EP1167499B1 - Compositions détergentes liquides contenant des hydroxyéthers mélangés - Google Patents

Compositions détergentes liquides contenant des hydroxyéthers mélangés Download PDF

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Publication number
EP1167499B1
EP1167499B1 EP01114927A EP01114927A EP1167499B1 EP 1167499 B1 EP1167499 B1 EP 1167499B1 EP 01114927 A EP01114927 A EP 01114927A EP 01114927 A EP01114927 A EP 01114927A EP 1167499 B1 EP1167499 B1 EP 1167499B1
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acid
alcohol
alkyl
carbon atoms
weight
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EP1167499A1 (fr
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Manfred Dr. Weuthen
Michael Elsner
Ditmar Kischkel
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BASF Personal Care and Nutrition GmbH
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Cognis Deutschland GmbH and Co KG
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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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/722—Ethers of polyoxyalkylene glycols having mixed oxyalkylene groups; Polyalkoxylated fatty alcohols or polyalkoxylated alkylaryl alcohols with mixed oxyalkylele groups
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/72—Ethers of polyoxyalkylene glycols
    • C11D1/721—End blocked ethers
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/825—Mixtures of compounds all of which are non-ionic
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/83—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
    • C11D1/66—Non-ionic compounds
    • C11D1/835—Mixtures of non-ionic with cationic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/88—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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/04—Carboxylic acids or salts thereof
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • 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
    • C11D1/62—Quaternary ammonium compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • 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
    • C11D1/667—Neutral esters, e.g. sorbitan 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
    • C11D1/88—Ampholytes; Electroneutral compounds
    • C11D1/90—Betaines

Definitions

  • the invention is in the field of liquid detergents and relates to the use of selected nonionic surfactants Manufacture of liquid detergents.
  • Liquid detergents have had a firm market share in the area of detergents in recent years acquired because they are characterized by a particularly simple dosage and especially in the area of low temperature laundry for only lightly soiled laundry solid detergents have advantages. Because of their inverse solubility behavior, So the increasing solubility with decreasing temperature are suitable nonoinic surfactants such as ethoxylated fatty alcohols in a special way for production liquid detergent. The disadvantage, however, is that these substances are not entirely satisfactory Show solubility behavior and tend to form undesirable gel phases; the network assets are also not sufficient.
  • EP 0916717 and WO 99/27047 describe agents for cleaning hard surfaces which contain at least one hydroxy mixed ether and C 9 -C 15 -oxoalcohol-EO adducts with a degree of ethoxylation of 2 to 8.
  • WO 96/12001 discloses rinse aid which (a) is a carrier material that is selected from the group formed by water, organic solvents or Contains mixtures thereof and a hydroxy mixed ether, or (b) a liquid mixture of two different hydroxy mixed ethers. It also becomes a liquid for cleaning hard surfaces, which either the surfactant system (a) or contains the liquid mixture (b) as mentioned above.
  • WO 94/22800 describes a liquid agent for cleaning hard surfaces in automatic dishwasher using an aqueous or organic solvent and contains a hydroxy mixed ether as surfactants.
  • US 4,898,621 discloses a rinse aid containing a hydroxy mixed ether and Water.
  • the object of the present invention was therefore primarily liquid detergents to provide based on nonionic surfactants, which are characterized by a characterized by optimized resolving power and improved network properties. Beside it existed the desire to develop preparations that are also in the absence of cationic Surfactants give the treated textiles a pleasant soft feel and in combination with polymers improve the inhibition of color transfer in colored laundry.
  • the invention relates to Use of hydroxy mixed ethers as nonionic surfactants for the production of liquid detergents.
  • hydroxy mixed ethers are the liquid detergent impart desired properties: the resolving power is compared to other nonionic Surfactants greatly improved, in particular there is no longer any formation of Gel phases, instead a good wetting ability is observed, which is not that The level of anionic surfactants is reached, but is significantly higher than that of nonionic ones Is used to surfactants.
  • Hydroxy mixed ethers are known nonionic surfactants with an asymmetrical ether structure and polyalkylene glycol components, which can be obtained, for example, by subjecting olefin epoxides to a ring-opening reaction with fatty alcohol polyglycol ethers.
  • HME Hydroxy mixed ethers
  • Corresponding products and their use in the field of cleaning hard surfaces is, for example, the subject of the European patent EP 0693049 B1 as well as the international patent application WO 94/22800 (Olin) and the documents mentioned therein.
  • hydroxy mixed ethers of the general formula (I) are known nonionic surfactants with an asymmetrical ether structure and polyalkylene glycol components, which can be obtained, for example, by subjecting olefin epoxides to a ring-opening reaction with fatty alcohol polyglycol ethers.
  • Corresponding products and their use in the field of cleaning hard surfaces is, for example, the subject of the
  • R 1 represents a linear or branched alkyl radical having 2 to 18, preferably 10 to 16 carbon atoms
  • R 2 represents hydrogen or a linear or branched alkyl radical having 2 to 18 carbon atoms
  • R 3 represents hydrogen or methyl
  • R 4 represents a linear or branched, alkyl and / or alkenyl radical having 1 to 22, preferably 8 to 18 carbon atoms and n being numbers from 1 to 50, preferably 2 to 25 and in particular 5 to 15, with the proviso that the sum of the carbon atoms in the radicals R 1 and R 2 is at least 6 and preferably 12 to 18.
  • the HME ring opening products can be either internal olefins (R 2 not equal to hydrogen) or terminal olefins (R 2 not equal to hydrogen), the latter being preferred in view of the easier preparation and the more advantageous application properties.
  • the polar part of the molecule can be a polyethylene or a polypropylene chain; Mixed chains of PE and PP units are also suitable, be it in statistical or block distribution.
  • Typical examples are ring opening products of 1,2-hexenepoxide, 2,3-hexenepoxide, 1,2-octene epoxide, 2,3-octene epoxide, 3,4-octene epoxide, 1,2-decene epoxide, 2,3-decene epoxide, 3,4 -Decenepoxid, 4,5-Decenepoxid, 1,2-Dodecenepoxid, 2,3-Dodecenepoxid, 3,4-Dodecenepoxid, 4,5-Dodecenepoxid, 5,6-Dodecenepoxid, 1,2-Tetradecenepoxid, 2,3-Tetradecenepoxid , 3,4-Tetradecenepoxid, 4,5-Tetradecenepoxid, 5,6-Tetradecenepoxid, 6,7-Tetradecenepoxid, 1,2-Hexadecenepoxid, 2,3
  • the liquid detergents can furthermore be anionic, nonionic, contain cationic and / or amphoteric or zwitterionic co-surfactants, where Share 1 to 40, preferably 5 to 35 and in particular 10 to 15 wt .-% of the can.
