EP1592767A1 - Detergents or cleaning agents containing a bleaching agent, 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 is comprised of: (1) alkali metal percarbonate; (2) 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 10% 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 (3) 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 alkali metal percarbonates and contain only water-soluble builders.

Description

 Washing or cleaning agents containing bleaching agents with a water-soluble builder system and dirt-releasing cellulose derivative

The present invention relates to detergents or cleaning agents which, as a builder component, have only water-soluble components and contain cellulose derivative which is able to remove dirt and bleach.

In addition to the surfactants that are indispensable for washing or cleaning performance, detergents and cleaning agents normally also contain so-called builder substances, which have the task of supporting the performance of the surfactants by removing hardening agents, i.e. essentially calcium and magnesium ions Eliminate wash liquor so that they do not interact negatively with the surfactants. In the past, polyphosphates, especially trisodium polyphosphate, have been used very successfully for this purpose. Another known example of such builders that improve the primary washing power is zeolite Na-A, which is known to be able to form complexes with calcium ions in particular that their reaction with water hardness-forming anions, especially carbonate, is suppressed to form insoluble compounds. In addition, the builders, in particular in laundry detergents, are intended to prevent the redeposition of the dirt detached from the fiber or generally from the surface to be cleaned, and also from the reaction of water-hardness-forming cations with water-hardness-forming anions on the cleaned textile or the surface of the insoluble compounds. For this purpose, so-called co-builders, usually polymeric polycarboxylates, are usually used, which, in addition to their contribution to the secondary washing ability, advantageously also have a compounding action against the water hardness-forming cations.

In addition to the indispensable active ingredients mentioned, such as surfactants and builder materials, detergents generally contain other components that can be summarized under the term washing aids and the different active ingredient groups such as foam regulators, graying inhibitors, bleaches, enzymes and color transfer inhibitors. Such auxiliaries also include substances which impart dirt-repellent properties to the laundry fiber and which, if present during the washing process, support the dirt-removing ability of the other detergent constituents. The same applies analogously to cleaning agents for hard surfaces. Such dirt-releasing substances are often referred to as "soil release" active ingredients or because of their ability to make the treated surface, for example the fiber, dirt-repellent, "soil repellents". For example, the dirt-releasing effect of methyl cellulose is known from US Pat. No. 4,136,038. European patent application EP 0 213 729 discloses the reduced redeposition when using detergents which contain a combination of soap and nonionic surfactant with alkyl-hydroxyalkyl cellulose. Textile treatment agents are known from European patent application EP 0213 730, which contain cationic surfactants and nonionic Ceüuloseether with HLB values of 3.1 to 3.8. The US Pat. No. 4,000,093 discloses detergents which contain 0.1% by weight to 3% by weight of alkyl Ceüulose, hydroxyalkyl cellulose or alkyl-hydroxyalkyl cellulose and 5% by weight to 50% by weight. % Surfactant, the surfactant component consists essentially of C ₁₀ - to -C ₃ alkyl sulfate and has up to 5 wt .-% C ₁ alkyl sulfate and less than 5 wt .-% alkyl sulfate with alkyl radicals of C ₁ 5 and higher. The US Pat. No. 4,174,305 discloses detergents which contain 0.1% by weight to 3% by weight of alkyl cellulose, hydroxyalkyl cellulose or alkyl hydroxyalkyl cellulose and 5% by weight to 50% by weight Contain surfactant, the surfactant component consists essentially of C1.0 to Cπ-alkylbenzenesulfonate and has less than 5 wt .-% alkylbenzenesulfonate with alkyl radicals of C ₁₃ and higher. European patent application EP 0 634481 relates to a detergent which contains alkali percarbonate and one or more nonionic cellulose derivatives. The latter expressly disclose only hydroxyethyl cellulose, hydroxypropyl cellulose and methyl cellulose and, in the context of the examples, the methyl hydroxyethyl cellulose Tylose® MH50, the hydroxypropyl methyl cellulose Methocel® F4M and hydroxybutyl ethyl cellulose. European patent EP 0 271 312 P&G) relates to dirt-releasing active substances, among them cellulose alkyl ether and cellulose hydroxyalkyl ether (with DS 1.5 up to 2.7 and molecular weights from 2000 to 100000) such as methyl cellulose and ethyl cellulose, which are to be used with peroxygen bleaching agents in a weight ratio (based on the active oxygen content of the bleaching agent) of 10: 1 to 1:10. A detergent in liquid or granular form is known from European patent EP 0 948 591 Bl, which gives fabrics and textiles that are washed with them, textile appearance advantages such as pill / lint reduction, anti-color fading, improved abrasion resistance and / or increased softness and the 1 to Contains 80 wt .-% surfactant, 1 to 80 wt .-% organic or inorganic builder, 0.1 to 80 wt .-% of a hydrophobically modified nonionic cellulose ether with a molecular weight of 10,000 to 2,000,000, the modification in the Presence of optionally oligomerized (degree of polymerization up to 20) ethyleneoxy or 2-propyleneoxy ether units and of Cs- _24- alkyl substituents and the alkyl substituents are present in amounts of 0.1-5% by weight, based on the cellulose ether material have to be.

