigungsvermögen wurde photometrisch gegen eine Stand ardrezeptur (= 100 % Remission) ermittelt. Zur Bestimmung des Schaumverhaltens der Tensidmischungen wurden 2 Eier (ca. 100 bis 110 g) in einem elektrischen Mixgerät im Verhältnis 1 :1 mit Wasser von 16°d verdünnt und 2 min verrührt. 100 g der resultierenden Emulsion wurden dann in einem doppelwandigen Meßzylinder von 2000 ml auf 500 ml mit Wasser von 16°d aufgefüllt und auf 50°C temperiert. Nach Erreichen der Prüftemperatur wurden dieser Mischung 20 g der Tensidmischungen zugesetzt. Mit Hilfe einer Labor-Schlauchpumpe wurde die Lösung mit einem Glasrohr vom Boden des Meßzylinders angesaugt. Die Rückführung erfolgte über ein zweites Rohr, dessen unteres Ende in der Höhe der 2000-ml-Markierung des Meßzylinders endete. Die Flüssigkeit wurde mit einer Geschwindigkeit von 4 l/min umgepumpt. Nach 5, 15, und 30 min wurde das Volumen aus dem entstandenen Schaum und der Flüssigkeit abgelesen. Zur Bestimmung der hautkosmetischen Verträglichkeit wurde die Hautverträglichkeit der Vergleichsrezeptur V1 gemäß Zeintest als Standard gewählt und alle Angaben darauf bezogen. Die Rezepturen 1 bis 8 sind erfindungsgemäß, die Rezepturen V1 und V2 dienen dem Vergleich. Die Ergebnisse sind in Tabelle 1 zusammengefaßt. The cleaning ability was determined photometrically against a standard formulation (= 100% remission). To determine the foaming behavior of the surfactant mixtures, 2 eggs (approx. 100 to 110 g) were diluted 1: 1 with water at 16 ° d in an electric mixer and stirred for 2 minutes. 100 g of the resulting emulsion were then made up in a double-walled measuring cylinder from 2000 ml to 500 ml with water at 16 ° C. and the temperature was raised to 50 ° C. After reaching the test temperature, 20 g of the surfactant mixtures were added to this mixture. With the help of a laboratory peristaltic pump, the solution was sucked from the bottom of the measuring cylinder with a glass tube. The return was carried out via a second tube, the lower end of which ended at the level of the 2000 ml mark on the measuring cylinder. The liquid was pumped around at a rate of 4 l / min. After 5, 15 and 30 minutes, the volume was read from the foam and liquid formed. To determine the skin cosmetic tolerance, the skin tolerance of the comparison formulation V1 was selected as the standard according to the zeintest and all the information related to it. Formulations 1 to 8 are according to the invention, formulations V1 and V2 are used for comparison. The results are summarized in Table 1.
Tabelle 1Table 1
Eigenschaften von Alizweckreinigem (Mengenangaben als Gew.-%)Properties of ali purpose cleaners (quantities as% by weight)
Figure imgf000013_0001
Figure imgf000013_0001

Claims

Patentansprüche claims
1. Wäßrige Mittel für die Reinigung harter Oberflächen, enthaltend1. Containing aqueous agents for cleaning hard surfaces
(a) Fettsäurepolyglycolestersulfate,(a) fatty acid polyglycol ester sulfates,
(b) Mischether und gegebenenfalls(b) mixed ether and optionally
(c) anionische, nichtionische und/oder amphotere bzw. zwitterionische Tenside.(c) anionic, nonionic and / or amphoteric or zwitterionic surfactants.
