EP1240290B1 - Tenside granules with improved disintegration rate - Google Patents

Description

Field of the invention

The invention is in the field of solid washing, rinsing and cleaning agents and relates new surfactant granules, which are characterized by an improved dissolution rate, a method for their production and their use.

State of the art

For the preparation of solid detergents, dishwashing detergents and cleaners, preference is given today to surfactants used in granular, practically anhydrous form. To produce such forms of offer the most diverse methods proved to be suitable. Common is the in-store Surfactant granules, however, that they have an insufficient dissolution rate in particular in cold water. Detergent tablets, for example based on alkyl sulfate or Alkylglucosidgranulaten can be prepared for this reason, despite the concomitant use of considerable quantities of disintegrants are not used directly in the dispensing chamber of the washing machine, but must be added directly to the wash liquor.

Document WO-A-9 936 493 discloses surfactant granules with improved dissolution rate, the nonionic surfactants, such as. ethoxylated alcohols, disintegrants and possibly contain further ingredients. Such surfactant granules can be added to a detergent granule.

The object of the present invention has thus been to provide surfactant granules available which decompose particularly rapidly on contact with cold water without formation of a gel phase, so that the disadvantages of the prior art are reliably overcome.

Description of the invention

The invention relates to surfactant granules with improved dissolution rate, the one obtained by mixing nonionic surfactants of the type of hydroxy mixed ether in the presence of disintegrants granulated and compacted.

Surprisingly, it has been found that the granules of the invention are not only excellent Washing and cleaning performance, but also on a significantly improved Dissolution speed, in particular their use for the production of such Detergent tablets possible, which meters directly through the dispensing compartment of the washing machines can be. The concomitant use of other disintegrants is in the production of such Tablets often no longer required. Compared to the conventional granules in which one to speak of "solving" the product, the description "decay" is more applicable here. The Surfactant is thus released very quickly and can be active. In a preferred embodiment of the invention, the hydroxy mixed ethers, together with other anionic, nonionic, cationic and / or amphoteric or zwitterionic surfactants used.

Another object of the present invention relates to a process for the preparation of surfactant granules with improved dissolution rate, in which nonionic surfactants of the Hydroxymischether granulated and compacted in the presence of disintegrants.

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 6 bis 22, vorzugsweise 12 bis 18 Kohlenstoffatomen 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 4 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. Gleichfalls kann der polare Teil des Moleküls eine Polyethylenglycol- oder eine Polypropylenglycolkette sein; ebenfalls geeignet sind gemischte Ketten von PE- und PP-Einheiten, sei es in statistischer oder Blockverteilung. Typische Beispiele sind Ringöffnungsprodukte von 1,2-Hexenepoxid, 2,3-Hexen-epoxid, 1,2-Octenepoxid, 2,3-Ocetenepoxid, 3,4-Octenepoxid, 1,2-Decenepoxid, 2,3-Decenepoxid, 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-Tetradecen-epoxid, 4,5-Tetradecenepoxid, 5,6-Tetradecenepoxid, 6,7-Tetradecenepoxid, 1,2-Hexadecenepoxid, 2,3-Hexadecenepoxid, 3,4-Hexadecenepoxid, 4,5-Hexadecenepoxid, 5,6-Hexadecenepoxid, 6,7-Hexa-decenepoxid, 7,8-Hexadecenepoxid, 1,2-Octadecenepoxid, 2,3-Octadecenepoxid, 3,4-Octadecen-epoxid, 4,5-Octadecenepoxid, 5,6-Octadecenepoxid, 6,7-Octadecenepoxid, 7,8-Octadecenepoxid und 8,9-Octadecenepoxid sowie deren Gemische mit Anlagerungsprodukten von durchschnittlich 1 bis 50, vorzugsweise 2 bis 25 und insbesondere 5 bis 15 Mol Ethylenoxid und/oder 1 bis 10, vorzugsweise 2 bis 8 und insbesondere 3 bis 5 Mol Propylenoxid an gesättigte und/oder ungesättigte primäre Alkohole mit 6 bis 22, vorzugsweise 12 bis 18 Kohlenstoffatomen, wie z.B. Capronalkohol, Caprylalkohol, 2-Ethylhexylalkohol, Caprinalkohol, Laurylalkohol, Isotridecylalkohol, Myristylalkohol, Cetylalkohol, Palmoleylalkohol, Stearylalkohol, Isostearylalkohol, Oleylalkohol, Elaidylalkohol, Petroselinylalkohol, Linolylalkohol, Linolenylalkohol, Elaeostearylalkohol, Arachylalkohol, Gadoleylalkohol, Behenylalkohol, Erucylalkohol und Brassidylalkohol sowie deren technische Mischungen. Üblicherweise sind die HME in den Formkörpem in Mengen von 0,1 bis 20, vorzugsweise 0,5 bis 8 und insbesondere 3 bis 5 Gew.-% enthaltenHydroxy mixed ethers (HME) are known non-ionic surfactants having unsymmetrical ether structure and polyalkylene glycol moieties which are obtained, for example, by subjecting olefin epoxides to a ring opening reaction with fatty alcohol polyglycol ethers. Corresponding products and their use in the area of hard surface cleaning are the subject of, for example, European Patent EP 0693049 B1 and international patent application WO 94/22800 (Olin) and the publications cited therein . The hydroxy mixed ethers of the general formula (I) typically follow

in the R ^{1 is} a linear or branched alkyl radical having 2 to 18, preferably 10 to 16 carbon atoms, R ^{2 is} hydrogen or a linear or branched alkyl radical having 2 to 18 carbon atoms, R ^{3 is} hydrogen or methyl, R ^{4 is} a linear or branched, alkyl and / or alkenyl radical having 6 to 22, preferably 12 to 18 carbon atoms and n is from 1 to 50, preferably 2 to 25 and especially 5 to 15, with the proviso that the sum of the carbon atoms in the radicals R ¹ and R ^{2 is} at least 4 and preferably 12 to 18. As can be seen from the formula, the HME ring opening products may be both internal olefins (R ² not hydrogen) or terminal olefins (R ² hydrogen), the latter being preferred for ease of preparation and more advantageous performance properties. Likewise, the polar portion of the molecule may be a polyethylene glycol or a polypropylene glycol chain; Also suitable are mixed chains of PE and PP units, whether in statistical or block distribution. Typical examples are ring-opening products of 1,2-hexene epoxide, 2,3-hexene-epoxide, 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-tetradecenepoxide, 2,3 -Tetradecenepoxide, 3,4-tetradecene-epoxide, 4,5-tetradecenepoxide, 5,6-tetradecenepoxide, 6,7-tetradecenepoxide, 1,2-hexadecenepoxide, 2,3-hexadecenepoxide, 3,4-hexadecenepoxide, 4,5 Hexadecene epoxide, 5,6-hexadecene epoxide, 6,7-hexa-decene epoxide, 7,8-hexadecene epoxide, 1,2-octadecene epoxide, 2,3-octadecene epoxide, 3,4-octadecene epoxide, 4,5-octadecene epoxide, 5 , 6-Octadecenepoxid, 6,7-Octadecenepoxid, 7,8-Octadecenepoxid and 8,9-Octadecenepoxid and mixtures thereof with addition products of on average 1 to 50, preferably 2 to 25 and especially 5 to 15 moles of ethylene oxide and / or 1 to 10 , preferably 2 to 8 and especially 3 to 5 moles of propylene oxide to saturated and / or u N-saturated primary alcohols having 6 to 22, preferably 12 to 18 carbon atoms, such as caproic 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 and their technical mixtures. Usually, the HME in the Formkörpem in amounts of 0.1 to 20, preferably 0.5 to 8 and especially 3 to 5 wt .-% contained

Cosurfactants

Typical examples of anionic surfactants are soaps, alkylbenzenesulfonates, alkanesulfonates, olefinsulfonates, alkyl ether sulfonates, glycerol ether sulfonates, α-methyl ester sulfonates, sulfo fatty acids, alkyl sulfates, fatty alcohol ether sulfates, glycerol ether sulfates, hydroxy mixed ether sulfates, monoglyceride (ether) sulfates, fatty acid amide (ether) sulfates, mono- and dialkyl sulfosuccinates, Mono- and dialkylsulfosuccinamates, sulfotriglycerides, amide soaps, ether carboxylic acids and their salts, fatty acid isethionates, fatty acid sarcosinates, fatty acid taurides, N-acyl amino acids such as acyl lactylates, acyl tartrates, acyl glutamates and acylaspartates, alkyl oligoglucoside sulfates, protein fatty acid condensates (especially wheat-based vegetable products) and alkyl (ether) phosphates. If the anionic surfactants contain polyglycol ether chains, these may have a conventional, but preferably a narrow homolog distribution. Preference is given to using alkylbenzenesulfonates, alkyl sulfates, soaps, alkanesulfonates, olefinsulfonates, methyl ester sulfonates and mixtures thereof.

Preferred alkylbenzenesulfonates preferably follow the formula (II) , R ⁵ -Ph-SO ₃ X (II)

in which R ^{5 is} a branched, but preferably linear, alkyl radical having 10 to 18 carbon atoms, Ph is a phenyl radical and X is an alkali and / or alkaline earth metal, ammonium, alkylammonium, alkanolammonium or glucammonium. Especially suitable of these are dodecylbenzenesulfonates, tetradecylbenzenesulfonates, hexadecylbenzenesulfonates and their technical mixtures in the form of the sodium salts.