Because of their chemical similarity to polyester fibers in textiles made from this material, particularly effective dirt-releasing active ingredients are copolyesters which contain dicarboxylic acid units, alkylene glycol units and polyalkylene glycol units. Soil-removing copolyesters of the type mentioned and 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. German laid-open specification DT 22 53 063 lists acidic textile finishing agents which contain a copolymer of a dibasic carboxylic acid and an alkylene or cycloalkylene polyglycol and, if appropriate, an alkylene or cycloalkylene glycol. Polymers made from ethylene terephthalate and polyethylene oxide terephthalate, in which the polyethylene glycol units have molecular weights from 750 to 5000 and the molar ratio of ethylene terephthalate to polyethylene oxide terephthalate is 50:50 to 90:10, and their use in detergents are described in the German patent DE 28 57292 described. Polymers with a molecular weight of 15,000 to 50,000 Ethylene terephthalate and polyethylene oxide terephthalate, the polyethylene glycol units having molecular weights of 1000 to 10,000 and the molar ratio of ethylene terephthalate to polyethylene oxide terephthalate being 2: 1 to 6: 1, can be used in detergents according to German published patent application DE 33 24 258. European patent EP 066 944 relates to textile treatment agents which contain a copolyester of ethylene glycol, polyethylene glycol, aromatic dicarboxylic acid and sulfonated aromatic dicarboxylic acid in certain molar ratios. European or European patent EP 185 427 discloses methyl or ethyl end-capped polyesters with ethylene and / or propylene terephthalate and polyethylene oxide terephthalate units and detergents which contain such a soil release polymer. 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 polyesters are known which contain, in addition to oxyethylene groups and terephthalic acid units, 1,2-propylene, 1,2-butylene and / or 3-methoxy-1,2-propylene groups and glycerol units and with ci- until C ₄ alkyl groups are end group-capped. European patent specification EP 253 567 relates to soil release polymers with a molecular weight of 900 to 9000 made of ethylene terephthalate and polyethylene oxide terephthalate, the polyethylene glycol units having molecular weights of 300 to 3000 and the molar ratio of ethylene terephthalate to polyethylene oxide terephthalate 0.6 to Is 0.95. From European patent application EP 272 033, polyesters with poly-propylene terephthalate and polyoxyethylene terephthalate units which are end group-capped by C _M alkyl or acyl radicals are known. European patent EP 274 907 describes sulfoethyl end-capped terephthalate-containing soil-release polyesters. In European patent application EP 357 280, soil-release polyesters with terephthalate, alkylene glycol and poly-Ca ^ glycol units are produced by sulfonation of unsaturated end groups. German patent application DE 26 55 551 describes the reaction of such polyesters with polymers containing isocyanate groups and the use of the polymers prepared in this way to prevent dirt from being re-absorbed when washing synthetic fibers. From the German patent DE 28 46 984, detergents are known which, as a dirt-releasing polymer, are a reaction product of a polyester with a prepolymer containing terminal isocyanate groups, obtained from a diisocyanate and a hydrophilic nonionic macrodiol.

The majority of the polymers known from this extensive prior art have the disadvantage that they have no or only inadequate activity in textiles which do not consist, or at least not predominantly, of polyester. However, a large part of today's textiles consists of cotton or cotton-polyester blended fabrics, so that there is a need for polymers which are more effective at removing dirt and soiling on such textiles.

Among the above-mentioned washing auxiliaries, the bleaching agents are particularly important with regard to the strengthening of the washing or cleaning performance in relation to a large number of different types of soiling. Such auxiliaries include substances which support detergent performance in detergents through the oxidative degradation of soils on the textile or those which are in the liquor after detachment from the textile. The same applies analogously to cleaning agents for hard surfaces. Inorganic peroxygen compounds, in particular hydrogen peroxide and solid peroxygen compounds, which dissolve in water with the release of hydrogen peroxide or so-called active oxygen, such as sodium perborate and sodium carbonate perhydrate, have long been used as oxidizing agents for disinfection and bleaching purposes. The latter compound, which is often abbreviated as sodium percarbonate, is the addition compound of hydrogen peroxide with sodium carbonate (empirical formula 2 Na ₂ CO ₃ '3 H ₂ O ₂ ). The carbonate salts of the other alkali metals also form H2θ2 addition compounds. Due to the storage stability of the alkali percarbonate, which is often perceived as insufficient, in a warm, humid environment and in the presence of other common detergent and cleaning agent components, the alkali percarbonate must normally be stabilized against the loss of active oxygen. An essential principle for stabilization is to surround the alkali percarbonate particles with a shell, which can be of one or more layers. Each coating layer can contain one or more inorganic and / or organic coating components. Surprisingly, it has now been found that the dirt-releasing effect of cellulose derivatives is particularly pronounced when used in detergents or cleaning agents which contain alkali percarbonate and are free from water-insoluble builder material, that is to say they only contain water-soluble builders.

