EP1592762B1 - Detergents or cleaning agents comprising a water-soluble building block system and a cellulose derivative with dirt dissolving properties - Google Patents

Abstract

A builder-containing laundry detergent or cleaning composition comprising: (1) a water-soluble builder block which comprised of: a) from 5% by weight to 35% by weight of citric acid, an alkali metal citrate, an alkali metal carbonate, and/or an alkali metal hydrogen carbonate, b) up to 5% by weight of alkali metal silicate having a modulus in the range from 1.8 to 2.5, c) up to 2% by weight of phosphonic acid and/or alkali metal phosphate, d) up to 50% by weight of alkali metal phosphate, and e) up to 10% by weight of polymeric polycarboxylate, wherein at least two of components b), c), d) and e) are present in amounts greater than 0% by weight, and (2) a soil release-capable alkyl or hydroxyalkyl cellulose derivative. The soil release-capable action of cellulose derivatives is particularly marked when they are used in laundry detergents or cleaning compositions which comprise only water-soluble builders.

Description

The present invention relates to detergents or cleaners which have only water-soluble constituents as builder component and contain soil release-capable cellulose derivative.

Washing and cleaning agents normally contain, in addition to the surfactants which are indispensable for the washing or cleaning performance, so-called builder substances which have the task of supporting the performance of the surfactants by eliminating hardness formers, ie essentially calcium and magnesium ions, from the wash liquor should not interact negatively with the surfactants. In the past, polyphosphates, in particular trisodium polyphosphate, have been used very successfully for this purpose. Another known. An example of such primary detergency-improving builders is zeolite Na-A, which is known to be capable of forming complexes which are particularly stable with calcium ions in particular, so that their reaction with water-hard-forming anions, especially carbonate, is suppressed to insoluble compounds. In addition, builders, particularly in laundry detergents, are expected to prevent the redeposition of soil detached from the fiber or generally from the surface to be cleaned, as well as the formation of insoluble compounds on the cleaned fabric or surface due to the reaction of water hardness cations with water hardness forming anions. For this purpose, commonly used are so-called co-builders, usually polymeric polycarboxylates, which in addition to their contribution to the secondary washing ability advantageously also have a complexing action against the water-hardness-forming cations.

In addition to the indispensable active ingredients mentioned, such as surfactants and builder materials, detergents generally contain further constituents, which can be summarized under the term washing auxiliaries and the groups of active ingredients that are so different such as foam control agents, grayness inhibitors, bleaches, enzymes and dye transfer inhibitors. Such adjuvants also include substances which impart soil repellency properties to the laundry fiber and, if present during the wash, aid the soil release properties of the remaining detergent ingredients. The same applies mutatis mutandis to cleaners for hard surfaces. Such soil release agents are often referred to as "soil release" agents or because of their ability to impart soil repellency to the treated surface, such as the fiber, as "soil repellents". For example, from the US patent US 4,136,038 the soil release ability of methyl cellulose is known. The European patent application EP 0 213 729 discloses the reduced redeposition when using detergents containing a combination of soap and nonionic surfactant with alkyl hydroxyalkyl cellulose. From the European patent application EP 0 213 730 Textile treatment agents are known which contain cationic surfactants and nonionic cellulose ethers with HLB values of 3.1 to 3.8. The US patent US 4,000,093 discloses detergents containing from 0.1% to 3% by weight of alkyl cellulose, hydroxyalkyl cellulose or alkyl hydroxyalkyl cellulose and from 5% to 50% by weight surfactant, wherein the surfactant component is substantially consists of C _{10 to} C ₁₃ alkyl sulfate and up to 5 wt .-% C ₁₄ alkyl sulfate and less than 5 wt .-% alkyl sulfate having alkyl radicals of C ₁₅ and higher. The US patent US 4,174,305 discloses detergents containing from 0.1% to 3% by weight of alkyl cellulose, hydroxyalkyl cellulose or alkyl hydroxyalkyl cellulose and from 5% to 50% by weight surfactant, wherein the surfactant component is substantially is C ₁₀ -C ₁₂ alkyl benzene sulfonate and has less than 5% by weight alkyl benzene sulfonate with alkyl radicals of C ₁₃ and higher. The European patent application EP 0 634 481 relates to a detergent containing alkali metal percarbonate and one or more nonionic cellulose derivatives. Are explicitly disclosed with the latter only hydroxyethyl cellulose, hydroxypropyl cellulose and methyl cellulose, as well as - in the context of the Beispiele- methyl hydroxyethylcellulose Tylose ^® MH50, the hydroxypropyl methyl cellulose Methocel ^® F4M, and hydroxybutyl methylcellulose. The European patent specification EP 0271 312 (P & G) relates to soil release agents, among these cellulose alkyl ethers and cellulose hydroxyalkyl ethers (with DS 1.5 to 2.7 and molecular weights of 2000 to 100000) such as methylcellulose and ethylcellulose to be used with peroxygen bleach in a weight ratio (based on the active oxygen content of the bleaching agent) of 10: 1 to 1:10. From the European patent EP 0 948 591 B1 For example, a detergent in liquid or granular form is known which imparts textile appearance benefits such as pilling / lint reduction, anti-color fading, improved abrasion resistance and / or enhanced softness to fabrics and textiles washed therewith, and from 1 to 80% by weight of surfactant, 1 to 80 wt .-% organic or inorganic builder, 0.1 to 80 wt .-% of a hydrophobically modified nonionic cellulose ether having a molecular weight of 10,000 to 2,000,000, wherein the modification in the presence of optionally oligomerized (degree of oligomerization up to 20 ) Ethyleneoxy or 2-propyleneoxy ether units and C _8-24 alkyl substituents and the alkyl substituents must be present in amounts of 0.1-5 wt .-%, based on the cellulose ether material.

Because of their chemical similarity to polyester fibers in textiles made of this material particularly effective soil release agents are copolyesters containing the dicarboxylic acid units, alkylene glycol units and polyalkylene glycol units. Dirt-releasing copolyesters of the type mentioned as well as their use in detergents have been known for a long time.

For example, German Offenlegungsschrift DT 16 17 141 describes a washing process using polyethylene terephthalate-polyoxyethylene glycol copolymers. German laid-open specification DT 22 00 911 relates to detergents which contain nonionic surfactant and a copolymer of polyoxyethylene glycol and polyethylene terephthalate. In the German patent application DT 22 53 063 acidic textile finishing agents are mentioned which contain a copolymer of a dibasic carboxylic acid and an alkylene or Cycloalkylenpolyglykol and optionally an alkylene or cycloalkylene glycol. Polymers of ethylene terephthalate and polyethylene oxide terephthalate in which the polyethylene glycol units have molecular weights of 750 to 5,000 and the molar ratio of ethylene terephthalate to polyethylene oxide terephthalate is 50:50 to 90:10, and their use in detergents are disclosed in the German Patent DE 28 57 292 described. Polymers with a molecular weight of 15,000 to 50,000 Ethylene terephthalate and polyethylene oxide terephthalate, wherein the polyethylene glycol units have molecular weights of 1000 to 10,000 and the molar ratio of ethylene terephthalate to polyethylene oxide terephthalate is 2: 1 to 6: 1, can according to the German Offenlegungsschrift DE 33 24 258 be used in detergents. The European patent EP 066 944 relates to textile treatment compositions containing a copolyester of ethylene glycol, polyethylene glycol, aromatic dicarboxylic acid and sulfonated aromatic dicarboxylic acid in certain molar ratios. From the European patent EP 185 427 For example, methyl or ethyl group-end capped polyesters having ethylene and / or propylene terephthalate and polyethylene oxide terephthalate units and detergents containing such soil release polymer are known. The European patent EP 241 984 relates to a polyester which in addition to oxyethylene groups and terephthalic acid units also contains substituted ethylene units and glycerol units. From the European patent EP 241 985 are known polyester containing in addition to oxyethylene groups and terephthalic acid units 1,2-propylene, 1,2-butylene and / or 3-methoxy-1,2-propylene and glycerol units and endgruppenverschlossen with C ₁ - to C ₄ alkyl groups are. The European patent EP 253 567 relates to soil release polymers having a molecular weight of 900 to 9000 of ethylene terephthalate and polyethylene oxide terephthalate, wherein the polyethylene glycol units have molecular weights of 300 to 3000 and the molar ratio of ethylene terephthalate to polyethylene oxide terephthalate is 0.6 to 0.95. From the European patent application EP 272 033 are at least partially by C _1-4 alkyl or acyl radicals end-capped polyester with poly-propylene terephthalate and polyoxyethylene terephthalate units known. The European patent EP 274 907 describes sulfoethyl end-capped terephthalate-containing soil release polyesters. In the European patent application EP 357,280 are prepared by sulfonation of unsaturated end groups soil release polyester with terephthalate, alkylene glycol and poly-C _2-4 glycol units. The German patent application DE 26 55 551 describes the reaction of such polyesters with isocyanate group-containing polymers and the use of the polymers thus prepared against the repulping of dirt during the washing of synthetic fibers. From the German patent DE 28 46 984 Detergents are known which use a reaction product of a polyester as a dirt-repellent-rich polymer terminal prepolymer containing isocyanate groups, obtained from a diisocyanate and a hydrophilic nonionic macrodiol.

