WO1999010460A1 - Flowable tenside preparations containing fatty acid polyglycol ester sulphates - Google Patents

Flowable tenside preparations containing fatty acid polyglycol ester sulphates Download PDF

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Publication number
WO1999010460A1
WO1999010460A1 PCT/EP1998/005203 EP9805203W WO9910460A1 WO 1999010460 A1 WO1999010460 A1 WO 1999010460A1 EP 9805203 W EP9805203 W EP 9805203W WO 9910460 A1 WO9910460 A1 WO 9910460A1
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Prior art keywords
fatty acid
alkyl
sulfates
alcohol
ether
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PCT/EP1998/005203
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German (de)
French (fr)
Inventor
Hermann Hensen
Bernd Fabry
Karl Heinz Schmid
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 DE1998120811 external-priority patent/DE19820811A1/en
Application filed by Cognis Deutschland Gmbh filed Critical Cognis Deutschland Gmbh
Publication of WO1999010460A1 publication Critical patent/WO1999010460A1/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
    • C11D1/88—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
    • C11D1/14—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
    • C11D1/22—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic 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
    • C11D1/02—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
    • C11D1/75—Amino oxides
    • 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 is in the field of liquid detergents and relates to aqueous, easy-to-handle surfactant preparations containing selected surface-active substances and their use.
  • Liquid detergents are generally understood to be aqueous preparations of surface-active substances which are used for manual, but preferably machine washing of, in particular, lightly soiled textiles. Compared to powder detergents, the liquid detergents have the advantage of being easier to dose. In addition to these low-viscosity products, pasty agents are also on the market, which generally have a significantly lower water content or are almost water-free. These agents can be applied directly to stubborn stains and rubbed in, which makes subsequent washing in the washing machine easier.
  • anionic surfactants are often poorly soluble in cold water; Because of their inverse solubility behavior, nonionic surfactants are therefore often preferred to anionic compounds. Anionic surfactants also tend to form highly viscous gel phases, which leads to Difficulties arise when trying to formulate anion-based liquid detergents with a higher active substance content. On the other hand, anionic surfactants make a very considerable contribution to the removal of a large number of stains, so that this group of surfactants is difficult to do without when producing an effective detergent.
  • the complex object of the invention was to provide liquid detergents which have a high anionic surfactant content, but which are flowable and pumpable, do not crystallize or evaporate during storage and have optimum cleaning performance over the largest possible range of contaminants.
  • the preparations have a significantly lower viscosity compared to aqueous solutions of other anionic surfactants and, moreover, have an excellent cleaning ability against a large number of very different types of soiling.
  • Another advantage is that the agents neither crystallize nor lose when stored.
  • the invention includes the finding that clear, storage-stable liquid detergents with a high active substance content and low to medium viscosity can be prepared using the fatty acid polycarbon ester sulfates, preferably in a mixture with anionic and / or nonionic surfactants.
  • the preferred co-surfactants are alkylbenzoisulfonates, alkyl sulfates, alkyl oligoglucosides, alcohol ethoxylates and their mixtures.
  • RiCOO (AO) ⁇ S ⁇ 3X (I) in the R 1 CO for a linear or branched, saturated or unsaturated acyl radical with 6 to 22 carbon atoms, x for numbers from 1 to 3 on average and AO for a CH2CH2O-, CH2CH (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 are prepared by sulfating the corresponding fatty acid polyglycol esters. These in turn can be obtained using the relevant preparative methods in organic chemistry.
  • 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.
  • molar amounts of fatty acid polyglycol ester to sulfating agent from 1: 0.5 to 1: 0.95, mixtures of fatty acid polyglycol ester sulfates and fatty acid polyglycol esters are obtained which are also advantageous for a whole series of applications.
  • Typical examples of suitable starting materials are the addition products of 1 to 3 moles of ethylene oxide and / or propylene oxide, but preferably the adducts with 1 mole of ethylene oxide or 1 mole of propylene oxide with caproic acid, caprylic acid, 2-ethylhexanoic acid, capric acid, lauric acid, isotridecanoic acid, myristic acid, palmitic acid acid, palmoleic acid, stearic acid, isostearic acid, oleic acid, elaidic acid, petroselinic acid, linoleic acid, linolenic acid, elaeostearic acid, arachidic 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 + 1EO sulfate sodium salt, tallow fatty acid + 1EO- sulfate ammonium salt and mixtures thereof.
  • Co-surfactants 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 +
  • anionic surfactants nonionic surfactants or mixtures thereof can be contained as surface-active co-surfactants which form group (b).
  • anionic surfactants are soaps, alkyl benzene sulfonates, alkane sulfonates, olefin sulfonates, alkyl ether sulfonates, glycerol ether sulfonates, ⁇ -methyl ester sulfonates, sulfo fatty acids, alkyl sulfates, fatty alcohol ether sulfates, glycerol ether sulfates, hydroxy mixed ether sulfates, fatty (ether) sulfate monates, monoglyl ether sulfate and dialkyl sulfosuccinates, mono- and dialkyl sulfosuccinamates, sulfotriglycerides, amide soaps, ether carboxylic acids and their
  • anionic surfactants contain glycol ether chains, these can have a conventional, but preferably a narrow, homolog distribution.
  • Typical examples of nonionic surfactants are fatty alcohol polyglycol ethers, alkylphenol polyglycol ethers, fatty acid polyglycol esters, fatty acid amide polyglycol ethers, fatty amine polyglycol ethers, alkoxylated triglycerides, mixed ethers or mixed formals, optionally partially oxidized alk (en) yl oligoglycosides or gluco-acidic acid-based vegetable products, fatty acid-based glycate acid derivatives, and glycuric acid-derived products Wheat base), polyol fatty acid esters, sugar esters, sorbitan esters, polysorbates and amine oxides.
  • nonionic surfactants contain glycol ether chains, these can have a conventional, but preferably a narrow, homolog distribution.
  • these nonionic surfactants contain glycol ether chains, these can have a conventional, but preferably a narrow, homolog distribution.
  • J.Falbe ed.
  • J.Falbe ed.
  • Catalysts, surfactants and mineral oil additives e.g., Thieme Verlag, Stuttgart, 1978, pp. 123-217.
  • Alkylbenzenesulfonates which are suitable as preferred anionic cosurfactants preferably follow the formula (II),
  • R 2 is a branched, but preferably linear alkyl radical having 10 to 18 carbon atoms
  • Ph is a phenyl radical
  • X is X is an alkali and / or alkaline earth metal, ammonium, alkylammonium, alkanolammonium or glucammonium.
  • Dodecylbenzenesulfonates, tetradecylbenzenesulfonates, hexadecylbenzenesulfonates and their technical mixtures in the form of the sodium salts are preferably used.
  • Alkyl and / or alkenyl sulfates which are also referred to as fatty alcohol or oxo alcohol sulfates depending on the raw material base and are preferred as the preferred anionic co-surfactant of group (b), are the sulfation products of primary alcohols which have the formula ( III) follow
  • R 3 represents a linear or branched, aliphatic alkyl and / or alkenyl radical having 6 to 22, preferably 12 to 18 carbon atoms and X represents an alkali and / or alkaline earth metal, ammonium, alkylammonium, alkanolammonium or glucammonium.
  • alkyl sulfates that can be used in the context of the invention are the sulfation products of capron alcohol, caprylic alcohol, capric alcohol, 2-ethylhexyl alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, palm oleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, aridyl alcohol, elaidyl alcohol, elaidyl alcohol, elaidyl alcohol, alcohol, gadoleyl alcohol, behenyl alcohol and erucyl alcohol and their technical mixtures, which are obtained from high pressure hydrogenation of technical methyl ester fractions or aldehydes from Roelen's oxosynthesis.
  • the sulfation products can preferably be used in the form of their alkali metal salts and in particular their sodium salts.
  • Alkyl sulfates based on Ci6 / ⁇ are particularly preferred .
  • Alkyl and alkenyl oligoglycosides which are preferred nonionic cosurfactants of group (b), preferably follow the formula (IV),
  • 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 (IV) 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, those alkyl and / or alkenyl oligoglycosides are preferred whose degree of oligomerization is less than 1.7 and is 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, petroseiinyl 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 hydrogenated Ci2 / 14 coconut alcohol with a DP of 1 to 3 are preferred.
  • a further group of preferred nonionic co-surfactants are alcohol ethoxylates, which are referred to as fatty alcohol or oxo alcohol ethoxylates for production reasons and preferably follow the formula (V),
  • R 5 represents a linear or branched alkyl and / or alkenyl radical having 6 to 22 carbon atoms and n represents numbers from 1 to 50.
  • Typical examples are the adducts of on average 1 to 50, preferably 5 to 40 and in particular 10 to 25 moles of capron alcohol, caprylic alcohol, 2-ethylhexyl alcohol, capric alcohol, lauryl alcohol, isotridecyl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, oleyl alcohol Arachyl Petroseiinyl Alcohol alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol and brassidyl alcohol and their technical mixtures, which are obtained, for example, in the high-pressure hydrogenation of technical methyl esters based on fats and oils or aldehydes from Roelen's oxosynthesis and as a monomer fraction in the dim
  • the preparations according to the invention can contain the fatty acid polyglycol ester sulfates and the co-surfactants in a weight ratio of 10:90 to 90:10, preferably 25:75 to 75:25 and in particular 40:60 to 60:40.
  • Preparations of mixtures of anionic and nonionic cosurfactants, in particular of alkyl sulfates with alkyl oligoglucosides or fatty alcohol ethoxylates, have proven to be particularly advantageous.
  • Another object of the invention therefore relates to that of fatty acid polyglycol ester sulfates, alone or in a mixture with anionic and / or nonionic surfactants for the production of liquid detergents.
  • the liquid detergents obtainable for the purposes of the invention can have a non-aqueous fraction in the range from 5 to 50 and preferably 15 to 35% by weight. In the simplest case, these are aqueous solutions of the surfactant mixtures mentioned.
  • the liquid detergents can, however, also be essentially water-free detergents. In the context of this invention, "essentially anhydrous" means that the agent preferably contains no free water which is not bound as water of crystallization or in a comparable form. In some cases, small amounts of free water are tolerable, especially in amounts up to 5% by weight.
