EP1167499A1 - Liquid detergent compositions comprising mixed hydroxyethers - Google Patents

Abstract

Liquid detergent contains mixed hydroxyethers. Liquid detergent contains mixed hydroxyethers. An Independent claim is included for the use of a mixture of mixed hydroxyethers as nonionic surfactants in the production of liquid detergents.

Description

Field of the Invention

The invention is in the field of liquid detergents and relates to preparations with selected nonionic surfactants and the use of nonionic surfactants Manufacture of liquid detergents.

State of the art

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 non-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. You try to compensate for this disadvantage by combining the nonionic surfactants with anionic surfactants combined, but this leads to the fact that the washing ability is just in the cold or Low temperature laundry - where the anionic surfactants have their weakness - in many cases is no longer sufficient.

The primary object of the present invention was to create new liquid detergents 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.

Description of the invention

The invention relates to liquid detergents containing hydroxy mixed ethers and Use of the hydroxy mixed ethers as nonionic surfactants for the production of liquid detergents.

Surprisingly, it has been found that 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

in der R¹ für einen linearen oder verzweigten Alkylrest mit 2 bis 18, vorzugsweise 10 bis 16 Kohlenstoffatomen, R² für Wasserstoff oder einen linearen oder verzweigten Alkylrest mit 2 bis 18 Kohlenstoffatomen, R³ für Wasserstoff oder Methyl, R⁴ für einen linearen oder verzweigten, Alkyl- und/oder Alkenylrest mit 1 bis 22, vorzugsweise 8 bis 18 Kohienstoffatomen und n für Zahlen von 1 bis 50, vorzugsweise 2 bis 25 und insbesondere 5 bis 15 steht, mit der Maßgabe, daß die Summe der Kohlenstoffatome in den Resten R¹ und R² mindestens 6 und vorzugsweise 12 bis 18 beträgt. Wie aus der Formel hervorgeht, können die HME Ringöffnungsprodukte sowohl von innenständigen Olefinen (R² ungleich Wasserstoff) oder endständigen Olefinen (R² gleich Wasserstoff) sein, wobei letztere im Hinblick auf die leichtere Herstellung und die vorteilhafteren anwendungstechnischen Eigenschaften bevorzugt sind. Hydroxy mixed ethers (HME) are known nonionic surfactants with an asymmetrical ether structure and polyalkylene glycol components, which can be obtained, for example, by subjecting olefin epoxides to fatty alcohol polyglycol ethers to a ring-opening reaction. Corresponding products and their use in the field of cleaning hard surfaces is the subject of, for example, European patent EP 0693049 B1 and international patent application WO 94/22800 (Olin) and the documents mentioned therein. Typically the following hydroxy mixed ethers of the general formula (I),

in which 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. As can be seen from the formula, 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.

Likewise, the polar part of the molecule can be a polyethylene or a polypropylene chain his; 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-decene epoxide, 4,5-decene epoxide, 1,2-dodecene epoxide, 2,3-dodecene epoxide, 3,4-dodecene epoxide, 4,5-dodecene epoxide, 5,6-dodecene epoxide, 1,2-tetradecene epoxide, 2,3-tetradecenepoxide, 3,4-tetradecenepoxide, 4,5-tetradecenepoxide, 5,6-tetradecenepoxide, 6,7-tetradecene epoxide, 1,2-hexadecene epoxide, 2,3-hexadecene epoxide, 3,4-hexadecene epoxide, 4,5-hexadecene epoxide, 5,6-hexadecene epoxide, 6,7-hexadecene epoxide, 7,8-hexadecene epoxide, 1,2-octadecene epoxide, 2,3-octadecene epoxide, 3,4-octadecene epoxide, 4,5-octadecene epoxide, 5,6-octadecene epoxide, 6,7-octadecene epoxide, 7,8-octadecene epoxide and 8,9-octadecene epoxide and their mixtures with addition products of average 1 to 50, preferably 2 to 25 and in particular 5 to 15 moles of ethylene oxide and / or 1 to 10, preferably 2 to 8 and in particular 3 to 5 moles of saturated and / or propylene oxide unsaturated primary alcohols with 6 to 22, preferably 12 to 18 carbon atoms, such as e.g. Capronic alcohol, caprylic alcohol, 2-ethylhexyl alcohol, capric alcohol, lauryl alcohol, isotridecyl alcohol, Myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, Oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, linolyl alcohol, linolenyl alcohol, elaeostearyl alcohol, Arachyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol and brassidyl alcohol as well as their technical mixtures. The hydroxy mixed ethers can be 1 to 60, preferably 5 to 35 and in particular 10 to 15% by weight of the liquid detergents according to the invention turn off.