The majority of known from this extensive prior art polymers has the disadvantage that they have no or only insufficient effectiveness in textiles that do not or at least not predominantly made of polyester. However, much of today's textiles are made of cotton or cotton-polyester blend fabrics, so there is a need for soil release agents that are more effective at greasy soiling on such fabrics.

From the European patent application EP 0 276 997 A2 are textile _treatment compositions containing at least 10 wt .-% C _8-24 fatty acid soap and 0.1 to 3 wt.% Nonionic substituted cellulose ethers having an HLB value between 3.1 and 3.8 and a gel point below 58 ° C known.

Surprisingly, it has now been found that the Schmutzablösvermögende effect of cellulose derivatives is particularly pronounced when used in detergents or cleaners that are free of water-insoluble builder material, that is contain only water-soluble builder.

1. a) 5 Gew.-% bis 35 Gew.-% Citronensäure, Alkalicitrat und/oder Alkalicarbonat, welches zumindest anteilig durch Alkalihydrogencarbonat ersetzt sein kann,
2. b) bis zu 5 Gew.-% Alkalisilikat mit einem Modul im Bereich von 1,8 bis 2,5,
3. c) bis zu 2 Gew.-% Phosphonsäure und/oder Alkaliphosphonat,
4. d) bis zu 50 Gew.-% Alkaliphosphat, und
5. e) bis zu 10 Gew.-% polymerem Polycarboxylat,

Bleichmittel auf Persauerstoffbasis und schmutzablösevermögendes Cellulosederivat, das erhältlich ist durch Alkylierung und Hydroxyalkylierung von Cellulose.The invention therefore relates to a builder-containing washing or cleaning agent containing a water-soluble builder block which is composed of the components

1. a) 5% by weight to 35% by weight of citric acid, alkali citrate and / or alkali metal carbonate, which may at least partly be replaced by alkali hydrogencarbonate,
2. b) up to 5% by weight of alkali silicate having a modulus in the range of 1.8 to 2.5,
3. c) up to 2% by weight of phosphonic acid and / or alkali phosphonate,
4. d) up to 50% by weight of alkali metal phosphate, and
5. e) up to 10% by weight of polymeric polycarboxylate,

Peroxygen-based bleach and soil release cellulose derivative obtainable by alkylation and hydroxyalkylation of cellulose.

In addition to the builder block, the bleaching agent and the soil release wealthy cellulose derivative, the agent can contain all other ingredients commonly used in detergents, unless they are unduly negatively associated with these or any of them interact from these. By using the term "builder block" is to be expressed, however, that the means contain no builders other than those which are water-soluble, that is all builders contained in the agent are summarized in the so characterized "block °, wherein at most the amounts of Substances are excluded, which may be present as impurities or stabilizing additives in small amounts in the other ingredients of the products commercially.

1. a) 5 Gew.-% bis 35 Gew.-% Citronensäure, Alkalicitrat und/oder Alkalicarbonat, welches zumindest anteilig durch Alkalihydrogencarbonat ersetzt sein kann,
2. b) bis zu 5 Gew.-% Alkalisilikat mit einem Modul im Bereich von 1,8 bis 2,5,
3. c) bis zu 2 Gew.-% Phosphonsäure und/oder Alkaliphosphonat,
4. d) bis zu 50 Gew.-% Alkaliphosphat, und
5. e) bis zu 10 Gew.-% polymerem Polycarboxylat,

beim Waschen von Textilien, die insbesondere aus Baumwolle bestehen oder Baumwolle enthalten.A second object of the invention is the use of soil release cellulose derivative obtainable by alkylation and hydroxyalkylation of cellulose to enhance the cleaning performance of detergents having peroxygen bleaching agents and a water-soluble builder block composed of the components

1. a) 5% by weight to 35% by weight of citric acid, alkali citrate and / or alkali metal carbonate, which may at least partly be replaced by alkali hydrogencarbonate,
2. b) up to 5% by weight of alkali silicate having a modulus in the range of 1.8 to 2.5,
3. c) up to 2% by weight of phosphonic acid and / or alkali phosphonate,
4. d) up to 50% by weight of alkali metal phosphate, and
5. e) up to 10% by weight of polymeric polycarboxylate,

when washing textiles, in particular made of cotton or containing cotton.

The use according to the invention can be carried out as part of a washing process by adding a detergent having a water-soluble builder block, and the cellulose derivative of an aqueous liquor, the cellulose derivative added separately by dissolving a detergent containing a water-soluble builder block, detergent-containing liquor or preferably introduces the cellulose derivative as part of a detergent according to the invention in the liquor.

The use according to the invention in the context of a laundry after-treatment process can be carried out in such a way that the cellulose derivative of the rinsing liquor is added separately, which after using a detergent with water-soluble Builderblock completed wash cycle is used, or it as a component of the laundry aftertreatment, in particular a softener, brings. In this aspect of the invention, said water-soluble builder block detergent may also contain, but may be free from, a cellulose derivative to be used in accordance with the invention. Conversely, said laundry aftertreatment agent may also contain, but may be free of, a water-soluble builder block.

1. a) 5 Gew.-% bis 35 Gew.-% Citronensäure, Alkalicitrat und/oder Alkalicarbonat, welches zumindest anteilig durch Alkalihydrogencarbonat ersetzt sein kann,
2. b) bis zu 5 Gew.-% Alkalisilikat mit einem Modul im Bereich von 1,8 bis 2,5,
3. c) bis zu 2 Gew.-% Phosphonsäure und/oderAlkaliphosphonat,
4. d) bis zu 50 Gew.-% Alkaliphosphat, und
5. e) bis zu 10 Gew.-% polymerem Polycarboxylat

und ein schmutzablösevermögendes Cellulosederivat, das erhältlich ist durch Alkylierung und Hydroxyalkylierung von Cellulose, zum Einsatz kommen. Dieses Verfahren kann manuell oder vorzugsweise mit Hilfe einer üblichen Haushaltswaschmaschine ausgeführt werden. Dabei ist es möglich, das Waschmittel mit dem wasserlöslichen Builderblock und das schmutzablösevermögende Cellulosederivat gleichzeitig oder nacheinander ' anzuwenden. Die gleichzeitige Anwendung läßt sich besonders vorteilhaft durch den Einsatz eines erfindungsgemäßen Waschmittels durchführen.Another object of the invention is a process for washing textiles in which a detergent with peroxygen-based bleach and a water-soluble builder block composed of the components

1. a) 5% by weight to 35% by weight of citric acid, alkali citrate and / or alkali metal carbonate, which may at least partly be replaced by alkali hydrogencarbonate,
2. b) up to 5% by weight of alkali silicate having a modulus in the range of 1.8 to 2.5,
3. c) up to 2% by weight of phosphonic acid and / or alkali phosphonate,
4. d) up to 50% by weight of alkali metal phosphate, and
5. e) up to 10% by weight of polymeric polycarboxylate

and a soil release cellulosic derivative obtainable by alkylation and hydroxyalkylation of cellulose. This method can be carried out manually or preferably by means of a conventional household washing machine. It is possible, the detergent with the water-soluble builder block and the soil release-capable cellulose derivative simultaneously or successively ' apply. The simultaneous application can be carried out particularly advantageously by the use of a detergent according to the invention.

Particularly pronounced is the washing performance-enhancing effect of the cellulose derivatives to be used according to the invention with repeated use, that is to say in particular for removing soiling of corresponding textiles which had already been washed and / or post-treated in the presence of the cellulose derivative before being provided with the soil. In connection with the aftertreatment, it should be noted that the positive aspect referred to can also be realized by a washing process in which the textile after the actual washing process, with the aid of a detergent with water-soluble builder block - which may contain a called cellulose derivative, but in this Case can also be free of this - is carried out, with an aftertreatment agent, for example - in the context of a fabric softening step, which contains a cellulose derivative to be used according to the invention, is brought into contact. In this procedure as well, if desired again, although a detergent with water-soluble builder block, but no detergent is used with a cellulose derivative mentioned, occurs during the next wash, the washing performance enhancing effect of the cellulose derivatives to be used according to the invention.