2. Mittel nach Anspruch 1 , dadurch gekennzeichnet, daß sie Fettsäurepoiyglycolestersulfate der Formel (I) enthalten,2. Composition according to claim 1, characterized in that they contain fatty acid polyglycol ester sulfates of the formula (I),
Figure imgf000014_0001
Figure imgf000014_0001
in der R1CO für einen linearen oder verzweigten, gesättigten oder ungesättigten Acylrest mit 6 bis 22 Kohlenstoffatomen, x für Zahlen von durchschnittlich 1 bis 3 und AO für einen CH2CH2O-, CH2CH(CH3)0- und/oder CH(CH3)CH20-Rest und X für ein Alkali- und/oder Erdalkalimetall, Ammonium, Alkylammonium, Alkanolammonium oder Glucammonium steht.in which R 1 CO is a linear or branched, saturated or unsaturated acyl radical having 6 to 22 carbon atoms, x is an average of 1 to 3 and AO is a CH2CH2O-, CH 2 CH (CH 3 ) 0- and / or CH ( CH 3 ) CH 2 0 radical and X represents an alkali and / or alkaline earth metal, ammonium, alkylammonium, alkanolammonium or glucammonium.
3. Mittel nach den Ansprüchen 1 und 2, dadurch gekennzeichnet, daß sie Mischether der Formel (II) enthalten,3. Composition according to claims 1 and 2, characterized in that they contain mixed ethers of the formula (II),
CH3 CH3 CH 3 CH 3
I II I
R20(CH2CH2θ)nl(CH2CHO)ml(CH2CH2θ)n2(CH2CHO)m2R3 (II)R 2 0 (CH2CH2θ) nl (CH2CHO) ml (CH2CH2θ) n2 (CH2CHO) m2 R 3 (II)
in der R2 für einen linearen oder verzweigten Alkyl- und/oder Alkenylrest mit 6 bis 22 Kohlenstoffatomen, R3 für Wasserstoff, einen Aikylrest mit 1 bis 8 Kohlenstoffatomen oder einen Benzyl- rest, n1 und n2 unabhängig voneinander für 0 oder Zahlen von 1 bis 20 und m1 und m2 unabhängig voneinander für 0 oder Zahlen von 1 bis 3 stehen, mit der Maßgabe, daß mindestens einer der beiden Parameter n1 und n2 ungleich 0 ist.in which R 2 represents a linear or branched alkyl and / or alkenyl radical having 6 to 22 carbon atoms, R 3 represents hydrogen, an aikyl radical having 1 to 8 carbon atoms or a benzyl radical, n1 and n2 independently of one another for 0 or numbers of 1 to 20 and m1 and m2 independently of one another represent 0 or numbers from 1 to 3, with the proviso that at least one of the two parameters n1 and n2 is not equal to 0.
4. Mittel nach den Ansprüchen 1 bis 3, dadurch gekennzeichnet, daß sie anionische Tenside enthalten, die ausgewählt sind aus der Gruppe, die gebildet wird von Alkaliseifen, Alkylsulfaten, Alkylbenzolsulfonaten, Alkylethersulfaten, Monoglyceridsulfaten und Sulfosuccinaten.4. Composition according to claims 1 to 3, characterized in that they contain anionic surfactants which are selected from the group formed by alkali soaps, alkyl sulfates, alkylbenzenesulfonates, alkyl ether sulfates, monoglyceride sulfates and sulfosuccinates.
5. Mittel nach den Ansprüchen 1 bis 4, dadurch gekennzeichnet, daß sie die Komponenten (a) und (b) bzw. (a) und (c) im Gewichtsverhältnis 90 : 10 bis 10 : 90 enthalten. 5. Composition according to claims 1 to 4, characterized in that they contain the components (a) and (b) or (a) and (c) in a weight ratio of 90:10 to 10:90.
6. Mittel nach den Ansprüchen 1 bis 5 dadurch gekennzeichnet, daß sie nichtionische und/oder amphotere bzw. zwitterionische Tenside enthalten, die ausgewählt sind aus der Gruppe, die gebildet wird von Fettalkoholpolyglycolethem, Alkyloligoglucosiden, Fettsäure-N-alkylglucamiden und/oder Betainen.6. Composition according to claims 1 to 5, characterized in that they contain nonionic and / or amphoteric or zwitterionic surfactants which are selected from the group formed by fatty alcohol polyglycol ethers, alkyl oligoglucosides, fatty acid N-alkyl glucamides and / or betaines.