  • the liquid detergents may also have other typical ingredients, such as, for example, solvents, hydrotropes, bleaches, builders, viscosity regulators, enzymes, enzyme stabilizers, optical brighteners, soil repellants, foam inhibitors, inorganic salts and fragrances and colorants, provided that these are sufficiently stable in an aqueous environment.
  • suitable organic solvents are monofunctional and / or polyfunctional alcohols having 1 to 6 carbon atoms, preferably having 1 to 4 carbon atoms.
  • Preferred alcohols are ethanol, 1, 2-propanediol, glycerol and mixtures thereof.
  • compositions preferably contain 2 to 20% by weight and in particular 5 to 15% by weight of ethanol or any mixture of ethanol and 1, 2-propanediol or in particular of ethanol and glycerol. It is also possible that the preparations either contain, in addition to the mono- and / or polyfunctional alcohols having 1 to 6 carbon atoms or solely polyethylene glycol with a relative molecular weight between 200 and 2000, preferably up to 600, in amounts of 2 to 17% by weight . For example, toluenesulfonate, xylenesulfonate, cumene sulfonate or mixtures thereof can be used as hydrotropes.
  • sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance.
  • Other bleaching agents are, for example, peroxy carbonate, citrate perhydrates and salts of peracids such as perbenzoates, peroxyphthalates or diperoxydodecanedioic acid. They are usually used in amounts of 8 to 25% by weight.
  • the use of sodium perborate monohydrate in amounts of 10 to 20% by weight and in particular 10 to 15% by weight is preferred. Due to its ability to bind free water with the formation of the tetrahydrate, it contributes to increasing the stability of the agent. However, the preparations are preferably free from such bleaching agents.
  • Suitable builders are ethylenediaminetetraacetic acid, nitrilotriacetic acid, citric acid and inorganic phosphonic acids, e.g. the neutral-reacting sodium salts of 1-hydroxyethane-1,1-diphosphonate, which can be present in amounts of 0.5 to 5, preferably 1 to 2,% by weight.
  • Viscosity regulators which can be used are, for example, hardened castor oil, salts of long-chain fatty acids, preferably in amounts of 0 to 5% by weight and in particular in amounts of 0.5 to 2% by weight, for example sodium, potassium, aluminum, magnesium - And titanium stearates or the sodium and / or potassium salts of behenic acid, and other polymeric compounds are used.
  • the latter preferably include polyvinylpyrrolidone, urethanes and the salts of polymeric polycarboxylates, for example homopolymeric or copolymeric polyacrylates, polymethacrylates and in particular copolymers of acrylic acid with maleic acid, preferably those composed of 50% to 10% maleic acid.
  • the relative molecular weight of the homopolymers is generally between 1000 and 100000, that of the copolymers between 2000 and 200000, preferably between 50,000 to 120,000, based on the free acid.
  • Water-soluble polyacrylates which are crosslinked, for example, with about 1% of a polyallyl ether of sucrose and which have a relative molecular weight above one million are also particularly suitable. Examples of this are the polymers with thickening action available under the name Carbopol® 940 and 941.
  • the crosslinked polyacrylates are preferably used in amounts not exceeding 1% by weight, preferably in amounts of 0.2 to 0.7% by weight.
  • the agents can additionally about 5 to 20 wt .-% of a partially esterified copolymer included, as described in European patent application EP-A 0367049.
  • These partially esterified polymers are obtained by copolymerizing (a) at least one C -C28 olefin or mixtures of at least one C -C28 olefin with up to 20 mol% of C 1 -C 2 -alkyl vinyl ether and (b) ethytenically unsaturated dicarboxylic acid anhydrides with 4 to 8 carbon atoms in a molar ratio of 1: 1 to copolymers with K values from 6 to 100 and subsequent partial esterification of the copolymers with reaction products such as -C-C ⁇ _ alcohols, C_-C22 fatty acids, C ⁇ -Ci2-alkylphenols, secondary C2-C3 .
  • copolymers contain maleic anhydride as the ethylenically unsaturated dicarboxylic acid anhydride.
  • the partially esterified copolymers can be present either in the form of the free acid or preferably in partially or completely neutralized form.
  • the copolymers are advantageously used in the form of an aqueous solution, in particular in the form of a 40 to 50% strength by weight solution.
  • the copolymers not only contribute to the primary and secondary washing performance of the liquid washing and cleaning agent, but also bring about a desired reduction in the viscosity of the concentrated liquid washing agent.
  • the use of these partially esterified copolymers gives concentrated aqueous liquid detergents which are flowable under the sole influence of gravity and without the action of other shear forces.
  • the concentrated aqueous liquid detergents preferably contain partially esterified copolymers in amounts of 5 to 15% by weight and in particular in amounts of 8 to 12% by weight.
  • Suitable enzymes are those from the class of proteases, lipases, amylases, cellulases or mixtures thereof. Enzymes obtained from bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis and Streptomyces griseus are particularly suitable. Proteases of the subtilisin type and in particular proteases which are obtained from Bacillus lentus are preferably used. Their proportion can be about 0.2 to about 2% by weight. The enzymes can be adsorbed on carriers and / or embedded in coating substances in order to protect them against premature decomposition. In addition to the mono- and polyfunctional alcohols and the phosphonates, the agents can contain further enzyme stabilizers.
  • sodium formate 0.5 to 1% by weight sodium formate can be used. It is also possible to use proteases which are stabilized with soluble calcium salts and a calcium content of preferably about 1.2% by weight, based on the enzyme.
  • proteases which are stabilized with soluble calcium salts and a calcium content of preferably about 1.2% by weight, based on the enzyme.
  • boron compounds for example boric acid, boron oxide, borax and other alkali metal borates such as the salts of orthoboric acid (H3BO3), metaboric acid (HBO2) and pyrobic acid (tetraboric acid H2B4O7), is particularly advantageous.
  • Suitable soil-repellants are substances which preferably contain ethylene terephthalate and / or polyethylene glycol terephthalate groups, the molar Ratio of ethylene terephthalate to polyethylene glycol terephthalate can range from 50:50 to 90:10.
  • the molecular weight of the linking polyethylene glycol units is in particular in the range from 750 to 5000, ie the degree of ethoxylation of the polymers containing polyethylene glycol groups can be approximately 15 to 100.
  • the polymers are characterized by an average molecular weight of about 5000 to 200,000 and can have a block, but preferably a random structure.
  • Preferred polymers are those with molar ratios of ethylene terephthalate / polyethylene glycol terephthalate from about 65:35 to about 90:10, preferably from about 70:30 to 80:20. Also preferred are those polymers which have linking polyethylene glycol units with a molecular weight of 750 to 5000. preferably from 1000 to about 3000 and a molecular weight of the polymer from about 10,000 to about 50,000. Examples of commercially available polymers are the products Milease® T (ICI) or Repelotex® SRP 3 (Rhône-Poulenc).
  • foam inhibitors When used in machine washing processes, it can be advantageous to add conventional foam inhibitors to the agents.
  • Suitable for this are, for example, soaps of natural or synthetic origin that have a high proportion of C 0 -C 24 fatty acids.
  • Suitable non-surfactant-like foam inhibitors are, for example, organopolysiloxanes and their mixtures with microfine, optionally silanized silica, and paraffins, waxes, microcrystalline waxes and their mixtures with silanized silica or bistearylethylenediamide. Mixtures of various foam inhibitors are also used with advantages, for example those made of silicones, paraffins or waxes.
  • the foam inhibitors, in particular silicone or paraffin-containing foam inhibitors are preferably bound to a granular, water-soluble or dispersible carrier substance. Mixtures of paraffins and bistearylethylenediamides are particularly preferred.
  • the pH of the concentrated agents according to the invention is generally 7 to 10.5, preferably 7 to 9.5 and in particular 7 to 8.5. Higher pH values, for example above 9, can be set by using small amounts of sodium hydroxide solution or alkaline salts such as sodium carbonate or sodium silicate.
  • the liquid detergents according to the invention generally have viscosities between 150 and 10,000 mPas (Brookfield viscometer, spindle 1, 20 revolutions per minute, 20 ° C.). Viscosities between 150 and 5000 mPas are preferred for the essentially water-free agents.
  • the viscosity of the aqueous compositions is preferably below 2000 mPas and in particular between 150 and 1000 mPas. Examples
  • Wash program Color wash program (without prewash) at 40 ° C
  • SH-PBV Dust-skin grease on a mixture of polyester and refined cotton
  • BMR-B blood, milk and soot on cotton
  • R-BV Red wine on refined cotton
  • T-BV Tea on refined cotton
  • LS-PBV lipstick on a mixture of polyester and finished cotton
  • MU-PBV Make-up on a mixture of polyester and finished cotton

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Abstract

The invention relates to flowable tenside preparations, characterised in that they consist essentially of a) fatty acid polyglycol ester sulphates and b) anionic and/or non-anionic tensides.

Description

FLIESSFÄHIGE TENSIDZUBEREITUNGEN ENTHALTEND FETTSÄUREPOLYGLYCOLESTERSULFATEFLOWABLE SURFACTANT PREPARATIONS CONTAINING FATTY ACID POLYGLYCOLESTER SULFATES
Gebiet der ErfindungField of the Invention
Die Erfindung befindet sich auf dem Gebiet der Flüssigwaschmittel und betrifft wäßrige, leicht handhabbare Tensidzubereitungen mit einem Gehalt an ausgewählten oberflächenaktiven Substanzen sowie deren Verwendung.The invention is in the field of liquid detergents and relates to aqueous, easy-to-handle surfactant preparations containing selected surface-active substances and their use.