  • anionic surfactants are soaps, alkylbenzenesulfonates, alkanesulfonates, olefin sulfonates, alkyl ether sulfonates, glycerol ether, ⁇ -methyl ester sulfonates, sulfofatty acids, alkyl sulfates, fatty alcohol ether sulfates, Glycerol ether, Hydroxymischethersulfate, monoglyceride (ether) sulfates, fatty acid amide (ether) sulfates, mono- and dialkyl sulfosuccinates, mono - sulfotriglycerides, amide soaps, ether carboxylic acids and salts thereof, fatty acid taurides, N-acylamino acids such as acyl lactylates, acyl tartrates, acyl glutamates and acyl aspartates, alkyl oligoglucoside s
  • Alkyl benzene sulfonates alkyl sulfates, soaps, alkane sulfonates, paraffin sulfonates, methyl ester sulfonates and mixtures thereof are preferably used.
  • Preferred alkylbenzenesulfonates follow the formula (II) R 5 -Ph-SO 3 X
  • R 5 is a branched, but preferably linear alkyl radical having 10 to 18 carbon atoms
  • Ph is a phenyl radical
  • 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 particularly suitable.
  • Alkyl and / or alkenyl sulfates which are also often referred to as fatty alcohol sulfates, are to be understood as meaning the sulfation products of primary and / or secondary alcohols, which preferably follow the formula (III) R 6 O-SO 3 X
  • R 6 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 which 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, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, arylselyl alcohol, elaidyl alcohol, elaidyl alcohol Behenyl alcohol and erucyl alcohol as well as their technical mixtures, which are obtained by 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 C 16/18 tallow fatty alcohols or vegetable fatty alcohols of comparable C chain distribution in the form of their sodium salts are particularly preferred.
  • these are oxo alcohols, as are obtainable, for example, by converting carbon monoxide and hydrogen to alpha-containing olefins using the shop process.
  • Such alcohol mixtures are commercially available under the trade names Dobanol® or Neodol®. Suitable alcohol mixtures are Dobanol 91®, 23®, 25®, 45®.
  • oxo alcohols such as those obtained by the classic Enichema or Condea oxo process by adding carbon monoxide and hydrogen to olefins.
  • These alcohol mixtures are a mixture of strongly branched alcohols.
  • Such alcohol mixtures are commercially available under the trade name Lial®.
  • Suitable alcohol mixtures are Lial 91®, 111®, 123®, 125®, 145®.
  • R 7 CO is a linear or branched, saturated or unsaturated acyl radical having 6 to 22 and preferably 12 to 18 carbon atoms and again X is alkali and / or alkaline earth metal, ammonium, alkylammonium or alkanolammonium.
  • Typical examples are the sodium, potassium, magnesium, ammonium and triethanolammonium salts of caproic acid, caprylic acid, 2-ethylhexanoic acid, capric acid, lauric acid, isotridecanoic acid, myristic acid, palmitic acid, palmoleic acid, stearic acid, isostearic acid, oleic acid, elaoleic acid, petoleic acid, linoleic acid, petoleic acid, linoleic acid, petoleic acid, linoleic acid, linoleic acid, Linolenic acid, elaeostearic acid, arachic acid, gadoleic acid, behenic acid and erucic acid and their technical mixtures.
  • Coconut or palm kernel fatty acid is preferably used in the form of its sodium or potassium salts, which also have defoaming properties. It has proven to be particularly advantageous if the content of anionic surfactants does not exceed 20 and in particular 10% by weight of the total surfactant content.
  • 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, alk (en) yl oligoglycosides, fatty acid-N-alkyl glate amide, especially vegetable ester polyglycol fatty acids, vegetable hydrosol ester, sugar hydrolysis acid, vegetable ester polyglycol fatty acids, vegetable hydrolysis acid, vegetable ester polyglycol fatty acids, vegetable hydrolysis acid, vegetable ester polyglycol fatty acids, protein hydrolysis acid, vegetable ester polyglycol fatty acids, protein hydrolysis acid, vegetable ester glycol fatty acids, vegetable hydrolysis acid, vegetable ester polyglycol fatty acids, protein hydrolysis acid, vegetable ester polyglycol fatty acids, vegetable hydrolysis acid, vegetable hydrolysis
  • nonionic surfactants contain polyglycol ether chains, they can have a conventional, but preferably a narrow, homolog distribution.
  • Fatty alcohol polyglycol ethers, alkoxylated fatty acid lower alkyl esters or alkyl oligoglucosides are preferably used, with which a soft hand of the treated textiles is obtained, as is otherwise known only from the use of cationic softening agents.
  • the preferred fatty alcohol polyglycol ethers follow the formula (V) R 8 O (CH 2 CHR 9 O) n1 H
  • R 8 represents a linear or branched alkyl and / or alkenyl radical having 6 to 22, preferably 12 to 18 carbon atoms
  • R 9 represents hydrogen or methyl
  • n1 represents numbers from 1 to 20.
  • Typical examples are the addition products of an average of 1 to 20 and preferably 5 to 10 moles of ethylene and / or propylene oxide with capron alcohol, caprylic alcohol, 2-ethylhexyl alcohol, capric alcohol, lauryl alcohol, isotridecyl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, oleyl alcohol, isostyl alcohol , Petroselinyl alcohol, unolyl alcohol, linolenyl alcohol, elaeostearyl alcohol, arachyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol and brassidyl alcohol and their technical mixtures. Addition products of 3, 5 or 7 moles of ethylene
  • Suitable alkoxylated fatty acid lower alkyl esters are surfactants of the formula (VI) R 10 CO- (OCH 2 CHR 11 ) n2 OR 12
  • R 10 CO stands for a linear or branched, saturated and / or unsaturated acyl radical with 6 to 22 carbon atoms
  • R 11 for hydrogen or methyl
  • R 12 for linear or branched alkyl radicals with 1 to 4 carbon atoms
  • n2 for numbers from 1 to 20 stands.
  • Typical examples are the formal insert products of on average 1 to 20 and preferably 5 to 10 moles of ethylene and / or propylene oxide in the methyl, ethyl, propyl, isopropyl, butyl and tert-butyl esters of caproic acid, caprylic acid, 2 -Ethylhexanoic acid, capric acid, lauric acid, isotridecanoic acid, myristic acid, palmitic acid, palmoleic acid, stearic acid, isostearic acid, oleic acid, elaidic acid, petroselinic acid, unolic acid, unolenic acid, elaeostearic acid, arachidic acid, gadoleic acid, behenic acid and technical grade and erucas.
  • the products are usually prepared by inserting the alkylene oxides into the carbonyl ester bond in the presence of special catalysts, such as, for example, calcined hydrotalcite. Reaction products of an average of 5 to 10 moles of ethylene oxide into the ester linkage of technical coconut fatty acid methyl esters are particularly preferred.