7. Mittel nach den Ansprüchen 1 bis 6, dadurch gekennzeichnet, daß sie als nichtionische Tenside Alkyl- und Alkenyloligoglykoside der Formel (III),7. Composition according to claims 1 to 6, characterized in that they are alkyl and alkenyl oligoglycosides of the formula (III) as nonionic surfactants,
R40-[G]P (III)R 4 0- [G] P (III)
in der R4 für einen Alkyl- und/oder Alkenylrest mit 4 bis 22 Kohlenstoffatomen, G für einen Zuckerrest mit 5 oder 6 Kohlenstoffatomen und p für Zahlen von 1 bis 10 steht.in which R 4 is an alkyl and / or alkenyl radical having 4 to 22 carbon atoms, G is a sugar radical having 5 or 6 carbon atoms and p is a number from 1 to 10.
8. Mittel nach den Ansprüchen 1 bis 7, dadurch gekennzeichnet, daß sie als nichtionische Tenside Fettsäure-N-alkylpoiyhydroxyalkylamide der Formel (IV) enthalten,8. Composition according to claims 1 to 7, characterized in that they contain fatty acid-N-alkylpolyhydroxyalkylamides of the formula (IV) as nonionic surfactants,
R8 R 8
Figure imgf000015_0001
Figure imgf000015_0001
in der R5CO für einen aliphatischen Acylrest mit 6 bis 22 Kohlenstoffatomen, R4 einen Alkyl- oder Hydroxyalkylrest mit 1 bis 4 Kohlenstoffatomen und [Z] für einen linearen oder verzweigten Polyhydroxyalkylrest mit 3 bis 12 Kohlenstoffatomen und 3 bis 10 Hydroxylgruppen steht.in which R 5 CO represents an aliphatic acyl radical with 6 to 22 carbon atoms, R 4 represents an alkyl or hydroxyalkyl radical with 1 to 4 carbon atoms and [Z] stands for a linear or branched polyhydroxyalkyl radical with 3 to 12 carbon atoms and 3 to 10 hydroxyl groups.
9. Mittel nach den Ansprüchen 1 bis 8, dadurch gekennzeichnet, daß sie als amphotere Tenside Betaine der Formel (VI) enthalten,9. Composition according to claims 1 to 8, characterized in that they contain betaines of the formula (VI) as amphoteric surfactants,
R8 R 8
I R7-N-(CH2)nCOOX (VI)IR 7 -N- (CH 2 ) nCOOX (VI)
I R9 IR 9
in der R7 für Alkyl- und/oder Alkenyireste mit 6 bis 22 Kohlenstoffatomen, R8 für Wasserstoff oder Alkylreste mit 1 bis 4 Kohienstoffatomen, R9 für Alkylreste mit 1 bis 4 Kohlenstoffatomen, n für Zahlen von 1 bis 6 und X für ein Alkali- und/oder Erdalkalimetall oder Ammonium steht.in which R 7 for alkyl and / or alkenyi radicals with 6 to 22 carbon atoms, R 8 for hydrogen or alkyl radicals with 1 to 4 carbon atoms, R 9 for alkyl radicals with 1 to 4 carbon atoms, n for numbers from 1 to 6 and X for a Alkali and / or alkaline earth metal or ammonium.
10. Mittel nach den Ansprüchen 1 bis 9, dadurch gekennzeichnet, daß sie als amphotere Tenside Betaine der Formel (VII) enthalten, R8 10. Composition according to claims 1 to 9, characterized in that they contain betaines of the formula (VII) as amphoteric surfactants, R 8
I RioCO-NH-(CH2)m-N-(CH2)nCOOX (VII)I RioCO-NH- (CH2) mN- (CH 2 ) n COOX (VII)
I R9 IR 9
in der R10CO für einen aliphatischen Acylrest mit 6 bis 22 Kohlenstoffatomen und 0 oder 1 bis 3 Doppelbindungen, m für Zahlen von 1 bis 3 steht und R8, R9, n und X die oben angegebenen Bedeutungen haben.in which R 10 CO represents an aliphatic acyl radical having 6 to 22 carbon atoms and 0 or 1 to 3 double bonds, m represents numbers from 1 to 3 and R 8 , R 9 , n and X have the meanings given above.