Cosurfactants

The liquid detergents according to the invention 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

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, hydroxymixed ether sulfates, mono (sulfide) sulfate, monoglyl sulfate fatty acids, monoglyl sulfate fatty acids, monoglyl sulfate fatty acids, monoglyl sulfate fatty acids, monoglyl sulfate fatty acids, monoglyl sulfate fatty acids, monoglyl sulfate fatty acids, monoglyl sulfate fatty acids, monoglyl sulfate fatty acids, monoglyl sulfate fatty acids, monoglyl sulfate fatty acids, monoglyl sulfate fatty acids, monoglyl sulfate fatty acids, monoglyl sulfate fatty acids, monoglyl sulfate fatty acids, monoglyl sulfate fatty acids - 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 sulfates, protein fatty acid condensates (in particular vegetable products based on wheat) and alkyl (ether) phosphates , If the anionic surfactants contain polyglycol ether chains, they can have a conventional, but preferably a narrow, homolog distribution. 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 in which R ^{5 represents} a branched, but preferably linear alkyl radical having 10 to 18 carbon atoms, Ph a phenyl radical and X an alkali and / or alkaline earth metal, ammonium, alkylammonium, alkanolammonium or glucammonium. Of these, 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 frequently 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 in which 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. Typical examples of 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, aryl selenyl alcohol, elaidyl 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 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. In the case of branched primary alcohols, these are oxo alcohols, as are obtainable, for example, by converting carbon monoxide and hydrogen to alpha-olefins using the shop method. Such alcohol mixtures are commercially available under the trade names Dobanol® or Neodol®. Suitable alcohol mixtures are Dobanol 91®, 23®, 25®, 45®. Another possibility are oxo alcohols, such as those obtained by the classic Enichema or Condea oxo process by addition of carbon monoxide and hydrogen onto 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®.

Soaps are also to be understood as meaning fatty acid salts of the formula (IV) R ⁷ CO-OX in which R ⁷ CO represents a linear or branched, saturated or unsaturated acyl radical having 6 to 22 and preferably 12 to 18 carbon atoms and again X represents 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, linoleic acid, petol 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

Typical examples of nonionic surfactants are fatty alcohol polyglycol ethers, alkylphenol polyglycol ethers, fatty acid, fatty acid amide, fatty amine polyglycol ethers, alkoxylated triglycerides, mixed ethers and mixed formals, alk (en) yl oligoglycosides, fatty acid N-alkylglucamides, protein hydrolysates (in particular vegetable products based on wheat), polyol, Zuckerester, sorbitan esters , Polysorbates and amine oxides. If the nonionic surfactants contain polyglycol ether chains, these 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 in which 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 and 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 mol of ethylene and / or propylene oxide onto 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, linolyl 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 oxide onto technical coconut oil alcohols are particularly preferred.