  • Alkyl and alkenyl oligoglycosides which are also preferred nonionic surfactants, usually follow the formula (VII), R 13 O- [G] p
  • R 13 represents an alkyl and / or alkenyl radical having 4 to 22 carbon atoms
  • G represents a sugar radical having 5 or 6 carbon atoms
  • p represents numbers from 1 to 10. They can be obtained according to the relevant procedures in preparative organic chemistry.
  • 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 oligo glucosides .
  • alkyl and / or alkenyl oligoglycosides 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 13 can be derived from primary alcohols having 4 to 11, preferably 8 to 10, carbon atoms. Typical examples are butanol, capronic 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 13 can also be derived from primary alcohols having 12 to 22, preferably 12 to 14, carbon atoms.
  • Typical examples are lauryl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, arachyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol, brassidyl alcohol and their technical mixtures, which can be obtained as described above.
  • Alkyl oligoglucosides based on hardened C 12/14 coconut alcohol with a DP of 1 to 3 are preferred.
  • cationic surfactants are, in particular, tetraalkylammonium compounds, such as, for example, dimethyldistearylammonium chloride or hydroxyethyl hydroxycetyldimmonium chloride (Dehyquart E) or esterquats. These are, for example, quaternized fatty acid triethanolamine ester salts of the formula (VIII),
  • R 14 CO stands for an acyl radical with 6 to 22 carbon atoms
  • R 15 and R 16 independently of one another for hydrogen or R 14 CO
  • ester quats that can be used in the context of the invention are products based on caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, isostearic acid, stearic acid, oleic acid, elaidic acid, arachic acid, behenic acid and erucic acid and their technical mixtures, such as they occur, for example, in the pressure splitting of natural fats and oils.
  • Technical C 12/18 coconut fatty acids and in particular partially hardened C 16/18 tallow or palm fatty acids as well as C 16/18 fatty acid cuts rich in elaidic acid are preferably used.
  • the fatty acids and the triethanolamine can be used in a molar ratio of 1.1: 1 to 3: 1 to produce the quaternized esters.
  • an application ratio of 1.2: 1 to 2.2: 1, preferably 1.5: 1 to 1.9: 1 has proven to be particularly advantageous.
  • the preferred esterquats are technical mixtures of mono-, di- and triesters with an average degree of esterification of 1.5 to 1.9 and are derived from technical C 16/18 - tallow or palm fatty acid (iodine number 0 to 40).
  • quaternized fatty acid triethanolamine ester salts of the formula (VIII) have proven particularly advantageous, in which R 14 CO for an acyl radical having 16 to 18 carbon atoms, R 15 for R 15 CO, R 16 for hydrogen, R 17 for a methyl group, m1 , m2 and m3 stands for 0 and Y for methyl sulfate
  • quaternized ester salts of fatty acids with diethanolalkylamines of the formula (IX) are also suitable as esterquats.
  • R 18 CO for an acyl radical with 6 to 22 carbon atoms
  • R 19 for hydrogen or R 18 CO
  • R 20 and R 21 independently of one another for alkyl radicals with 1 to 4 carbon atoms
  • m5 and m6 in total for 0 or numbers from 1 to 12
  • Y again represents halide, alkyl sulfate or alkyl phosphate.
  • ester quats are the quaternized ester salts of fatty acids with 1,2-dihydroxypropyidialkylamines of the formula (X)
  • R 22 CO for an acyl radical with 6 to 22 carbon atoms
  • R 23 for hydrogen or R 22 CO
  • R 24 , R 25 and R 26 independently of one another for alkyl radicals with 1 to 4 carbon atoms, m7 and m8 in total for 0 or numbers from 1 to 12
  • X again represents halide, alkyl sulfate or alkyl phosphate.
  • esterquats are substances in which the ester bond is replaced by an amide bond and which preferably follow the formula (XI) based on diethylenetriamine,
  • R 27 CO represents an acyl radical with 6 to 22 carbon atoms
  • R 29 and R 30 independently of one another for alkyl radicals with 1 to 4 carbon atoms
  • amide ester quats are available on the market, for example, under the Incroquat® (Croda) brand.
  • amphoteric or zwitterionic surfactants are alkyl betaines, alkyl amido betaines, aminopropionates, aminoglycinates, imidazolinium betaines and sulfobetaines.
  • alkyl betaines are the carboxyalkylation products of secondary and in particular tertiary amines which follow the formula (XII)
  • R 31 for alkyl and / or alkenyl radicals with 6 to 22 carbon atoms
  • R 32 for hydrogen or alkyl radicals with 1 to 4 carbon atoms
  • R 33 for alkyl radicals with 1 to 4 carbon atoms
  • q1 for numbers from 1 to 6 and Z for a Alkali and / or alkaline earth metal or ammonium.
  • Typical examples are the carboxymethylation products of hexylmethylamine, hexyldimethylamine, octyldimethylamine, decyldimethylamine, dodecylmethylamine, dodecyldimethylamine, Dodecylethylmethylamin, C 12/14 -Kokosalkyldimethylamin, myristyldimethylamine, cetyldimethylamine, stearyldimethylamine, Stearylethylmethyl-amine, oleyl dimethyl amine, C 16/18 tallow alkyl dimethyl amine and technical mixtures thereof.
  • Carboxyalkylation products of amidoamines which follow the formula (XIII) are also suitable, in the R 34 CO for an aliphatic acyl radical with 6 to 22 carbon atoms and 0 or 1 to 3 double bonds, R 35 for hydrogen or alkyl radicals with 1 to 4 carbon atoms, R 36 for alkyl radicals with 1 to 4 carbon atoms, q2 for numbers from 1 to 6, q3 for numbers from 1 to 3 and Z again represents an alkali and / or alkaline earth metal or ammonium.
  • Typical examples are reaction products of fatty acids with 6 to 22 carbon atoms, namely caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, palmoleic acid, stearic acid, isostearic acid, oleic acid, elaidic acid, petroselinic acid, linoleic acid, linolenic acid, elaeostearic acid, gadoleic acid and arachic acid, arachic acid and their technical mixtures, with N, N-dimethylaminoethylamine, N, N-dimethylaminopropylamine, N, N-diethylaminoethylamine and N, N-diethylaminopropylamine, which are condensed with sodium chloroacetate. It is preferred to use a condensation product of C 8/18 coconut fatty acid N, N-dimethylaminopropylamide with sodium chloroacetate.
  • Imidazolinium betaines are also suitable. These substances are also known substances which can be obtained, for example, by cydizing condensation of 1 or 2 moles of fatty acid with polyhydric amines such as aminoethylethanolamine (AEEA) or diethylene triamine. The corresponding carboxyalkylation products are mixtures of different open-chain betaines. Typical examples are condensation products of the above-mentioned fatty acids with AEEA, preferably imidazolines based on lauric acid or again C 12/14 coconut fatty acid, which are subsequently betainized with sodium chloroacetate.