Preferred cellulose derivatives are those which are alkylated with C ₁ to C ₁₀ groups, in particular C _{1 to} C ₃ groups, and additionally carry C ₂ to C ₁₀ hydroxyalkyl groups, in particular C ₂ to C ₃ hydroxyalkyl groups. These can be obtained in known manner by reaction of cellulose with appropriate alkylating agents, for example alkyl halides or alkyl sulfates, and subsequent reaction with corresponding alkylene oxides, such as, for example, ethylene oxide and / or propylene oxide. In a preferred embodiment of the invention, a mean of 0.5 to 2.5, in particular 1 to 2, alkyl groups and 0.02 to 0.5, in particular 0.05 to 0.3, hydroxyalkyl groups per anhydroglycosemonomer unit are contained in the cellulose derivative. The average molar mass of the cellulose derivatives used according to the invention is preferably in the range from 10,000 D to 150,000 D, in particular from 40,000 D to 120,000 D and particularly preferably in the range from 80,000 D to 110,000 D. The determination of the degree of polymerization or of the molecular weight of the dirt-divisive Cellulose derivative is based on the determination of the intrinsic viscosity of sufficiently dilute aqueous solutions by means of a Ubbelohde capillary viscometer (capillary 0c). Using a constant [ H. Staudinger and F. Reinecke, "On Molecular Weight Determination on Cellulose Ethers", Liebigs Annalen der Chemie 535, 47 (1938 )] and a correction factor [ F. Rodriguez and LAGoettler, "The Flow of Moderately Concentrated Polymer Solutions in Water," Transactions of the Society of Rheology VIII, 3, 17 (1964 )] can be calculated from the degree of polymerization and, taking into account the degrees of substitution (DS and MS), the corresponding molecular weight.

Another essential feature of agents according to the invention is that they contain a water-soluble builder block. The term "water-soluble" is to be understood as meaning that the builder block dissolves without leaving any residue at least 3 g / l, in particular at least 6 g / l, in water of pH 7 at room temperature. The builder block is preferably soluble without residue at the concentration which results from the use amount of the detergent containing it in the customary washing conditions.

1. a) 5 Gew.-% bis 35 Gew.-% Citronensäure, Alkalicitrat und/oder Alkalicarbonat, welches auch zumindest anteilig durch Alkalihydrogencarbonat ersetzt sein kann,
2. b) bis zu 5 Gew.-% Alkalisilikat mit einem Modul im Bereich von 1,8 bis 2,5,
3. c) bis zu 2 Gew.-% Phosphonsäure und/oder Alkaliphosphonat,
4. d) bis zu 50 Gew.-% Alkaliphosphat, und
5. e) bis zu 10 Gew.-% polymerem Polycarboxylat,

wobei die Mengenangaben sich auf das gesamte Wasch- beziehungsweise Reinigungsmittel beziehen. Dies gilt auch für alle folgenden Mengenangaben, sofern nicht ausdrücklich anders angegeben.Preferably, at least 15 wt .-% and up to 55 wt .-%, in particular 25 wt .-% to 50 wt .-% of water-soluble builder block in the inventive compositions. This is composed of the components

1. a) 5% by weight to 35% by weight of citric acid, alkali citrate and / or alkali metal carbonate, which may also be replaced at least proportionally by alkali metal bicarbonate,
2. b) up to 5% by weight of alkali silicate having a modulus in the range of 1.8 to 2.5,
3. c) up to 2% by weight of phosphonic acid and / or alkali phosphonate,
4. d) up to 50% by weight of alkali metal phosphate, and
5. e) up to 10% by weight of polymeric polycarboxylate,

wherein the quantities are based on the total detergent or cleaning agent. This also applies to all following quantities, unless expressly stated otherwise.

In a preferred embodiment of the composition according to the invention, the water-soluble builder block comprises at least 2 of components b), c), d) and e) in amounts greater than 0% by weight.

With regard to component a), in a preferred embodiment of the composition according to the invention, 15% by weight to 25% by weight of alkali carbonate, which may at least partly be replaced by alkali metal hydrogencarbonate, and up to 5% by weight, in particular 0.5% by weight. % to 2.5% by weight of citric acid and / or alkali citrate. In an alternative embodiment of inventive compositions are as component a) 5 wt .-% to 25 wt .-%, in particular 5 wt .-% to 15 wt .-% citric acid and / or alkali citrate and up to 5 wt .-%, in particular 1 wt .-% to 5 wt .-% alkali carbonate, which may be at least partially replaced by alkali metal bicarbonate included. If both alkali metal carbonate and alkali metal bicarbonate are present, the component comprises a) alkali carbonate and alkali metal bicarbonate, preferably in a weight ratio of 10: 1 1 to 1: 1.

With regard to component b), in a preferred embodiment of the composition according to the invention, 1% by weight to 5% by weight alkali silicate with a modulus in the range from 1.8 to 2.5 are contained.

With regard to component c), in a preferred embodiment, agents according to the invention contain from 0.05% by weight to 1% by weight of phosphonic acid and / or alkali metal phosphonate. Phosphonic acids are also understood as meaning optionally substituted alkylphosphonic acids, which may also have a plurality of phosphonic acid groups (so-called polyphosphonic acids). They are preferably selected from the hydroxy and / or aminoalkylphosphonic acids and / or their alkali salts, for example dimethylaminomethane diphosphonic acid, 3-aminopropane-1-hydroxy-1,1-diphosphonic acid, 1-amino-1-phenylmethane diphosphonic acid, 1-hydroxyethane 1,1-diphosphonic acid, amino-tris (methylenephosphonic acid), N, N, N ', N'-ethylenediamine tetrakis (methylenephosphonic acid) and those described in German Auslegeschrift DE 11 07 207 described acylated derivatives of phosphorous acid, which can also be used in any mixtures.