The invention therefore relates to a builder-containing washing or cleaning agent containing a water-soluble builder block, alkali percarbonate and dirt-releasing cellulose derivative which can be obtained by alkylation and hydroxyalkylation of cellulose

In addition to alkali percarbonate, the water-soluble builder block and the dirt-releasing cellulose derivative, the agent can contain all other ingredients commonly used in detergents or cleaning agents, provided that they do not unreasonably interact negatively with them or with one of them. However, the use of the term “builder block” is intended to express that the agents contain no other builders than those that are water-soluble, that is to say all of the builder substances contained in the agent are summarized in the “block” characterized in this way, the quantities being at most Exceptions are made to substances that may be contained in the other ingredients of the agents in small amounts as impurities or stabilizing additives in the commercial manner. In preferred agents according to the invention, in addition to the alkali percarbonate mentioned, there is no additional bleaching agent, although this is possible if desired. Preferred are agents in which the proportion of alkali percarbonate is 6% by weight to 30% by weight, in particular 10% by weight to 25% by weight. The preferred alkali metal here, as in all other places in the present description, is sodium, although lithium, potassium and rubidium salts can also be used if desired.

A second object of the invention is the use of dirt-releasing cellulose derivative, which can be obtained by alkylation and hydroxyalkylation of cellulose, for enhancing the cleaning performance of detergents containing alkipercarbonate, which have a water-soluble builder block have, when washing textiles that consist in particular of cotton or contain cotton.

Another object of the invention is a method for washing textiles, in which an alkalipercarbonate-containing detergent with a water-soluble builder block and a dirt-releasing cellulose derivative, which is obtainable by alkylation and hydroxyalkylation of cellulose, are used. This method can be carried out manually or, preferably, using a conventional household washing machine. It is possible to use the bleach-containing detergent and the dirt-releasing cellulose derivative at the same time or in succession. The simultaneous use can be carried out particularly advantageously by using a detergent containing bleach, which contains the cellulose derivative which is capable of removing dirt.

The washing performance-enhancing effect of the cellulose derivatives to be used according to the invention is particularly pronounced when used repeatedly, that is to say in particular for removing stains from corresponding textiles which had already been washed and / or aftertreated in the presence of the cellulose derivative before they were soiled. In connection with the aftertreatment, it should be pointed out that the positive aspect described can also be realized by a washing process in which the textile after the actual washing process, which can contain a cellulose derivative mentioned, using a percarbonate-containing detergent with a water-soluble builder block If this can also be free - is carried out, is brought into contact with an aftertreatment agent, for example in the course of a fabric softening step, which contains a cellulose derivative to be used according to the invention. With this procedure, too, the washing performance-enhancing effect of the cellulose derivatives to be used according to the invention occurs during the next washing process, even if, if desired, no detergent with a cellulose derivative mentioned is used again.

Preferred cellulose derivatives are those with to Cio groups, in particular Ci to C ₃ groups, are alkylated and additionally C ₂ to Cio-hydroxyalkyl groups, in particular C ₂ - to C ₃ hydroxyalkyl groups. These can be obtained in a known manner by reacting cellulose with appropriate alkylating agents, for example alkyl halides or alkyl sulfates, and then reacting with corresponding alkylene oxides, such as ethylene oxide and / or propylene oxide. In a preferred embodiment of the invention, the cellulose derivative contains on 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 anhydroglycol monomer unit. 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 the molecular weight of the slurry detachment - Wealthy cellulose derivative is based on the determination of the intrinsic viscosity of sufficiently dilute aqueous solutions using an Ubbelohde capillary viscometer (capillary 0c). Using a constant [H. Staudinger and F. Reinecke, "About molecular weight determination on cellulose ethers", Liebigs Annalen der Chemie 535, 47 (1938)] and a correction factor [F. Rodriguez and L. AGoettler, "The Flow of Moderately Concentrated Polymer Solutions in Water", Transactions of the Society of Rheology VHI, 3 17 (1964)], the degree of polymerization and the corresponding molecular weight, including the degrees of substitution (DS and MS) to calculate.

As described, the cellulose derivatives used according to the invention are simple to produce and ecologically and toxicologically harmless. They lead to a significantly better detachment of, in particular, grease and cosmetic stains on cotton or cotton-containing fabrics than is the case with compounds of the FaU known hitherto for this purpose. Alternatively, significant amounts of surfactants can be saved while maintaining the ability to remove fat.