  • AEEA aminoethylethanolamine
  • diethylene triamine diethylene triamine
  • the preparations can of course be others for liquid detergents usual auxiliaries and additives, e.g. Builders, polymers, bleaches, bleach activators, Enzymes, enzyme stabilizers, graying inhibitors, optical brighteners, hydrotropes, fragrances, Electrolyte salts and the like in amounts of 1 to 25, preferably 5 to 20 and contain in particular 5 to 15 wt .-%.
  • the water content of the preparations can are in the range from 25 to 75 and in particular 30 to 50% by weight.
  • liquid detergents are both universal and special detergents including liquid detergents and color detergents.
  • Examples of usable organic builders that can be used as co-builders are the polycarboxylic acids which can be used in the form of their sodium salts, such as citric acid, Adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids, aminocarboxylic acids, Nitrilotriacetic acid (NTA), provided that such use is not permitted for ecological reasons is objectionable, and mixtures of these.
  • Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures of these. The acids themselves can also be used.
  • acids typically also have the property of an acidifying component and thus also serve to set a lower and milder pH value of detergents or cleaning agents.
  • acids typically also have the property of an acidifying component and thus also serve to set a lower and milder pH value of detergents or cleaning agents.
  • dextrins for example oligomers or polymers of carbohydrates, which can be obtained by partial hydrolysis of starches.
  • the hydrolysis can be carried out by customary, for example acid or enzyme-catalyzed, processes. They are preferably hydrolysis products with average molecular weights in the range from 400 to 500,000.
  • DE dextrose equivalent
  • Both maltodextrins with a DE between 3 and 20 and dry glucose syrups with a DE between 20 and 37 as well as so-called yellow dextrins and white dextrins with higher molar masses in the range from 2,000 to 30,000 can be used.
  • a preferred dextrin is described in British patent application GB 9419091 A1 ,
  • the oxidized derivatives of such dextrins are their reaction products with oxidizing agents which are capable of oxidizing at least one alcohol function of the saccharide ring to the carboxylic acid function.
  • Such oxidized dextrins and processes for their preparation are known, for example, from European patent applications EP 0232202 A1, EP 0427349 A1, EP 0472042 A1 and EP 0542496 A1 and international patent applications WO 92/18542, WO 93/08251, WO 93/16110, WO 94 / 28030, WO 95/07303, WO 95/12619 and WO 95/20608 are known. Also suitable is an oxidized oligosaccharide according to German patent application DE 19600018 A1. A product oxidized at C 6 of the saccharide ring can be particularly advantageous.
  • Suitable cobuilders are oxydisuccinates and other derivatives of disuccinates, preferably ethylenediamine disuccinate. Also particularly preferred in this context are glycerol disuccinates and glycerol trisuccinates , such as are described, for example, in US Pat. Nos. 4,524,009, 4,639,325, in European patent application EP 0150930 A1 and in Japanese patent application JP 93/339896 . Suitable amounts for use in zeolite-containing and / or silicate-containing formulations are 3 to 15% by weight.
  • organic cobuilders are, for example, acetylated hydroxycarboxylic acids or salts thereof, which may also be in lactone form and which have at least 4 carbon atoms and at least one hydroxyl group and at most contain two acid groups.
  • Such cobuilders are described, for example, in international patent application WO 95/20029 .
  • Suitable polymeric polycarboxylates are, for example, the sodium salts of polyacrylic acid or polymethacrylic acid, for example those with a relative molecular weight of 800 to 150,000 (based on acid and measured in each case against polystyrene sulfonic acid).
  • Suitable copolymeric polycarboxylates are, in particular, those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid. Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven to be particularly suitable.
  • the relative molecular weight, based on free acids, is generally 5,000 to 200,000, preferably 10,000 to 120,000 and in particular 50,000 to 100,000 (measured in each case against polystyrene sulfonic acid).
  • the (co) polymeric polycarboxylates can be used either as a powder or as an aqueous solution, with 20 to 55% by weight aqueous solutions being preferred.
  • Granular polymers are usually subsequently mixed into one or more basic granules.
  • biodegradable polymers composed of more than two different monomer units, for example those which, according to DE 4300772 A1, are monomers salts of acrylic acid and maleic acid and vinyl alcohol or vinyl alcohol derivatives, or, according to DE 4221381 C2, are monomers salts of acrylic acid and the 2-alkylallylsulfonic acid and sugar derivatives.
  • Further preferred copolymers are those which are described in German patent applications DE 4303320 A1 and DE 4417734 A1 and which preferably contain acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate as monomers.
  • polymeric aminodicarboxylic acids are also to be mentioned as further preferred builder substances. Polyaspartic acids or their salts and derivatives are particularly preferred.
  • polyacetals which can be obtained by reacting dialdehydes with polyolcarboxylic acids which have 5 to 7 carbon atoms and at least 3 hydroxyl groups, for example as described in European patent application EP 0280223 A1 .
  • Preferred polyacetals are obtained from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and mixtures thereof and from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.
  • the agents can also contain components that make the oil and fat washable made of textiles.
  • the preferred oil and fat dissolving Components include, for example, nonionic cellulose ethers such as methyl cellulose and Methyl hydroxypropyl cellulose with a proportion of methoxyl groups of 15 to 30% by weight and on hydroxypropoxyl groups from 1 to 15% by weight, based in each case on the nonionic Cellulose ether, as well as the polymers of phthalic acid known from the prior art and / or terephthalic acid or its derivatives, in particular polymers Ethylene terephthalates and / or polyethylene glycol terephthalates or anionic and / or nonionically modified derivatives of these. Of these, those are particularly preferred sulfonated derivatives of phthalic acid and terephthalic acid polymers.
  • bleaching agents which can be used are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H 2 O 2 -producing peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperic acid or diperdodecanedioic acid.
  • the bleaching agent content of the agents is preferably 5 to 35% by weight and in particular up to 30% by weight, advantageously using perborate monohydrate or percarbonate.
  • Bleach activators which can be used are compounds which, under perhydrolysis conditions, give aliphatic peroxocarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid. Substances are suitable which carry O- and / or N-acyl groups of the number of carbon atoms mentioned and / or optionally substituted benzoyl groups.
  • Multi-acylated alkylenediamines in particular tetraacetylethylene diamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), N- Acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl- or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic acid anhydrides, in particular phthalic anhydride, acylated polyhydric alcohols, in particular triacetyloxy, 2,5-acetiacetyl, ethylene glycol 2,5-dihydrofuran and the enol esters known from
  • hydrophilically substituted acylacetals known from German patent application DE 19616769 A1 and the acyl lactams described in German patent application DE 196 16 770 and international patent application WO 95/14075 are also preferably used.