Suitable alkoxylated fatty acid lower alkyl esters are surfactants of the formula (VI) R ¹⁰ CO- (OCH ₂ CHR ¹¹ ) _n2 OR ¹² in which 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 and n2 for numbers from 1 to 20 stands. Typical examples are the formal insert products of an average of 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, linoleic acid, linolenic acid, elaeostearic acid, arachidic acid, gadoleic acid, behenic acid, and technical grade mixtures 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. Conversion 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 in which 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 and p represents numbers from 1 to 10. They can be obtained according to the relevant procedures in preparative organic chemistry. As representative of the extensive literature, reference is made here to the documents EP 0301298 A1 and WO 90/03977 . 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 . The index number p in the general formula (VII) indicates the degree of oligomerization (DP), ie the distribution of mono- and oligoglycosides, and stands for a number between 1 and 10. While p must always be an integer in a given compound and especially here can assume the values p = 1 to 6, the value p for a certain alkyl oligoglycoside is an analytically determined arithmetic parameter, which usually represents a fractional number. Alkyl and / or alkenyl oligoglycosides with an average degree of oligomerization p of 1.1 to 3.0 are preferably used. From an application point of view, preference is given to those alkyl and / or alkenyl oligoglycosides whose degree of oligomerization is less than 1.7 and in particular between 1.2 and 1.4. The alkyl or. Alkenyl radical R ¹³ 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 C ₈ -C ₁₀ (DP = 1 to 3) are preferred, which are obtained as a preliminary step in the separation of technical C ₈ -C ₁₈ coconut fatty alcohol by distillation and with a proportion of less than 6% by weight of C ₁₂ - Alcohol can be contaminated and alkyl oligoglucosides based on technical C _9/11 oxo alcohols (DP = 1 to 3). 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

in der R¹⁴CO für einen Acylrest mit 6 bis 22 Kohlenstoffatomen, R¹⁵ und R¹⁶ unabhängig voneinander für Wasserstoff oder R¹⁴CO, R¹⁵ für einen Alkylrest mit 1 bis 4 Kohlenstoffatomen oder eine (CH₂CH₂O)_m4H-Gruppe, m1, m2 und m3 in Summe für 0 oder Zahlen von 1 bis 12, m4 für Zahlen von 1 bis 12 und Y für Halogenid, Alkylsulfat oder Alkylphosphat steht. Typische Beispiele für Esterquats, die im Sinne der Erfindung Verwendung finden können, sind Produkte auf Basis von Capronsäure, Caprylsäure, Caprinsäure, Laurinsäure, Myristinsäure, Palmitinsäure, Isostearinsäure, Stearinsäure, Ölsäure, Elaidinsäure, Arachinsäure, Behensäure und Erucasäure sowie deren technische Mischungen, wie sie beispielsweise bei der Druckspaltung natürlicher Fette und Öle anfallen. Vorzugsweise werden technische C_12/18-Kokosfettsäuren und insbesondere teilgehärtete C_16/18-Talg- bzw. Palmfettsäuren sowie elaidinsäurereiche C_16/18-Fettsäureschnitte eingesetzt. Zur Herstellung der quaternierten Ester können die Fettsäuren und das Triethanolamin im molaren Verhältnis von 1,1 : 1 bis 3 : 1 eingesetzt werden. Im Hinblick auf die anwendungstechnischen Eigenschaften der Esterquats hat sich ein Einsatzverhältnis von 1,2 : 1 bis 2,2 : 1, vorzugsweise 1,5 : 1 bis 1,9 : 1 als besonders vorteilhaft erwiesen. Die bevorzugten Esterquats stellen technische Mischungen von Mono-, Di- und Triestern mit einem durchschnittlichen Veresterungsgrad von 1,5 bis 1,9 dar und leiten sich von technischer C_16/18- Talg- bzw. Palmfettsäure (Iodzahl 0 bis 40) ab. Aus anwendungstechnischer Sicht haben sich quaternierte Fettsäuretriethanolaminestersalze der Formel (VIII) als besonders vorteilhaft erwiesen, in der R¹⁴CO für einen Acylrest mit 16 bis 18 Kohlenstoffatomen, R¹⁵ für R¹⁵CO, R¹⁶ für Wasserstoff, R¹⁷ für eine Methylgruppe, m1, m2 und m3 für 0 und Y für Methylsulfat steht. Typical examples of 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),

in which R ¹⁴ CO represents an acyl radical with 6 to 22 carbon atoms, R ¹⁵ and R ¹⁶ independently of one another for hydrogen or R ¹⁴ CO, R ^{15 represents} an alkyl radical with 1 to 4 carbon atoms or a (CH ₂ CH ₂ O) _m4 H- Group, m1, m2 and m3 in total for 0 or numbers from 1 to 12, m4 for numbers from 1 to 12 and Y for halide, alkyl sulfate or alkyl phosphate. Typical examples of ester quats which 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 high elaidic acid C _16/18 fatty acid cuts 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. With regard to the application properties of the ester quats, 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). From an application point of view, quaternized fatty acid triethanolamine ester salts of the formula (VIII) have proven to be 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.