Alkyl and / or alkenyl sulfates, which are also frequently referred to as fatty alcohol sulfates, are the sulfation products of primary and / or secondary alcohols which preferably follow the formula (III) , R ⁶ O-SO ₃ X (III) in which R ^{6 is} a linear or branched, aliphatic alkyl and / or alkenyl radical having 6 to 22, preferably 12 to 18 carbon atoms and X is an alkali and / or alkaline earth metal, ammonium, alkylammonium, alkanolammonium or glucammonium. Typical examples of alkyl sulfates which can be used according to the invention are the sulfation products of caproic alcohol, caprylic alcohol, capric alcohol, 2-ethylhexyl alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, arachyl alcohol, gadoleyl alcohol, Behenyl alcohol and erucyl alcohol and their technical mixtures obtained by high-pressure hydrogenation of technical methyl ester fractions or aldehydes from Roelen's oxo synthesis. The sulfation products can preferably be used in the form of their alkali metal salts and in particular their sodium salts. Particular preference is given to 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. In the case of branched primary alcohols are oxo alcohols, as they are accessible, for example, by reacting carbon monoxide and hydrogen to alpha-olefins by 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®. Another possibility are oxo alcohols, as obtained by the classical oxo process of Enichema or the Condea by addition of carbon monoxide and hydrogen to olefins. These alcohol mixtures are a mixture of highly branched alcohols. Such alcohol mixtures are commercially available under the trade name Lial®. Suitable alcohol mixtures are Lial 91®, 111®, 123®, 125®, 145®.

Under soaps are finally fatty acid salts of the formula (IV) to understand R ⁷ CO-OX (IV) in which 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 in turn X is alkali metal and / or alkaline earth metal, ammonium, alkylammonium or alkanolammonium. Typical examples are the sodium, potassium, magnesium, ammonium and triethanolammonium salts of caproic, caprylic, 2-ethylhexanoic, capric, lauric, isotridecanoic, myristic, palmitic, palmitic, stearic, isostearic, oleic, elaidic, petroselic, linoleic, Linolenic acid, elaeostearic acid, arachidic acid, gadoleic acid, behenic acid and erucic acid and their technical mixtures. Preferably, coconut or palm kernel fatty acids are used in the form of their sodium or potassium salts.

Typical examples of nonionic surfactants are fatty alcohol polyglycol ethers, alkylphenol polyglycol ethers, fatty acid polyglycol ethers, fatty acid amide polyglycol ethers, fatty amine polyglycol ethers, alkoxylated triglycerides, mixed ethers, alk (en) yloligoglycosides, fatty acid N-alkylglucamides, protein hydrolysates (especially wheat-based vegetable products), polyol fatty acid esters, sugar esters, sorbitan esters , Polysorbates and amine oxides. If the nonionic surfactants contain polyglycol ether chains, these may have a conventional, but preferably a narrow homolog distribution. Preference is given to using fatty alcohol polyglycol ethers, alkoxylated fatty acid lower alkyl esters or alkyl oligoglucosides.

The preferred fatty alcohol polyglycol ethers follow the formula (V) , R ⁸ O (CH ₂ CHR ⁹ O) _{n 1} H (V) in which R ^{8 is} a linear or branched alkyl and / or alkenyl radical having 6 to 22, preferably 12 to 18 carbon atoms, R ^{9 is} hydrogen or methyl and n 1 is a number from 1 to 20. Typical examples are the addition products of on average 1 to 20 and preferably 5 to 10 moles of ethylene and / or propylene oxide to caproic 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 , Petroselinylalkohol, Linolylalkohol, Linolenylalkohol, Elaeostearylalkohol, Arachylalkohol, Gadoleylalkohol, Behenylalkohol, Erucylalkohol and Brassidylalkohol as well as their technical mixtures. Particularly preferred are addition products of 3, 5 or 7 moles of ethylene oxide to technical Kokosfettalkohole.

Suitable alkoxylated fatty acid lower alkyl esters are surfactants of the formula (VI) , R ¹⁰ CO (OCH ₂ CHR ¹¹⁾ _{n 2} OR ¹² (VI) in the R ¹⁰ CO for a linear or branched, saturated and / or unsaturated acyl radical having 6 to 22 carbon atoms, R ¹¹ for hydrogen or methyl, R ¹² for linear or branched alkyl radicals having 1 to 4 carbon atoms and n 2 for numbers from 1 to 20 stands. Typical examples are the formal charge 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, palmitoleic acid, stearic acid, isostearic acid, oleic acid, elaidic acid, petroselinic acid, linoleic acid, linolenic acid, elaeostearic acid, arachidic acid, gadoleic acid, behenic acid and erucic acid, and technical mixtures thereof. Usually, the products are prepared by insertion of the alkylene oxides into the carbonyl ester bond in the presence of special catalysts, such as, for example, calcined hydrotalcite. Particularly preferred are reaction products of on average 5 to 10 moles of ethylene oxide in the ester bond of technical Kokosfettsäuremethylestem.

Alkyl and alkenyl oligoglycosides, which are also preferred nonionic surfactants, usually follow the formula (VII) , R ¹³ O- [G] _p (VII) in which R ^{13 is} an alkyl and / or alkenyl radical having 4 to 22 carbon atoms, G is a sugar radical having 5 or 6 carbon atoms and p is a number from 1 to 10. They can be obtained by the relevant methods of preparative organic chemistry. Representative of the extensive literature reference should be made here to the documents EP-A1 0301298 and WO 90/03977 . The alkyl and / or alkenyl oligoglycosides can be derived from aldoses or ketoses having 5 or 6 carbon atoms, preferably glucose. The preferred alkyl and / or Alkenyloligoglykoside are thus alkyl and / or Alkenyloligo glucoside . The index number p in the general formula ( VII ) indicates the degree of oligomerization (DP), ie the distribution of monoglycerides and oligoglycosides, and stands for a number between 1 and 10. While p in a given compound must always be an integer, and here especially If p = 1 to 6 can be assumed, the value p for a given alkyloligoglycoside is an analytically determined arithmetic quantity, which usually represents a fractional number.

Preference is given to using alkyl and / or alkenyl oligoglycosides having an average degree of oligomerization p of from 1.1 to 3.0. From an application point of view, those alkyl and / or alkenyl oligoglycosides whose degree of oligomerization is less than 1.7 and in particular between 1.2 and 1.4 are preferred. 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, caproic alcohol, caprylic alcohol, capric alcohol and undecyl alcohol and technical mixtures thereof, as obtained, for example, in the hydrogenation of technical fatty acid methyl esters or in the hydrogenation of aldehydes from Roelen's oxo synthesis. Preference is given to alkyl oligoglucosides of the chain length C ₈ -C ₁₀ (DP = 1 to 3) which are obtained as a feedstock in the distillative separation of technical C ₈ -C ₁₈ coconut fatty alcohol and in a proportion of less than 6% by weight C ₁₂ - Alcohol may be contaminated as well as alkyl oligoglucosides based on technical C _9/11 oxo alcohols (DP = 1 to 3). The alkyl or alkenyl radical R ¹³ can furthermore 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 technical mixtures thereof which can be obtained as described above. Preference is given to alkyl oligoglucosides based on hydrogenated C _12/14 coconut alcohol having a DP of 1 to 3.

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 Triestem mit einem durchschnittlichen Veresterungsgrad von 1,5 bis 1,9 dar und leiten sich von technischer C_16/18- Talg- bzw. Palmfettsäure (lodzahl 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, dimethyl distearyl ammonium chloride or hydroxyethyl hydroxycetyl dimmonium chloride (Dehyquart E) or esterquats. These are, for example, quaternized fatty acid triethanolamine ester salts of the formula (VIII)

in the R ¹⁴ CO for an acyl radical having 6 to 22 carbon atoms, R ¹⁵ and R ¹⁶ are each independently hydrogen or R ¹⁴ CO, R ^{15 is} an alkyl radical having 1 to 4 carbon atoms or a (CH ₂ CH ₂ O) _m4 H Group, m1, m2 and m3 are in total 0 or numbers from 1 to 12, m4 is numbers from 1 to 12 and Y is halide, alkylsulfate or alkyl phosphate. Typical examples of esterquats 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, arachidic 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. It is preferred to use technical C _12/18 coconut _fatty acids and, in particular, partially hydrogenated C _16/18 tallow or palm oil fatty acids and also high-acid C _16/18 fatty acid cuts having high elaidic acid content. To prepare the quaternized esters, the fatty acids and the triethanolamine in a molar ratio of 1.1: 1 to 3: 1 can be used. In view of the performance properties of the esterquats, an employment 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 oil 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 is an acyl radical having 16 to 18 carbon atoms, R ^{15 is} R ¹⁵ CO, R ^{16 is} hydrogen, R ^{17 is} a methyl group, m1 , m2 and m3 are 0 and Y is methylsulfate.

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) are also suitable as esterquats.

in the R ¹⁸ CO for an acyl radical having 6 to 22 carbon atoms, R ^{19 is} hydrogen or R ¹⁸ CO, R ²⁰ and R ^{21 are} independently alkyl radicals having 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-dihydroxypropyldialkylamines of the formula (X) should be mentioned as a further group of suitable esterquats.

in the R ²² CO for an acyl radical having 6 to 22 carbon atoms, R ^{23 is} hydrogen or R ²² CO, R ²⁴ , R ²⁵ and R ^{26 are} independently alkyl radicals having 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, other suitable esterquats are substances in which the ester is replaced by an amide bond and which preferably follow the formula ( XI ) based on diethylenetriamine,

in which R ^{27 is} CO for an acyl radical having 6 to 22 carbon atoms, R ^{28 is} hydrogen or R ²⁷ CO, R ²⁹ and R ^{30 are} independently alkyl radicals having 1 to 4 carbon atoms and Y is again halide, alkyl sulfate or alkyl phosphate. Such Amidesterquats are available for example under the brand Incroquat® (Croda) in the market.