  • the combinations of conventional bleach activators known from German patent application DE 4443177 A1 can also be used. Bleach activators of this type are present in the customary quantitative range, preferably in amounts of 1% by weight to 10% by weight, in particular 2% by weight to 8% by weight, based on the total agent.
  • the sulfonimines and / or bleach-enhancing transition metal salts or transition metal complexes known from European patents EP 0446982 B1 and EP 0453 003 B1 can also be present as so-called bleaching catalysts.
  • the transition metal compounds in question include in particular the manganese, iron, cobalt, ruthenium or molybdenum-salt complexes known from German patent application DE 19529905 A1 and their N-analog compounds known from German patent application DE 19620267 A1, which are known from German Patent application DE 19536082 A1 known manganese, iron, cobalt, ruthenium or molybdenum carbonyl complexes, the manganese, iron, cobalt, ruthenium, molybdenum, titanium, vanadium, described in German patent application DE 19605688 A1 and copper complexes with nitrogen-containing tripod ligands that from German patent application DE known cobalt 19620411 A1, iron-, copper- and ruthenium-ammine complexes, the manganese, copper described in the German patent application DE 4416438 A1 and cobalt complexes , the cobalt complexes described in European patent application EP 0272030 A1, which are known from the European patent application EP 0693550 A1 manganese
  • Bleach-enhancing transition metal complexes in particular with the central atoms Mn, Fe, Co, Cu, Mo, V, Ti and / or Ru, are used in customary amounts, preferably in an amount of up to 1% by weight, in particular 0.0025% by weight. % to 0.25% by weight and particularly preferably from 0.01% by weight to 0.1% by weight, in each case based on the total agent.
  • Enzymes in particular include those from the class of hydrolases, such as proteases, esterases, lipases or lipolytically active enzymes, amylases, cellulases or other glycosyl hydrolases and mixtures of the enzymes mentioned. All of these hydrolases contribute to the removal of stains, such as stains containing protein, fat or starch, and graying in the laundry. By removing pilling and microfibrils, cellulases and other glycosyl hydrolases can help maintain color and increase the softness of the textile. Oxidoreductases can also be used for bleaching or for inhibiting color transfer.
  • hydrolases such as proteases, esterases, lipases or lipolytically active enzymes, amylases, cellulases or other glycosyl hydrolases and mixtures of the enzymes mentioned. All of these hydrolases contribute to the removal of stains, such as stains containing protein, fat or starch, and graying in the laundry. By removing pilling and micro
  • Enzymes obtained from bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis, Streptomyces griseus and Humicola insolens are particularly suitable.
  • Proteases of the subtilisin type and in particular proteases obtained from Bacillus lentus are preferably used.
  • Enzyme mixtures for example from protease and amylase or protease and lipase or lipolytically active enzymes or protease and cellulase or from cellulase and upase or lipolytically active enzymes or from protease, amylase and lipase or lipolytically active enzymes or protease, lipase or lipolytically active enzymes and cellulase, but especially protease- and / or lipase-containing mixtures or mixtures with lipolytically active enzymes of particular interest.
  • Known cutinases are examples of such lipolytically active enzymes.
  • Peroxidases or oxidases have also proven to be suitable in some cases.
  • Suitable amylases include in particular ⁇ -amylases, iso-amylases, pullulanases and pectinases.
  • Cellobiohydrolases, endoglucanases and ⁇ -glucosidases, which are also called cellobiases, or mixtures thereof, are preferably used as cellulases. Since the different cellulase types differ in their CMCase and avicelase activities, the desired activities can be set by targeted mixtures of the cellulases.
  • the enzymes can be adsorbed on carriers and / or embedded in coating substances in order to protect them against premature decomposition.
  • the proportion of the enzymes, enzyme mixtures or enzyme granules can be, for example, 0.1 to 5% by weight, preferably 0.1 to 2% by weight.
  • 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. In addition to calcium salts, magnesium salts also serve as stabilizers.
  • boron compounds for example boric acid, boron oxide, borax and other alkali metal borates such as the salts of orthoboric acid (H 3 BO 3 ), metaboric acid (HBO 2 ) and pyrobic acid (tetraboric acid H 2 B 4 O 7 ), is particularly advantageous.
  • Graying inhibitors have the task of removing the dirt detached from the fiber in the Keep the liquor suspended and thus prevent the dirt from re-opening.
  • Water-soluble colloids of mostly organic nature are suitable for this purpose, for example the water-soluble salts of polymeric carboxylic acids, glue, gelatin, salts of ether carboxylic acids or ether sulfonic acids of starch or cellulose or salts of acidic sulfuric acid esters cellulose or starch. Also water-soluble containing acidic groups Polyamides are suitable for this purpose. Soluble starch preparations can also be used and use starch products other than the above, e.g. degraded starch, aldehyde starches Cellulose ethers such as carboxymethyl cellulose (sodium salt) are preferred.
  • Methyl cellulose, hydroxyalkyl cellulose and mixed ethers such as methyl hydroxyethyl cellulose, Methyl hydroxypropyl cellulose, methyl carboxymethyl cellulose and mixtures thereof, and Polyvinylpyrrolidone, for example in amounts of 0.1 to 5% by weight, based on the composition, used.
  • PVP copolymers have been proven to avoid color transfer.
  • the combination with hydroxy mixed ethers as a surfactant component has another advantage because the color transfer is inhibited particularly effectively.
  • the agents can contain derivatives of diaminostilbenedisulfonic acid or their alkali metal salts as optical brighteners. Suitable are, for example, salts of 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or compounds of similar structure which instead of the morpholino- Group carry a diethanolamino group, a methylamino group, anilino group or a 2-methoxyethylamino group.
  • Brighteners of the substituted diphenylstyryl type may also be present, for example the alkali salts of 4,4'-bis (2-sulfostyryl) diphenyl, 4,4'-bis (4-chloro-3-sulfostyryl) diphenyl, or 4- (4-chlorostyryl) -4 '- (2-sulfostyryl). Mixtures of the aforementioned brighteners can also be used.
  • Uniformly white granules are obtained if, in addition to the usual brighteners, the agents are also present in customary amounts, for example between 0.1 and 0.5% by weight, preferably between 0.1 and 0.3% by weight, even in small amounts, for example Contain 10 -6 to 10 -3 wt .-%, preferably by 10 -5 wt .-%, of a blue dye.
  • a particularly preferred dye is Tinolux® (commercial product from Ciba-Geigy).
  • Suitable soil-repellants are substances which preferably Contain ethylene terephthalate and / or polyethylene glycol terephthalate groups, wherein the molar ratio of ethylene terephthalate to polyethylene glycol terephthalate is in the range of 50: 50 to 90: 10 can be.