in der R¹⁸CO für einen Acylrest mit 6 bis 22 Kohlenstoffatomen, R¹⁹ für Wasserstoff oder R¹⁸CO, R²⁰ und R²¹ unabhängig voneinander für Alkylreste mit 1 bis 4 Kohlenstoffatomen, m5 und m6 in Summe für 0 oder Zahlen von 1 bis 12 und Y wieder für Halogenid, Alkylsulfat oder Alkylphosphat steht.In addition to the quaternized fatty acid triethanolamine ester salts, quaternized ester salts of fatty acids with diethanolalkylamines of the formula (IX) may also be used as ester quats.

in which 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 and Y again represents halide, alkyl sulfate or alkyl phosphate.

in der R²²CO für einen Acylrest mit 6 bis 22 Kohlenstoffatomen, R²³ für Wasserstoff oder R²²CO, R²⁴, R²⁵ und R²⁶ unabhängig voneinander für Alkylreste mit 1 bis 4 Kohlenstoffatomen, m7 und m8 in Summe für 0 oder Zahlen von 1 bis 12 und X wieder für Halogenid, Alkylsulfat oder Alkylphosphat steht.Finally, the quaternized ester salts of fatty acids with 1,2-dihydroxypropyidialkylamines of the formula (X) should be mentioned as a further group of suitable ester quats,

in which 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 and X again represents halide, alkyl sulfate or alkyl phosphate.

in der R²⁷CO für einen Acylrest mit 6 bis 22 Kohlenstoffatomen, R²⁸ für Wasserstoff oder R²⁷CO, R²⁹ und R³⁰ unabhängig voneinander für Alkylreste mit 1 bis 4 Kohlenstoffatomen und Y wieder für Halogenid, Alkylsulfat oder Alkylphosphat steht. Derartige Amidesterquats sind beispielsweise unter der Marke Incroquat® (Croda) im Markt erhältlich.Finally, suitable ester quats are substances in which the ester bond is replaced by an amide bond and which preferably follow the formula (XI) based on diethylenetriamine,

in which R ²⁷ CO represents an acyl radical with 6 to 22 carbon atoms, R ²⁸ for hydrogen or R ²⁷ CO, R ²⁹ and R ³⁰ independently of one another for alkyl radicals with 1 to 4 carbon atoms and Y again for halide, alkyl sulfate or alkyl phosphate. Such amide ester quats are available on the market, for example, under the Incroquat® (Croda) brand.

Amphoteric or zwitterionic surfactants

in der R³¹ für Alkyl- und/oder Alkenylreste mit 6 bis 22 Kohlenstoffatomen, R³² für Wasserstoff oder Alkylreste mit 1 bis 4 Kohlenstoffatomen, R³³ für Alkylreste mit 1 bis 4 Kohlenstoffatomen, q1 für Zahlen von 1 bis 6 und Z für ein Alkali- und/oder Erdalkalimetall oder Ammonium steht. Typische Beispiele sind die Carboxymethylierungsprodukte von Hexylmethylamin, Hexyldimethylamin, Octyldimethylamin, Decyldimethylamin, Dodecylmethylamin, Dodecyldimethylamin, Dodecylethylmethylamin, C_12/14-Kokosalkyldimethylamin, Myristyldimethylamin, Cetyldimethylamin, Stearyldimethylamin, Stearylethylmethyl-amin, Oleyldimethylamin, C_16/18-Talgalkyldimethylamin sowie deren technische Gemische.Examples of suitable amphoteric or zwitterionic surfactants are alkyl betaines, alkyl amido betaines, aminopropionates, aminoglycinates, imidazolinium betaines and sulfobetaines. Examples of suitable alkyl betaines are the carboxyalkylation products of secondary and in particular tertiary amines which follow the formula (XII)

in which 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.