The use according to the invention can take place in the course of a washing process in such a way that alkali percarbonate and the cehulose derivative are added to a detergent-containing liquor, and the cehulose derivative is separately added to a bleaching and detergent-containing liquor adds or preferably introduces the cellulose derivative into the liquor as part of a detergent according to the invention.

The use according to the invention in the context of a

The post-treatment process for the laundry can accordingly be carried out by adding the cellulose derivative separately to the rinsing liquor which is used after the washing step using a percarbonate-containing detergent with a water-soluble builder block, or as a component of the post-washing agent, in particular a fabric softener. In this aspect of the invention, said percarbonate-containing detergent with a water-soluble builder block can also contain a cellulose derivative to be used according to the invention, but can also be free of this. Conversely, the laundry post-treatment agent mentioned may also contain a percarbonate and / or water-soluble builder block, but may also be free of and / or these.

The alkali percarbonate contained in the agents according to the invention is preferably used in the form of coated alkali percarbonate particles which have an alkali percarbonate core which can be produced by any manufacturing process and can 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 converted to alkali percarbonate in the aqueous phase and the latter is separated from the aqueous mother liquor after crystallization. While in older processes alkali percarbonate was crystallized out in the presence of a higher concentration of an inert salt, such as sodium chloride, processes are now also known in which the crystallization can also take place in the absence of a salting-out agent. Reference is made, for example, to European patent application EP 0 703 190. In fluidized bed spray granulation, an aqueous hydrogen peroxide solution and an aqueous alkali carbonate solution are sprayed onto alkali carbonate nuclei which are in a fluidized bed, and water is evaporated at the same time. The granules growing in the fluidized bed are removed as a whole or in a classifying manner subtracted from the fluidized bed. As examples of such a manufacturing process, reference is made to the international patent application WO 96/06615. Finally, alkali percarbonate produced by a method comprising contacting solid alkali carbonate or a hydrate thereof with an aqueous hydrogen peroxide solution and drying may be the core of the alkali percarbonate particles.

An alkali percarbonate particularly preferably contained in the agents according to the invention is particulate and has at least two coating layers, an innermost layer containing at least one hydrate-forming inorganic salt and an outer layer of alkali silicate. The outer layer of alkali silicate can be either the outermost layer of an envelope comprising at least two layers or a layer which is not the innermost layer located directly on the alkali percarbonate, which in turn can be overlaid by one or more layers. Although here as well as in the prior art there is talk of individual layers, it should be noted that the components of the layers lying one above the other can merge into one another at least in the border area. This at least partial penetration results from the fact that when coating alkali percarbonate particles which have an innermost shell layer, this is at least superficially partially dissolved when a solution which contains a shell component or the shell components of a second shell layer is sprayed on.

Another essential feature of agents according to the invention is that they contain a water-soluble broth block. The term “water-soluble” should be understood to mean that the builder block dissolves to a residue of at least 3 g / 1, in particular at least 6 g / 1, in water of pH 7 at room temperature Use of the detergent containing it under normal washing conditions results in residue-free dissolving.

Preferably at least 15% by weight and up to 55% by weight, in particular 25% by weight to 50% by weight, of water-soluble builder block are contained in the agents according to the invention. This is preferably composed of the components a) 5% by weight to 35% by weight of citric acid, alkali citrate and / or alkali carbonate, which can also be replaced at least in part by alkali metal bicarbonate, b) up to 10% by weight of alkali silicate with a modulus in the range of 1.8 up to 2.5, c) up to 2% by weight of phosphonic acid and / or alkali metal phosphonate, d) up to 50% by weight of alkali metal phosphate, and e) up to 10% by weight of polymeric polycarboxylate, the quantities given being based on the obtain all detergents or cleaning agents. This is also good for the following quantities, unless expressly stated otherwise.

In a preferred embodiment of agents according to the invention, the water-soluble broth block contains 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 compositions according to the invention, 15% by weight to 25% by weight of alkali metal carbonate, which can be replaced at least in part by alkali metal bicarbonate, and up to 5% by weight, in particular 0.5% by weight. -% to 2.5 wt .-% contain citric acid and / or alkali citrate. In an alternative embodiment of agents according to the invention, component a) is 5% by weight to 25% by weight, in particular 5% by weight to 15% by weight of citric acid and / or alkali citrate and up to 5% by weight, in particular 1 wt .-% to 5 wt .-% alkali carbonate, which can be at least partially replaced by alkali hydrogen carbonate. If both alkali carbonate and alkali hydrogen carbonate are present, component a) has alkali carbonate and alkali hydrogen carbonate preferably in a weight ratio of 10: 1 to 1: 1.