  • the molecular weight of the linking polyethylene glycol units is in particular in the range from 750 to 5000, i.e. 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 5000 to 200,000 and can have a block structure, but preferably a random structure.
  • preferred Polymers are those with molar ratios of ethylene terephthalate / polyethylene glycol terephthalate from 65:35 to 90:10, preferably from 70:30 to 80:20. Furthermore preferred are those polymers which link polyethylene glycol units with a Molecular weight from 750 to 5000, preferably from 1000 to 3000 and a molecular weight of the polymer have from 10,000 to 50,000. Examples of commercially available Polymers are the products Milease® T (ICI) or Repelotex® SRP 3 (Rhône-Poulenc).
  • fragrance compounds e.g. the synthetic Products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type be used.
  • Fragrance compounds of the ester type are e.g. benzyl acetate, Phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinyl acetate, Phenylethyl acetate, linalyl benzoate, benzyl formate, ethyl methylphenylglycinate, allyl cyclohexyl propionate, Styrallyl propionate and benzyl salicylate.
  • the ethers include, for example Benzyl ethyl ether, to the aldehydes e.g. the linear alkanals with 8-18 C atoms, Citral, Citronellal, Citronellyloxyacetaldehyde, Cyclamenaldehyde, Hydroxycitronellal, Lilial and bourgeonal, to the ketones e.g.
  • the hydrocarbons mainly include terpenes such as limonene and pinene.
  • terpenes such as limonene and pinene.
  • perfume oils can also be natural Fragrance mixtures contain, as are available from vegetable sources, e.g. pine, Citrus, jasmine, patchouly, rose or ylang-ylang oil.
  • Muscatels are also suitable, Sage oil, chamomile oil, clove oil, lemon balm oil, mint oil, cinnamon leaf oil, linden blossom oil, juniper berry oil, Vetiver oil, olibanum oil, galbanum oil and labdanum oil as well as orange blossom oil, neroliol, Orange peel oil and sandalwood oil.
  • the fragrances can be used directly in the invention Agents are incorporated, but it can also be advantageous to apply the fragrances Apply carriers that increase and adhere the perfume to the laundry a slower fragrance release ensures a long-lasting fragrance of the textiles.
  • Carrier materials have proven themselves, for example, cyclodextrins, the cyclodextrin-perfume complexes can also be coated with other auxiliaries.
  • Suitable ingredients of the agents are water-soluble inorganic salts such as bicarbonates, carbonates, citrates, amorphous silicates, normal water glasses, which have no outstanding builder properties, or mixtures of these;
  • alkali carbonate and / or amorphous alkali silicate especially sodium silicate with a molar ratio Na 2 O: SiO 2 of 1: 1 to 1: 4.5, preferably of 1: 2 to 1: 3.5, are used.
  • the content of Sodium carbonate in the final preparations is preferably up to 40% by weight, advantageously between 2 and 35% by weight.
  • the content of sodium silicate in the agents (without special builder properties) is generally up to 10% by weight and preferably between 1 and 8% by weight.
  • the washing performance was determined in a Miele W 918 washing machine at 30 ° C and a water hardness of 16 ° d with 3.5 kg standard washing and a detergent dosage of 70 g.
  • the dissolving behavior was determined indirectly by determining the viscosity when diluting the preparations with water. It was assumed that a high viscosity over a wide range of dilution is synonymous with slow dissolution during the washing cycle.For this purpose, 50 ml of liquid detergent were diluted step by step with 5, 10 and 25 ml of water and the viscosity according to Brookfield (20 ° C, 10 rpm).
  • Table 1 to 8 are according to the invention, examples V1 to V6 are used for comparison.

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Claims (8)

  1. Utilisation d'éthers mixtes hydroxylés de formule (I)
    Figure 00300001
       dans laquelle
    R1 représente un reste alkyle linéaire ou ramifié ayant de 2 à 18 atomes de carbone, R2 représente de l'hydrogène ou un reste alkyle linéaire ou ramifié, ayant de 2 à 18 atomes de carbone, R3 représente de l'hydrogène ou un méthyle, R4 représente un reste alkyle et/ou alkényle, linéaire ou ramifié, ayant de 1 à 22 atomes de carbone, et n représente des nombres allant de 1 à 50, avec la précision que la somme des atomes de carbone dans les restes R1 et R2 s'élève à au moins 6, comme agents tensioactifs non ioniques en vue de la production de produits de lavage liquides.
  2. Utilisation selon la revendication 1,
    caractérisée en ce que
    les éthers mixtes hydroxylés sont utilisés pour la production de produits de lavage liquides en quantités allant de 1 à 60 % en poids, rapporté à la composition.
  3. Utilisation selon au moins une des revendications 1 ou 2,
    caractérisée en ce que
    dans les produits de lavage liquides en outre des co-agents tensioactifs anioniques, non ioniques, cationiques et/ou amphotères ou zwitterioniques sont présents.
  4. Utilisation selon la revendication 3,
    caractérisée en ce qu'
    on utilise des co-agents tensioactifs, qui sont choisis dans le groupe formé des alkyl benzène sulfonates, des alkylsulfates, des savons, des alkanesulfonates des paraffines sulfonates, des méthylester sulfonates, des éthers d'alcool gras et de polyglycol, des éthers d'alkyle inférieur d'acide gras alkoxylés, des alkyloligoglucosides, des esterquats et des bétaïnes.
  5. Utilisation selon les revendications 3 et/ou 4,
    caractérisée en ce que
    les co-agents tensioactifs sont présents en quantités allant de 1 à 40 % en poids.
  6. Utilisation selon au moins une des revendications 1 à 5,
    caractérisée en ce que
    des adjuvants et des additifs usuels en outre sont présents.
  7. Utilisation selon la revendication 6,
    caractérisée en ce que
    les adjuvants et additifs supplémentaires sont présents en quantités allant de 1 à 25 % en poids.