With regard to component d), in a preferred embodiment of the composition according to the invention, 15% by weight to 35% by weight of alkali metal phosphate, in particular trisodium polyphosphate, are contained. Alkaliphosphat is the summary term for the alkali metal (especially sodium and potassium) salts of the various phosphoric acids, in which one can distinguish metaphosphoric acids (HPO ₃ ) _n and orthophosphoric H ₃ PO _{4 in} addition to high molecular weight representatives. The phosphates combine several advantages: they act as alkali carriers, prevent lime deposits on machine parts or lime incrustations in fabrics and also contribute to the cleaning performance. Sodium dihydrogen phosphate, NaH ₂ P0 ₄ , exists as a dihydrate (density 1.91 gcm ^-3 , melting point 60 °) and as a monohydrate (density 2.04 gcm ^-3 ). Both salts are white powders which are very soluble in water and which lose the water of crystallization on heating and at 200 ° C into the weak acid diphosphate (disodium hydrogen diphosphate, Na ₂ H ₂ P ₂ O ₇ ) at higher temperature in sodium trimetaphosphate (Na ₃ P ₃ O ₉ ) and pass on Madrell's salt. NaH ₂ PO _{4 is} acidic; It arises when phosphoric acid is adjusted to a pH of 4.5 with sodium hydroxide solution and the mash is sprayed. Potassium dihydrogen phosphate (primary or monobasic potassium phosphate, potassium biphosphate, KDP), KH ₂ PO ₄ , is a white salt of density 2.33 gcm ^-3 . has a melting point of 253 ° (decomposition to form (KPO ₃ ) _x , potassium polyphosphate) and is readily soluble in water. Disodium hydrogen phosphate (secondary sodium phosphate), Na ₂ HPO ₄ , is a colorless, very slightly water-soluble crystalline salt. It exists anhydrous and with 2 moles (density 2.066 gcm ^-3 , loss of water at 95 °), 7 moles (density 1.68 gcm ^-3 , melting point 48 ° with loss of 5 H ₂ O) and 12 moles water ( Density 1.52 gcm ^-3 , melting point 35 ° with loss of 5 H ₂ O) becomes anhydrous at 100 ° C and, upon increased heating, passes into the diphosphate Na ₄ P ₂ O ₇ . Disodium hydrogen phosphate is prepared by neutralization of phosphoric acid with soda solution using phenolphthalein as an indicator. Dipotassium hydrogen phosphate (secondary or dibasic potassium phosphate), K ₂ HPO ₄ , is an amorphous, white salt that is readily soluble in water. Trisodium phosphate, tertiary sodium phosphate, Na ₃ PO ₄ , are colorless crystals which have a density of 1.62 gcm ^-3 as dodecahydrate and a melting point of 73-76 ° C (decomposition), as decahydrate (corresponding to 19-20% P ₂ O ₅ ) have a melting point of 100 ° C and in anhydrous form (corresponding to 39-40% P ₂ O ₅ ) have a density of 2.536 gcm ^-3 . trisodium phosphate is readily soluble in water under an alkaline reaction and is prepared by evaporation of a solution of exactly 1 mole of disodium phosphate and 1 mole of NaOH. Tripotassium phosphate (tertiary or tribasic potassium phosphate), K ₃ PO ₄ , is a white, deliquescent, granular powder of density 2.56 gcm ^-3 , has a melting point of 1340 ° and is readily soluble in water with an alkaline reaction. It arises, for example, when heating Thomasschlacke with coal and potassium sulfate. Despite the higher price, the more soluble, therefore highly effective, potassium phosphates are often preferred over the corresponding sodium compounds in the detergent industry. Tetrasodium diphosphate (sodium pyrophosphate), Na ₄ P ₂ O ₇ , exists in anhydrous form (density 2.534 gcm ^-3 , melting point 988 °, also indicated 880 °) and as decahydrate (density 1.815-1.836 gcm ^-3 , melting point 94 ° with loss of water) , For substances are colorless, in water with alkaline reaction soluble crystals. Na ₄ P ₂ O ₇ is formed on heating of disodium phosphate to> 200 ° or by reacting phosphoric acid with soda in a stoichiometric ratio and dewatering the solution by spraying. The decahydrate complexes heavy metal salts and hardness agents and therefore reduces the hardness of the water. Potassium diphosphate (potassium pyrophosphate), K ₄ P ₂ O ₇ , exists in the form of the trihydrate and is a colorless, hygroscopic powder with a density of 2.33 gcm ^-3 , which is soluble in water, the pH being 1% Solution at 25 ° 10.4. Condensation of NaH ₂ PO ₄ or KH ₂ PO ₄ results in higher mol. Sodium and potassium phosphates, in which one can distinguish cyclic representatives, the sodium or Kaliummetaphosphate and chain types, the sodium or potassium polyphosphates. In particular, for the latter are a variety of names in use: melting or annealing phosphates, Graham's salt, Kurrolsches and Madrell's salt. All higher sodium and potassium phosphates are collectively referred to as condensed phosphates. The technically important pentasodium triphosphate, Na ₅ P ₃ O ₁₀ (sodium tripolyphosphate), is an anhydrous or with 6 H ₂ O crystallizing, non-hygroscopic, white, water-soluble salt of the general formula NaO- [P (O) (ONa) -O] _n -Na with n = 3. In 100 g of water dissolve at room temperature about 17 g, at 60 ° about 20 g, at 100 ° around 32 g of kristaffwasserfreien salt; after two hours of heating the solution to 100 ° caused by hydrolysis about 8% orthophosphate and 15% diphosphate. In the preparation of pentasodium triphosphate is phosphoric acid with sodium carbonate solution or sodium hydroxide in the Stoichiometric ratio brought to the reaction and the solution dehydrated by spraying. Similar to Graham's salt and sodium diphosphate, pentasodium triphosphate dissolves many insoluble metal compounds (including lime soaps, etc.). Pentakaliumtriphosphat, K ₅ P ₃ O ₁₀ (potassium tripolyphosphate), for example, in the form of a 50 wt .-% solution (> 23% P ₂ O ₅ , 25% K ₂ O) in the trade. The potassium polyphosphates are widely used in the washing and cleaning industry. There are also sodium potassium tripolyphosphates which can also be used in the context of the present invention. These arise, for example, when hydrolyzed sodium trimetaphosphate with KOH:
(NaPO ₃ ) ₃ + 2 KOH → Na ₃ K ₂ P ₃ O ₁₀ + H ₂ O

These are used according to the invention exactly as sodium tripolyphosphate, potassium tripolyphosphate or mixtures of these two; Mixtures of sodium tripolyphosphate and sodium potassium tripolyphosphate or mixtures of potassium tripolyphosphate and sodium potassium tripolyphosphate or mixtures of sodium tripolyphosphate and potassium tripolyphosphate and sodium potassium tripolyphosphate can also be used according to the invention.

With regard to component e), in a preferred embodiment, agents according to the invention contain from 1.5% by weight to 5% by weight of polymeric polycarboxylate, in particular selected from the polymerization or copolymerization products of acrylic acid, methacrylic acid and / or maleic acid. Among these, particularly preferred are the homopolymers of acrylic acid and, among these, those having an average molecular weight in the range from 5,000 D to 15,000 D (PA standard).

Detergents or cleaning agents which contain a cellulose derivative or water-soluble builder block to be used according to the invention or are used together or used in the process according to the invention may contain all customary other constituents of such agents which do not undesirably interact with the cellulose derivative or the water-soluble cellulose derivative Builder block interact. Preferably, the cellulose derivative in amounts of from 0.1 wt .-% to 5 wt .-%, in particular 0.5 wt .-% to 2.5 wt .-% incorporated in detergents or cleaning agents.

It has surprisingly been found that such cellulose derivatives having the abovementioned properties have a positive effect on the action of certain other washing and cleaning agent ingredients and conversely that the effect of the cotton-active soil-release cellulose derivative is additionally enhanced by certain other detergent ingredients. These effects occur in particular with enzymatic active substances, in particular proteases and lipases, with peroxygen bleaching agents, in particular alkali percarbonates, with sulphate and sulphonate synthetic anionic surfactants, with color transfer inhibitors, for example vinylpyrrolidone, vinylpyridine or vinylimidazole polymers or copolymers or corresponding polybetaines, and in grayness inhibitors, for example other, in particular anionic cellulose ethers such as carboxymethylcellulose, which is why the use of at least one of said further ingredients together with the cellulose derivatives to be used according to the invention is preferred.

In a preferred embodiment, an agent used according to the invention or used in the process according to the invention comprises nonionic surfactant selected from fatty alkyl polyglycosides, fatty alkyl polyalkoxylates, in particular ethoxylates and / or propoxylates, fatty acid polyhydroxyamides and / or ethoxylation and / or propoxylation products of fatty alkylamines, vicinal diols, Fatty acid alkyl esters and / or fatty acid amides and mixtures thereof, in particular in an amount in the range of 2 wt .-% to 25 wt .-%.

Another embodiment of such agents comprises the presence of sulfate and / or sulfonate synthetic anionic surfactant, in particular fatty alkyl sulfate, fatty alkyl ether sulfate, sulfo fatty acid ester and / or sulfo fatty acid salt, in particular in an amount in the range from 2% to 25% by weight. The anionic surfactant is preferably selected from the alkyl or alkenyl sulfates and / or the alkyl or alkenyl ether sulfates in which the alkyl or alkenyl group has 8 to 22, in particular 12 to 18, carbon atoms. These are usually not around Individual substances, but cuts or mixtures. Of these, preference is given to those whose content of compounds having longer-chain radicals in the range from 16 to 18 carbon atoms is more than 20% by weight.