in der R³⁴CO für einen aliphatischen Acylrest mit 6 bis 22 Kohlenstoffatomen und 0 oder 1 bis 3 Doppelbindungen, R³⁵ für Wasserstoff oder Alkylreste mit 1 bis 4 Kohlenstoffatomen, R³⁶ für Alkylreste mit 1 bis 4 Kohlenstoffatomen, q2 für Zahlen von 1 bis 6, q3 für Zahlen von 1 bis 3 und Z wieder für ein Alkali- und/oder Erdalkalimetall oder Ammonium steht. Typische Beispiele sind Umsetzungsprodukte von Fettsäuren mit 6 bis 22 Kohlenstoffatomen, namentlich Capronsäure, Caprylsäure, Caprinsäure, Laurinsäure, Myristinsäure, Palmitinsäure, Palmoleinsäure, Stearinsäure, Isostearinsäure, Ölsäure, Elaidinsäure, Petroselinsäure, Linolsäure, Linolensäure, Elaeostearinsäure, Arachinsäure, Gadoleinsäure, Behensäure und Erucasäure sowie deren technische Gemische, mit N,N-Dimethylaminoethylamin, N,N-Dimethylaminopropylamin, N,N-Diethylaminoethylamin und N,N-Diethyl-aminopropylamin, die mit Natriumchloracetat kondensiert werden. Bevorzugt ist der Einsatz eines Kondensationsproduktes von C_8/18-Kokosfettsäure-N,N-dimethylaminopropylamid mit Natriumchloracetat.Carboxyalkylation products of amidoamines which follow the formula (XIII) are also suitable,

in which 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-diethylamino propylamine, 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 cyclizing condensation of 1 or 2 moles of fatty acid with polyhydric amines such as, for example, 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.

liquid detergent

The preparations according to the invention can of course be further 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. Under the term In this context, liquid detergents are both universal and special detergents including liquid detergents and color detergents.

Builder

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 the 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. The In addition to their builder effect, 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. In particular, citric acid, succinic acid, Glutaric acid, adipic acid, gluconic acid and any mixtures of these call.

Other suitable organic builder substances are 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 processes, for example acid-catalyzed or enzyme-catalyzed. They are preferably hydrolysis products with average molar masses in the range from 400 to 500,000. A polysaccharide with a dextrose equivalent (DE) in the range from 0.5 to 40, in particular from 2 to 30, is preferred, DE being a customary measure for the reducing effect of a polysaccharide compared to dextrose, which has a DE of 100. 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 as well as from 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. An oxidized oligosaccharide according to German patent application DE 19600018 A1 is also suitable . A product oxidized at C _{6 of} the saccharide ring can be particularly advantageous.

Other suitable cobuilders are oxydisuccinates and other derivatives of disuccinates, preferably ethylenediamine disuccinate. Also particularly preferred in this context are glycerol disuccinates and glycerol trisuccinates , as 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 from 3 to 15% by weight. Other useful 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 a maximum 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. Their 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. Also particularly preferred are 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 2 -Alkylallylsulfonic acid and sugar derivatives contain. Further preferred copolymers are those which are described in German patent applications DE 4303320 A1 and DE 4417734 A1 and which preferably have acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate as monomers. Also to be mentioned as further preferred builder substances are polymeric aminodicarboxylic acids, their salts or their precursor substances. Polyaspartic acids or their salts and derivatives are particularly preferred.

Other suitable builder substances are 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 their mixtures and from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.

Oil and fat dissolving substances

In addition, the agents can also contain components that make the oil and fat washable made of textiles. Among 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, the are particularly preferred sulfonated derivatives of phthalic acid and terephthalic acid polymers.