Stand der TechnikState of the art
Unter flüssigen Waschmitteln versteht man in der Regel wäßrige Zubereitungen oberflächenaktiver Stoffe, die in zur manuellen, vorzugsweise aber maschinellen Wäsche von insbesondere leicht verschmutzten Textilien dient. Gegenüber Pulverwaschmitteln besitzen die flüssigen Mittel den Vorteil einer leichteren Dosierbarkeit. Neben diesen niedrigviskosen Produkten kommen auch pastöse Mittel in den Handel, die in der Regel einen deutlich geringeren Wassergehalt aufweisen oder auch annähernd wasserfrei sind. Diese Mittel können direkt auf hartnäckige Flecken aufgebracht und eingerieben werden, was die spätere Reinigung in der Waschmaschine erleichtert. Stellvertretend für den umfangreichen Stand der Technik sei hier nur beispielhaft auf die Druckschriften DE-A1 3726327, DE-A1 4236109 und DE-A1 4220423 (Henkel) verwiesen, welche Flüssigwaschmittel mit Kombinationen von anionischen Sulfat- oder Sulfonattensiden mit nichtionischen Tensiden offenbaren. Flüssigwaschmittel mit anionischen Tensiden und Enzymen (Lipasen und Cellulasen) sind aus der DE-A1 4344154 (Henkel) bekannt. Gegenstand der DE-A1 4338113 (Henkel) sind flüssige Wollwaschmittel mit Anion- tensiden, Alkylpolyglucosiden und Lecithin.Liquid detergents are generally understood to be aqueous preparations of surface-active substances which are used for manual, but preferably machine washing of, in particular, lightly soiled textiles. Compared to powder detergents, the liquid detergents have the advantage of being easier to dose. In addition to these low-viscosity products, pasty agents are also on the market, which generally have a significantly lower water content or are almost water-free. These agents can be applied directly to stubborn stains and rubbed in, which makes subsequent washing in the washing machine easier. As a representative of the extensive state of the art, reference is made here only to DE-A1 3726327, DE-A1 4236109 and DE-A1 4220423 (Henkel), which disclose liquid detergents with combinations of anionic sulfate or sulfonate surfactants with nonionic surfactants. Liquid detergents with anionic surfactants and enzymes (lipases and cellulases) are known from DE-A1 4344154 (Henkel). DE-A1 4338113 (Henkel) relates to liquid wool detergents with anionic surfactants, alkyl polyglucosides and lecithin.
Bei der Formulierung von Flüssigwaschmitteln sind im Vergleich zu festen Zubereitungen bestimmte physikochemische Gegebenheiten zu berücksichtigen. Da die flüssigen Mittel in der Regel bei Raumtemperatur gelagert werden, muß z.B. sicher gestellt sein, daß die Tensidkomponente in Lösung bleibt und nicht auskristallisiert. Aniontenside sind jedoch vielfach in kaltem Wasser schlecht löslich; wegen ihres inversen Löslichkeitsverhaltens werden daher nichtionische Tenside anionischen Verbindungen häufig vorgezogen. Aniontenside neigen ferner dazu hochviskose Gelphasen zu bilden, was zu Schwierigkeiten führt, wenn man anionbasierte Flüssigwaschmittel mit höherem Aktivsubstanzgehalt formulieren will. Andererseits leisten Aniontenside einen ganz erheblichen Beitrag zur Entfernung einer Vielzahl von Flecken, so daß man auf diese Gruppe von Tensiden bei der Herstellung eines effektiven Waschmittels nur schwer verzichten kann.When formulating liquid detergents, certain physicochemical conditions must be taken into account when compared to solid preparations. Since the liquid agents are generally stored at room temperature, it must be ensured, for example, that the surfactant component remains in solution and does not crystallize out. However, anionic surfactants are often poorly soluble in cold water; Because of their inverse solubility behavior, nonionic surfactants are therefore often preferred to anionic compounds. Anionic surfactants also tend to form highly viscous gel phases, which leads to Difficulties arise when trying to formulate anion-based liquid detergents with a higher active substance content. On the other hand, anionic surfactants make a very considerable contribution to the removal of a large number of stains, so that this group of surfactants is difficult to do without when producing an effective detergent.
Demzufolge hat die komplexe Aufgabe der Erfindung darin bestanden, Flüssigwaschmittel zur Verfügung zu stellen, die einen hohen Aniontensidgehalt aufweisen, dabei jedoch fließ- und pumpfähig sind, bei Lagerung weder auskristallisieren noch vergeien und über eine möglichst große Spanne von Verunreinigungen eine optimale Reinigungsleistung aufweisen.Accordingly, the complex object of the invention was to provide liquid detergents which have a high anionic surfactant content, but which are flowable and pumpable, do not crystallize or evaporate during storage and have optimum cleaning performance over the largest possible range of contaminants.
Beschreibung der ErfindungDescription of the invention
Gegenstand der Erfindung sind fließfähige Tensidzubereitungen, weiche sich dadurch auszeichnen, daß sie im wesentlichen ausThe invention relates to flowable surfactant preparations which are characterized in that they essentially consist of
(a) Fettsäurepolyglycolestersulfaten und(a) fatty acid polyglycol ester sulfates and
(b) anionischen und/oder nichtionischen Tensiden(b) anionic and / or nonionic surfactants
bestehen.consist.
Überraschenderweise wurde gefunden, daß die Zubereitungen im Vergleich zu wäßrigen Lösungen anderer anionischer Tenside eine deutlich geringere Viskosität aufweisen und darüber hinaus über ein ausgezeichnetes Reinigungsvermögen gegenüber einer Vielzahl sehr unterschiedlicher Anschmutzungen besitzen. Ein weiterer Vorteil besteht darin, daß die Mittel bei Lagerung weder auskristallisieren noch vergeien. Die Erfindung schließt die Erkenntnis ein, daß sich unter Einsatz der Fettsäurepoly- giycolestersulfate, vorzugsweise in Abmischung mit anionischen und/oder nichtionischen Tensiden klare, lagerstabile Flüssigwaschmittel mit hohem Aktivsubstanzgehalt und niedriger bis mittlerer Viskosität herstellen lassen. Die bevorzugten Co-Tenside sind dabei - neben Alkaliseifen - Alkylbenzoisulfonate, Alkylsulfate, Alkyloligoglucoside, Alkoholethoxylate sowie deren Abmischungen.Surprisingly, it was found that the preparations have a significantly lower viscosity compared to aqueous solutions of other anionic surfactants and, moreover, have an excellent cleaning ability against a large number of very different types of soiling. Another advantage is that the agents neither crystallize nor lose when stored. The invention includes the finding that clear, storage-stable liquid detergents with a high active substance content and low to medium viscosity can be prepared using the fatty acid polycarbon ester sulfates, preferably in a mixture with anionic and / or nonionic surfactants. In addition to alkali soaps, the preferred co-surfactants are alkylbenzoisulfonates, alkyl sulfates, alkyl oligoglucosides, alcohol ethoxylates and their mixtures.
FettsäurepolvqlvcolestersulfateFatty acid polypropylene sulfates
Fettsäurepolyglycolestersulfate, die die anionische Tensidkomponente (a) bilden und der Formel (I) folgen,Fatty acid polyglycol ester sulfates which form the anionic surfactant component (a) and follow the formula (I),
RiCOO(AO)χSθ3X (I) 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, werden durch Sulfatierung der entsprechenden Fettsäurepolyglycolester hergestellt. Diese wiederum sind nach den einschlägigen pr parativen Verfahren der organischen Chemie erhältlich. Hierzu wird Ethylenoxid, Propylenoxid oder deren Gemisch - in random- oder Blockverteilung - an die entsprechenden Fettsäuren angelagert, wobei diese Reaktion säurekatalysiert, vorzugsweise aber in Gegenwart von Basen, wie z.B. Natrium- methylat 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 Reaktionstemperatur 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 stöchio- metrisch erforderlich wäre. Wählt man beispielsweise molare Einsatzmengen von Fettsäurepolyglycolester zu Sulfatierungsmittel von 1 : 0,5 bis 1 : 0,95 werden Mischungen von Fettsäurepolyglycolester- sulfaten und Fettsäurepolyglycolestern 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 Propylenoxid, vorzugsweise aber die Addukte mit 1 Mol Ethylenoxid oder 1 Mol Propylenoxid an Capronsäure, Caprylsäure, 2-Ethylhexansäure, Caprinsäure, Laurinsäure, Isotridecansäure, Myristinsäure, Palmitin- säure, Palmoleinsäure, Stearinsäure, Isostearinsäure, Ölsäure, Elaidinsäure, Petroselinsäure, Linol- säure, Linolensäure, Elaeostearinsäure, Arachinsäure, Gadoleinsäure, Behensäure und Erucasäure sowie deren technische Mischungen, die dann wie oben beschrieben sulfatiert und neutralisiert werden. Vorzugsweise werden Fettsäurepolyglycolestersulfate 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-Ammonium-salz,Talgfettsäure+1EO-sulfat-Natriumsalz,Talgfettsäure+1EO-sulfat-Ammoniumsalz sowie deren Mischungen. Co-TensideRiCOO (AO) χSθ3X (I) in the R 1 CO for a linear or branched, saturated or unsaturated acyl radical with 6 to 22 carbon atoms, x for numbers from 1 to 3 on average and AO for a CH2CH2O-, CH2CH (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 are prepared by sulfating the corresponding fatty acid polyglycol esters. These in turn can be obtained using the relevant preparative methods 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. If, for example, one chooses molar amounts of fatty acid polyglycol ester to sulfating agent from 1: 0.5 to 1: 0.95, mixtures of fatty acid polyglycol ester sulfates and fatty acid polyglycol esters are obtained which are also advantageous for a whole series 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 moles of ethylene oxide and / or propylene oxide, but preferably the adducts with 1 mole of ethylene oxide or 1 mole of propylene oxide with caproic acid, caprylic acid, 2-ethylhexanoic acid, capric acid, lauric acid, isotridecanoic acid, myristic acid, palmitic acid acid, palmoleic acid, stearic acid, isostearic acid, oleic acid, elaidic acid, petroselinic acid, linoleic acid, linolenic acid, elaeostearic acid, arachidic 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 + 1EO sulfate sodium salt, tallow fatty acid + 1EO- sulfate ammonium salt and mixtures thereof. Co-surfactants