Suitable nonionic surfactants include the alkoxylates, in particular the ethoxylates and / or propoxylates of saturated or mono- to polyunsaturated linear or branched-chain alcohols having 10 to 22 C atoms, preferably 12 to 18 C atoms. The degree of alkoxylation of the alcohols is generally between 1 and 20, preferably between 3 and 10. They can be prepared in a known manner by reacting the corresponding alcohols with the corresponding alkylene oxides. Particularly suitable are the derivatives of fatty alcohols, although their branched-chain isomers, in particular so-called oxo alcohols, can be used for the preparation of usable alkoxylates. Useful are accordingly the alkoxylates, in particular the ethoxylates, primary alcohols with linear, in particular dodecyl, tetradecyl, hexadecyl or octadecyl radicals and mixtures thereof. In addition, suitable alkoxylation products of alkylamines, vicinal diols and carboxamides, which correspond to the said alcohols with respect to the alkyl part, usable. In addition, the ethylene oxide and / or propylene oxide insertion products of fatty acid alkyl esters, as described in the international patent application WO 90/13533 as well as fatty acid polyhydroxyamides, as prepared according to the methods of US Pat US 1,985,424 . US 2 016 962 and US 2,703,798 as well as the international patent application WO 92/06984 can be prepared. So-called alkylpolyglycosides which are suitable for incorporation in the compositions according to the invention are compounds of the general formula (G) _n -OR ¹² , in which R ^{12 is} an alkyl or alkenyl radical having 8 to 22 C atoms, G is a glycose unit and n is a number between 1 and 10 mean. Such compounds and their preparation are described, for example, in the European patent applications EP 92 355 . EP 301 298 . EP 357 969 and EP 362,671 or the US patent US 3,547,828 described. The glycoside component (G) _n are oligomers or polymers of naturally occurring aldose or ketose monomers, in particular glucose, mannose, fructose, galactose, talose, gulose, altrose, allose, idose, ribose, arabinose, xylose and lyxose. The oligomers consisting of such glycosidically linked monomers are characterized not only by the nature of the sugars contained in them by their number, the so-called Oligomerisierungsgrad. The degree of oligomerization n assumes as the value to be determined analytically generally broken numerical values; it is between 1 and 10, with the glycosides preferably used below a value of 1.5, in particular between 1.2 and 1.4. Preferred monomer building block is glucose because of its good availability. The alkyl or alkenyl moiety R ^{12 of} the glycosides preferably also originates from readily available derivatives of renewable raw materials, in particular from fatty alcohols, although their branched-chain isomers, in particular so-called oxoalcohols, can also be used for the preparation of useful glycosides. Accordingly, the primary alcohols having linear octyl, decyl, dodecyl, tetradecyl, hexadecyl or octadecyl radicals and mixtures thereof are particularly suitable. Particularly preferred alkyl glycosides contain a Kokosfettalkylrest, that is, mixtures having substantially R ¹² = dodecyl and R ¹² = tetradecyl.

Nonionic surfactant is used in accordance with the invention or used in the method according to the invention in agents which contain a soil-release agent used in the invention, preferably in amounts of 1 wt .-% to 30 wt.%, In particular from 1 wt .-% to 25 wt .-%, wherein amounts in the upper part of this range are more likely to be found in liquid detergents and particulate detergents preferably contain rather lower amounts of up to 5 wt .-%.

The agents may instead or additionally contain other surfactants, preferably synthetic anionic surfactants of the sulfate or sulfonate type, such as, for example, alkylbenzenesulfonates, in amounts of preferably not more than 20% by weight, in particular from 0.1% by weight to 18% by weight. %, in each case based on total resources. Suitable synthetic anionic surfactants which are particularly suitable for use in such compositions are the alkyl and / or alkenyl sulfates having 8 to 22 C atoms which carry an alkali, ammonium or alkyl or hydroxyalkyl-substituted ammonium ion as counter cation. Preference is given to the derivatives of the fatty alcohols having in particular 12 to 18 carbon atoms and their branched-chain analogs, the so-called oxo alcohols. The alkyl and alkenyl sulfates can be prepared in a known manner by reaction of the corresponding alcohol component with a conventional sulfating reagent, in particular sulfur trioxide or chlorosulfonic acid, and subsequent neutralization with alkali metal, ammonium or alkyl or hydroxyalkyl-substituted ammonium bases are prepared. Sulfur-type surfactants which can be used also include the sulfated alkoxylation products of the alcohols mentioned, known as ether sulfates. Such ether sulfates preferably contain from 2 to 30, in particular from 4 to 10, ethylene glycol groups per molecule. Suitable anionic surfactants of the sulfonate type include the α-sulfoesters obtainable by reaction of fatty acid esters with sulfur trioxide and subsequent neutralization, in particular those of fatty acids having 8 to 22 C atoms, preferably 12 to 18 C atoms, and linear alcohols having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, derivative sulfonation, as well as the formal saponification resulting from these sulfo fatty acids.

Other optional surface-active ingredients are soaps, suitable being saturated fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid or stearic acid, and soaps derived from natural fatty acid mixtures, for example coconut, palm kernel or tallow fatty acids. In particular, those soap mixtures are preferred which are composed of 50 wt.% To 100 wt.% Of saturated C ₁₂ -C ₁₈ fatty acid soaps and up to 50 wt.% Of oleic acid soap. Preferably, soap is included in amounts of from 0.1% to 5% by weight. However, especially in liquid compositions containing a polymer used according to the invention, higher amounts of soap, as a rule up to 20% by weight, can also be present.

If desired, the compositions may also contain betaines and / or cationic surfactants which, if present, are preferably used in amounts of from 0.5% to 7% by weight. Among them, the esterquats discussed below are particularly preferred.

An agent which contains a cellulose derivative to be used according to the invention or is used together or used in the process according to the invention contains peroxygen-based bleaches, in particular in amounts ranging from 5% to 70% by weight, and optionally bleach activator , especially in quantities in Range from 2% to 10% by weight. The bleaches in question are preferably the peroxygen compounds generally used in detergents, such as percarboxylic acids, for example dodecanediperic acid or phthaloylaminoperoxicaproic acid, hydrogen peroxide, alkali metal perborate, which may be present as tetra- or monohydrate, percarbonate, perpyrophosphate and persilicate, which are generally used as alkali metal salts, in particular as sodium salts. Such bleaching agents are present in the compositions preferably in amounts of up to 25 wt .-%, in particular up to 15 wt .-% and particularly preferably from 5 wt .-% to 15 wt .-%, each based on the total agent, wherein in particular alkali metal percarbonate is used. Preferred alkali metal herein is sodium, as well as any other part of the present specification, although lithium, potassium and rubidium salts may be used if desired. The encapsulated alkali metal percarbonate particles which are preferably contained in compositions according to the invention have an alkali percarbonate core which may have been produced by any desired preparation process and may also contain stabilizers known per se, such as magnesium salts, silicates and phosphates. The manufacturing processes customary in practice are, in particular, so-called crystallization processes and fluidized-bed spray granulation processes. In the crystallization process, hydrogen peroxide and alkali carbonate are reacted in aqueous phase to alkali metal percarbonate and the latter is separated from the aqueous mother liquor after crystallization. While alkali metal percarbonate has been crystallized in the presence of a higher concentration of an inert salt, such as sodium chloride, in older processes, methods are now known in which crystallization can also take place in the absence of a salting-out agent. By way of example, the European patent application EP 0 703 190 directed. In fluidized bed spray granulation, an aqueous solution of hydrogen peroxide and an aqueous solution of alkali carbonate are sprayed onto alkali carbonate seeds which are in a fluidized bed and water is evaporated at the same time. The growing in the fluidized bed granules is withdrawn in total or in a classifying manner from the fluidized bed. As examples of such a production process, reference is made to the international patent application WO 96/06615 directed. Finally, alkali metal percarbonate produced by a process comprising contacting solid alkali carbonate or a hydrate thereof with an aqueous hydrogen peroxide solution and drying, core of the alkali metal percarbonate particles.

The alkali metal percarbonate optionally contained in compositions according to the invention preferably has at least two coating layers, an innermost layer containing at least one hydrate-forming inorganic salt and an outer layer alkali silicate. In this case, the outer alkali metal silicate-containing coating layer can either be the outermost coating layer of a coating comprising at least two layers or a coating layer which is not the innermost one, directly on the alkali metal percarbonate, which in turn can be superposed by one or more layers. Although here as well as in the prior art of individual layers is mentioned, it should be noted that the components of the superimposed layers can merge into each other at least in the border area. This at least partial penetration results from the fact that during the coating of alkali metal percarbonate particles, which have an innermost coating layer, this is at least superficially dissolved when a solution containing a coating component or the coating components of a second coating layer is sprayed on.

The optionally present component of the bleach activators comprises the commonly used N- or O-acyl compounds, for example polyacylated alkylenediamines, in particular tetraacetylethylenediamine, acylated glycolurils, in particular tetraacetylglycoluril, N-acylated hydantoins, hydrazides, triazoles, urazoles, diketopiperazines, sulphurylamides and cyanurates, and also carboxylic acid anhydrides , in particular phthalic anhydride, carboxylic acid esters, in particular sodium isononanoylphenolsulfonat, and acylated sugar derivatives, in particular pentaacetylglucose, as well as cationic nitrile derivatives such as trimethylammoniumacetonitrile salts. The bleach activators may have been coated or granulated in a known manner with coating substances in order to avoid the interaction with the per compounds, with the aid of carboxymethylcellulose granulated tetraacetylethylenediamine having average particle sizes of 0.01 mm to 0.8 mm, as for example according to the in the European patent specification EP 37 026 granulated 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine, as described in the German Patent DD 255 884 described method can be prepared, and / or after in the international patent applications WO 00/50553 . WO 00/50556 . WO 02/12425 . WO 02/12426 or WO 02/26927 Particularly preferred is the trialkylammonium acetonitrile formulated in particulate form. In detergents and cleaners, such bleach activators are preferably present in amounts of up to 8% by weight, in particular from 2% by weight to 6% by weight, based in each case on the total agent.