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, Stearylethylmethylamin, Oleyldimethylamin, C_16/18-Talgalkyldimethylamin sowie deren technische Gemische.Examples of suitable amphoteric or zwitterionic surfactants are alkylbetaines, alkylamidobetaines, aminopropionates, aminoglycinates, imidazolinium betaines and sulfobetaines. Examples of suitable alkylbetaines are the carboxyalkylation products of secondary and in particular tertiary amines which follow the formula (XII) ,

R ^{31 is} alkyl and / or alkenyl radicals having from 6 to 22 carbon atoms, R ^{32 is} hydrogen or alkyl radicals having from 1 to 4 carbon atoms, R ^{33 is} alkyl radicals having from 1 to 4 carbon atoms, q 1 is from 1 to 6, and Z is from 1 to 6 Alkali and / or alkaline earth metal or ammonium. Typical examples are the carboxymethylation products of hexylmethylamine, hexyldimethylamine, octyldimethylamine, decyldimethylamine, dodecylmethylamine, dodecyldimethylamine, dodecylethylmethylamine, C _12/14 cocoalkyldimethylamine, myristyldimethylamine, cetyldimethylamine, stearyldimethylamine, stearylethylmethylamine, oleyldimethylamine, C _16/18 tallowalkyldimethylamine, 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-Diethylaminopropylamin, die mit Natriumchloracetat kondensiert werden. Bevorzugt ist der Einsatz eines Kondensationsproduktes von C_8/18-Kokosfettsäure-N,N-dime-thylaminopropylamid mit Natriumchloracetat.Also suitable are carboxyalkylation products of amidoamines which follow the formula (XIII) ,

in the R ³⁴ CO is an aliphatic acyl radical having 6 to 22 carbon atoms and 0 or 1 to 3 double bonds, R ^{35 is} hydrogen or alkyl radicals having 1 to 4 carbon atoms, R ^{36 is} alkyl radicals having 1 to 4 carbon atoms, q 2 is from 1 to 4 6, q3 represents 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 having 6 to 22 carbon atoms, namely caproic, caprylic, capric, lauric, myristic, palmitic, palmitic, stearic, isostearic, oleic, elaidic, petroselic, linoleic, linolenic, elaeostearic, arachidic, gadoleic, behenic and erucic acids and their technical mixtures, with N, N-dimethylaminoethylamine, N, N-dimethylaminopropylamine, N, N-diethylaminoethylamine and N, N-diethylaminopropylamine, which are condensed with sodium chloroacetate. The use of a condensation product of C _8/18 coconut fatty acid N, N-dimethylaminopropylamide with sodium chloroacetate is preferred.

Furthermore, 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 diethylenetriamine. The corresponding carboxyalkylation products are mixtures of different open-chain betaines. Typical examples are condensation products of the abovementioned 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.

If hydroxy mixed ethers are used together with one or more of said cosurfactants, so it is recommended that these in a weight ratio of 1: 10 to 10: 1, preferably 1: 5 to 5: 1 and in particular 1: 2 to 2: 1 use. The surfactants can be used both as aqueous pastes with Solid contents (= active substance contents) of, for example, 1 to 60, preferably 5 to 50 and in particular 15 to 35 wt .-% or as dry solids or melts with residual water contents of typically less than 10 and preferably less than 5 wt .-% used. become.

explosives

The term disintegrants means substances which are contained in the surfactant granules in order to accelerate their disintegration on contact with water. Overviews can be found, for example, in J. Pharm. Sci. 61 (1972), Römpp Chemilexikon, 9th edition, Volume 6, page 4440 and Voigt "textbook of pharmaceutical technology " (6th edition, 1987, pp. 182-184). These substances increase their volume when water enters, whereby on the one hand increases the intrinsic volume (swelling), on the other hand, on the release of gases, a pressure can be generated, which can disintegrate the tablet into smaller particles. Well-known disintegration aids are, for example, carbonate / citric acid systems, although other organic acids can also be used. Swelling disintegration aids are, for example, synthetic polymers such as polyvinylpyrrolidone (PVP) or natural polymers or modified natural substances such as cellulose and starch and their derivatives, alginates or casein derivatives. Disintegrating agents based on cellulose are used as preferred disintegrating agents in the context of the present invention. Pure cellulose has the formal gross composition (C ₆ H ₁₀ O ₅ ) _n and is formally a β-1,4-polyacetal of cellobiose, which in turn is composed of two molecules of glucose. Suitable celluloses consist of about 500 to 5000 glucose units and therefore have average molecular weights of 50,000 to 500,000. Cellulose-based disintegrating agents which can be used in the context of the present invention are also cellulose derivatives obtainable by polymer-analogous reactions of cellulose. Such chemically modified celluloses include, for example, products of esterifications or etherifications in which hydroxy hydrogen atoms have been substituted. However, celluloses in which the hydroxyl groups have been replaced by functional groups which are not bonded via an oxygen atom can also be used as cellulose derivatives. The group of cellulose derivatives includes, for example, alkali metal celluloses, carboxymethylcellulose (CMC), cellulose esters and ethers, and aminocelluloses. The said cellulose derivatives are preferably not used alone as disintegrating agents based on cellulose, but used in admixture with cellulose. The content of these mixtures of cellulose derivatives is preferably below 50% by weight, particularly preferably below 20% by weight, based on the cellulose-based disintegrating agent. It is particularly preferred to use cellulose-based disintegrating agent which is free of cellulose derivatives. As a further disintegrating agent based on cellulose or as a component of this component, microcrystalline cellulose can be used. This microcrystalline cellulose is obtained by partial hydrolysis of celluloses under conditions which attack and completely dissolve only the amorphous regions (about 30% of the total cellulose mass) of the celluloses, leaving the crystalline regions (about 70%) intact. Subsequent deaggregation of the microfine celluloses produced by the hydrolysis yields the microcrystalline celluloses which have primary particle sizes of about 5 μm and, for example, can be compacted into granules having an average particle size of 200 μm. The disintegrating agents can be homogeneously distributed macroscopically in the molded body, but microscopically they form zones of increased concentration due to their production. Disintegrants which may be added according to the invention, such as Kollidon, alginic acid and their alkali metal salts, amorphous or partially crystalline layered silicates (bentonites), polyacrylates, polyethylene glycols are, for example, the publications WO 98/40462 (Rettenmaier), WO 98/55583 and WO 98/55590 (Unilever) and WO 98/40463, DE 19709991 and DE 19710254 A1 (Henkel). The teaching of these documents is expressly incorporated by reference.

Granulation and compaction

The preparation of the surfactant granules, so the granulation and compaction can in the detergent meet well-known manner. It is particularly possible, the granules before, during or to compact after granulation. The compaction is mandatory to a to achieve sufficient increase in the dissolution rate.

A particularly preferred way of preparing the surfactant granules is to subject the mixtures to fluidized bed granulation ("SKET" granulation). This is to be understood as meaning a granulation with simultaneous drying, which preferably takes place batchwise or continuously. The mixtures of surfactants and disintegrants can be used both in the dried state and as an aqueous preparation. Preferably used fluidized bed apparatus have bottom plates with dimensions of 0.4 to 5 m. Preferably, the granulation is carried out at fluidized air velocities in the range of 1 to 8 m / s. The discharge of the granules from the fluidized bed is preferably carried out via a size classification of the granules. The classification can be carried out, for example, by means of a sieve device or by a countercurrent air stream (classifier air) which is regulated so that only particles above a certain particle size are removed from the fluidized bed and smaller particles are retained in the fluidized bed. Usually, the incoming air is composed of the heated or unheated classifier air and the heated bottom air. The soil air temperature is between 80 and 400, preferably 90 and 350 ° C. Advantageously, a starting material, for example a surfactant granulate from a previous experimental batch, is initially introduced at the beginning of the granulation.

Other methods such as compaction by extrusion or in the roll mill are in the following in the chapter "production of washing, rinsing and cleaning agents" explained. The application These techniques can be applied analogously to the preparation of the surfactant granules according to the invention.

In order to facilitate the processing in said processes, it has proven to be advantageous the surfactant granules granulating and compacting aids, such as polyethylene glycol waxes in amounts of 1 to 10 and preferably 2 to 5 wt .-% - based on the granules - add Above all, they improve the gliding and adhesion behavior of the products and the necessary energy input decrease. If the desired particle size distribution not alone by the compaction reached, further steps, such as a classification can be followed.

Industrial Applicability

Another object of the invention relates to the use of the surfactant granules for the production of solid washing, rinsing and cleaning agents in which they are used in quantities of 1 to 90, preferably 5 to 50 and in particular 10 to 25 wt .-% - based on the means - may be included. The means can be used both in the form of powders, granules, extrudates, agglomerates or in particular Tablets and contain other typical ingredients.

Primary constituents of the final formulations can be, for example, further surfactants, in addition to the surfactant granules anionic, nonionic, cationic, amphoteric and / or zwitterionic surfactants, preferably However, they are anionic surfactants or combinations of anionic and nonionic surfactants present. These may be identical or different with the surfactants in the granules.

Builder

The washing, rinsing, cleaning and softening compositions according to the invention may additionally be additional inorganic and organic builders, for example in amounts of from 10 to 50 and preferably 15 to 35 wt .-% - based on the means - containing as inorganic builders mainly zeolites crystalline phyllosilicates, amorphous silicates and - as far as permissible - also Phosphates, e.g. Tripolyphosphate be used. The amount of co-builder is on the to include preferred amounts of phosphates.

The finely crystalline, synthetic and bound water-containing zeolite frequently used as detergent builder is preferably zeolite A and / or P. As zeolite P, for example, zeolite MAP ^(R) (commercial product from Crosfield) is particularly preferred. However, zeolite X and mixtures of A, X and / or P as well as Y are also suitable. Of particular interest is also a cocrystallized sodium / potassium aluminosilicate of zeolite A and zeolite X, which is known as VEGOBOND AX® (commercial product from Condea Augusta SpA) is commercially available. The zeolite can be used as a spray-dried powder or else as undried, still moist, stabilized suspension of its preparation. In the event that the zeolite is used as a suspension, it may contain minor additions of nonionic surfactants as stabilizers, for example 1 to 3 wt .-%, based on zeolite, of ethoxylated C ₁₂ -C ₁₈ fatty alcohols having 2 to 5 ethylene oxide groups , C ₁₂ -C ₁₄ fatty alcohols having 4 to 5 ethylene oxide groups or ethoxylated isotridecanols. Suitable zeolites have an average particle size of less than 10 μm (volume distribution, measuring method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water.