Als oberflächenaktive Co-Tenside, die die Gruppe (b) bilden, können weitere Aniontenside, nichtionische Tenside oder deren Gemische enthalten sein. Typische Beispiele für anionische Tenside sind Seifen, Alkylbenzolsulfonate, Alkansulfonate, Olefinsulfonate, Alkylethersulfonate, Glycerinether- sulfonate, α-Methylestersuifonate, Sulfofettsäuren, Alkylsulfate, Fettalkoholethersulfate, Glycerinether- sulfate, Hydroxymischethersulfate, Monoglycerid(ether)sulfate, Fettsäureamid(ether)sulfate, Mono- und Dialkyl-sulfosuccinate, Mono- und Dialkylsulfosuccinamate, Sulfotriglyceride, Amidseifen, Ethercarbon- säuren und deren Salze, Fettsäureisethionate, Fettsäuresarcosinate, Fettsäuretauride, N-Acylamino- säuren, wie beispielsweise Acyllactylate, Acyltartrate, Acylglutamate und Acylaspartate, Alkyloligogluco- sidsulfate, Proteinfettsäurekondensate (insbesondere pflanzliche Produkte auf Weizenbasis) und Al- kyl(ether)phosphate. Sofern die anionischen Tenside Poiygiycoletherketten enthalten, können diese eine konventionelle, vorzugsweise jedoch eine eingeengte Homologenverteilung aufweisen. Typische Beispiele für nichtionische Tenside sind Fettalkoholpolyglycolether, Alkylphenolpolyglycolether, Fettsäurepolyglycolester, Fettsäureamidpolyglycolether, Fettaminpolyglycolether, alkoxylierte Triglyceride, Mischether bzw. Mischformale, gegebenenfalls partiell oxidierte Alk(en)yloligoglykoside bzw. Glu- coronsäurederivate, Fettsäure-N-alkylglucamide, Proteinhydroiysate (insbesondere pflanzliche Produkte auf Weizenbasis), Polyolfettsäureester, Zuckerester, Sorbitanester, Polysorbate und Aminoxide. Sofern die nichtionischen Tenside Poiygiycoletherketten enthalten, können diese eine konventionelle, vorzugsweise jedoch eine eingeengte Homologenverteilung aufweisen. Hinsichtlich Struktur und Herstellung dieser Stoffe sei auf einschlägige Übersichtsarbeiten beispielsweise J.Falbe (ed.), "Sur- factants in Consumer Products", Springer Verlag, Berlin, 1987, S. 54-124 oder J.Falbe (ed.), "Katalysatoren, Tenside und Mineralöladditive", Thieme Verlag, Stuttgart, 1978, S. 123-217 verwiesen.Other anionic surfactants, nonionic surfactants or mixtures thereof can be contained as surface-active co-surfactants which form group (b). Typical examples of anionic surfactants are soaps, alkyl benzene sulfonates, alkane sulfonates, olefin sulfonates, alkyl ether sulfonates, glycerol ether sulfonates, α-methyl ester sulfonates, sulfo fatty acids, alkyl sulfates, fatty alcohol ether sulfates, glycerol ether sulfates, hydroxy mixed ether sulfates, fatty (ether) sulfate monates, monoglyl ether sulfate and dialkyl sulfosuccinates, mono- and dialkyl sulfosuccinamates, sulfotriglycerides, amide soaps, ether carboxylic acids and their salts, fatty acid isethionates, fatty acid sarcosinates, fatty acid taurides, N-acylamino acids, such as, for example, acyl lactyl acylate tate trate, acyl glucosate trate, acyl glucosate trate, acyl glucosate trate, acyl glucosate trate, acyl glucosate trate, acyl glucosate trate, acyl glucosate trate, acyl glucosate trate, acyl glucosate trate, acyl glucosate trate, acyl glucosate trate, acyl glutate acate, vegetable products based on wheat) and alkyl (ether) phosphates. If the anionic surfactants contain glycol ether chains, these can have a conventional, but preferably a narrow, homolog distribution. Typical examples of nonionic surfactants are fatty alcohol polyglycol ethers, alkylphenol polyglycol ethers, fatty acid polyglycol esters, fatty acid amide polyglycol ethers, fatty amine polyglycol ethers, alkoxylated triglycerides, mixed ethers or mixed formals, optionally partially oxidized alk (en) yl oligoglycosides or gluco-acidic acid-based vegetable products, fatty acid-based glycate acid derivatives, and glycuric acid-derived products Wheat base), polyol fatty acid esters, sugar esters, sorbitan esters, polysorbates and amine oxides. If the nonionic surfactants contain glycol ether chains, these can have a conventional, but preferably a narrow, homolog distribution. With regard to the structure and manufacture of these substances, reference is made, for example, to relevant reviews by J.Falbe (ed.), "Factors in Consumer Products", Springer Verlag, Berlin, 1987, pp. 54-124 or J.Falbe (ed.), " Catalysts, surfactants and mineral oil additives ", Thieme Verlag, Stuttgart, 1978, pp. 123-217.
AlkylbenzolsulfonateAlkylbenzenesulfonates
Alkylbenzolsulfonate, die als bevorzugte anionische Co-Tenside in Frage kommen, folgen vorzugsweise der Formel (II),Alkylbenzenesulfonates which are suitable as preferred anionic cosurfactants preferably follow the formula (II),
R2-Ph-S03X (II)R 2 -Ph-S0 3 X (II)
in der R2 für einen verzweigten, vorzugsweise jedoch linearen Alkylrest mit 10 bis 18 Kohlenstoffatomen, Ph für einen Phenylrest und X für X für ein Alkali- und/oder Erdalkalimetall, Ammonium, Alkylammonium, Alkanolammonium oder Glucammonium steht. Vorzugsweise werden Dodecylbenzol- sulfonate, Tetradecylbenzolsulfonate, Hexadecylbentolsulfonate sowie deren technische Gemische in Form der Natriumsalze eingesetzt. Alkyl- und/oder Alkenylsuifatein which R 2 is a branched, but preferably linear alkyl radical having 10 to 18 carbon atoms, Ph is a phenyl radical and X is X is an alkali and / or alkaline earth metal, ammonium, alkylammonium, alkanolammonium or glucammonium. Dodecylbenzenesulfonates, tetradecylbenzenesulfonates, hexadecylbenzenesulfonates and their technical mixtures in the form of the sodium salts are preferably used. Alkyl and / or alkenyl sulfates
Unter Alkyl- und/oder Alkenylsulfaten, die auch je nach Rohstoffbasis als Fettalkohol- oder Oxoalkohol- sulfate bezeichnet werden und als bevorzugtes anionisches Co-Tensid der Gruppe (b) in Frage kommen, sind die Sulfatierungsprodukte primärer Alkohole zu verstehen, die der Formel (III) folgen,Alkyl and / or alkenyl sulfates, which are also referred to as fatty alcohol or oxo alcohol sulfates depending on the raw material base and are preferred as the preferred anionic co-surfactant of group (b), are the sulfation products of primary alcohols which have the formula ( III) follow
R30-S03X (III)R 3 0-S0 3 X (III)
in der R3 für einen linearen oder verzweigten, aliphatischen Alkyl- und/oder Alkenylrest mit 6 bis 22, vorzugsweise 12 bis 18 Kohlenstoffatomen und X für ein Alkali- und/oder Erdalkalimetall, Ammonium, Alkylammonium, Alkanolammonium oder Glucammonium steht. Typische Beispiele für Alkylsulfate, die im Sinne der Erfindung Anwendung finden können, sind die Sulfatierungsprodukte von Capronalkohol, Caprylalkohol, Caprinalkohol, 2-Ethylhexylalkohol, Laurylalkohol, Myristylalkohoi, Cetylalkohol, Palm- oleylalkohol, Stearylalkohol, Isostearylalkohol, Oleylalkohol, Elaidylaikohol, Petroselinylalkohol, Arachyl- alkohol, Gadoleylalkohol, Behenylalkohol und Erucylalkohol sowie deren technischen Gemischen, die durch Hochdruckhydrierung technischer Methylesterfraktionen oder Aldehyden aus der Roelen'schen Oxosynthese erhalten werden. Die Sulfatierungsprodukte können vorzugsweise in Form ihrer Alkalisalze und insbesondere ihrer Natriumsalze eingesetzt werden. Besonders bevorzugt sind Alkylsulfate auf Basis von Ci6/ι.-Talgfettalkoholen bzw. pflanzliche Fettalkohole vergleichbarer C-Kettenverteilung in Form ihrer Natriumsalze.in which R 3 represents a linear or branched, aliphatic alkyl and / or alkenyl radical having 6 to 22, preferably 12 to 18 carbon atoms and X represents an alkali and / or alkaline earth metal, ammonium, alkylammonium, alkanolammonium or glucammonium. Typical examples of alkyl sulfates that can be used in the context of the invention are the sulfation products of capron alcohol, caprylic alcohol, capric alcohol, 2-ethylhexyl alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, palm oleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, aridyl alcohol, elaidyl alcohol, elaidyl alcohol, elaidyl alcohol, alcohol, gadoleyl alcohol, behenyl alcohol and erucyl alcohol and their technical mixtures, which are obtained from high pressure hydrogenation of technical methyl ester fractions or aldehydes from Roelen's oxosynthesis. The sulfation products can preferably be used in the form of their alkali metal salts and in particular their sodium salts. Alkyl sulfates based on Ci6 / ι are particularly preferred . Tallow fatty alcohols or vegetable fatty alcohols of comparable carbon chain distribution in the form of their sodium salts.
Alkyl- und/oder AlkenyloliqoqlykosideAlkyl and / or alkenyl olefin glycosides
Alkyl- und Alkenyloligoglykoside, die bevorzugte nichtionsiche Co-Tenside der Gruppe (b) darstellen, folgen vorzugsweise der Formel (IV),Alkyl and alkenyl oligoglycosides, which are preferred nonionic cosurfactants of group (b), preferably follow the formula (IV),
R 0-[G]p (IV)R 0- [G] p (IV)
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 praparativen 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 using the relevant methods of 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 (IV) gibt den Oligomerisierungsgrad (DP), d. h. die Verteilung von Mono- und Oligoglykosiden an und steht für eine Zahl zwischen 1 und 10. Während p in einer gegebenen Verbindung stets ganzzahlig sein muß und hier vor allem die Werte p = 1 bis 6 annehmen kann, ist der Wert p für ein bestimmtes Alkyloligo- glykosid eine analytisch ermittelte rechnerische Größe, die meistens eine gebrochene Zahl darstellt. Vorzugsweise werden Alkyl- und/oder Alkenyloligoglykoside mit einem mittleren Oligomerisierungsgrad p von 1 ,1 bis 3,0 eingesetzt. Aus anwendungstechnischer Sicht sind solche Alkyl- und/oder Alkenyloligoglykoside bevorzugt, deren Oligomerisierungsgrad kleiner als 1 ,7 ist und insbesondere zwischen 1 ,2 und 1 ,4 liegt. Der Alkyl- bzw. Alkenylrest 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 Alkyloligo- glucoside der Kettenlänge Cs-Cio (DP = 1 bis 3), die als Vorlauf bei der destillativen Auftrennung von technischem Cβ-Ci8-Kokosfettalkohol anfallen und mit einem Anteil von weniger als 6 Gew.-% C12- Alkohol verunreinigt sein können sowie Alkyloligoglucoside auf Basis technischer C9/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, Petroseiinylalkohol, Arachylalkohol, Gadoleylalkohol, Behenylalkohol, Erucylalkohol, Brassidylalkohol sowie deren technische Gemische, die wie oben beschrieben erhalten werden können. Bevorzugt sind Alkyloligoglucoside auf Basis von gehärtetem Ci2/14-Kokosalkohol mit einem DP von 1 bis 3.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 (IV) indicates the degree of oligomerization (DP), ie the distribution of mono- and oligoglycosides, and stands for a number between 1 and 10. While p in a given compound must always be an integer, 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, those alkyl and / or alkenyl oligoglycosides are preferred whose degree of oligomerization is less than 1.7 and is 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. Alkyl oligoglucosides of chain length Cs-Cio (DP = 1 to 3) are preferred, which are obtained as a preliminary step in the separation of technical Cβ-Ci8 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 C9 / 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, petroseiinyl 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 hydrogenated Ci2 / 14 coconut alcohol with a DP of 1 to 3 are preferred.