  8. Utilisation selon au moins une des revendications 1 à 7,
    caractérisée en ce que
    les éthers mixtes hydroxylés sont utilisés pour la préparation de produits de lavage liquides qui possèdent une teneur en eau dans la zone de 25 à 75 % en poids.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6921744B2 (en) 2001-02-01 2005-07-26 Cognis Deutschland Gmbh & Co. Kg Hydroxy mixed ethers having a high degree of ethoxylation, compositions containing the same and anti-foam uses therefor

Families Citing this family (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10019344A1 (de) * 2000-04-18 2001-11-08 Cognis Deutschland Gmbh Wasch- und Reinigungsmittel
DE10031620A1 (de) * 2000-06-29 2002-01-10 Cognis Deutschland Gmbh Flüssigwaschmittel
EP1229104B1 (fr) * 2001-02-01 2004-09-15 Cognis Deutschland GmbH & Co. KG Produit de rinçage et de nettoyage
DE10162696A1 (de) * 2001-02-01 2002-09-19 Cognis Deutschland Gmbh Spül- und Reinigungsmittel
US20030166488A1 (en) * 2001-12-19 2003-09-04 Michael Elsner Dishwashing and cleaning compositions
US6911417B2 (en) * 2003-04-29 2005-06-28 Conocophillips Company Water block removal with surfactant based hydrocarbonaceous liquid system
DE50305183D1 (de) * 2003-06-24 2006-11-09 Cognis Ip Man Gmbh Perlglänzende wässrige Zubereitungen
DE102005044028A1 (de) 2005-09-14 2007-03-15 Cognis Ip Management Gmbh Mischung oberflächenaktiver Substanzen zur Verwendung in Reinigungsmitteln
US8980813B2 (en) 2008-02-21 2015-03-17 S. C. Johnson & Son, Inc. Cleaning composition having high self-adhesion on a vertical hard surface and providing residual benefits
US8143206B2 (en) 2008-02-21 2012-03-27 S.C. Johnson & Son, Inc. Cleaning composition having high self-adhesion and providing residual benefits
US9410111B2 (en) 2008-02-21 2016-08-09 S.C. Johnson & Son, Inc. Cleaning composition that provides residual benefits
US8993502B2 (en) 2008-02-21 2015-03-31 S. C. Johnson & Son, Inc. Cleaning composition having high self-adhesion to a vertical hard surface and providing residual benefits
ES2422261T5 (es) 2008-02-21 2017-05-12 S.C. Johnson & Son, Inc. Composición para limpieza que tiene alta autoadhesión y que proporciona beneficios residuales
US9481854B2 (en) 2008-02-21 2016-11-01 S. C. Johnson & Son, Inc. Cleaning composition that provides residual benefits
PL2380961T3 (pl) 2010-04-23 2018-10-31 The Procter & Gamble Company Kompozycja detergentu
EP2383329A1 (fr) 2010-04-23 2011-11-02 The Procter & Gamble Company Particule
ES2579217T3 (es) 2010-04-23 2016-08-08 The Procter & Gamble Company Partícula
DE102016205344A1 (de) * 2016-03-31 2017-10-05 Henkel Ag & Co. Kgaa Geschirrspülmittel mit verbesserter Klarspülleistung

Family Cites Families (67)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA1238917A (fr) 1984-01-31 1988-07-05 Vivian B. Valenty Adjuvant pour detergent
US4524009A (en) 1984-01-31 1985-06-18 A. E. Staley Manufacturing Company Detergent builder
US4639325A (en) 1984-10-24 1987-01-27 A. E. Staley Manufacturing Company Detergent builder
FR2597473B1 (fr) 1986-01-30 1988-08-12 Roquette Freres Procede d'oxydation de di-, tri-, oligo- et polysaccharides en acides polyhydroxycarboxyliques, catalyseur mis en oeuvre et produits ainsi obtenus.
GB8629837D0 (en) 1986-12-13 1987-01-21 Interox Chemicals Ltd Bleach activation
DE3706036A1 (de) 1987-02-25 1988-09-08 Basf Ag Polyacetale, verfahren zu deren herstellung aus dialdehyden und polyolcarbonsaeuren und verwendung der polyacetale
DE3723873A1 (de) * 1987-07-18 1989-01-26 Henkel Kgaa Verwendung von hydroxyalkylpolyethylenglykolethern in klarspuelmitteln fuer die maschinelle geschirreinigung
DE3723826A1 (de) 1987-07-18 1989-01-26 Henkel Kgaa Verfahren zur herstellung von alkylglykosiden
US5576425A (en) 1988-10-05 1996-11-19 Henkel Kommanditgesellschaft Auf Aktien Process for the direct production of alkyl glycosides
DE3833780A1 (de) 1988-10-05 1990-04-12 Henkel Kgaa Verfahren zur direkten herstellung von alkylglykosiden
GB8908416D0 (en) 1989-04-13 1989-06-01 Unilever Plc Bleach activation
ATE124960T1 (de) 1989-11-10 1995-07-15 Tno Verfahren zur herstellung von polydicarboxysacchariden.
GB9003741D0 (en) 1990-02-19 1990-04-18 Unilever Plc Bleach activation
US5041232A (en) 1990-03-16 1991-08-20 Lever Brothers Company, Division Of Conopco, Inc. Sulfonimines as bleach catalysts
US5047163A (en) 1990-03-16 1991-09-10 Lever Brothers Company, Division Of Conopco, Inc. Activation of bleach precursors with sulfonimines
EP0458397B1 (fr) 1990-05-21 1997-03-26 Unilever N.V. Activation du blanchiment
IT1249883B (it) 1990-08-13 1995-03-30 Ferruzzi Ricerca & Tec Agenti sequestranti del calcio a base di carboidrati ossidati e loro impiego come builder per detergenti
IT1245063B (it) 1991-04-12 1994-09-13 Ferruzzi Ricerca & Tec Procedimento per l'ossidazione di carboidrati
DE69126778T2 (de) 1991-07-31 1998-01-02 Ausimont Spa Verfahren zur Erhöhung der Bleichwirksamkeit eines inorganischen Persalzes
DE4134914A1 (de) 1991-10-23 1993-04-29 Henkel Kgaa Wasch- und reinigungsmittel mit ausgewaehlten builder-systemen
ATE166362T1 (de) 1991-11-14 1998-06-15 Procter & Gamble C6/c2-c3 oxidierte stärke als waschmittelbestandteil
US5194416A (en) 1991-11-26 1993-03-16 Lever Brothers Company, Division Of Conopco, Inc. Manganese catalyst for activating hydrogen peroxide bleaching
EP0544490A1 (fr) 1991-11-26 1993-06-02 Unilever Plc Compositions détergentes de blanchiment
GB9127060D0 (en) 1991-12-20 1992-02-19 Unilever Plc Bleach activation
CA2085642A1 (fr) 1991-12-20 1993-06-21 Ronald Hage Activation de blanchiment
DE4221381C1 (de) 1992-07-02 1994-02-10 Stockhausen Chem Fab Gmbh Pfropf-Copolymerisate von ungesättigten Monomeren und Zuckern, Verfahren zu ihrer Herstellung und ihre Verwendung
DE4203923A1 (de) 1992-02-11 1993-08-12 Henkel Kgaa Verfahren zur herstellung von polycarboxylaten auf polysaccharid-basis
JPH05339896A (ja) 1992-06-03 1993-12-21 Arakawa Chem Ind Co Ltd 紙用サイズ剤および紙サイジング方法
DE4300772C2 (de) 1993-01-14 1997-03-27 Stockhausen Chem Fab Gmbh Wasserlösliche, biologisch abbaubare Copolymere auf Basis von ungesättigten Mono- und Dicarbonsäuren, Verfahren zu ihrer Herstellung und ihre Verwendung
DE4303320C2 (de) 1993-02-05 1995-12-21 Degussa Waschmittelzusammensetzung mit verbessertem Schmutztragevermögen, Verfahren zu dessen Herstellung und Verwendung eines geeigneten Polycarboxylats hierfür
US5576281A (en) * 1993-04-05 1996-11-19 Olin Corporation Biogradable low foaming surfactants as a rinse aid for autodish applications
CA2161213A1 (fr) 1993-05-20 1994-12-08 Alan David Willey Composes de blanchiment renfermant du caprolactame n-acyle pour lavage a la main ou autres methodes de nettoyage utilisant peu d'eau
JP3238406B2 (ja) 1993-05-20 2001-12-17 ザ、プロクター、エンド、ギャンブル、カンパニー 置換ベンゾイルカプロラクタム漂白活性剤を含む漂白コンパウンド
BR9406306A (pt) 1993-05-20 1995-12-26 Procter & Gamble Composições de branqueamento compreendendo ativadores n-acil caprolactama
DE4317519A1 (de) 1993-05-26 1994-12-01 Henkel Kgaa Herstellung von Polycarboxylaten auf Polysaccharid-Basis
US5405413A (en) 1993-06-24 1995-04-11 The Procter & Gamble Co. Bleaching compounds comprising acyl valerolactam bleach activators
NL194919C (nl) 1993-09-07 2003-07-04 Tno Werkwijze voor het oxideren van koolhydraten.