Suitable substitutes or sub-substituents for phosphates and zeolites are crystalline, layered sodium silicates of the general formula NaMSi _x O _{2x + 1} · yH ₂ O, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 is up to 20 and preferred values for x are 2, 3 or 4. Such crystalline layered silicates are described, for example, in European Patent Application EP 0164514 A1 . Preferred crystalline layered silicates of the formula given are those in which M is sodium and x assumes the values 2 or 3. In particular, both β- and δ-sodium disilicates Na ₂ Si ₂ O ₅ .yH ₂ O are preferred, whereby β-sodium disilicate can be obtained, for example, by the process described in international patent application WO 91/08171 . Further suitable phyllosilicates are known, for example, from the patent applications DE 2334899 A1, EP 0026529 A1 and DE 3526405 A1 . Its usability is not limited to any particular composition or structural formula. However, smectites, in particular bentonites, are preferred here. Suitable layered silicates which belong to the group of water-swellable smectites are, for example, those of the general formulas (OH) ₄ Si _8-y Al _y (Mg _x Al _4-x ) O ₂₀ montmorillonite (OH) ₄ Si _8-y Al _y (Mg _6-z Li _z ) O ₂₀ hectorite (OH) ₄ Si _8-y Al _y (Mg _6-z Al _z ) O ₂₀ Saponite with x = 0 to 4, y = 0 to 2, z = 0 to 6. In addition, small amounts of iron may be incorporated in the crystal lattice of the layered silicates according to the above formulas. Furthermore, the phyllosilicates may contain hydrogen, alkali, alkaline earth metal ions, in particular Na ⁺ and Ca ²⁺ , due to their ion-exchanging properties. The amount of water of hydration is usually in the range of 8 to 20 wt .-% and is dependent on the swelling state or on the type of processing. Useful layered silicates are known, for example, from US Pat. No. 3,966,629, US Pat. No. 4,062,647, EP 0026529 A1 and EP 0028432 A1 . Preferably, phyllosilicates are used, which are largely free of calcium ions and strong coloring iron ions due to an alkali treatment.

The preferred builder substances also include amorphous sodium silicates having a modulus of Na ₂ O: SiO _{2 of} from 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2, 6, which are delay-delayed and have secondary washing properties. The dissolution delay over conventional amorphous sodium silicates may have been caused in various ways, for example by surface treatment, compounding, compaction nebulization or by overdrying. In the context of this invention, the term "amorphous" is also understood to mean "X-ray amorphous". This means that in X-ray diffraction experiments, the silicates do not give sharp X-ray reflections typical of crystalline substances but at best one or more maxima of the scattered X-rays having a width of several degrees of diffraction angle. However, it may well even lead to particularly good builder properties if the silicate particles provide blurred or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning that the products have microcrystalline regions of size 10 to a few hundred nm, values of up to max. 50 nm and in particular up to max. 20 nm are preferred. Such so-called X-ray amorphous silicates, which likewise have a dissolution delay compared with the conventional water glasses, are described, for example, in German patent application DE 4400024 A1 . Especially preferred are densified / compacted amorphous silicates, compounded amorphous silicates and overdried X-ray amorphous silicates.

Of course, a use of the well-known phosphates as builders possible, unless such use should be avoided for environmental reasons. Suitable In particular, the sodium salts of orthophosphates, pyrophosphates and in particular the tripolyphosphates. Their content is generally not more than 25% by weight, preferably not more than 20 wt .-%, each based on the finished agent. In some cases it has been shown that in particular tripolyphosphates even in small amounts up to a maximum of 10 wt .-%, based on the finished agents, in combination with other builders to a synergistic improvement of secondary washing power.

Co-Builder

Useful organic builders which are suitable as co-builders are, for example, 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), if such use is for ecological reasons not to complain about, as well as 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 thereof. The acids themselves can also be used. In addition to their builder action, the acids typically also have the property of an acidifying component and thus also serve to set a lower and milder pH of detergents or cleaners. In particular, citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any desired mixtures of these can be mentioned here.

Further 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, for example acid or enzyme catalyzed processes. Preference is given to hydrolysis products having average molecular weights 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. Usable are both maltodextrins with a DE between 3 and 20 and dry glucose syrups with a DE between 20 and 37 and so-called yellow dextrins and white dextrins with higher molecular weights in the range of 2,000 to 30,000. A preferred dextrin is described in the 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 . Also suitable is an oxidized oligosaccharide according to the German patent application DE 19600018 A1. A product oxidized to C _{6 of} the saccharide ring may be particularly advantageous.

Other suitable co-builders 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, European Patent Application EP 0150930 A1 and Japanese Patent Application JP 93/339896 . Useful organic cobuilders are, for example, acetylated hydroxycarboxylic acids or their salts, which may optionally also be present in lactone form and which have at least 4 carbon atoms and at least one hydroxyl group and also at most contain two acid groups. Such co-builders 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 having a relative molecular weight of 800 to 150,000 (based on acid and measured in each case against polystyrenesulfonic 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 molecular weight relative to free acids is generally from 5,000 to 200,000, preferably from 10,000 to 120,000 and in particular from 50,000 to 100,000 (in each case measured 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 added later to one or more basic granules. Also particularly preferred are biodegradable polymers of more than two different monomer units, for example those according to DE 4300772 A1 as monomers salts of acrylic acid and maleic acid and vinyl alcohol or vinyl alcohol derivatives or according to DE 4221381 C2 as monomers salts of acrylic acid and 2-Alkylallylsulfonsäure and sugar derivatives.

Further preferred copolymers are those which are described in German patent applications DE 4303320 A1 and DE 4417734 A1 and preferably have as monomers acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate. Also to be mentioned as further preferred builders polymeric aminodicarboxylic acids, their salts or their precursors. Particular preference is given to polyaspartic acids or their salts and derivatives.

Further suitable builder substances are polyacetals which can be obtained by reacting dialdehydes with polyol carboxylic acids which have 5 to 7 C 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.
Additionally, the compositions may also contain components that positively affect oil and grease washability from fabrics. The preferred oil and fat dissolving components include, for example, nonionic cellulose ethers such as methylcellulose and methylhydroxypropylcellulose with a proportion of methoxyl groups of 15 to 30 wt .-% and hydroxypropoxyl groups of 1 to 15 wt .-%, each based on the nonionic Cellulose ethers, as well as known from the prior art polymers of phthalic acid and / or terephthalic acid or derivatives thereof, in particular polymers of ethylene terephthalates and / or polyethylene glycol terephthalates or anionic and / or nonionic modified derivatives thereof. Particularly preferred of these are the sulfonated derivatives of phthalic and terephthalic acid polymers.

Other suitable ingredients of the compositions are water-soluble inorganic salts such as bicarbonates, carbonates, amorphous silicates, normal water glasses which do not have outstanding builder properties, or mixtures of these; In particular, alkali metal carbonate and / or amorphous alkali silicate, especially sodium silicate with a molar ratio of Na ₂ O: SiO ₂ of 1: 1 to 1: 4.5, preferably from 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 (without any special builder properties) is generally up to 10% by weight and preferably between 1 and 8% by weight.

In addition to the ingredients mentioned, the agents may contain further known additives, for example Salts of polyphosphonic acids, optical brighteners, enzymes, enzyme stabilizers, defoamers, low Levels of neutral Füllsalzen and dyes and perfumes and the like included.

Bleaching agents and bleach activators

Among the compounds serving as bleaches in water H ₂ O ₂ , sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance. Other useful bleaching agents are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H ₂ O ₂ -producing peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid. The content of the bleaching agents is preferably from 5 to 35% by weight and in particular up to 30% by weight, it being advantageous to use perborate monohydrate or percarbonate.

As bleach activators, it is possible to use compounds which, under perhydrolysis conditions, give aliphatic peroxycarboxylic 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 stated C atom number and / or optionally substituted benzoyl groups. Preference is given to polyacylated 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, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic anhydrides, in particular phthalic anhydride, acylated polyhydric alcohols, in particular triacetin, ethylene glycol diacetate, 2,5-diacetoxy- 2,5-dihydrofuran and the enol esters known from German patent applications DE 19616693 A1 and DE 19616767 A1, and also acetylated sorbitol and mannitol or their mixtures (SORMAN) described in European patent application EP 0525239 A1 , acylated sugar derivatives, in particular pentaacetylglucose (PAG), pentaacetylfructose , Tetraacetylxylose and Octaacetyllactose and acetylated, optionally N-alkyl glucamine and gluconolactone, and / or N-acylated lactams, for example N- benzoylcaprolactam, disclosed in international patent applications WO 94/27970, WO 94128102, WO 94/28103, WO 95/00626, WO 95/14759 and WO 95/17498 are known. The hydrophilic substituted acyl acetals known from German patent application DE 19616769 A1 and the acyllactams described in German patent application DE 19616 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. Such bleach activators are contained in the customary amount range, preferably in amounts of from 1% by weight to 10% by weight, in particular from 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 sulfone imines 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 bleach catalysts. Suitable transition metal compounds include, in particular, the manganese, iron, cobalt, ruthenium or molybdenum salt complexes known from German patent application DE 19529905 A1 and their N- analogues 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, the described in the German patent application DE 19605688 A1 manganese, iron, cobalt, ruthenium, molybdenum, titanium, vanadium and copper complexes with nitrogen-containing tripod ligands that from German patent application DE 19620411 A1 known cobalt-, iron-, copper- and ruthenium-ammine complexes, the manganese described in the German patent application DE 4416438 A1, copper and cobalt complexes Cobalt complexes described in the European patent application EP 0272030 A1 , the manganese K known from the European patent application EP 0693550 A1 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, Manganese complexes described in EP 0549272 A1, EP 0544490 A1 and EP 0544519 A1 . 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 having 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 wt .-% and particularly preferably from 0.01 wt .-% to 0.1 wt .-%, each based on the total agent used.