AlkoholethoxylateAlcohol ethoxylates
Als weitere Gruppe bevorzugter nichtionischer Co-Tenside kommen Alkoholethoxylate in Frage, die herstellungsbedingt als Fettalkohol- oder Oxoalkoholethoxylate bezeichnet werden und vorzugsweise der Formel (V) folgen,A further group of preferred nonionic co-surfactants are alcohol ethoxylates, which are referred to as fatty alcohol or oxo alcohol ethoxylates for production reasons and preferably follow the formula (V),
R50(CH2CH20)nH (V)R 5 0 (CH 2 CH 2 0) nH (V)
in der R5 für einen linearen oder verzweigten Alkyl- und/oder Alkenylrest mit 6 bis 22 Kohlenstoffatomen und n für Zahlen von 1 bis 50 steht. Typische Beispiele sind die Addukte von durchschnittlich 1 bis 50, vorzugsweise 5 bis 40 und insbesondere 10 bis 25 Mol an Capronalkohol, Caprylalkohol, 2- Ethylhexylalkohol, Caprinalkohol, Laurylalkohol, Isotridecylalkohol, Myristylalkohol, Cetylalkohol, Palmoleylalkohol, Stearylalkohol, Isostearylalkohol, Oleylalkohol, Elaidylalkohol, Petroseiinylalkohol, Arachyl- alkohol, Gadoleylalkohol, Behenylalkohol, Erucylalkohol und Brassidylalkohol sowie deren technische Mischungen, die z.B. bei der Hochdruckhydrierung von technischen Methylestern auf Basis von Fetten und Ölen oder Aldehyden aus der Roelen'schen Oxosynthese sowie als Monomerfraktion bei der Dimerisierung von ungesättigten Fettalkoholen anfallen. Bevorzugt sind Addukte von 10 bis 40 Mol Ethylenoxid an technische Fettalkohole mit 12 bis 18 Kohlenstoffatomen, wie beispielsweise Kokos-, Palm-, Palmkern- oder Taigfettalkohol.in which R 5 represents a linear or branched alkyl and / or alkenyl radical having 6 to 22 carbon atoms and n represents numbers from 1 to 50. Typical examples are the adducts of on average 1 to 50, preferably 5 to 40 and in particular 10 to 25 moles of capron alcohol, caprylic alcohol, 2-ethylhexyl alcohol, capric alcohol, lauryl alcohol, isotridecyl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, oleyl alcohol Arachyl Petroseiinyl Alcohol alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol and brassidyl alcohol and their technical mixtures, which are obtained, for example, in the high-pressure hydrogenation of technical methyl esters based on fats and oils or aldehydes from Roelen's oxosynthesis and as a monomer fraction in the dimerization of unsaturated fatty alcohols. Adducts of 10 to 40 moles of ethylene oxide with technical fatty alcohols with 12 to 18 carbon atoms, such as, for example, coconut, palm, palm kernel or tallow fatty alcohol, are preferred.
Die erfindungsgemäßen Zubereitungen können die Fettsäurepolyglycolestersulfate und die Co-Tenside im Gewichtsverhältnis 10 : 90 bis 90 : 10, vorzugsweise 25 : 75 bis 75 : 25 und insbesondere 40 : 60 bis 60 : 40 enthalten. Dabei haben sich Zubereitungen Mischungen von anionischen und nichtionischen Co-Tensiden, insbesondere von Alkylsulfaten mit Alkyloligoglucosiden bzw. Fettalkoholethoxylaten als besonders vorteilhaft erwiesen.The preparations according to the invention can contain the fatty acid polyglycol ester sulfates and the co-surfactants in a weight ratio of 10:90 to 90:10, preferably 25:75 to 75:25 and in particular 40:60 to 60:40. Preparations of mixtures of anionic and nonionic cosurfactants, in particular of alkyl sulfates with alkyl oligoglucosides or fatty alcohol ethoxylates, have proven to be particularly advantageous.
Gewerbliche AnwendbarkeitIndustrial applicability
Ein weiterer Gegenstand der Erfindung betrifft daher die von Fettsäurepolyglycolestersulfaten, alleine oder in Abmischung mit anionischen und/oder nichtionischen Tensiden zur Herstellung von Flüssigwaschmitteln.Another object of the invention therefore relates to that of fatty acid polyglycol ester sulfates, alone or in a mixture with anionic and / or nonionic surfactants for the production of liquid detergents.
FlüssiqwaschmittelLiquid detergent
Die im Sinne der Erfindung erhältlichen Flüssigwaschmittel können einen nicht wäßrigen Anteil im Bereich von 5 bis 50 und vorzugsweise 15 bis 35 Gew.-% aufweisen. Im einfachsten Fall handelt es sich um wäßrige Lösungen der genannten Tensidmischungen. Bei den Flüssigwaschmitteln kann es sich aber auch um im wesentlichen wasserfreie Mittel handeln. Dabei bedeutet "im wesentlichen wasserfrei" im Rahmen dieser Erfindung, daß das Mittel vorzugsweise kein freies, nicht als Kristallwasser oder in vergleichbarer Form gebundenes Wasser enthält. In einigen Fällen sind geringe Menge an freiem Wasser tolerierbar, insbesondere in Mengen bis zu 5 Gew.-%.The liquid detergents obtainable for the purposes of the invention can have a non-aqueous fraction in the range from 5 to 50 and preferably 15 to 35% by weight. In the simplest case, these are aqueous solutions of the surfactant mixtures mentioned. The liquid detergents can, however, also be essentially water-free detergents. In the context of this invention, "essentially anhydrous" means that the agent preferably contains no free water which is not bound as water of crystallization or in a comparable form. In some cases, small amounts of free water are tolerable, especially in amounts up to 5% by weight.
Die Flüssigwaschmittel können neben den genannten Tensiden noch weitere typische Inhaltsstoffe, wie beispielsweise Lösungsmittel, Hydrotrope, Bleichmittel, Builder, Viskositätsregulatoren, Enzyme, Enzymstabilisatoren, optische Aufheller, Soil repellants, Schauminhibitoren, anorganische Salze sowie Duft- und Farbstoffe aufweisen, unter der Voraussetzung, daß diese im wäßrigen Milieu hinreichend lagerstabil sind. Als organische Lösungsmittel kommen beispielsweise mono- und/oder polyfunktionelle Alkohole mit 1 bis 6 Kohlenstoffatomen, vorzugsweise mit 1 bis 4 Kohlenstoffatomen in Frage. Bevorzugte Alkohole sind Ethanol, 1 ,2-Propandiol, Glycerin sowie deren Gemische. Die Mittel enthalten vorzugsweise 2 bis 20 Gew.-% und insbesondere 5 bis 15 Gew.-% Ethanol oder ein beliebiges Gemisch aus Ethanol und 1 ,2-Propandiol oder insbesondere aus Ethanol und Glycerin. Ebenso ist es möglich, daß die Zubereitungen entweder zusätzlich zu den mono- und/oder polyfunktionellen Alkoholen mit 1 bis 6 Kohlenstoffatomen oder allein Polyethylenglykol mit einer relativen Molekülmasse zwischen 200 und 2000, vorzugsweise bis 600 in Mengen von 2 bis 17 Gew.-% enthalten. Als Hydrotrope können beispielsweise Toluolsulfonat, Xylolsulfonat, Cumolsulfonat oder deren Mischungen eingesetzt werden.In addition to the surfactants mentioned, the liquid detergents may also have other typical ingredients, such as, for example, solvents, hydrotropes, bleaches, builders, viscosity regulators, enzymes, enzyme stabilizers, optical brighteners, soil repellants, foam inhibitors, inorganic salts and fragrances and colorants, provided that these are sufficiently stable in an aqueous environment. Examples of suitable organic solvents are monofunctional and / or polyfunctional alcohols having 1 to 6 carbon atoms, preferably having 1 to 4 carbon atoms. Preferred alcohols are ethanol, 1, 2-propanediol, glycerol and mixtures thereof. The compositions preferably contain 2 to 20% by weight and in particular 5 to 15% by weight of ethanol or any mixture of ethanol and 1, 2-propanediol or in particular of ethanol and glycerol. It is also possible that the preparations either contain, in addition to the mono- and / or polyfunctional alcohols having 1 to 6 carbon atoms or solely polyethylene glycol with a relative molecular weight between 200 and 2000, preferably up to 600, in amounts of 2 to 17% by weight . For example, toluenesulfonate, xylenesulfonate, cumene sulfonate or mixtures thereof can be used as hydrotropes.