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

With regard to component c), a preferred embodiment of agents according to the invention contains 0.05% by weight to 1% by weight of phosphonic acid and / or alkali metal phosphonate. Phosphonic acids are also given here Substituted alkylphosphonic acids understood, which can also have several phosphonic acid groups (so-called polyphosphonic acids). They are preferably selected from the hydroxy- and / or aminoalkylphosphonic acids and / or their alkali salts, such as, for example, dimethylaminomethane diphosphonic acid, 3-aminopropane-1-hydroxy-1,1-diphosphonic acid, 1-amino-1-phenylmethane diphosphonic acid, 1 -Hydroxyethan- 1, 1 -diphosphonic acid, amino-tris (methylenephosphonic acid), NjNjN ^ N'-ethylenediarnine-tetrakis ^ ethylenephosphonic acid) and the acytherten derivatives of phosphorous acid described in German Auslegeschrift DE 11 07 207, which also in any mixtures can be used.

With regard to component d), in a preferred embodiment of agents according to the invention, 15% by weight to 35% by weight of alkali metal phosphate, in particular trisodium polyphosphate, are present. Alkali phosphate is the general term for the AU alimetaU (especially sodium and KaHum) salts of the various phosphoric acids, in which one can distinguish between metaphosphoric acids (HPO ₃ ) _n and orthophosphoric acid H ₃ PO _{4 in} addition to higher molecular weight representatives. The phosphates combine several advantages: They act as alkali carriers, prevent limescale deposits on machine doors and KaUrin encrustations in fabrics and also contribute to cleaning performance. Sodium dihydrogen phosphate, NaH ₂ PO ₄ , exists as a dihydrate (density 1.91 like ^"3 , melting point 60 °) and as a monohydrate (density 2.04 like ^{" 3} ). Both salts are white powders which are very easily soluble in water, which prevent the crystalline water when heated and into the weakly acidic diphosphate (dmatrium hydrogen diphosphate, Na ₂ H2P ₂ O) at 200 ° C, and at higher temperatures in sodium trimetaphosphate (Na ₃ P ₃ O ₉ ) and pass over MadreUsches salt. NaH2PO is acidic; it occurs when phosphoric acid with sodium hydroxide solution is at a pH of 4.5 and the mash is sprayed. Potassium dihydrogen phosphate (primary or monobasic potassium phosphate, KaHumbiphosphat, KDP), KH ₂ PO, is a white salt with a density of 2.33 ^"3 , has a melting point of 253 ° (decomposition with the formation of (KPO ₃ ) _x , potassium polyphosphate) and is light soluble in water Disodium hydrogen phosphate (secondary sodium phosphate), Na ₂ HPO, is a colorless, very easily water-soluble crystalline salt. It exists anhydrous and with 2 moles (density 2.066 like ^" , water loss at 95 °), 7 moles (density 1 , 68 like ^"3 , melting point 48 ° with loss of 5 H ₂ O) and 12 mol. Of water (density 1.52, preferably ^"3 , melting point 35 ° with loss of 5 H2O), becomes anhydrous at 100 ° and changes into the diphosphate Na ₄ P θ when heated. The sodium hydrogenphosphate passes through NeutraHsation of phosphoric acid with soda solution using phenolphthalein as indicator. Dipotassium hydrogen phosphate (secondary or dibasic potassium phosphate), K ₂ HPO, is an amorphous, white salt, which is easily soluble in water. Trisodium phosphate, tertiary sodium phosphate, NasPO ^ U are colorless , which like a dodecahydrate a density of 1.62 ^"3 and a melting point of 73-76 ° C (decomposition), as a decahydrate (corresponding to 19-20% P ₂ O ₅ ) a melting point of 100 ° C and in anhydrous form ( corresponding to 39-40% P ₂ O) have a density of 2.536 ^"3. Trisodium phosphate is readily soluble in water under an alkaline reaction and is evaporated by evaporating a solution of exactly 1 mol of disodium phosphate and 1 mol of NaOH Tripotassium phosphate (tertiary or triphase potassium phosphate), K ₃ PO ₄ , is a white, deliquescent, granular powder with a density of 2.56 ^"3 , has a melting point of 1340 ° and is readily soluble in water with an alkaline reaction. It arises, for example, when Thomas slag is heated with coal and potassium sulfate. Despite the higher price, the more soluble, therefore highly effective, potassium phosphates are often preferred over corresponding sodium compounds in the cleaning agent industry. Tetrasodium diphosphate (sodium pyrophosphate), Na4P ₂ θ ₇ , exists in anhydrous form (density 2.534 like ^"3 , melting point 988 °, also given 880 °) and as decahydrate (density 1.815-1.836 like ^{" 3} , melting point 94 ° with loss of water). Substances are colorless crystals that are soluble in water with an alkaline reaction. Na ^ O? is formed by heating 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 baths and therefore reduces the hardness of the water. Potassium diphosphate (potassium pyrophosphate), K4P2O7, exists in the form of the trihydrate and is a colorless, hygroscopic powder with a density of 2.33 ^"3 , which is soluble in water, the pH of the 1% solution being at 25 ° 10 , 4. The condensation of NaH ₂ PO ₄ or KH ₂ PO ₄ produces higher molar sodium and potassium phosphates, in which a distinction is made between cyclic representatives, the sodium and potassium metaphosphates, and chain-like types, the sodium and potassium polyphosphates Especially for the latter are a variety of terms in use: melt or glow phosphates, Graham's salt, Kurrolsches and MadreUsches salt. AUe higher sodium and potassium phosphates are collectively referred to as condensed phosphates. The technically important pentasodium triphosphate, Na5P3θj.o (sodium tripolyphosphate), is a water-free or non-hygroscopic, water-soluble salt of the general formula NaO- | T (O) (ONa) -O] _n --Na that crystallizes with 6 H ₂ O. with n = 3. Approx. 17 g of the salt free of salt and water dissolve in 100 g of water at room temperature, approx. 20 g at 60 ° and around 32 g at 100 °; after heating the solution at 100 ° for two hours, hydrolysis produces about 8% orthophosphate and 15% diphosphate. In the manufacture of pentasodium triphosphate, phosphoric acid is reacted with sodium carbonate solution or sodium hydroxide solution in a stoichiometric ratio and the solution is dewatered by spraying. Similar to Graham's salt and sodium diphosphate, pentasodium triphosphate dissolves many insoluble metal compounds (including lime soaps, etc.). Pentakaum triphosphate, K ₅ P ₃ O ₁₀ (KaHum tripolyphosphate), is commercially available, for example, in the form of a 50% by weight solution (> 23% P ₂ O ₅ , 25% K ₂ O). The potassium polyphosphates are widely used in the detergent and cleaning agent industry. There are also sodium potassium tripolyphosphates which can also be used in the context of the present invention. These occur, for example, when hydrolysing sodium trinetaphosphate with KOH:

(NaPO ₃ ) ₃ + 2 KOH - Na ₃ K ₂ P3θ ₁₀ + H ₂ O

According to the invention, these can be used just like 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 of agents according to the invention, 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 contain. Among these, the homopolymers of acrylic acid and among them in turn those with an average poppy mass in the range from 5,000 D to 15,000 D (PA standard) are particularly preferred.

Detergents or cleaning agents which contain a CeUulose derivative or water-soluble Buüderblock or Alkalipercarbonat to be used according to the invention or are used together with this or these or are used in the process according to the invention can also contain other ingredients of such agents which do not undesirably combine with the cellulose derivative essential to the invention, interact with the alkali percarbonate or the water-soluble broth block. The cellulose derivative is preferably incorporated into washing or cleaning agents in amounts of 0.1% by weight to 5% by weight, in particular 0.5% by weight to 2.5% by weight.

Surprisingly, it was found that CeUulose derivatives of this type with the properties indicated above have a positive effect on the action of certain other detergent and cleaning agent ingredients, and conversely that the action of the tree-active Soü-release CeUulose derivative is additionally enhanced by certain other detergent ingredients. These effects occur in particular in the case of enzymatic active substances, in particular proteases and lipases, in the case of synthetic anionic surfactants of the sulfate and sulfonate type, in the case of color transfer inhibitors, for example vinylpyrroHdon, vinylpyridine or vinylimidazole polymers or copolymers or corresponding polybetaines, and in the case of graying inhibitors, for example others , in particular anionic cellulose ethers such as carboxymethyl cellulose, which is why the use of at least one of the other ingredients mentioned together with cellulose derivatives to be used according to the invention is preferred.

In a preferred embodiment, an agent according to the invention, used according to the invention or used in the method according to the invention, contains 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, vicinals Diols, fatty acid alkyl esters and / or fatty acid amides and mixtures thereof, in particular in an amount in the range from 2% by weight to 25% by weight.

A further embodiment of such agents comprises the presence of synthetic anionic surfactants of the sulfate and / or sulfonate type, in particular fatty alkyl sulfate, fatty alkyl ether sulfate, sulfofatty acid esters and / or sulfofatty acid disalts, in particular in an amount in the range from 2% by weight 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 individual substances, but cuts or mixtures. Among them, preference is given to those whose content of compounds with longer-chain radicals in the range from 16 to 18 carbon atoms is above 20% by weight.