Enzymes and enzyme stabilizers

Suitable enzymes are, in particular, those from the class of the hydrolases, such as the proteases, esterases, lipases or lipolytic enzymes, amylases, cellulases or other glycosyl hydrolases and mixtures of the enzymes mentioned. All of these hydrolases in the wash contribute to the removal of stains such as proteinaceous, greasy or starchy stains, and graying. Cellulases and other glycosyl hydrolases can contribute to color retention and increase the softness of the fabric by removing pilling and microfibrils. It is also possible to use oxidoreductases for bleaching or inhibiting color transfer. Particularly suitable are enzymatic agents obtained from bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis, Streptomyces griseus and Humicola insolens. Preferably, subtilisin-type proteases and in particular proteases derived from Bacillus lentus are used. These are enzyme mixtures, for example from protease and amylase or protease and lipase or lipolytic enzymes or protease and cellulase or from cellulase and lipase or lipolytic enzymes or from protease, amylase and lipase or, lipolytic enzymes or protease, lipase or lipolytic enzymes and cellulase, but in particular protease and / or lipase-containing mixtures or mixtures with lipolytic enzymes of particular interest. Examples of such lipolytic enzymes are the known cutinases. Peroxidases or oxidases have also proved suitable in some cases. Suitable amylases include in particular α-amylases, iso-amylases, pullulanases and pectinases. As cellulases are preferably cellobiohydrolases, endoglucanases and β-glucosidases, which are also called cellobiases, or mixtures thereof used. Since the different cellulase types differ by their CMCase and avicelase activities, targeted mixtures of the cellulases can be used to set the desired activities. The enzymes may be adsorbed to carriers and / or embedded in encapsulants to protect against premature degradation. The proportion of enzymes, enzyme mixtures or enzyme granules may be, for example, about 0.1 to 5 wt .-%, preferably 0.1 to about 2 wt .-%.

In addition to the mono- and polyfunctional alcohols, the agents may contain other enzyme stabilizers. For example, 0.5 to 1 wt .-% 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, it is particularly advantageous to use 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 pyroboric acid (tetraboric acid H ₂ B ₄ O ₇ ).

graying

Graying inhibitors have the task of suspending the fiber-removed dirt in the liquor to keep the dirt from being rebuilt. These are water-soluble Colloids mostly organic nature suitable, for example, the water-soluble salts polymeric Carboxylic acids, glue, gelatin, salts of ether carboxylic acids or ether sulfonic acids or the cellulose or salts of acidic sulfuric acid esters of cellulose or starch. Also, water-soluble polyamides containing acidic groups are suitable for this purpose. Farther soluble starch preparations and other starch products than those mentioned above can be used e.g. degraded starch, aldehyde levels, etc. Also polyvinylpyrrolidone is useful. Prefers however, cellulose ethers such as carboxymethyl cellulose (Na salt), methyl cellulose, hydroxyalkyl cellulose and mixed ethers such as methylhydroxyethylcellulose, methylhydroxypropylcellulose, methylcarboxymethylcellulose and mixtures thereof, and polyvinylpyrrolidone, for example, in amounts of 0.1 to 5 wt .-%, based on the agents used.

Optical brighteners

The agents may contain as optical brighteners derivatives of Diaminostilbendisulfonsäure or their alkali metal salts. Suitable salts are, for example, salts of 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazinyl-6-amino) stilbene-2,2'-disulphonic acid or compounds of similar construction which are used in place of the morpholino Group a Diethanolaminogruppe, a methylamino group, an anilino group or a 2-Methoxyethylaminogruppe carry. Furthermore, brighteners of the substituted diphenylstyrene type may be present, for example the alkali metal salts of 4,4'-bis (2-sulfostyryl) -diphenyl, 4,4'-bis (4-chloro-3-sulfostyryl) -diphenyl, or (4-chlorostyryl) -4 '- (2-sulfostyryl). Mixtures of the aforementioned brightener can be used. Uniformly white granules are obtained when the means except the usual brighteners in conventional amounts, for example between 0.1 and 0.5 wt .-%, preferably between 0.1 and 0.3 wt .-%, even small amounts, for example 10 ^-6 to 10 ^-3 wt .-%, preferably by 10 ^-5 wt .-%, of a blue dye. A particularly preferred dye is Tinolux® (commercial product of Ciba-Geigy).

polymers

Suitable soil repellent polymers are those which are preferred Contain ethylene terephthalate and / or polyethylene glycol terephthalate groups, wherein the molar ratio Ethylene terephthalate to polyethylene glycol terephthalate may range from 50:50 to 90:10. The molecular weight of the linking polyethylene glycol units is in particular in the range of 750 to 5,000, that is, the degree of ethoxylation of the polymers containing polyethylene glycol groups may be about 15 to 100. The polymers are characterized by an average molecular weight of about 5000 to 200,000 and may have a block, but preferably a random structure. Preferred polymers are those with molar ratios of ethylene terephthalate / polyethylene glycol terephthalate from about 65:35 to about 90:10, preferably from about 70:30 to 80:20. Further preferred are those polymers which have linking molecular weight polyethylene glycol units from 750 to 5000, preferably from 1000 to about 3000 and a molecular weight of Have polymers of about 10,000 to about 50,000. Examples of commercially available polymers are the Products Milease® T (ICI) or Repelotex® SRP 3 (Rhöne-Poulenc).

defoamers

As defoamers waxy compounds can be used. As "waxy" are such Understood compounds having a melting point at atmospheric pressure above 25 ° C (room temperature), preferably above 50 ° C and in particular above 70 ° C. The waxy defoamer substances are practically insoluble in water, i. at 20 ° C, they are in 100 g of water a solubility below 0.1 wt .-% on. In principle, all known from the prior art be included waxy defoamer substances. Suitable waxy compounds are, for example Bisamides, fatty alcohols, fatty acids, carboxylic acid esters of monohydric and polyhydric alcohols and paraffin waxes or mixtures thereof. Alternatively, of course, the for this Purpose known silicone compounds are used.

Suitable paraffin waxes are generally a complex mixture without a sharp melting point. For characterization is usually determined its melting range by differential thermal analysis (DTA), as described in "The Analyst" 87 (1962), 420 , and / or its solidification point , This is the temperature at which the paraffin passes from the liquid to the solid state by slow cooling. In this case, at room temperature completely liquid paraffins, that is those with a solidification point below 25 ° C, according to the invention not useful. Soft waxes having a melting point in the range of 35 to 50 ° C preferably include the group of petrolates and their hydrogenation products. They are composed of microcrystalline paraffins and up to 70 wt .-% oil, have an ointment-like plastic to solid consistency and represent bitumen-free residues from petroleum processing. Particularly preferred are distillation residues (Petrolatumstock) certain paraffin-based and mixed basic crude oils, which is further processed to Vaseline become. Preference is furthermore given to distillate residues of paraffin and mixed basic crude oils and cylinder oil distillates by means of solvent-deposited bitumen-free, oily to solid hydrocarbons. They are of semi-solid, rapid, sticky to plastic-solid consistency and have melting points between 50 and 70 ° C. These petrolates represent the most important starting point for the production of microwaxes. Also suitable are the solid hydrocarbons deposited from high-viscosity, paraffin-containing lubricating oil distillates during the dewaxing, with melting points between 63 and 79.degree. These petrolatum are mixtures of microcrystalline waxes and refractory n-paraffins. For example, the paraffin wax mixtures known from EP 0309931 A1 can be used, for example, from 26% by weight to 49% by weight of microcrystalline paraffin wax having a solidification point of from 62 ° C. to 90 ° C., from 20% by weight to 49% by weight hard paraffin with a solidification point of 42 ° C to 56 ° C and 2 wt .-% to 25 wt .-% soft paraffin with a solidification point of 35 ° C to 40 ° C. Preferably, paraffins or paraffin mixtures are used which solidify in the range of 30 ° C to 90 ° C. It should be noted that even at room temperature appearing paraffin wax mixtures may contain different proportions of liquid paraffin.

In the case of the paraffin waxes which can be used according to the invention, this liquid fraction is as low as possible and preferably completely absent. Thus, particularly preferred paraffin wax mixtures at 30 ° C. a liquid content of less than 10 wt .-%, in particular from 2 wt .-% to 5 wt .-%, at 40 ° C a Liquid content of less than 30 wt .-%, preferably from 5 wt .-% to 25 wt .-% and in particular of 5 wt .-% to 15 wt .-%, at 60 ° C, a liquid content of 30 wt .-% to 60 wt .-%, in particular from 40 wt .-% to 55 wt .-%, at 80 ° C, a liquid content of 80 wt .-% to 100 wt .-%, and at 90 ° C to a liquid content of 100 wt .-% to. The temperature at which a liquid content of 100% by weight of the paraffin wax is still particularly preferred paraffin wax mixtures below 85 ° C, especially at 75 ° C to 82 ° C. The paraffin waxes may be petrolatum, microcrystalline waxes or hydrogenated or partially hydrogenated paraffin waxes act.

Suitable bisamides as defoamers are those which are derived from saturated fatty acids containing 12 to 22, preferably 14 to 18, carbon atoms and alkylenediamines having 2 to 7 carbon atoms. Suitable fatty acids are lauric, myristic, stearic, arachic and behenic acid and mixtures thereof, such as those obtainable from natural fats or hardened oils, such as tallow or hydrogenated palm oil. Suitable diamines are, for example, ethylenediamine, 1,3-propylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, p-phenylenediamine and toluenediamine. Preferred diamines are ethylenediamine and hexamethylenediamine. Particularly preferred bisamides are bis-myristoylethylenediamine, bispalmitoylethylenediamine, bisstearoylethylenediamine and mixtures thereof and the corresponding derivatives of hexamethylenediamine.