Unter den als Bleichmittel dienenden, in Wasser Wasserstoffperoxid liefernden Verbindungen haben das Natriumperborat-Tetrahydrat und das Natriumperborat-Monohydrat eine besondere Bedeutung. Weitere Bleichmittel sind beispielsweise Peroxy-carbonat, Citratperhydrate sowie Salze der Persäuren, wie Perbenzoate, Peroxyphthalate oder Diperoxydodecandisäure. Sie werden üblicherweise in Mengen von 8 bis 25 Gew.-% eingesetzt. Bevorzugt ist der Einsatz von Natriumperborat-Monohydrat in Mengen von 10 bis 20 Gew.-% und insbesondere von 10 bis 15 Gew.-%. Durch seine Fähigkeit, unter Ausbildung des Tetrahydrats freies Wasser binden zu können, trägt es zur Erhöhung der Stabilität des Mittels bei. Vorzugsweise sind die Zubereitungen jedoch frei von derartigen Bleichmitteln.Among the compounds which serve as bleaching agents and which supply hydrogen peroxide in water, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance. Other bleaching agents are, for example, peroxy carbonate, citrate perhydrates and salts of peracids such as perbenzoates, peroxyphthalates or diperoxydodecanedioic acid. They are usually used in amounts of 8 to 25% by weight. The use of sodium perborate monohydrate in amounts of 10 to 20% by weight and in particular 10 to 15% by weight is preferred. Due to its ability to bind free water with the formation of the tetrahydrate, it contributes to increasing the stability of the agent. However, the preparations are preferably free from such bleaching agents.
Geeignete Builder sind Ethylendiamintetraessigsäure, Nitrilotriessigsäure, Citronensäure sowie anorganische Phosphonsäuren, wie z.B. die neutral reagierenden Natriumsalze von 1 -Hydroxyethan-1 , 1 ,-di- phosphonat, die in Mengen von 0,5 bis 5, vorzugsweise 1 bis 2 Gew.-% zugegen sein können.Suitable builders are ethylenediaminetetraacetic acid, nitrilotriacetic acid, citric acid and inorganic phosphonic acids, e.g. the neutral-reacting sodium salts of 1-hydroxyethane-1,1-diphosphonate, which can be present in amounts of 0.5 to 5, preferably 1 to 2,% by weight.
Als Viskositätsregulatoren können beispielsweise gehärtetes Rizinusöl, Salze von langkettigen Fettsäuren, die vorzugsweise in Mengen von 0 bis 5 Gew.-% und insbesondere in Mengen von 0,5 bis 2 Gew.-%, beispielsweise Natrium-, Kalium-, Aluminium-, Magnesium- und Titanstearate oder die Natrium- und/oder Kaliumsalze der Behensäure, sowie weitere polymere Verbindungen eingesetzt werden. Zu den letzteren gehören bevorzugt Polyvinylpyrrolidon, Urethane und die Salze polymerer Polycarboxylate, beispielsweise homopolymerer oder copolymerer Polyacrylate, Polymethacrylate und insbesondere Copolymere der Acrylsäure mit Maleinsäure, vorzugsweise solche aus 50 % bis 10 % Maleinsäure. Die relative Molekülmasse der Homopolymeren liegt im allgemeinen zwischen 1000 und 100000, die der Copolymeren zwischen 2000 und 200000, vorzugsweise zwischen 50000 bis 120000, bezogen auf die freie Säure. Insbesondere sind auch wasserlösliche Polyacrylate geeignet, die beispielsweise mit etwa 1 % eines Polyallylethers der Sucrose quervernetzt sind und die eine relative Molekülmasse oberhalb einer Million besitzen. Beispiele hierfür sind die unter dem Namen Carbopol® 940 und 941 erhältlichen Polymere mit verdickender Wirkung. Die quervernetzten Polyacrylate werden vorzugsweise in Mengen nicht über 1 Gew.-%, vorzugsweise in Mengen von 0,2 bis 0,7 Gew.-% eingesetzt. Die Mittel können zusätzlich etwa 5 bis 20 Gew.-% eines partiell veresterten Copolymerisats enthalten, wie es in der europäischen Patentanmeldung EP-A 0367049 beschrieben ist. Diese partiell veresterten Polymere werden durch Copolymerisation von (a) mindestens einem C -C28-Olefin oder Mischungen aus mindestens einem C -C28-Olefin mit bis zu 20 Mol-% Cι-C2_-Alkylvinylethem und (b) ethytenisch ungesättigten Dicarbonsäureanhydriden mit 4 bis 8 Kohlenstoffatomen im Molverhältnis 1 : 1 zu Copolymerisaten mit K-Werten von 6 bis 100 und anschließende partielle Veresterung der Copolymerisate mit Umsetzungsprodukten wie Cι-Cι_-Alkoholen, C_-C22-Fettsäuren, Cι-Ci2-Alkylphe- nolen, sekundären C2-C3.-Aminen oder deren Mischungen mit mindestens einem C2-C -Alkylenoxid oder Tetrahydrofuran sowie Hydrolyse der Anhydridgruppen der Copolymerisate zu Carboxylgruppen erhalten, wobei die partielle Veresterung der Copolymerisate soweit geführt wird, daß 5 bis 50 % der Carboxylgruppen der Copolymerisate verestert sind. Bevorzugte Copolymerisate enthalten als ethylenisch ungesättigtes Dicarbonsäureanhydrid Maleinsäureanhydrid. Die partiell veresterten Copolymerisate können entweder in Form der freien Säure oder vorzugsweise in partiell oder vollständig neutralisierter Form vorliegen. Vorteilhafterweise werden die Copolymerisate in Form einer wäßrigen Lösung, insbesondere in Form einer 40 bis 50 Gew.-%igen Lösung eingesetzt. Die Copolymerisate leisten nicht nur einen Beitrag zur Primär- und Sekundärwaschleistung des flüssigen Wasch- und Reinigungsmittels, sondern bewirken auch eine gewünschte Viskositätserniedrigung der konzentrierten flüssigen Waschmittel. Durch den Einsatz dieser partiell veresterten Copolymerisate werden konzentrierte wäßrige Flüssigwaschmittel erhalten, die unter dem alleinigen Einfluß der Schwerkraft und ohne Einwirkung sonstiger Scherkräfte fließfähig sind. Vorzugsweise beinhalten die konzentrierten wäßrigen Flüssigwaschmittel partiell veresterte Copolymerisate in Mengen von 5 bis 15 Gew.-% und insbesondere in Mengen von 8 bis 12 Gew.-%.Viscosity regulators which can be used are, for example, hardened castor oil, salts of long-chain fatty acids, preferably in amounts of 0 to 5% by weight and in particular in amounts of 0.5 to 2% by weight, for example sodium, potassium, aluminum, magnesium - And titanium stearates or the sodium and / or potassium salts of behenic acid, and other polymeric compounds are used. The latter preferably include polyvinylpyrrolidone, urethanes and the salts of polymeric polycarboxylates, for example homopolymeric or copolymeric polyacrylates, polymethacrylates and in particular copolymers of acrylic acid with maleic acid, preferably those composed of 50% to 10% maleic acid. The relative molecular weight of the homopolymers is generally between 1000 and 100000, that of the copolymers between 2000 and 200000, preferably between 50,000 to 120,000, based on the free acid. Water-soluble polyacrylates which are crosslinked, for example, with about 1% of a polyallyl ether of sucrose and which have a relative molecular weight above one million are also particularly suitable. Examples of this are the polymers with thickening action available under the name Carbopol® 940 and 941. The crosslinked polyacrylates are preferably used in amounts not exceeding 1% by weight, preferably in amounts of 0.2 to 0.7% by weight. The agents can additionally about 5 to 20 wt .-% of a partially esterified copolymer included, as described in European patent application EP-A 0367049. These partially esterified polymers are obtained by copolymerizing (a) at least one C -C28 olefin or mixtures of at least one C -C28 olefin with up to 20 mol% of C 1 -C 2 -alkyl vinyl ether and (b) ethytenically unsaturated dicarboxylic acid anhydrides with 4 to 8 carbon atoms in a molar ratio of 1: 1 to copolymers with K values from 6 to 100 and subsequent partial esterification of the copolymers with reaction products such as -C-Cι_ alcohols, C_-C22 fatty acids, Cι-Ci2-alkylphenols, secondary C2-C3 . -Amines or mixtures thereof with at least one C2-C-alkylene oxide or tetrahydrofuran and hydrolysis of the anhydride groups of the copolymers to give carboxyl groups, the partial esterification of the copolymers being carried out to such an extent that 5 to 50% of the carboxyl groups of the copolymers are esterified. Preferred copolymers contain maleic anhydride as the ethylenically unsaturated dicarboxylic acid anhydride. The partially esterified copolymers can be present either in the form of the free acid or preferably in partially or completely neutralized form. The copolymers are advantageously used in the form of an aqueous solution, in particular in the form of a 40 to 50% strength by weight solution. The copolymers not only contribute to the primary and secondary washing performance of the liquid washing and cleaning agent, but also bring about a desired reduction in the viscosity of the concentrated liquid washing agent. The use of these partially esterified copolymers gives concentrated aqueous liquid detergents which are flowable under the sole influence of gravity and without the action of other shear forces. The concentrated aqueous liquid detergents preferably contain partially esterified copolymers in amounts of 5 to 15% by weight and in particular in amounts of 8 to 12% by weight.
Als Enzyme kommen solche aus der Klasse der Proteasen, Lipasen, Amylasen, Cellulasen bzw. deren Gemische in Frage. Besonders gut geeignet sind aus Bakterienstämmen oder Pilzen, wie Bacillus subtilis, Bacillus licheniformis und Streptomyces griseus gewonnene enzymatische Wirkstoffe. Vorzugsweise werden Proteasen vom Subtilisin-Typ und insbesondere Proteasen, die aus Bacillus lentus gewonnen werden, eingesetzt. Ihr Anteil kann etwa 0,2 bis etwa 2 Gew.-% betragen. Die Enzyme können an Trägerstoffen adsorbiert und/oder in Hüllsubstanzen eingebettet sein, um sie gegen vorzeitige Zersetzung zu schützen. Zusätzlich zu den mono- und polyfunktionellen Alkoholen und den Phosphonaten können die Mittel weitere Enzymstabilisatoren enthalten. Beispielsweise können 0,5 bis 1 Gew.-% Natriumformiat eingesetzt werden. Möglich ist auch der Einsatz von Proteasen, die mit löslichen Calciumsalzen und einem Caiciumgehalt von vorzugsweise etwa 1 ,2-Gew.-%, bezogen auf das Enzym, stabilisiert sind. Besonders vorteilhaft ist jedoch der Einsatz von Borverbindungen, beispielsweise von Borsäure, Boroxid, Borax und anderen Alkalimetallboraten wie den Salzen der Orthoborsäure (H3BO3), der Metaborsäure (HBO2) und der Pyroborsäure (Tetraborsäure H2B4O7).Suitable enzymes are those from the class of proteases, lipases, amylases, cellulases or mixtures thereof. Enzymes obtained from bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis and Streptomyces griseus are particularly suitable. Proteases of the subtilisin type and in particular proteases which are obtained from Bacillus lentus are preferably used. Their proportion can be about 0.2 to about 2% by weight. The enzymes can be adsorbed on carriers and / or embedded in coating substances in order to protect them against premature decomposition. In addition to the mono- and polyfunctional alcohols and the phosphonates, the agents can contain further enzyme stabilizers. For example, 0.5 to 1% by weight sodium formate can be used. It is also possible to use proteases which are stabilized with soluble calcium salts and a calcium content of preferably about 1.2% by weight, based on the enzyme. However, the use of boron compounds, for example boric acid, boron oxide, borax and other alkali metal borates such as the salts of orthoboric acid (H3BO3), metaboric acid (HBO2) and pyrobic acid (tetraboric acid H2B4O7), is particularly advantageous.