The nonionic surfactants in question 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 carbon atoms, preferably 12 to 18 carbon 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. The derivatives of fatty alcohols are particularly suitable, although their branched chain isomers, in particular so-called oxo alcohols, can also be used to prepare alkoxylates which can be used. Accordingly, the alkoxylates, in particular the ethoxylates, of primary alcohols with linear, in particular dodecyl, tetradecyl, hexadecyl or octadecyl radicals, and mixtures thereof, can be used. Corresponding alkoxylation products of alkylamines, vicinal diols and carboxamides, which correspond to the alcohols mentioned with regard to the alkyl part, can also be used. In addition, there are the ethylene oxide and / or propylene oxide insertion products of fatty acid alkyl esters, as can be prepared in accordance with the process specified in international patent application WO 90/13533, and fatty acid polyhydroxyamides, as in accordance with the processes of US Pat. No. 1 985 424. US 2 016 962 and US 2 703 798 and international patent application WO 92/06984 can be considered. So-called alkyl polyglycosides suitable for incorporation into the agents 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 production are described, for example, in European patent applications EP 92 355, EP 301 298, EP 357 969 and EP 362 671 or US Pat. No. 3,547,828. The glycoside component (G) _n is an oligomer or polymer from naturally occurring aldose or ketose monomers, in particular glucose, mannose, fructose, galactose, talose, gulose, altrose, AUose, idose, ribose, Include arabinose, xylose and lyxose. The OHgomers consisting of such glycosidically linked monomers are characterized not only by the type of sugar they contain, but also by their number, the so-called degree of oligomerization. The degree of OHomerization n generally takes fractional numerical values as the quantity to be determined analytically; it is between 1 and 10, for the glycosides preferably used below 1.5, in particular between 1.2 and 1.4. The preferred monomer building block is glucose because of its good availability. The alkyl or alkenyl part R ^{12 of} the glycosides preferably also originates from easily accessible derivatives of renewable raw materials, in particular from fatty alcohols, although their branched chain isomers, in particular so-called oxo alcohols, can also be used to produce usable glycosides. Accordingly, the primary alcohols with linear octyl, decyl, dodecyl, tetradecyl, hexadecyl or octadecyl radicals and mixtures thereof are particularly useful. Particularly preferred alkyl glycosides contain a coconut fatty alkyl residue, ie mixtures with essentially R ¹² = dodecyl and R ¹² = tetradecyl.

Nonionic surfactant is used in agents which contain a so-release active ingredient used according to the invention, are used according to the invention or are used in the process according to the invention, preferably in amounts of 1% by weight to 30% by weight, in particular from 1% by weight to 25 % By weight, with amounts in the upper part of this range being more likely to be found in liquid detergents and detergent-like detergents preferably containing relatively small amounts of up to 5% by weight. Instead or in addition, the agents can contain further 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. %, each based on the total mean. Synthetic anionic surfactants which are particularly suitable for use in agents of this type are the alkyl and / or alkenyl sulfates having 8 to 22 carbon atoms and carrying an alkali metal, ammonium or alkyl or hydroxyalkyl-substituted ammonium ion as countercation. The derivatives of fatty alcohols with in particular 12 to 18 carbon atoms and their branched-chain analogs, the so-called oxo alcohols, are preferred. The alkyl and alkenyl sulfates can be prepared in a known manner by reacting the corresponding alcohol component with a customary sulfating reagent, in particular sulfur trioxide or chlorosulfonic acid, and then neutralizing with alkali, ammonium or alkyl or hydroxyalkyl-substituted ammonium bases. The sulfate-type surfactants that can be used also include the sulfated alkoxylation products of the alcohols mentioned, so-called ether sulfates. Such ether sulfates preferably contain 2 to 30, in particular 4 to 10, ethylene glycol groups per molecule. Suitable sulfonate-type anionic surfactants include the α-sulfoesters obtainable by reacting fatty acid esters with sulfur trioxide and subsequent neutralization, in particular those derived from fatty acids with 8 to 22 C atoms, preferably 12 to 18 C atoms, and linear alcohols with 1 up to 6 carbon atoms, preferably 1 to 4 carbon atoms, derived sulfonation products, and the sulfofatty acids resulting from these by formal saponification.

Soaps can be considered as further optional surfactant ingredients, whereby saturated fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid or stearic acid, as well as soaps derived from natural fatty acid mixtures, for example coconut, palm kernel or tallow fatty acids, are suitable. In particular, those soap mixtures are preferred which are composed of 50% by weight to 100% by weight of saturated Ci2-C ₁₈ fatty acid soaps and up to 50% by weight of oleic acid soap. Soap is preferably contained in amounts of 0.1% by weight to 5% by weight. However, in particular in liquid compositions which contain 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 agents can also contain betaines and / or cationic surfactants which, if present, are preferably used in amounts of 0.5% by weight to 7% by weight. Among them, the ester quats discussed below are particularly preferred.