Bleaching agents and bleach activators

Among the compounds which serve as bleaching agents and supply H ₂ O ₂ in water, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance. Further bleaching agents that can be used are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H ₂ O ₂ -supplying 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. Suitable substances are those 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 tetraacetylethylenediamine (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, especially N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, especially n-nonanoyl- or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic acid anhydrides, especially phthalic anhydride, acylated polyhydric alcohols, especially triacetyloxy, 2,5-acetiacetyl, ethylene glycol 2,5-dihydrofuran and the enol esters known from German patent applications DE 19616693 A1 and DE 19616767 A1 as well as acetylated sorbitol and mannitol or their mixtures described in European patent application EP 0525239 A1 (SORMAN), acylated sugar derivatives, in particular pentaacetylglucose (PAG), pentaacetylfructose , Tetraacetylxylose and Octaacetyllactose as well as acetylated, optionally N-alkyl ized glucamine and gluconolactone, and / or N-acylated lactams, for example N-benzoylcaprolactam, which are known from international patent applications WO 94/27970, WO 94/28102, WO 94/28103, WO 95/00626, WO 95/14759 and WO 95 / 17498 are known. The 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. In addition to the conventional bleach activators listed above or in their place, 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 -Complexes, the manganese, iron, cobalt and copper complexes known from European patent EP 0392592 A1 and / or those described in European patent EP 0443651 B1 or European patent applications EP 0458397 A1, EP 0458398 A1, EP 0549271 A1 , EP 0549272 A1, EP 0544490 A1 and EP 0544519 A1 described manganese complexes. Combinations of bleach activators and transition metal bleach catalysts are known, for example, from German patent application DE 19613103 A1 and international patent application WO 95/27775 . 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 and enzyme stabilizers

Enzymes in particular come from the class of hydrolases, such as proteases, Esterases, lipases or lipolytic enzymes, amylases, cellulases or others Glycosyl hydrolases and mixtures of the enzymes mentioned in question. All of these hydrolases contribute to the removal of stains in the laundry, such as those containing protein, fat or starch Stains, and graying. Cellulases and other glycosyl hydrolases can by removing pilling and microfibrils for color retention and enhancement contribute to the softness of the textile. For bleaching or to inhibit color transfer can also be used oxidoreductases. Bacterial strains are particularly suitable or fungi such as Bacillus subtilis, Bacillus licheniformis, Streptomyces griseus and Humicola insolens obtained enzymatic agents. Proteases are preferred of the subtilisin type and in particular proteases obtained from Bacillus lentus, used. Enzyme mixtures, for example of protease and amylase or Protease and lipase or lipolytic enzymes or protease and cellulase or from cellulase and lipase or lipolytically active enzymes or from protease, amylase and lipase or lipolytic enzymes or protease, lipase or lipolytic 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 too or oxidases have been found to be suitable in some cases. To the appropriate ones Amylases include in particular α-amylases, iso-amylases, pullulanases and pectinases. Cellobiohydrolases, endoglucanases and β-glucosidases are preferably used as cellulases, which are also called cellobiases, or mixtures of these are used. Because the different cellulase types are characterized by their CMCase and Avicelase activities can differentiate, by targeted mixtures of the cellulases the desired activities can be set. The enzymes can be adsorbed on carrier substances and / or in coating substances embedded to protect them against premature decomposition. The share of Enzymes, enzyme mixtures or enzyme granules can, for example, about 0.1 to 5 wt .-%, preferably 0.1 to about 2% by weight.

In addition to the mono- and polyfunctional alcohols, 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. 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 (H ₃ BO ₃ ), metaboric acid (HBO ₂ ) and pyrobic acid (tetraboric acid H ₂ B ₄ O ₇ ), is particularly advantageous.

graying

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 etc. Cellulose ethers such as carboxymethyl cellulose (Na 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. In color detergents, the use of polyvinylpyrrolidone or equivalent has been found PVP copolymers have been proven to avoid color transfer. Here The combination with hydroxy mixed ethers as a surfactant component has another advantage because the color transfer is particularly effectively inhibited.