Als schmutzabweisenden Polymere („soil repellants") kommen solche Stoffe in Frage, die vorzugsweise Ethylenterephthalat- und/oder Polyethylenglycolterephthalatgruppen enthalten, wobei das Mol- Verhältnis Ethylenterephthalat zu Polyethylenglycolterephthalat im Bereich von 50 : 50 bis 90 : 10 liegen kann. Das Molekulargewicht der verknüpfenden Polyethylenglycoleinheiten liegt insbesondere im Bereich von 750 bis 5000, d.h., der Ethoxylierungsgrad der Polyethylenglycolgruppenhaltigen Polymere kann ca. 15 bis 100 betragen. Die Polymeren zeichnen sich durch ein durchschnittliches Molekulargewicht von etwa 5000 bis 200.000 aus und können eine Block-, vorzugsweise aber eine Random- Struktur aufweisen. Bevorzugte Polymere sind solche mit Molverhältnissen Ethylenterephtha- lat/Polyethylenglycolterephthalat von etwa 65 : 35 bis etwa 90 : 10, vorzugsweise von etwa 70 : 30 bis 80 : 20. Weiterhin bevorzugt sind solche Polymeren, die verknüpfende Polyethylenglycoleinheiten mit einem Molekulargewicht von 750 bis 5000, vorzugsweise von 1000 bis etwa 3000 und ein Molekulargewicht des Polymeren von etwa 10.000 bis etwa 50.000 auf- weisen. Beispiele für handelsübliche Polymere sind die Produkte Milease® T (ICI) oder Repelotex® SRP 3 (Rhöne-Poulenc).Suitable soil-repellants are substances which preferably contain ethylene terephthalate and / or polyethylene glycol terephthalate groups, the molar Ratio of ethylene terephthalate to polyethylene glycol terephthalate can range from 50:50 to 90:10. The molecular weight of the linking polyethylene glycol units is in particular in the range from 750 to 5000, ie the degree of ethoxylation of the polymers containing polyethylene glycol groups can be approximately 15 to 100. The polymers are characterized by an average molecular weight of about 5000 to 200,000 and can have a block, but preferably a random structure. Preferred polymers are those with molar ratios of ethylene terephthalate / polyethylene glycol terephthalate from about 65:35 to about 90:10, preferably from about 70:30 to 80:20. Also preferred are those polymers which have linking polyethylene glycol units with a molecular weight of 750 to 5000. preferably from 1000 to about 3000 and a molecular weight of the polymer from about 10,000 to about 50,000. Examples of commercially available polymers are the products Milease® T (ICI) or Repelotex® SRP 3 (Rhône-Poulenc).
Beim Einsatz in maschinellen Waschverfahren kann es von Vorteil sein, den Mitteln übliche Schauminhibitoren zuzusetzen. Hierfür eignen sich beispielsweise Seifen natürlicher oder synthetischer Herkunft, die einen hohen Anteil an Cι0-C24-Fettsäuren aufweisen. Geeignete nichttensidartige Schauminhibitoren sind beispielsweise Organopolysiloxane und deren Gemische mit mikrofeiner, gegebenenfalls silanierter Kieselsäure sowie Paraffine, Wachse, Mikrokristailinwachse und deren Gemische mit silanierter Kieselsäure oder Bistearylethylendiamid. Mit Vorteilen werden auch Gemische aus verschiedenen Schauminhibitoren verwendet, z.B. solche aus Silikonen, Paraffinen oder Wachsen. Vorzugsweise sind die Schauminhibitoren, insbesondere silikon- oder paraffinhaltige Schauminhibitoren, an eine granuläre, in Wasser lösliche bzw. dispergierbare Trägersubstanz gebunden. Insbesondere sind dabei Mischungen aus Paraffinen und Bistearylethylendiamiden bevorzugt.When used in machine washing processes, it can be advantageous to add conventional foam inhibitors to the agents. Suitable for this are, for example, soaps of natural or synthetic origin that have a high proportion of C 0 -C 24 fatty acids. Suitable non-surfactant-like foam inhibitors are, for example, organopolysiloxanes and their mixtures with microfine, optionally silanized silica, and paraffins, waxes, microcrystalline waxes and their mixtures with silanized silica or bistearylethylenediamide. Mixtures of various foam inhibitors are also used with advantages, for example those made of silicones, paraffins or waxes. The foam inhibitors, in particular silicone or paraffin-containing foam inhibitors, are preferably bound to a granular, water-soluble or dispersible carrier substance. Mixtures of paraffins and bistearylethylenediamides are particularly preferred.
Der pH-Wert der erfindungsgemäßen und insbesondere bevorzugten konzentrierten Mittel beträgt im allgemeinen 7 bis 10,5, vorzugsweise 7 bis 9,5 und insbesondere 7 bis 8,5. Die Einstellung höherer pH- Werte, beispielsweise oberhalb von 9, kann durch den Einsatz geringer Mengen an Natronlauge oder an alkalischen Salzen wie Natriumcarbonat oder Natriumsiiicat erfolgen. Die erfindungsgemäßen Flüssigwaschmittel weisen im allgemeinen Viskositäten zwischen 150 und 10000 mPas (Brookfield-Viskosi- meter, Spindel 1 , 20 Umdrehungen pro Minute, 20°C). Dabei sind bei den im wesentlichen wasserfreien Mitteln Viskositäten zwischen 150 und 5000 mPas bevorzugt. Die Viskosität der wäßrigen Mittel liegt vorzugsweise unter 2000 mPas und liegt insbesondere zwischen 150 und 1000 mPas. BeispieleThe pH of the concentrated agents according to the invention, which are particularly preferred, is generally 7 to 10.5, preferably 7 to 9.5 and in particular 7 to 8.5. Higher pH values, for example above 9, can be set by using small amounts of sodium hydroxide solution or alkaline salts such as sodium carbonate or sodium silicate. The liquid detergents according to the invention generally have viscosities between 150 and 10,000 mPas (Brookfield viscometer, spindle 1, 20 revolutions per minute, 20 ° C.). Viscosities between 150 and 5000 mPas are preferred for the essentially water-free agents. The viscosity of the aqueous compositions is preferably below 2000 mPas and in particular between 150 and 1000 mPas. Examples
Die nachfolgenden Beispiele beschreiben die zur Prüfung des Waschvermögens der erfindungsgemäßen Zubereitungen in einer Haushaltswaschmaschine (Typ: Miele W 717) unter folgenden Bedingungen durchgeführten Versuche:The following examples describe the tests carried out to test the washability of the preparations according to the invention in a household washing machine (type: Miele W 717) under the following conditions:
Waschprogramm : Buntwaschprogramm (ohne Vorwäsche) bei 40°CWash program: Color wash program (without prewash) at 40 ° C
Dosierung : 180 g pro MaschineDosage: 180 g per machine
Wasserhärte : 16°dWater hardness: 16 ° d
Textilproben : 3,5 kg saubere Füllwäsche (normale Haushaltswäsche)Textile samples: 3.5 kg clean laundry (normal household laundry)
Bestimmungen : 3fachDeterminations: 3 times
Meßtechnische BedingungenMeasurement conditions
• künstliche Anschmutzungen : RFC3/24 (465nm, Ausblendung des Aufhellereffektes)• artificial soiling: RFC3 / 24 (465nm, suppression of the brightening effect)
• natürliche Anschmutzungen : Länge-Gerät (Y-Filter)• natural soiling: length device (Y filter)
• Remissionsunterschiede von 2 % und mehr sind als signifikant anzusehen.• Differences in remission of 2% and more can be regarded as significant.
Verwendete Anschmutzunqen:Soiling used:
SW-B : Staub-Wollfett auf BaumwolleSW-B: Dust-wool grease on cotton
SH-BV : Staub-Hautfett auf veredelter BaumwolleSH-BV: Dust-skin fat on refined cotton
SH-P : Staub-Hautfett auf PolyesterSH-P: dusty skin oil on polyester
SH-PBV : Staub-Hautfett auf einem Gemisch aus Polyester und veredelter BaumwolleSH-PBV: Dust-skin grease on a mixture of polyester and refined cotton
BMR-B : Blut, Milch und Ruß auf BaumwolleBMR-B: blood, milk and soot on cotton
R-BV : Rotwein auf veredelter BaumwolleR-BV: Red wine on refined cotton
T-BV : Tee auf veredelter BaumwolleT-BV: Tea on refined cotton
LS-PBV : Lippenstift auf einem Gemisch aus Polyester und veredelter BaumwolleLS-PBV: lipstick on a mixture of polyester and finished cotton
MU-PBV : Make-up auf einem Gemisch aus Polyester und veredelter BaumwolleMU-PBV: Make-up on a mixture of polyester and finished cotton
Die Ergebnisse sind in Tabelle 1 zusammengefaßt. Die Zubereitungen 1 bis 5 sind erfindungsgemäß und bei 20°C flüssig bis leicht viskos; das Flüssigwaschmittel V1 ist bei 20°C hochviskos und dient zum Vergleich. Alle Mengenangaben verstehen sich als Gew.-%.The results are summarized in Table 1. Preparations 1 to 5 are in accordance with the invention and are liquid to slightly viscous at 20 ° C .; liquid detergent V1 is highly viscous at 20 ° C and is used for comparison. All quantities are understood as% by weight.
n Tabelle 1 Flüssigwaschmitteln Table 1 Liquid detergent
Figure imgf000014_0001
Figure imgf000014_0001
Die Beispiele zeigen, daß ein Flüssigwaschmittel, welches als einziges Tensid Laurinsäure+1 EO-suifat (Bsp.1) enthält, gegenüber einem in seiner Rezeptur bereits optimierten handelsüblichen Fiüssigwasch- mittel mit einer Anion/Niotensidmischung (V1) vergleichbare Remissionen über den gesamten Bereich der Anschmutzungen iiefert. Von Vorteil ist jedoch die deutlich niedrigere Viskosität. Setzt man dem Fettsäurepolyglycolestersulfat weitere Anion- und/oder Niotenside zu, wird die Waschleistung deutlich verbessert, ohne daß es zu einem starken Anstieg der Viskosität kommt. The examples show that a liquid detergent which contains lauric acid + 1 EO-suifat (Example 1) as the only surfactant, compared to a commercially available liquid detergent already optimized in its formulation with an anion / nonionic surfactant mixture (V1), has comparable remissions over the entire range of the soiling. However, the significantly lower viscosity is an advantage. If additional anionic and / or nonionic surfactants are added to the fatty acid polyglycol ester sulfate, the washing performance is significantly improved without a sharp increase in viscosity.