In addition, the agents may contain other ingredients customary in detergents and cleaners. These optional ingredients include, in particular, enzymes, enzyme stabilizers, foam inhibitors, for example organopolysiloxanes or paraffins, solvents and optical brighteners, for example stilbene disulfonic acid derivatives. Preferably, in compositions which comprise a cellulose derivative used according to the invention, up to 1% by weight, in particular 0.01% by weight to 0.5% by weight, of optical brighteners, in particular compounds from the class of the substituted 4,4 ' -Bis (2,4,6-triamino-s-triazinyl) -stilbene-2,2'-disulfonic acids and up to 2 wt .-%, in particular 0.1 wt .-% to 1 wt .-% foam inhibitors , Wherein said weight content in each case relate to the total mean.

Solvents which can be used in particular for liquid agents are, in addition to water, preferably those which are water-miscible. These include the lower alcohols, for example, ethanol, propanol, isopropanol, and the isomeric butanols, glycerol, lower glycols, such as ethylene and propylene glycol, and the derivable from said classes of compounds ether. In such liquid agents, the cellulose derivatives used in the invention are usually dissolved or in suspended form.

Optionally present enzymes are preferably selected from the group comprising protease, amylase, lipase, cellulase, hemicellulase, oxidase, peroxidase or mixtures thereof. First and foremost, proteases derived from microorganisms, such as bacteria or fungi, come into question. It can be obtained in a known manner by fermentation processes from suitable microorganisms, for example, in the German Offenlegungsschriften DE 19 40 488 . DE 20 44 161 . DE 21 01 803 and DE 21 21 397 , the US patents US Pat. No. 3,623,957 and US 4,264,738 , the European patent application EP 006 63 8 as well as the international patent application WO 91/02792 are described. Proteases are commercially available, for example, under the names BLAP®, Savinase®, Esperase®, Maxatase®, Optimase®, Alcalase®, Durazym® or Maxapem®. The lipase which can be used can be obtained from Humicola lanuginosa, as for example in European patent applications EP 258,068 . EP 305 216 and EP 341 947 described from Bacillus species, such as in the international patent application WO 91/16422 or the European patent application EP 384 717 described, from Pseudomonas species, such as in the European patent applications EP 468 102 . EP 385 401 . EP 375 102 . EP 334 462 . EP 331 376 . EP 330 641 . EP 214,761 . EP 218 272 or EP 204 284 or the international patent application WO 90/10695 described, from Fusarium species, such as in the European patent application EP 130 064 described from Rhizopus species, such as in the European patent application EP 117 553 described or from Aspergillus species, such as in the European patent application EP 167,309 be described. Suitable lipases are for example available under the names Lipolase ^®, Lipozym ^®, Lipomax® ^®, Lipex ^{®, ®} Amano lipase, Toyo Jozo ^® lipase, Meito ^® lipase and Diosynth lipase ^® commercially. Suitable amylases are commercially available for example under the name Maxamyl ^®, Termamyl ^®, Duramyl ^® and Purafect ^® OxAm. The usable cellulase may be a recoverable from bacteria or fungi enzyme, which has a pH optimum, preferably in the weakly acidic to slightly alkaline range of 6 to 9.5. Cellulases of this type are known, for example, from German Offenlegungsschriften DE 31 17 250 . DE 32 07 825 . DE 32 07 847 . DE 33 22 950 or the European patent applications EP 265 832 . EP 269 977 . EP 270 974 . EP 273 125 such as EP 339,550 and international patent applications WO 95/02675 and WO 97/14804 known and commercially available under the name Celluzyme ^{®, ®} and Carezyme Ecostone® ^®.

Among the usual, optionally present in liquid detergents usual enzyme stabilizers include amino alcohols, such as mono-, di-, triethanol- and -propanolamine and mixtures thereof, lower carboxylic acids, such as from the European patent applications EP 376,705 and EP 378,261 Boric acid or alkali borates, boric acid-carboxylic acid combinations, such as from the European patent application EP 451 921 known, boric acid esters, such as from the international patent application WO 93/11215 or the European patent application EP 511 456 known boronic acid derivatives, such as from the European patent application EP 583 536 known, calcium salts, for example from the European patent EP 28,865 known Ca-formic acid combination, magnesium salts, such as from the European patent application EP 378 262 known, and / or sulfur-containing reducing agents, such as from the European patent applications EP 080 748 or EP 080 223 known.

Suitable foam inhibitors include long-chain soaps, especially behenic soap, fatty acid amides, paraffins, waxes, microcrystalline waxes, organopolysiloxanes and mixtures thereof, which moreover can contain microfine, optionally silanated or otherwise hydrophobicized silica. For use in particulate agents, such foam inhibitors are preferably bound to granular, water-soluble carrier substances, as for example in the German Offenlegungsschrift DE 34 36 194 , the European patent applications EP 262 588 . EP 301 414 . EP 309 931 or the European patent specification EP 150 386 described.

It is also possible to use a combination of said cotton-active soil release cellulose derivative with a polyester active soil release polymer of a dicarboxylic acid and an optionally polymeric diol to enhance the cleaning performance of fabric washing. Also within the scope of the inventive composition and the process according to the invention, such combinations of said cotton-active soil release cellulose derivative with a polyester-active soil release-capable polymer are possible.

The known polyester-active soil release polymers which can be used in addition to the cellulosic derivatives essential to the invention include copolyesters of dicarboxylic acids, for example adipic acid, phthalic acid or terephthalic acid, diols, for example ethylene glycol or propylene glycol, and polydiols, for example polyethylene glycol or polypropylene glycol. Preferred soil release polymers include those compounds which formally accessible by esterification of two monomeric moieties, the first monomer being a dicarboxylic acid HOOC-Ph-COOH and the second monomer being a diol HO- (CHR ¹¹ -) _a OH, also known as polymeric diol H- (O- (CHR ₁₁ -) _a ) _b OH may be present. Therein, Ph is an o-, m- or p-phenylene radical which can carry 1 to 4 substituents selected from alkyl radicals having 1 to 22 C atoms, sulfonic acid groups, carboxyl groups and mixtures thereof, R ¹¹ denotes hydrogen, an alkyl radical having 1 to 22 C atoms and mixtures thereof, a is a number from 2 to 6 and b is a number from 1 to 300. Preferably, in the polyesters obtainable from these, both monomer diol units -O- (CHR ₁₁ -) _a O- and also polymeric diol units - ( O- (CHR ¹¹ -) _a ) _b O-. The molar ratio of monomer diol units to polymer diol units is preferably 100: 1 to 1: 100, in particular 10: 1 to 1:10. In the polymer diol units, the degree of polymerization b is preferably in the range of 4 to 200, especially 12 to 140. The molecular weight or the average molecular weight or the maximum molecular weight distribution of preferred soil release polyester is in the range of 250 to 100,000, especially 500 to 50,000 The acid underlying the remainder Ph is preferably selected from terephthalic acid, isophthalic acid, phthalic acid, trimellitic acid, mellitic acid, the isomers of sulfophthalic acid, sulfoisophthalic acid and sulfoterephthalic acid and mixtures thereof. If their acid groups are not part of the ester bonds in the polymer, they are preferably in salt form, in particular as alkali or ammonium salt. Among these, the sodium and potassium salts are particularly preferable. If desired, in place of the monomer HOOC-Ph-COOH small proportions, in particular not more than 10 mol% based on the proportion of Ph with the meaning given above, of other acids having at least two carboxyl groups, in the soil release-capable polyester be included. These include, for example, alkylene and alkenylene dicarboxylic acids such as malonic acid, succinic acid, fumaric acid, maleic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid and sebacic acid. The preferred diols HO- (CHR ¹¹ -) _a OH include those in which R ^{11 is} hydrogen and a is a number from 2 to 6, and those in which a is 2 and R ¹¹ is hydrogen and the alkyl radicals 1 to 10, in particular 1 to 3 C-atoms is selected. Among the latter diols, those of the formula HO-CH ₂ -CHR ¹¹ OH, in which R ^{11 has} the abovementioned meaning, are particularly preferred. Examples of diol components are ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,2-decanediol, 1,2-dodecanediol and neopentyl glycol. Particularly preferred among the polymeric diols is polyethylene glycol having an average molecular weight in the range of 1000 to 6000.