Optical brighteners

As optical brighteners, the agents can contain derivatives of diaminostilbenedisulfonic acid or its alkali metal salts. 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 present in customary amounts, for example between 0.1 and 0.5% by weight, preferably between 0.1 and 0.3% by weight, and also 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).

polymers

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 approximately 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 about 65:35 to about 90:10, preferably from about 70:30 to 80:20 preferred are those polymers which link polyethylene glycol units with a Molecular weight from 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).

hydrotropes

Glycerin;

Alkylenglycole, wie beispielsweise Ethylenglycol, Diethylenglycol, Propylenglycol, Butylenglycol, Hexylenglycol sowie Polyethylenglycole mit einem durchschnittlichen Molekulargewicht von 100 bis 1.000 Dalton;

technische Oligoglyceringemische mit einem Eigenkondensationsgrad von 1,5 bis 10 wie etwa technische Diglyceringemische mit einem Diglyceringehalt von 40 bis 50 Gew.-%;

Methyolverbindungen, wie insbesondere Trimethylolethan, Trimethylolpropan, Trimethylolbutan, Pentaerythrit und Dipentaerythrit;

Niedrigalkylglucoside, insbesondere solche mit 1 bis 8 Kohlenstoffen im Alkylrest, wie beispielsweise Methyl- und Butylglucosid;

Zuckeralkohole mit 5 bis 12 Kohlenstoffatomen, wie beispielsweise Sorbit oder Mannit,

Zucker mit 5 bis 12 Kohlenstoffatomen, wie beispielsweise Glucose oder Saccharose;

Aminozucker, wie beispielsweise Glucamin;

Dialkoholamine, wie Diethanolamin oder 2-Amino-1,3-propandiol.

Hydrotropes such as ethanol, isopropyl alcohol or polyols can also be used to improve the flow behavior. Polyols that come into consideration here preferably have 2 to 15 carbon atoms and at least two hydroxyl groups. The polyols can also contain further functional groups, in particular amino groups, or be modified with nitrogen. Typical examples are

glycerol;

Alkylene glycols, such as, for example, ethylene glycol, diethylene glycol, propylene glycol, butylene glycol, hexylene glycol and polyethylene glycols with an average molecular weight of 100 to 1,000 daltons;

technical oligoglycerol mixtures with a degree of self-condensation of 1.5 to 10 such as technical diglycerol mixtures with a diglycerol content of 40 to 50% by weight;

Methyl compounds, such as in particular trimethylolethane, trimethylolpropane, trimethylolbutane, pentaerythritol and dipentaerythritol;

Lower alkyl glucosides, especially those with 1 to 8 carbons in the alkyl radical, such as methyl and butyl glucoside;

Sugar alcohols with 5 to 12 carbon atoms, such as sorbitol or mannitol,

Sugars with 5 to 12 carbon atoms, such as glucose or sucrose;

Aminosugars such as glucamine;

Dialcohol amines, such as diethanolamine or 2-amino-1,3-propanediol.

fragrances

As perfume oils or fragrances, individual 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 methylphenyl glycinate, 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 Jonone, α-isomethylionon and methylcedrylketone, to the alcohols anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and terpineol, the hydrocarbons mainly include terpenes such as limonene and pinene. However, mixtures of different odoriferous substances are preferably used create an appealing fragrance together. Such perfume oils can also be natural Fragrance mixtures contain, as are available from plant sources, e.g. pine, Citrus, jasmine, patchouly, rose or ylang-ylang oil. Also suitable are muscatel, 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 inventive 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. As such Carrier materials have proven themselves, for example, cyclodextrins, the cyclodextrin-perfume complexes can also be coated with other auxiliaries.

Inorganic salts

Other 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; In particular, 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.