Claims

Patentansprüche claims
1. Fließfähige Tensidzubereitungen, dadurch gekennzeichnet, daß sie im wesentlichen aus1. Flowable surfactant preparations, characterized in that they consist essentially of
(a) Fettsäurepolyglycolestersulfaten und(a) fatty acid polyglycol ester sulfates and
(b) anionischen und/oder nichtionischen Tensiden(b) anionic and / or nonionic surfactants
bestehen.consist.
2. Zubereitungen nach Anspruch 1 , dadurch gekennzeichnet, daß sie Fettsäurepolyglycolestersul- fate der Formel (I) enthalten,2. Preparations according to claim 1, characterized in that they contain fatty acid polyglycol ester sulfates of the formula (I),
Figure imgf000015_0001
Figure imgf000015_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. Zubereitungen nach den Ansprüchen 1 oder 2, dadurch gekennzeichnet, daß sie anionische Tenside enthalten, die ausgewählt sind aus der Gruppe, die gebildet wird von Seifen, Alkylbenzol- sulfonaten, Alkansulfonaten, Olefinsulfonaten, Alkylethersulfonaten, Glycerinethersulfonaten, α- Methylestersulfonaten, Sulfofettsäuren, Alkylsulfaten, Fettalkoholethersulfaten, Glycerinethersul- faten, Hydroxymischethersulfaten, Monoglycerid(ether)sulfaten, Fettsäureamid(ether)sulfaten, Mono- und Dialkylsulfosuccinaten, Mono- und Dialkylsulfosuccinamaten, Sulfotrig lyceriden , Amidsei- fen, Ethercarbonsäuren und deren Salzen, Fettsäureisethionaten, Fettsäuresarcosinaten, Fettsäu- retauriden, N-Acylaminosäuren, Alkyloligoglucosidsulfaten, Proteinfettsäurekondensaten und Al- kyl(ether)phosphaten.3. Preparations according to claims 1 or 2, characterized in that they contain anionic surfactants which are selected from the group consisting of soaps, alkylbenzene sulfonates, alkane sulfonates, olefin sulfonates, alkyl ether sulfonates, glycerol ether sulfonates, α-methyl ester sulfonates, sulfofatty acids, Alkyl sulfates, fatty alcohol ether sulfates, glycerol ether sulfates, hydroxymixed ether sulfates, monoglyceride (ether) sulfates, fatty acid amide (ether) sulfates, mono- and dialkyl sulfosuccinates, mono- and dialkyl sulfosuccinamates, sulfotrig lycerides, amide soapsaric acid, fatty acid fatty acids and their salts, ether carboxylic acids, fatty acid fatty acids and their salts, retaurides, N-acylamino acids, alkyl oligoglucoside sulfates, protein fatty acid condensates and alkyl (ether) phosphates.
4. Zubereitungen nach den Ansprüchen 1 oder 2, dadurch gekennzeichnet, daß sie nichtionische Tenside enthalten, die ausgewählt sind aus der Gruppe, die gebildet wird von Fettalkoholpolygly- colethem, Alkylphenolpolyglycolethem, Fettsäurepolyglycolestem, Fettsäureamidpolyglycol-ethern, Fettaminpolyglycolethem, alkoxylierten Triglyceriden, Mischethern bzw. Mischformalen, gegebenenfalls partiell oxidierten Alk(en)yloligoglykosiden bzw. Glucoron-säurederivaten, Fettsäure- N-alkylglucamiden, Proteinhydrolysaten, Polyolfettsäureestem, Zuckerestern, Sorbitanestern, Polysorbaten und Aminoxiden. 4. Preparations according to claims 1 or 2, characterized in that they contain nonionic surfactants which are selected from the group formed by fatty alcohol polyglycol ethers, alkylphenol polyglycol ethers, fatty acid polyglycol esters, fatty acid amide polyglycol ethers, fatty amine polyglycol ethers, alkoxylated triglycerides, mixed ethers Mixed formals, optionally partially oxidized alk (en) yl oligoglycosides or glucoronic acid derivatives, fatty acid N-alkyl glucamides, protein hydrolyzates, polyol fatty acid esters, sugar esters, sorbitan esters, polysorbates and amine oxides.
5. Zubereitungen nach mindestens einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß sie als anionische Tenside Alkylbenzolsulfonate der Formel (II) enthalten,5. Preparations according to at least one of claims 1 to 4, characterized in that they contain alkylbenzenesulfonates of the formula (II) as anionic surfactants,
Figure imgf000016_0001
Figure imgf000016_0001
X für ein Alkali- und/oder Erdalkalimetall, Ammonium, Alkylammonium, Alkanolammonium oder Glucammonium steht.X represents an alkali and / or alkaline earth metal, ammonium, alkylammonium, alkanolammonium or glucammonium.
6. Zubereitungen nach mindestens einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, daß sie als anionische Tenside Alkyl- und/oder Alkenylsulfate der Formel (III) enthalten,6. Preparations according to at least one of claims 1 to 5, characterized in that they contain alkyl and / or alkenyl sulfates of the formula (III) as anionic surfactants,
R30-S03X (III)R 3 0-S0 3 X (III)
in der R1 für einen linearen oder verzweigten, aliphatischen Alkyl- und/oder Alkenylrest mit 6 bis 22, vorzugsweise 12 bis 18 Kohlenstoffatomen und X für ein Alkali- und/oder Erdalkalimetall, Ammonium, Alkylammonium, Alkanolammonium oder Glucammonium steht.in which R 1 is a linear or branched, aliphatic alkyl and / or alkenyl radical having 6 to 22, preferably 12 to 18 carbon atoms and X is an alkali and / or alkaline earth metal, ammonium, alkylammonium, alkanolammonium or glucammonium.
7. Zubereitungen nach mindestens einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, daß sie als nichtionische Tenside Alkyl- und/oder Alkenyloligoglykoside der Formel (IV) enthalten,7. Preparations according to at least one of claims 1 to 6, characterized in that they contain alkyl and / or alkenyl oligoglycosides of the formula (IV) as nonionic surfactants,
R40-[G]p (IV)R 4 0- [G] p (IV)
in der R1 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 1 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. Zubereitungen nach mindestens einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß sie als nichtionische Tenside Alkoholethoxylate der Formel (V) enthalten,8. Preparations according to at least one of claims 1 to 4, characterized in that they contain alcohol ethoxylates of the formula (V) as nonionic surfactants,
Figure imgf000016_0002
Figure imgf000016_0002
in der R5 für einen linearen oder verzweigten Alkyl- und/oder Alkenylrest mit 6 bis 22 Kohlenstoffatomen und n für Zahlen von 1 bis 50 steht.in which R 5 represents a linear or branched alkyl and / or alkenyl radical having 6 to 22 carbon atoms and n represents numbers from 1 to 50.
9. Zubereitungen nach mindestens einem der Ansprüche 1 bis 8, dadurch gekennzeichnet, daß sie die Fettsäurepolyglycolestersulfate und die Co-Tenside im Gewichtsverhältnis 10 : 90 bis 90 : 10 enthalten. Verwendung von Fettsäurepolyglycolestersulfaten, alleine oder in Abmischung mit anionischen und/oder nichtionischen Tensiden zur Hersteilung von Flüssigwaschmitteln. 9. Preparations according to at least one of claims 1 to 8, characterized in that they contain the fatty acid polyglycol ester sulfates and the co-surfactants in a weight ratio of 10:90 to 90:10. Use of fatty acid polyglycol ester sulfates, alone or in a mixture with anionic and / or nonionic surfactants, for the production of liquid detergents.
PCT/EP1998/005203 1997-08-25 1998-08-17 Flowable tenside preparations containing fatty acid polyglycol ester sulphates WO1999010460A1 (en)

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DE19741911A DE19741911C1 (en) 1997-09-25 1997-09-25 Fatty acid polyglycol ester sulphate as foam booster for surfactants
DE19741911.9 1997-09-25
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WO1999049006A1 (en) * 1998-03-25 1999-09-30 Henkel Kommanditgesellschaft Auf Aktien Fatty acid oligo-alkylene glycol ester sulfates in aqueous tenside solutions
WO2000017295A1 (en) * 1998-09-22 2000-03-30 Cognis Deutschland Gmbh Use of alkoxylated carboxylic acid esters for reducing viscosity of aqueous surfactant systems
CN113717008A (en) * 2021-08-13 2021-11-30 四川鸿康科技股份有限公司 Monoammonium phosphate anti-caking agent and application thereof

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Publication number Priority date Publication date Assignee Title
WO1999049006A1 (en) * 1998-03-25 1999-09-30 Henkel Kommanditgesellschaft Auf Aktien Fatty acid oligo-alkylene glycol ester sulfates in aqueous tenside solutions
WO2000017295A1 (en) * 1998-09-22 2000-03-30 Cognis Deutschland Gmbh Use of alkoxylated carboxylic acid esters for reducing viscosity of aqueous surfactant systems
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CN113717008A (en) * 2021-08-13 2021-11-30 四川鸿康科技股份有限公司 Monoammonium phosphate anti-caking agent and application thereof

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