Suitable carboxylic esters as defoamers are derived from carboxylic acids having 12 to 28 carbon atoms. In particular, they are esters of behenic acid, stearic acid, hydroxystearic acid, oleic acid, palmitic acid, myristic acid and / or lauric acid. The alcohol portion of the carboxylic acid ester contains a monohydric or polyhydric alcohol having 1 to 28 carbon atoms in the hydrocarbon chain. Examples of suitable alcohols are behenyl alcohol, arachidyl alcohol, coconut oil, 12-hydroxystearyl alcohol, oleyl alcohol and lauryl alcohol and also ethylene glycol, glycerol, polyvinyl alcohol, sucrose, erythritol, pentaerythritol, sorbitan and / or sorbitol. Preferred esters are those of ethylene glycol, glycerol and sorbitan, wherein the acid portion of the ester is selected in particular from behenic acid, stearic acid, oleic acid, palmitic acid or myristic acid. Candidate polyhydric alcohol esters include xylitol monopalmitate, pentarythritol monostearate, glycerol monostearate, ethylene glycol monostearate and sorbitan monostearate, sorbitan palmitate, sorbitan monolaurate, sorbitan dilaurate, sorbitan distearate, sorbitan dibehenate, sorbitan dioleate and mixed tallow alkyl sorbitan mono- and diesters. Useful glycerol esters are the mono-, di- or triesters of glycerol and said carboxylic acids, the mono- or diesters being preferred. Glycerol monostearate, glycerol monooleate, glycerol monopalmitate, glycerol monobehenate and glyceryl distearate are examples of this. Examples of suitable natural esters as defoamers are beeswax, which consists mainly of the esters CH ₃ (CH ₂ ) ₂₄ COO (CH ₂ ) ₂₇ CH ₃ and CH ₃ (CH ₂ ) ₂₆ COO (CH ₂ ) ₂₅ CH ₃ , and carnauba wax , which is a mixture of carnaubaic acid alkyl esters, often in combination with low levels of free carnaubaic acid, other long chain acids, high molecular weight alcohols and hydrocarbons.

Suitable carboxylic acids as further defoamer compound are, in particular, behenic acid, stearic acid, oleic acid, palmitic acid, myristic acid and lauric acid, and mixtures thereof, which are obtainable from natural fats or optionally hardened oils, such as tallow or hydrogenated palm oil. Preferred are saturated fatty acids having 12 to 22, in particular 18 to 22 C-atoms.

Suitable fatty alcohols as further antifoam compounds are the hydrogenated products of the described fatty acids.

Furthermore, dialkyl ethers may additionally be present as defoamers. The ethers may be asymmetric or symmetrical, ie containing two identical or different alkyl chains, preferably containing 8 to 18 carbon atoms. Typical examples are di-n-octyl ether, di-ioctyl ether and di-n-stearyl ether, particularly suitable are dialkyl ethers having a melting point above 25 ° C, in particular above 40 ° C.

Further suitable defoamer compounds are fatty ketones, which can be obtained by the relevant methods of preparative organic chemistry. They are prepared , for example, from carboxylic acid magnesium salts which are pyrolyzed at temperatures above 300 ° C. with elimination of carbon dioxide and water, for example in accordance with German laid-open specification DE 2553900 OS . Suitable fatty ketones are those prepared by pyrolysis of the magnesium salts of lauric, myristic, palmitic, palmitoleic, stearic, oleic, elaidic, petroselic, arachidic, gadoleic, behenic or erucic acid.

Further suitable defoamers are fatty acid polyethylene glycol esters, which are preferably obtained by basic homogeneously catalyzed addition of ethylene oxide to fatty acids. In particular, the addition of ethylene oxide to the fatty acids takes place in the presence of alkanolamines as catalysts. The use of alkanolamines, especially triethanolamine, results in extremely selective ethoxylation of the fatty acids, especially when it comes to producing low ethoxylated compounds. Within the group of fatty acid polyethylene glycol esters, preference is given to those which have a melting point above 25 ° C., in particular above 40 ° C.

Within the group of waxy defoamers, the paraffin waxes described are particularly preferably used alone as waxy defoamers or in admixture with one of the other waxy defoamers, wherein the proportion of paraffin waxes in the mixture is preferably more than 50% by weight, based on waxy defoamer mixture. The paraffin waxes can be applied to carriers as needed. As carrier material, all known inorganic and / or organic carrier materials are suitable. Examples of typical inorganic carrier materials are alkali metal carbonates, aluminosilicates, water-soluble phyllosilicates, alkali metal silicates, alkali metal sulphates, for example sodium sulphate, and alkali metal phosphates. The alkali metal silicates are preferably a compound having a molar ratio of alkali metal oxide to SiO _{2 of} from 1: 1.5 to 1: 3.5. The use of such silicates results in particularly good grain properties, in particular high abrasion stability and yet high dissolution rate in water. The aluminosilicates referred to as support material include, in particular, the zeolites, for example zeolite NaA and NaX. The compounds referred to as water-soluble layered silicates include, for example, amorphous or crystalline water glass. Furthermore, silicates can be used, which are under the name Aerosil® or Sipernat® commercially. Suitable organic support materials are, for example, film-forming polymers, for example polyvinyl alcohols, polyvinylpyrrolidones, poly (meth) acrylates, polycarboxylates, cellulose derivatives and starch. Useful cellulose ethers are, in particular, alkali metal carboxymethylcellulose, methylcellulose, ethylcellulose, hydroxyethylcellulose and so-called cellulose mixed ethers, such as, for example, methylhydroxyethylcellulose and methylhydroxypropylcellulose, and mixtures thereof. Particularly suitable mixtures are composed of sodium carboxymethylcellulose and methylcellulose, wherein the carboxymethylcellulose usually has a degree of substitution of 0.5 to 0.8 carboxymethyl groups per anhydroglucose unit and the methylcellulose has a degree of substitution of 1.2 to 2 methyl groups per anhydroglucose unit. The mixtures preferably contain alkali metal carboxymethylcellulose and nonionic cellulose ethers in weight ratios of from 80:20 to 40:60, in particular from 75:25 to 50:50. Native starch composed of amylose and amylopectin is also suitable as the carrier. Native starch is starch, as it is available as an extract from natural sources, such as rice, potatoes, corn and wheat. Native starch is a commercial product and thus easily accessible. As carrier materials, one or more of the abovementioned compounds can be used, in particular selected from the group of alkali metal carbonates, alkali metal sulphates, alkali metal phosphates, zeolites, water-soluble phyllosilicates, alkali silicates, polycarboxylates, cellulose ethers, polyacrylate / polymethacrylate and starch. Particularly suitable are mixtures of alkali metal carbonates, in particular sodium carbonate, alkali metal silicates, in particular sodium silicate, alkali metal sulphates, in particular sodium sulphate and zeolites.

Suitable silicones are customary organopolysiloxanes which may have a finely divided silica content, which in turn may also be silanated. Such organopolysiloxanes are described, for example, in European Patent Application EP 0496510 A1 . Particularly preferred are polydiorganosiloxanes and especially polydimethylsiloxanes known in the art. Suitable polydiorganosiloxanes have a nearly linear chain and have a degree of oligomerization of 40 to 1500. Examples of suitable substituents are methyl, ethyl, propyl, isobutyl, tert. Butyl and phenyl. Also suitable are amino-, fatty acid-, alcohol-, polyether-, epoxy-, fluoro-, glycoside- and / or alkyl-modified silicone compounds which may be both liquid and resinous at room temperature. Also suitable are simethicones, which are mixtures of dimethicones having an average chain length of from 200 to 300 dimethylsiloxane units and hydrogenated silicates. In general, the silicones in general and the polydiorganosiloxanes in particular contain finely divided silica, which may also be silanated. Especially suitable for the purposes of the present invention are siliceous dimethyl polysiloxanes. Advantageously, the polydiorganosiloxanes have a Brookfield viscosity at 25 ° C (spindle 1, 10 rpm) in the range from 5000 mPas to 30,000 mPas, in particular from 15,000 to 25,000 mPas. Preferably, the silicones are used in the form of their aqueous emulsions. In general, the silicone is added to the initially charged water with stirring. If desired, thickening agents known in the art may be added to increase the viscosity of the aqueous silicone emulsions. These may be inorganic and / or organic in nature, particular preference is given to nonionic cellulose ethers such as methylcellulose, ethylcellulose and mixed ethers such as methylhydoxyethylcellulose, methylhydroxypropylcellulose, methylhydroxybutylcellulose and anionic carboxycellulose types such as the carboxymethylcellulose sodium salt (abbreviation CMC). Particularly suitable thickeners are mixtures of CMC to nonionic cellulose ethers in a weight ratio of 80:20 to 40:60, in particular 75:25 to 60:40. As a rule, and especially when adding the described thickener mixtures, use concentrations of approximately 0.5 to 10, in particular from 2.0 to 6 wt .-% - calculated as a thickener mixture and based on aqueous silicone emulsion. The content of silicones of the type described in the aqueous emulsions is advantageously in the range of 5 to 50 wt .-%, in particular from 20 to 40 wt .-% - calculated as silicones and based on aqueous silicone emulsion. According to a further advantageous embodiment, the aqueous silicone solutions as thickener starch, which is accessible from natural sources, such as rice, potatoes, corn and wheat. The starch is advantageously present in amounts of from 0.1 to 50% by weight, based on the silicone emulsion, and in particular in a mixture with the already described thickener mixtures of sodium carboxymethylcellulose and a nonionic cellulose ether in the quantities already mentioned. For the preparation of the aqueous silicone emulsions, it is expedient to proceed in such a way that the thickeners, if present, are allowed to pre-swell in water before the addition of the silicones takes place. The incorporation of the silicones is expediently carried out with the aid of effective stirring and mixing devices.

fragrances

As perfume oils or fragrances, individual fragrance compounds, e.g. the synthetic products of the type of esters, ethers, aldehydes, ketones, alcohols and hydrocarbons. Fragrance compounds of the ester type are known e.g. Benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, Linalyl acetate, dimethylbenzylcarbinyl acetate, phenylethyl acetate, linalyl benzoate, Benzyl formate, ethyl methyl phenyl 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 ionone, α-isomethylionone and methyl cedryl ketone, to the alcohols anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and terpineol, The hydrocarbons mainly include the terpenes such as limonene and pinene. Prefers However, mixtures of different fragrances are used, which together create an appealing Create a fragrance. Such perfume oils may also contain natural fragrance mixtures, as available from plant sources, e.g. Pine, Citrus, Jasmine, Patchouly, Rose or Ylang-ylang oil. Also suitable are Muscat, sage oil, chamomile oil, clove oil, lemon balm oil, mint oil, Cinnamon leaf oil, lime blossom oil, juniper berry oil, vetiver oil, olibanum oil, galbanum oil and labdanum oil and orange blossom oil, neroliol, orange peel oil and sandalwood oil.