Examples

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 assessment was carried out photometrically on a washable (WA) and a cosmetic (KA) mixed soiling against a white standard (= 100% remission). The dissolving behavior was determined indirectly by determining the viscosity when diluting the preparations with water. It was assumed that high viscosity over a wide range of dilution is synonymous with slow dissolution during the wash cycle. For this purpose, 50 ml of liquid detergent were gradually diluted with 5, 10 and 25 ml of water with constant stirring and the Brookfield viscosity (20 ° C., 10 rpm) was determined. The composition of the agents and the application results are summarized in Table 1. Examples 1 to 8 are according to the invention, examples V1 to V6 are used for comparison. Washability and viscosity (quantities as% by weight) composition V1 1 2 V2 3 V3 4 C ₁₂ -C ₁₈ coconut alcohol + 7EO 25 17 12 - - - - C ₁₁ -C ₁₃ oxo alcohol + 7EO - - - 20 12 20 7 HME I - 8th - - - - 13 HME II - - 13 - 8th - - cocoalkyl oligoglucoside 4 4 4 - - - - C ₁₂ -C ₁₈ coconut fatty acid Na salt 14 14 14 14 14 14 14 Dodecylbenzenesulfonate Na salt 4 4 4 - - 10 10 C ₁₁ -C ₁₃ paraffin sulfonate Na salt - - - 11 11 - - sodium citrate 5 5 5 5 5 5 5 ethanol 5 5 5 5 5 5 5 propylene glycol 4 4 4 4 4 4 4 water ad 100 Washing power [% remission] - full wash (WA) 65 70 67 62 66 66 68 - full laundry (KA) 70 75 74 68 75 70 77 Viscosity [mPas] - 5 ml 500 400 300 - 10 ml 2000 1200 1800 - 25 ml > 2000 900 1000 continuation
Washability and viscosity (quantities as% by weight) composition V4 5 6 V5 7 V6 8th C ₁₂ -C ₁₈ coconut alcohol + 7EO 18 16 14 - - 14 - C ₁₁ -C ₁₃ oxo alcohol + 7EO - - - 18 14 - - HME I - 2 2 - 4 - 14 HME II - - 2 - - - - cocoalkyl oligoglucoside - - - - - - - - 4 4 C ₁₂ -C ₁₈ coconut fatty acid Na salt 4 4 4 4 4 4 4 Dodecylbenzenesulfonate Na salt 2 2 2 4 4 4 4 C ₁₂ -C ₁₄ coconut fatty alcohol + 2EO sulfate Na salt 6 6 6 4 4 4 4 sodium citrate 5 5 5 5 5 5 5 ethanol 2 2 2 2 2 2 2 propylene glycol 4 4 4 4 4 4 4 water ad 100 Washing power [% remission] - Delicates (WA) 55 63 60 52 55 57 63 - Delicates (KA) 60 67 63 60 65 64 70 Viscosity [mPas] - 5 ml 400 300 - 10 ml 1500 700 - 25 ml 1800 500

Claims (10)

Liquid detergents containing hydroxy mixed ethers. Agents according to claim 1, characterized in that they contain hydroxy mixed ethers of the formula (I) .

in which R ^{1 is} a linear or branched alkyl radical having 2 to 18 carbon atoms, R ^{2 is} hydrogen or a linear or branched alkyl radical is 2 to 18 carbon atoms, R ^{3 is} hydrogen or methyl, R ^{4 is} a linear or branched, alkyl and / or alkenyl radical with 1 to 22 carbon atoms and n stands for numbers from 1 to 50, with the proviso that the sum of the carbon atoms in the radicals R ¹ and R ^{2 is} at least 6. Agents according to claims 1 and / or 2, characterized in that they contain the hydroxy mixed ethers in amounts of 1 to 60 wt .-% - based on the agent. Agents according to at least one of claims 1 to 3, characterized in that they further contain anionic, nonionic, cationic and or amphoteric or zwitterionic co-surfactants. Agents according to claim 4, characterized in that they contain co-surfactants selected from the group consisting of alkylbenzenesulfonates, alkylsulfates, soaps, alkanesulfonates, paraffinsulfonates, methyl estersulfonates, fatty alcohol polyglycol ethers, alkoxylated fatty acid lower alkyl esters, alkyl oligoglucosides, esterquats and betaine quats. Agents according to claims 4 and / or 5, characterized in that they contain the co-surfactants in amounts of 1 to 40 wt .-%. Agents according to at least one of claims 1 to 6, characterized in that they further contain customary auxiliaries and additives. Agent according to claim 7, characterized in that they contain the further auxiliaries and additives in amounts of 1 to 25 wt .-%. Agent according to at least one of Claims 1 to 8, characterized in that it has a water content in the range from 25 to 75% by weight. Use of hydroxy mixed ethers as nonionic surfactants for the production of Liquid detergents.