If desired, the polyesters synthesized as described above may also be end-capped, alkyl groups having from 1 to 22 carbon atoms and esters of monocarboxylic acids being suitable as end groups. The ester groups bound by end groups alkyl, alkenyl and Arylmonocarbonsäuren with 5 to 32 carbon atoms, in particular 5 to 18 carbon atoms, based. These include valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, undecanoic acid, undecenoic acid, lauric acid, lauroleinic acid, tridecanoic acid, myristic acid, myristoleic acid, pentadecanoic acid, palmitic acid, stearic acid, petroselinic acid, petroselaidic acid, oleic acid, linoleic acid, linolaidic acid, linolenic acid, levostearic acid, arachidic acid , Gadoleic acid, arachidonic acid, behenic acid, erucic acid, brassidic acid, clupanodonic acid, lignoceric acid, cerotic acid, melissic acid, benzoic acid, which may carry 1 to 5 substituents having a total of up to 25 carbon atoms, in particular 1 to 12 carbon atoms, for example tert-butylbenzoic acid , The end groups may also be based on hydroxymonocarboxylic acids having 5 to 22 carbon atoms, which include, for example, hydroxyvaleric acid, hydroxycaproic acid, ricinoleic acid, their hydrogenation product hydroxystearic acid, and o-, m- and p-hydroxybenzoic acid. The hydroxymonocarboxylic acids may in turn be linked to one another via their hydroxyl group and their carboxyl group and thus be present several times in an end group. Preferably, the number of hydroxymonocarboxylic acid units per end group, that is to say their degree of oligomerization, is in the range from 1 to 50, in particular from 1 to 10. In a preferred embodiment of the invention, polymers of ethylene terephthalate and polyethylene oxide terephthalate in which the polyethylene glycol units have molecular weights of 750 to 5000 and the molar ratio of ethylene terephthalate to polyethylene oxide terephthalate is 50:50 to 90:10, used in combination with the cellulose derivatives.

The soil release polymers are preferably water-soluble, with the term "water-soluble" having a solubility of at least 0.01 g, preferably at least 0.1 g of the polymer per liter of water at room temperature and pH 8 is to be understood. However, preferred polymers have a solubility of at least 1 g per liter, in particular at least 10 g per liter, under these conditions.

Preferred laundry aftertreatment agents have a so-called ester quat, that is a quaternized ester of carboxylic acid and aminoalcohol, as a laundry softening agent. These are known substances which can be obtained by the relevant methods of preparative organic chemistry. In this connection, please refer to the international patent application WO 91/01295 referenced, after which triethanolamine partially esterified with fatty acids in the presence of hypophosphorous acid, air passes and then quaternized with dimethyl sulfate or ethylene oxide. From the German patent DE 43 08 794 Furthermore, a process for the preparation of solid ester quats is known, in which one carries out the quaternization of Triethanolaminestem in the presence of suitable dispersants, preferably fatty alcohols. Surveys on this topic are for example from R. Puchta et al. in Tens.Surf.Det., 30, 186 (1993 ) M.Brock in Tens.Surf.Det. 30, 394 (1993 ) R. Lagerman et al. in J.Am.Oil.Chem.Soc., 71, 97 (1994 ) such as I.Shapiro in Cosm.Toil. 109, 77 (1994 ) published.

in der R¹CO für einen Acylrest mit 6 bis 22 Kohlenstoffatomen, R² und R³ unabhängig voneinander für Wasserstoff oder R¹CO, R⁴ für einen Alkylrest mit 1 bis 4 Kohlenstoffatomen oder eine (CH₂CH₂O)_qH-Gruppe, m, n und p in Summe für 0 oder Zahlen von 1 bis 12, q für Zahlen von 1 bis 12 und X für ein ladungsausgleichendes Anion wie 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-Talgbeziehungsweise Palmfettsäuren sowie elaidinsäure-reiche C_16/18-Fettsäureschnitte eingesetzt. Zur Herstellung der quaternierten Ester können die Fettsäuren und das Triethanolamin in der Regel 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 bevorzugt eingesetzten Esterquats stellen technische Mischungen von Mono-, Di- und Triestern mit einem durchschnittlichen Veresterungsgrad von 1,5 bis 1,9 dar und leiten sich von technischer C_16/18- Talg- bzw. Palmfettsäure (Iodzahl 0 bis 40) ab. Quaternierte Fettsäuretriethanolaminestersalze der Formel (I), in der R¹CO für einen Acylrest mit 16 bis 18 Kohlenstoffatomen, R² für R¹CO, R³ für Wasserstoff, R⁴ für eine Methylgruppe, m, n und p für 0 und X für Methylsulfat steht, haben sich als besonders vorteilhaft erwiesen.Ester quats preferred in the compositions are quaternized fatty acid triethanolamine ester salts which follow formula (I),

in the R ¹ CO for an acyl radical having 6 to 22 carbon atoms, R ² and R ^{3 are} independently hydrogen or R ¹ CO, R ^{4 is} an alkyl radical having 1 to 4 carbon atoms or a (CH ₂ CH ₂ O) _q H Group, m, n and p in total are 0 or numbers from 1 to 12, q is numbers from 1 to 12 and X is a charge-balancing anion such as halide, alkyl sulfate 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, as used, for example, in US Pat the pressure splitting of natural fats and oils are incurred. 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 elaidic acid-rich C _16/18 fatty acid cuts. To prepare the quaternized esters, the fatty acids and the triethanolamine can generally be used in a molar ratio of 1.1: 1 to 3: 1. 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 used 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 value 0 to 40) , Quaternized fatty acid triethanolamine ester salts of the formula (I) in which R ^{1 is} CO for an acyl radical having 16 to 18 carbon atoms, R ^{2 is} R ¹ CO, R ^{3 is} hydrogen, R ^{4 is} a methyl group, m, n and p is 0 and X is Methyl sulfate is, have proven to be particularly advantageous.

in der R¹CO für einen Acylrest mit 6 bis 22 Kohlenstoffatomen, R² für Wasserstoff oder R¹CO, R⁴ und R⁵ unabhängig voneinander für Alkylreste mit 1 bis 4 Kohlenstoffatomen, m und n in Summe für 0 oder Zahlen von 1 bis 12 und X für ein ladungsausgleichendes Anion wie Halogenid, Alkylsulfat oder Alkylphosphat steht.In addition to the quaternized carboxylic acid triethanolamine ester salts, quaternized ester salts of carboxylic acids with diethanolalkylamines of the formula (II) are also suitable as esterquats.

in the R ¹ CO for an acyl radical having 6 to 22 carbon atoms, R ^{2 is} hydrogen or R ¹ CO, R ⁴ and R ^{5 are} independently alkyl radicals having 1 to 4 carbon atoms, m and n in total for 0 or numbers from 1 to 12 and X is a charge-balancing anion such as halide, alkyl sulfate or alkyl phosphate.

in der R¹CO für einen Acylrest mit 6 bis 22 Kohlenstoffatomen, R² für Wasserstoff oder R¹CO, R⁴, R⁶ und R⁷ unabhängig voneinander für Alkylreste mit 1 bis 4 Kohlenstoffatomen, m und n in Summe für 0 oder Zahlen von 1 bis 12 und X für ein ladungsausgleichendes Anion wie Halogenid, Alkylsulfat oder Alkylphosphat steht.Finally, the quaternized ester salts of carboxylic acids with 1,2-dihydroxypropyldialkylamines of the formula (III) should be mentioned as a further group of suitable esterquats.

in the R ¹ CO for an acyl radical having 6 to 22 carbon atoms, R ^{2 is} hydrogen or R ¹ CO, R ⁴ , R ⁶ and R ^{7 are} independently alkyl radicals having 1 to 4 carbon atoms, m and n in total for 0 or numbers from 1 to 12 and X is a charge-balancing anion such as halide, alkyl sulfate or alkyl phosphate.

With regard to the selection of the preferred fatty acids and the optimal degree of esterification, the exemplary statements given for (I) apply mutatis mutandis to the esterquats of the formulas (II) and (III). Typically, the esterquats are marketed in the form of 50 to 90 weight percent alcoholic solutions, which can also be easily diluted with water, with ethanol, propanol and isopropanol being the usual alcoholic solvents.