The perfumes can be incorporated directly into the compositions of the invention, but it can also be advantageous to apply the perfumes on carriers, which the adhesion of the perfume on the laundry strengthen and ensure a long-lasting scent of textiles through a slower release of fragrance. As such carrier materials, for example, cyclodextrins have been proven, the cyclodextrin-perfume complexes additionally can be coated with other excipients.

actuating means

If desired, the final preparations may also contain inorganic salts as fillers, such as sodium sulfate, which is preferably in amounts of 0 to 10, in particular 1 to 5 wt .-% - based on agent - is included.

Production of washing, rinsing and cleaning agents

The preparations obtainable using the surfactant granules according to the invention can be used as already made or used in the form of powders, extrudates, granules or agglomerates become. It may be both universal and fine or color detergents, if necessary in the form of compact data or super compact data. For the preparation of such agents are the corresponding methods known from the prior art suitable. To be favoured the agents are prepared by mixing various particulate components, the detergent ingredients contained, mixed together. The particulate components can by Spray drying, simple mixing or complex granulation processes, for example fluidized bed granulation, getting produced. Furthermore, it may be particularly preferred if aqueous Preparations of the alkali silicate and the alkali carbonate together with other detergent ingredients be sprayed in a drying device, at the same time as drying a Granulation can take place.

In the drying device, in which the aqueous preparation is sprayed, it may be any dry equipment. In a preferred process, the drying is carried out as spray drying in a drying tower. The aqueous preparations are exposed in a known manner a drying gas stream in finely divided form. Patent publications by Henkel describe an embodiment of spray drying with superheated steam. The working principle disclosed therein is hereby expressly also made the subject of the present invention disclosure. Reference is made in particular to the following publications: DE 4030688 A1 and the further publications according to DE 4204035 A1; DE 4204090 A1; DE 4206050 A1; DE 4206521 A1; DE 4206495 A1; DE 4208773 A1; DE 4209432 A1 and DE 4234376 A1. This process has already been presented in connection with the production of defoamer grain.

In another, especially when high bulk density agents are to be obtained, preferred Variant, the mixtures are then subjected to a compaction step, with more Ingredients are added to the funds only after the compaction step. The compaction the ingredients are found in a preferred embodiment of the invention in a press-agglomeration process instead of. The press agglomeration process involving the solid premix (dried base detergent) is subjected, can be realized in various apparatuses. Depending on Type of agglomerator used are different Preßagglomerationsverfahren distinguished. The four most common and preferred in the present invention Preßagglomerationsverfahren are the extrusion, the roll pressing or compacting, the hole pressing (Pelletizing) and tableting, so that in the present invention preferred Preßagglomerationsvorgänge Extrusion, roll compaction, pelletizing or tabletting operations and die pressing methods.

All methods have in common that the premix is compacted and plasticized under pressure, and the individual particles are pressed together to reduce porosity and to each other be liable. With all procedures (with the tabletting with restrictions) the tools can be heat up to higher temperatures or to dissipate the resulting by shear forces Cool heat.

In all methods, one or more binders can be used as an aid for compaction. However, it should be made clear that in itself always the use of several, different Binders and mixtures of different binders is possible. In a preferred embodiment The invention uses a binder which, at temperatures up to a maximum of 130 ° C., preferably up to a maximum of 100 ° C and in particular up to 90 ° C is already completely present as a melt. The binder must therefore be selected depending on the process and process conditions or the process conditions, in particular the process temperature, must - if a certain Binders is desired - be adapted to the binder.

The actual compression process is preferably carried out at processing temperatures, the at least in the densification step at least the temperature of the softening point, if not even the temperature of the melting point of the binder correspond. In a preferred embodiment the invention, the process temperature is significantly above the melting point or above the temperature at which the binder is present as a melt. but in particular it is preferred that the process temperature in the compression step not more than 20 ° C above the melting temperature or the upper limit of the melting range of the binder. Although it is technical quite possible to set even higher temperatures; but it has been shown that a Temperature difference to the melting temperature or to the softening temperature of the binder of 20 ° C is generally quite sufficient and even higher temperatures no additional benefits cause. That is why it is particularly preferred, especially for energy reasons. Although above, but as close as possible to the melting point or at the upper temperature limit the melting range of the binder to work. Such a temperature control has the other Advantage that also thermally sensitive raw materials, such as peroxy bleach such as perborate and / or percarbonate, but also enzymes, increasingly processed without serious losses of active substance can be. The possibility of accurate temperature control of the binder in particular in the decisive step of compression, ie between the mixing / homogenisation of the Premixing and shaping, allows an energetically very favorable and for the temperature-sensitive Components of the premix extremely gentle process, since the premix only exposed to higher temperatures for a short time. In preferred press agglomeration processes have the working tools of the press agglomerator (the screw (s) of the extruder, the roll (s) of the roll compactor and the press roll (s) of the pellet press) have a temperature of at most 150 ° C, preferably at most 100 ° C and in particular at most 75 ° C and the process temperature is at 30 ° C and in particular at most 20 ° C above the melting temperature or the upper temperature limit of the melting range of the binder. Preferably, the duration is the temperature effect in the compression region of the press agglomerators a maximum of 2 minutes and is in particular in a range between 30 seconds and 1 minute.

Preferred binders which can be used alone or in admixture with other binders are polyethylene glycols, 1,2-polypropylene glycols and modified polyethylene glycols and polypropylene glycols. The modified polyalkylene glycols include, in particular, the sulfates and / or the disulfates of polyethylene glycols or polypropylene glycols having a molecular weight between 600 and 12,000 and in particular between 1,000 and 4,000. Another group consists of mono- and / or disuccinates of the polyalkylene glycols in turn, have molecular weights between 600 and 6,000, preferably between 1,000 and 4,000. For a more detailed description of the modified polyalkylene glycol ethers, reference is made to the disclosure of international patent application WO 93/02176 . In the context of this invention, polyethylene glycols include polymers in the production of which, in addition to ethylene glycol, C ₃ -C ₅ glycols and also glycerol and mixtures thereof are used as starting molecules. Also included are ethoxylated derivatives such as trimethylolpropane having 5 to 30 EO. The polyethylene glycols preferably used may have a linear or branched structure, with particular preference being given to linear polyethylene glycols. Particularly preferred polyethylene glycols include those having molecular weights between 2,000 and 12,000, advantageously about 4,000, wherein polyethylene glycols having molecular weights below 3,500 and above 5,000, in particular in combination with polyethylene glycols having a molecular weight of about 4,000 can be used and Such combinations advantageously have more than 50% by weight, based on the total amount of polyethylene glycols, of polyethylene glycols having a molecular weight between 3,500 and 5,000. However, polyethylene glycols which are present in liquid state at room temperature and a pressure of 1 bar can also be used as binders; Here is mainly of polyethylene glycol with a molecular weight of 200, 400 and 600 the speech. However, these per se liquid polyethylene glycols should be used only in a mixture with at least one other binder, said mixture must meet the requirements of the invention again, ie must have a melting point or softening point of at least above 45 ° C. Likewise suitable as binders are low molecular weight polyvinylpyrrolidones and derivatives of these having molecular weights of not more than 30,000. Preference is given here to molecular weight ranges between 3,000 and 30,000, for example around 10,000. Polyvinylpyrrolidones are preferably not used as sole binders but in combination with others. especially in combination with polyethylene glycols used.

The compacted material preferably has temperatures directly after leaving the production apparatus not above 90 ° C, with temperatures between 35 and 85 ° C being particularly preferred are. It has been found that outlet temperatures - especially in the extrusion process - from 40 to 80 ° C, for example up to 70 ° C, are particularly advantageous.

In a preferred embodiment, the detergent according to the invention is produced by means of an extrusion, as described, for example, in European patent EP 0486592 B1 or international patent applications WO 93/02176 and WO 94/09111 or WO 98/12299 . In this case, a solid premix is extruded under pressure extruded and cut the strand after exiting the hole shape by means of a cutting device to the predeterminable granule dimension. The homogeneous and solid premix contains a plasticizer and / or lubricant which causes the premix to be plastically softened and extrudable under the pressure of specific work. Preferred plasticizers and / or lubricants are surfactants and / or polymers. To explain the actual extrusion process, reference is hereby expressly made to the abovementioned patents and patent applications. Preferably, the pre-mixture is preferably supplied to a planetary roller extruder or a 2-screw extruder with co-rotating or counter-rotating screw guide, whose housing and its extruder granulating head can be heated to the predetermined extrusion temperature. Under the shearing action of the extruder screws, the premix under pressure, which is preferably at least 25 bar, at extremely high throughputs depending on the apparatus used but also may be below, compacted, plasticized, extruded in the form of fine strands through the hole die plate in the extruder head and finally Preferably, the extrudate is reduced by means of a rotating doctor blade to approximately spherical to cylindrical Granulatkörnem. The hole diameter of the hole nozzle plate and the strand cut length are matched to the selected granule dimension. Thus, the production of granules succeeds a substantially uniformly predictable particle size, in particular, the absolute particle sizes can be adapted to the intended use. In general, particle diameters of at most 0.8 cm are preferred. Important embodiments provide for the production of uniform granules in the millimeter range, for example in the range of 0.5 to 5 mm and in particular in the range of about 0.8 to 3 mm. The length / diameter ratio of the chopped primary granules is preferably in the range from about 1: 1 to about 3: 1. It is furthermore preferred to feed the still plastic primary granulate to a further shaping processing step; In this process, edges present on the raw extrudate are rounded, so that ultimately spherical to approximately spherical extrudate grains can be obtained. If desired, small amounts of dry powder, for example, zeolite powder, such as zeolite NaA powder, may be included in this stage. This shaping can be done in commercially available Rondiergeräten. It is important to ensure that only small amounts of fine grain content occur in this stage. Drying, which is described in the above-mentioned prior art documents as a preferred embodiment, is subsequently possible, but not absolutely necessary. It may just be preferable to stop drying after the compaction step. Alternatively, extrusions can also be carried out in low-pressure extruders, in the Kahl press (Amandus Kahl) or in the Bexx Bextruder. Preferably, the temperature control in the transition region of the screw, the pre-distributor and the nozzle plate is designed such that the melting temperature of the binder or the upper limit of the melting range of the binder is at least achieved, but preferably exceeded. The duration of the action of temperature in the compression region of the extrusion is preferably less than 2 minutes and in particular in a range between 30 seconds and 1 minute.