NL9301905A (nl) 1993-11-04 1995-06-01 Inst Voor Agrotech Onderzoek Werkwijze voor het oxideren van koolhydraten.
DE4338922A1 (de) 1993-11-15 1995-05-18 Degussa Aktivatoren für anorganische Persauerstoffverbindungen
AU1074295A (en) 1993-11-25 1995-06-13 Warwick International Group Limited Bleaching compositions
US5534196A (en) 1993-12-23 1996-07-09 The Procter & Gamble Co. Process for making lactam bleach activator containing particles
DE4402051A1 (de) 1994-01-25 1995-07-27 Henkel Kgaa Gerüststoff für Wasch- oder Reinigungsmittel
DE4402851A1 (de) 1994-01-31 1995-08-03 Henkel Kgaa Wirbelschicht-Oxidationsverfahren zur Herstellung von Polycarboxylaten auf Polysaccharid-Basis
JP2941430B2 (ja) 1994-04-07 1999-08-25 ザ、プロクター、エンド、ギャンブル、カンパニー 金属含有漂白触媒を含む漂白組成物
DE4416438A1 (de) 1994-05-10 1995-11-16 Basf Ag Ein- oder mehrkernige Metall-Komplexe und ihre Verwendung als Bleich- und Oxidationskatalysatoren
DE4417734A1 (de) 1994-05-20 1995-11-23 Degussa Polycarboxylate
ES2221665T3 (es) 1994-07-21 2005-01-01 Ciba Specialty Chemicals Holding Inc. Composicion de blanqueo de tejidos.
GB9419091D0 (en) 1994-09-22 1994-11-09 Cerestar Holding Bv Process for decreasing the build up of inorganic incrustations on textiles and detergent composition used in such process
TW387937B (en) * 1994-10-14 2000-04-21 Olin Corp Biodegradable surfactant and blends thereof as a rinse aid
DE4443177A1 (de) 1994-12-05 1996-06-13 Henkel Kgaa Aktivatormischungen für anorganische Perverbindungen
DE19529905A1 (de) 1995-08-15 1997-02-20 Henkel Kgaa Aktivatorkomplexe für Persauerstoffverbindungen
DE19536082A1 (de) 1995-09-28 1997-04-03 Henkel Kgaa Aktivatorkomplexe für Persauerstoffverbindungen
DE19600018A1 (de) 1996-01-03 1997-07-10 Henkel Kgaa Waschmittel mit bestimmten oxidierten Oligosacchariden
DE19605688A1 (de) 1996-02-16 1997-08-21 Henkel Kgaa Übergangsmetallkomplexe als Aktivatoren für Persauerstoffverbindungen
DE19613103A1 (de) 1996-04-01 1997-10-02 Henkel Kgaa Übergangsmetallkomplex-haltige Systeme als Aktivatoren für Persauerstoffverbindungen
DE19620411A1 (de) 1996-04-01 1997-10-02 Henkel Kgaa Übergangsmetallamminkomplexe als Aktivatoren für Persauerstoffverbindungen
DE19616770A1 (de) 1996-04-26 1997-11-06 Henkel Kgaa Acyllactame als Bleichaktivatoren für Wasch- und Reinigungsmittel
DE19616693A1 (de) 1996-04-26 1997-11-06 Henkel Kgaa Enolester als Bleichaktivatoren für Wasch- und Reinigungsmittel
DE19616769A1 (de) 1996-04-26 1997-11-06 Henkel Kgaa Acylacetale als Bleichaktivatoren für Wasch- und Reinigungsmittel
DE19616767A1 (de) 1996-04-26 1997-11-06 Henkel Kgaa Bleichaktivatoren für Wasch- und Reinigungsmittel
DE19620267A1 (de) 1996-05-20 1997-11-27 Henkel Kgaa Katalytisch wirksame Aktivatorkomplexe mit N¶4¶-Liganden für Persauerstoffverbindungen
DE19738866A1 (de) * 1997-09-05 1999-03-11 Henkel Kgaa Schaumarme Tensidmischungen mit Hydroxymischethern
DE19750456A1 (de) * 1997-11-14 1999-05-27 Henkel Ecolab Gmbh & Co Ohg Mittel zum Reinigen von harten Oberflächen
DE19751859A1 (de) * 1997-11-22 1999-07-29 Henkel Ecolab Gmbh & Co Ohg Mittel zum Reinigen von harten Oberflächen
DE10017191A1 (de) * 2000-04-07 2001-10-18 Cognis Deutschland Gmbh Feuchttücher (I)
DE10019344A1 (de) * 2000-04-18 2001-11-08 Cognis Deutschland Gmbh Wasch- und Reinigungsmittel
DE10031620A1 (de) * 2000-06-29 2002-01-10 Cognis Deutschland Gmbh Flüssigwaschmittel

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6921744B2 (en) 2001-02-01 2005-07-26 Cognis Deutschland Gmbh & Co. Kg Hydroxy mixed ethers having a high degree of ethoxylation, compositions containing the same and anti-foam uses therefor

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DE50100539D1 (de) 2003-10-02
US20020107165A1 (en) 2002-08-08
DE10031620A1 (de) 2002-01-10
ES2206368T3 (es) 2004-05-16
EP1167499A1 (fr) 2002-01-02

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