Esterquats are preferably used in amounts of from 5% by weight to 25% by weight, in particular from 8% by weight to 20% by weight, in each case based on the total laundry aftertreatment agent. If desired, the laundering agent may additionally contain detergent ingredients listed above, unless they unduly interact negatively with the esterquat. It is preferably a liquid, water-containing agent.

Solid agents are preferably prepared by mixing a particulate soil release-containing cellulose derivative with other detergent ingredients present in solid form, especially the components of the water-soluble builder block. In this case, it is preferable to use a spray-drying step to produce the particle which contains the soil release-capable cellulose derivative. Alternatively it is also possible to have a compacting Use compounding step for the preparation of this particle and optionally also for the preparation of the finished composition.

example

A detergent (V1) containing SECTION 12 parts by weight C12 / 14 fatty alcohol * 7 EO 3 parts by weight TAED 2.5 parts by weight percarbonate 13 parts by weight soda 20 parts by weight sodium 5 parts by weight Sokalan ^® CP 5 ^a) 3 parts by weight sodium sulphate 27 parts by weight Tinopal ^® DMS-X ^b) 0.2 parts by weight a) Polymeric polycarboxylate, manufacturer BASF AG
b) Optical brightener, manufacturer Ciba 0.5 part by weight of methyl hydroxyethyl cellulose (DS 1.89, MS 0.15, average molecular weight 100,000) ( W1 ) was added. Pure cotton, finished cotton, and 50/50 polyester / cotton blends were treated as follows: Washer: Miele W 918 Novotronic ^® Primary washing power: Single-lye procedure normal program Washing temperature door: 40 ° C Determination: 5 times Fleet size: 18l Water hardness: 16 ° dH filling laundry: 3.5 kg of clean laundry

• 0,10 g Lippenstift
• 0,10 g schwarze Schuhcreme
• 0,10 g Staub / Hautfett

The fabrics were undeluted washed three times with each detergent to be tested under the conditions given above and dried after each wash. After prewashing three times, the fabrics were soiled by hand with the following standardized soiling:

• 0.10 g lipstick
• 0.10 g black shoe polish
• 0.10 g of dust / skin fat

The soiled fabrics were measured with a Minolta CR 200 and then aged at RT for 7 days. Thereafter, the soiled cloths were stapled on towels and washed under the conditions given above.

The fabrics were dried and measured again with a Minolta CR 200. This resulted in the following wash results (dde values): <u> Table 1: Pure cotton </ u> lipstick Shoe polish black Dust / skin fat V1 75.1 30.5 21.9 W1 78.5 34.7 25.4 lipstick Shoe polish black Dust / skin fat V1 76.4 55.3 47.2 W1 81.5 58.4 50.8 lipstick Shoe polish black Dust / skin fat V1 19.9 55.1 59.6 W1 24.0 58.3 63.8

It can be seen that, when using the detergent with the cellulose derivative to be used according to the invention, a significantly better washing performance results than when using the agent which lacks the cellulose derivative.

Claims (20)

1. A builder-containing washing agent or detergent, containing a water-soluble builder block, which is composed of components

   a) 5% by weight to 35% by weight of citric acid, alkali citrate and/or alkali carbonate, which may be at least partly replaced by alkali hydrogencarbonate,

   b) up to 5% by weight of alkali silicate with a module in the 1.8-2.5 range,

   c) up to 2% by weight of phosphonic acid and/or alkali phosphonate,

   d) up to 50% by weight of alkali phosphate, and

   e) up to 10% by weight of polymeric polycarboxylate,

   a peroxygen-based bleaching agent, and a cellulose derivative with dirt-removing power, which is obtainable by alkylation and hydroxyalkylation of cellulose.
2. The agent according to claim 1, characterized in that the cellulose derivative is alkylated with C₁-C₁₀ groups, in particular C₁-C₃ groups and in that it additionally bears C₂-C₁₀ hydroxyalkyl groups, in particular C₂-C₃ hydroxyalkyl groups.
3. The agent according to claim 1 or 2, characterized in that on the average, 0.5 to 2.5, in particular 1 to 2 alkyl groups and 0.02 to 0.5, in particular 0.05 to 0.3 hydroxyalkyl groups per monomer anhydroglycose unit are contained in the cellulose derivative.
4. The agent according to any of claims 1 to 3, characterized in that the average molar weight of the cellose derivative is in the 10,000 Da-150,000 Da range.
5. The agent according to any of claims 1 to 4, characterized in that the average molar weight of the cellulose derivative is in the 40,000 Da-120,000 Da range, in particular 80,000 Da-110,000 Da range.
6. The agent according to any of claims 1 to 5, characterized in that it contains from 0.1% by weight to 5% by weight, in particular from 0.5% by weight to 2.5% by weight, of the cellulose derivative with dirt-removing power.
7. The agent according to any of claims 1 to 6, characterized in that the proportion of the builder block is at least 15% by weight.
8. The agent according to any of claims 1 to 7, characterized in that the proportion of the builder block is up to 55% by weight, in particular from 25% by weight to 50% by weight.
9. The agent according to any of claims 1 to 8, characterized in that from 15% by weight to 25% by weight of alkali carbonate, which may be at least partly replaced by alkali hydrogencarbonate, and up to 5% by weight, in particular from 0.5% by weight to 2,5% by weight of citric acid and/or alkali citrate, are contained as component a).
10. The agent according to any of claims 1 to 8, characterized in that from 5% by weight to 25% by weight, in particular from 5% by weight to 15% by weight, of citric acid and/or alkali citrate, and up to 5% by weight, in particular from 1% by weight to 5% by weight of alkali carbonate, which may be at least partly replaced by alkali hydrogencarbonate, are contained as component a).
11. The agent according to any of claims 1 to 10, characterized in that the component a) has alkali carbonate and alkali hydrogencarbonate in a weight ratio of 10:1 to 1:1.
12. The agent according to any of claims 1 to 11, characterized in that from 1% by weight to 5% by weight of alkali silicate with a module in the 1.8-2.5 range, is contained as component b).
13. The agent according to any of claims 1 to 12, characterized in that from 0.05% by weight to 1% by weight of phosphonic acid and/or alkali phosphonate, in particular selected from hydroxy- and/or amino-alkylphosphonic acids and/or their alkali salts, are contained as component c).
14. The agent according to any of claims 1 to 13, characterized in that from 15% by weight to 35% by weight of alkali phosphate, in particular trisodium polyphosphate, are contained as component d).
15. The agent according to any of claims 1 to 14, characterized in that from 1,5% by weight to 5% by weight of polymeric polycarboxylate, in particular selected from polymerization or copolymerization of acrylic acid, methacrylic acid and/or maleic acid, are contained as component e).
16. The use of a cellulose derivative with dirt-removing power, which is obtainable by alkylation and hydroxyalkylation of cellulose, in order to increase cleaning performance of washing agents, which have a peroxygen-based bleaching agent and a water-soluble builder block which is composed of components

    a) 5% by weight to 35% by weight of citric acid, alkali citrate and/or alkali carbonate, which may be at least partly replaced by alkali hydrogencarbonate,

    b) up to 5% by weight of alkali silicate with a module in the 1.8-2.5 range,

    c) up to 2% by weight of phosphonic acid and/or alkali phosphonate,

    d) up to 50% by weight of alkali phosphate, and

    e) up to 10% by weight of polymeric polycarboxylate,

    for washing textiles, which are in particular made up of cotton, or which contain cotton.
17. A method for washing textiles, wherein a washing agent with a peroxygen-based bleaching agent and a water-soluble builder block, which is composed of components

    a) 5% by weight to 35% by weight of citric acid, alkali citrate and/or alkali carbonate, which may be at least partly replaced by alkali hydrogencarbonate,

    b) up to 5% by weight of alkali silicate with a module in the 1.8-2.5 range,

    c) up to 2% by weight of phosphonic acid and/or alkali phosphonate,

    d) up to 50% by weight of alkali phosphate, and

    e) up to 10% by weight of polymeric polycarboxylate,

    and a cellulose derivative with dirt-removing power which is obtainable by alkylation and hydroxyalkylation of cellulose.
18. A method for preparing solid agents according to any of claims 1 to 15, characterized in that a particle containing a cellulose derivative with dirt-removing power is mixed with other washing agent ingredients which exist as a solid.
19. The method according to claim 18, characterized in that a spray drying step is applied for producing the particle, which contains a cellulose derivative with dirt-removing power.
20. The method according to claim 18, characterized in that a compounding step with compaction is applied for producing the particle, which contains a cellulose derivative with dirt-removing power.