The detergents according to the invention can also be prepared by means of roll compaction . Here, the premix is selectively metered between two smooth or provided with wells of defined shape rollers and rolled between the two rollers under pressure to form a sheet-like Kompaktat, the so-called scoop. The rollers exert a high line pressure on the premix and can be additionally heated or cooled as required. When using smooth rolls, smooth, unstructured flake tapes are obtained, while by using structured rolls, correspondingly structured flakes can be produced in which, for example, certain shapes of the later detergent particles can be specified. The sling strip is subsequently broken by a tee and crushing process into smaller pieces and can be processed in this way to granules, which can be refined by further known per se surface treatment method, in particular brought into approximately spherical shape. Also in the case of roll compaction, the temperature of the pressing tools, ie the rolls, is preferably not more than 150 ° C., preferably not more than 100 ° C. and in particular not more than 75 ° C. Particularly preferred production processes work in the case of roll compaction with process temperatures which are 10 ° C., in particular at most 5 ° C. above the melting temperature or the upper temperature limit of the melting range of the binder. In this case, it is further preferred that the duration of the action of temperature in the compression region of the smooth rolls or rolls provided with depressions of defined shape amounts to a maximum of 2 minutes and is in particular in a range between 30 seconds and 1 minute.

The detergent according to the invention can also be produced by means of pelleting. Here, the premix is applied to a perforated surface and pressed by means of a pressure-emitting body under plasticization through the holes. In conventional embodiments of pellet presses, the premix is compressed under pressure, plasticized, pressed by means of a rotating roller in the form of fine strands through a perforated surface and finally comminuted with a knock-off device to Granulatkömem. Here are the most diverse designs of pressure roller and perforated die conceivable. For example, flat perforated plates are used as well as concave or convex ring matrices, through which the material is pressed through one or more pressure rollers. The press rollers may also be conically shaped in the plate devices, in the annular devices can matrices and press roll (s) have co-rotating or opposite sense of rotation. An apparatus suitable for carrying out the method is described, for example, in German Offenlegungsschrift DE 3816842 A1 . The ring die press disclosed in this document consists of a rotating ring die interspersed by press channels and at least one press roll operatively connected to its inner surface, which presses the material supplied to the die space through the press channels into a material discharge. In this case, ring die and pressing roller are drivable in the same direction, whereby a reduced shear stress and thus lower temperature increase of the premix can be realized. Of course, it is also possible to work with pelletizing with heatable or coolable rollers in order to set a desired temperature of the premix. Also in pelleting, the temperature of the pressing tools, so the pressure rollers or press rolls, preferably at a maximum of 150 ° C, preferably at a maximum of 100 ° C and in particular at a maximum of 75 ° C. Particularly preferred production processes work in the case of roll compaction with process temperatures which are 10 ° C., in particular at most 5 ° C. above the melting temperature or the upper temperature limit of the melting range of the binder.

The production of moldings, preferably those in tablet form, is generally carried out by tableting or press agglomeration. The resulting particulate Preßagglomerate can either be used directly as a detergent or aftertreated by conventional methods and / or processed. The usual post-treatments include, for example, powdering with finely divided ingredients of detergents or cleaners, whereby the bulk density is generally further increased. However, a preferred after-treatment is also the procedure according to the German patent applications DE 19524287 A1 and DE 19547457 A1 , wherein dust-like or at least finely divided ingredients (the so-called fines) are adhered to the particulate process end products according to the invention, which serve as a core, and thus arise means , which have these so-called fines as an outer shell. Advantageously, this is again done by melt agglomeration. For melt agglomeration of the fines on is expressly made to the disclosure in the German patent applications DE 19524287 A1 and DE 19547457 A1 . In the preferred embodiment of the invention, the solid detergents are in tablet form, these tablets preferably having rounded corners and edges, in particular for storage and transport reasons. The base of these tablets may, for example, be circular or rectangular. Multi-layer tablets, especially tablets with 2 or 3 layers, which may also be different in color, are especially preferred. Blue-white or green-white or blue-green-white tablets are particularly preferred. The tablets can also contain pressed and unpressed portions. Moldings having a particularly advantageous dissolution rate are obtained when the granular constituents before pressing have a proportion of particles which have a diameter outside the range from 0.02 to 6 mm of less than 20, preferably less than 10% by weight. A particle size distribution in the range from 0.05 to 2.0 and particularly preferably from 0.2 to 1.0 mm is preferred.

Examples

Production Example H1. 600 g of cellulose (Technocel® 150) were mixed with 400 g of hydroxy mixed ether (ring-opening product of 1,2-decene epoxide and C _12/14 coconut fatty alcohol + 3PO + 6EO) and compacted by a gear roller mill. Subsequently, a sieve fraction was taken between 1.2 and 1.6 mm.

Production example H2. 600 g of cellulose (Technocel® 150) were mixed with 200 g of hydroxy mixed ether (ring opening product of 1,2-dodecene epoxide and C _13/15 oxo alcohol + 7EO) and compacted by means of a gear roller mill. Subsequently, a sieve fraction was taken between 1.2 and 1.6 mm.

Production Example H3. 600 g of cellulose (Technocel® 150) were mixed with 300 g of hydroxy mixed ether (ring-opening product of 1,2-dodecene epoxide and C _13/15 oxo alcohol + 7EO) and 200 g of cocoalkyl oligoglucoside (Plantacare® 1200 G, residual water content 5% by weight, Cognis Germany GmbH / DE), whereby a water content of 9% by weight was established. Subsequently, the extrusion was carried out at 40 ° C through a sieve plate with holes of 2 mm diameter. The crude product was crushed and removed a sieve fraction between 1.2 mm and 1.6 mm.

Comparative Example C1. Surfactant granules consisting of 40% by weight C _12/18 coconut _fatty alcohol + 7EO (Dehydol® LT7, Cognis Deutschland GmbH / DE) and 60% by weight cellulose (Technocel® 150), prepared by spray-mixing granulation; Sieve fraction between 1.2 and 1.6 mm.

Comparative Example V2. Surfactant granules consisting of 20% by weight C _12/18 coconut _fatty alcohol + 7EO (Dehydol® LT7, Cognis Deutschland GmbH / DE) and 80% by weight zeolite A, prepared by spray-mixing granulation; Sieve fraction between 1.2 and 1.6 mm.

Application testing. A quantity of the granulate, corresponding in each case 10 g of surfactant, was added with constant stirring in 1 l of water (15 ° C.). The solution was filtered through a sieve (mesh size: 0.2 mm) after 30 s (T1), 60 s (T2) and 180 s (T3). The filter residue was air dried and then weighed. The results are summarized in Table 1: Dissolution rate (s) of surfactant granules V1 V2 H1 H2 H3 Quantity - T0 [g] 25 50 25 50 27 Backlog - T1 [g] 22 44 4 8th 10 Residue - T2 [g] 20 40 1 0 2 Backlog - T3 [g] 16 35 0 0 0

Claims (10)

1. Surfactant granules with an improved dissolving rate obtainable by granulating and compacting nonionic surfactants of the hydroxy mixed ether type in the presence of disintegrators.
2. A process for the production of surfactant granules with an improved dissolving rate in which nonionic surfactants of the hydroxy mixed ether type are granulated and compacted in the presence of disintegrators.
3. A process as claimed in claim 2, characterized in that hydroxy mixed ethers corresponding to formula (I):

   

   in which R¹ is a linear or branched alkyl group containing 2 to 18 carbon atoms, R² is hydrogen or a linear or branched alkyl group containing 2 to 18 carbon atoms, R³ is hydrogen or methyl, R⁴ is a linear or branched alkyl and/or alkenyl group containing 6 to 22 carbon atoms and n is a number of 1 to 50, with the proviso that the total number of carbon atoms in the substituents R¹ and R² is at least 4,
   are used.
4. A process as claimed in claims 2 and/or 3, characterized in that anionic, nonionic, cationic and/or amphoteric or zwitterionic co-surfactants are additionally used.
5. A process as claimed in claim 4, characterized in that co-surfactants selected from the group consisting of alkyl benzenesulfonates, alkyl sulfates, soaps, alkane sulfonates, olefin sulfonates, methyl ester sulfonates, fatty acid polyglycol ethers, alkyl and/or alkenyl oligoglycosides, alkoxylated fatty acid lower alkyl esters, esterquats and/or betaines are used.
6. A process as claimed in at least one of claims 2 to 5, characterized in that the hydroxy mixed ethers and the co-surfactants are used in a ratio by weight of 1:10 to 10:1.
7. A process as claimed in at least one of claims 2 to 6, characterized in that the surfactants are used in the form of water-containing pastes or dry solids or melts.
8. A process as claimed in at least one of claims 2 to 7, characterized in that disintegrators selected from the group consisting of polysaccharides, polyvinyl pyrrolidone, polyurethanes, polyacrylates, polyethylene glycols, collodion, alginic acids, alginates and layer silicates are used.
9. A process as claimed in at least one of claims 2 to 8, characterized in that the surfactants and the disintegrators are used in a ratio by weight of 1:10 to 10:1, based on their solids contents.
10. The use of the surfactant granules claimed in claim 1 for the production of laundry detergents, dishwashing detergents and cleaning compositions.