11. Mittel nach den Ansprüchen 1 bis 10 dadurch gekennzeichnet, daß sie die Komponenten (a), (b) und (c) im Gewichtsverhältnis (10 bis 90) : (5 bis 85) : (5 bis 85) enthalten, mit der Maßgabe, daß sich die Gewichtsangaben zu 100 Gew.-% ergänzen.11. Composition according to claims 1 to 10, characterized in that they contain the components (a), (b) and (c) in a weight ratio (10 to 90): (5 to 85): (5 to 85) with which Provided that the weight specifications add up to 100% by weight.
12. Verwendung der Zusammensetzungen nach Anspruch 1 zur Herstellung von Reinigungsmitteln für harte Oberflächen. 12. Use of the compositions according to claim 1 for the production of cleaning agents for hard surfaces.
PCT/EP1998/005202 1997-08-25 1998-08-17 Aqueous agents for cleaning hard surfaces WO1999010458A1 (en)

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
DE19736906A DE19736906A1 (en) 1997-08-25 1997-08-25 Process for the preparation of sulfated fatty acid alkylene glycol esters
DE19741911A DE19741911C1 (en) 1997-09-25 1997-09-25 Fatty acid polyglycol ester sulphate as foam booster for surfactants
DE19741911.9 1997-10-23
DE19736906.5 1997-10-23
DE19813059.7 1998-03-25
DE1998113059 DE19813059C2 (en) 1998-03-25 1998-03-25 Aqueous agents for cleaning hard surfaces

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FR2800385A1 (en) * 1999-10-29 2001-05-04 Cognis Deutschland Gmbh Hard surface cleaner for lacquered metal surfaces comprises alkyl- and/or alkenyl-sulfates, alcohol and polyethylene glycol ethers, N-alkylpolyhydroxyalkyl fatty acid amides and electrolyte salts
WO2001038468A1 (en) * 1999-11-23 2001-05-31 Henkel Ecolab Gmbh & Co. Ohg Use of dirt-removing formulations for treating surfaces
WO2001055288A1 (en) * 2000-01-28 2001-08-02 Cognis Deutschland Gmbh & Co. Kg Clear rinsing agents
WO2001055285A2 (en) * 2000-01-28 2001-08-02 Cognis Deutschland Gmbh & Co. Kg Rinsing and cleaning agents
EP3263682A1 (en) * 2016-06-27 2018-01-03 The Procter and Gamble Company Hard surface cleaning compositions

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2800385A1 (en) * 1999-10-29 2001-05-04 Cognis Deutschland Gmbh Hard surface cleaner for lacquered metal surfaces comprises alkyl- and/or alkenyl-sulfates, alcohol and polyethylene glycol ethers, N-alkylpolyhydroxyalkyl fatty acid amides and electrolyte salts
WO2001038468A1 (en) * 1999-11-23 2001-05-31 Henkel Ecolab Gmbh & Co. Ohg Use of dirt-removing formulations for treating surfaces
WO2001055288A1 (en) * 2000-01-28 2001-08-02 Cognis Deutschland Gmbh & Co. Kg Clear rinsing agents
WO2001055285A2 (en) * 2000-01-28 2001-08-02 Cognis Deutschland Gmbh & Co. Kg Rinsing and cleaning agents
WO2001055285A3 (en) * 2000-01-28 2001-12-13 Cognis Deutschland Gmbh Rinsing and cleaning agents
US6732748B2 (en) 2000-01-28 2004-05-11 Cognis Deutschland Gmbh & Co. Kg Clear rinsing agents
EP3263682A1 (en) * 2016-06-27 2018-01-03 The Procter and Gamble Company Hard surface cleaning compositions

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