The agents preferably contain, in addition to the percarbonate, a compound which releases an organic percarboxylic acid under perhydrolysis conditions (i.e. a so-called bleach activator) and / or an already formed organic percarboxylic acid, in particular in amounts of 0.5% by weight to 6% by weight. The optional component of the bleach activators comprises the commonly used N- or O-acyl compounds, for example multiply acylated alkylenediamines, in particular tefraacetylethylenediamine, acylated glycolurils, in particular tetraacetylglycol uru, N-acylated hydantoins, hydrazides, triazoles, urazoles, diketopamideazines, cyanuryl amide, cyanurate urethanes also carboxylic anhydrides, especially phthalic anhydride, carboxylic acid esters, especially sodium isononanoyl phenol sulfonate, and acylated sugar derivatives, especially pentaacetyl glucose, and cationic nitric acid derivatives such as trimethylammonium acetonitrile salts. The bleach activators can have been coated or granulated with known substances in order to avoid the interaction with the per compounds during storage, with the aid of carboxymethyl cellulose granulated tetraacetylethylenediamine with average grain sizes of 0.01 mm to 0.8 mm, as is the case, for example can be prepared according to the process described in European Patent EP 37 026, granulated 1,5-diacetyl-2,4-dioxohexahydro-1,5,5-triazine, as produced according to the process described in German Patent DD 255 884 and / or trialkylammonium acetonitrile prepared in particle form according to the processes described in international patent applications WO 00/50553, WO 00/50556, WO 02/12425, WO 02/12426 or WO 02/26927 is particularly preferred. Such bleach activators are preferably contained in detergents and cleaning agents in amounts of up to 8% by weight, in particular from 2% by weight to 6% by weight, in each case based on the total agent.

In addition, the detergents can contain other constituents customary in washing and cleaning agents. These optional components include in particular Enzymes, enzyme stabilizers, foam inhibitors, for example organopolysiloxanes or paraffins, solvents and optical heaters, for example stübensisulfonic acid derivatives. 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-, are preferred in agents which contain a CeUulose derivative used according to the invention. Contain bis- (2,4,6-triamino-s-triazinyl) -stübens-2,2 ^, -disulfonic acids and up to 2% by weight, in particular 0.1% by weight to 1% by weight, of foam inhibitors, wherein the weight range mentioned in each case relate to the entire mean.

In addition to water, solvents which can be used in particular in the case of liquid agents are preferably those which are water-miscible. These include the lower alcohols, for example ethanol, propanol, iso-propanol, and the isomeric butanols, glycerol, lower glycols, for example ethylene and propylene glycol, and the ethers which can be derived from the classes of compounds mentioned. The CeUulose derivatives used according to the invention are generally dissolved or in suspended form in such liquid compositions.

Any enzymes present are preferably selected from the group comprising protease, amylase, lipase, CeUulase, hemicellulase, oxidase, peroxidase or mixtures of these. Protease obtained from microorganisms, such as bacteria or puddles, is primarily suitable. It can be obtained in a known manner by fermentation processes from suitable microorganisms, which are described, for example, in German patent applications DE 19 40 488, DE 2044 161, DE 21 01 803 and DE 21 21 397, US Pat. Nos. 3,623,957 and US 4,264,738, European patent application EP 006 638 and international patent application WO 91/02792. Proteases are commercially available, for example, under the names BLAP®, Savinase®, Esperase®, Maxatase®, Optimase®, Alcalase®, Durazym® or Maxapem®. The lipase that can be used can be obtained from Humicola lanuginosa, as described, for example, in European patent applications EP 258 068, EP 305 216 and EP 341 947, from Bacülus species, as described, for example, in international patent application WO 91/16422 or European patent application EP 384717. from Pseudomonas species, such as in 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, from Fusarium species, as described for example in the European patent application EP 130 064, from Rhizopus species, as described, for example, in European patent application EP 117 553, or from Aspergülus species, as described, for example, in European patent application EP 167309. Suitable lipases are commercially available, for example, under the names Lipolase®, Lipozym®, Lipomax®, Lipex®, Amano® lipase, Toyo-Jozo® lipase, Meito® lipase and Diosynth® lipase. Suitable amylases are commercially available, for example, under the names Maxamyl®, Termamyl®, Duramyl® and Purafect® OxAm. The cellulase which can be used can be an enzyme which can be obtained from bacteria or puddles and which has a pH optimum, preferably in the weakly acidic to weakly alkaline range from 6 to 9.5. Such cellulases are known, for example, from German patent applications DE 31 17250, DE 32 07 825, DE 32 07 847, DE 33 22 950 or European patent applications EP 265 832, EP 269 977, EP 270 974, EP 273 125 and EP 339 550 and known from international patent applications WO 95/02675 and WO 97/14804 and commercially available under the names CeUuzyme®, Carezyme® and Ecostone®.

The customary enzyme stabilizers which are optionally present, in particular in liquid agents, include amino alcohols, for example mono-, di-, triethanol- and -propanolamine and mixtures thereof, lower carboxylic acids, as known, for example, from European patent applications EP 376705 and EP 378 261, boric acid or alkali borates, boric acid-carboxylic acid combinations, as known, for example, from European patent application EP 451 921, boric acid esters, such as known from international patent application WO 93/11215 or European patent application EP 511 456, boronic acid derivatives, such as from European patent application EP 583,536, calcium salts, for example the Ca-formic acid combination known from European patent EP 28 865, magnesium salts, such as known from European patent application EP 378 262, 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, in particular beech soap, fatty acid amides, paraffins, waxes, microcrystalline waxes, organopolysiloxanes and mixtures thereof, which may also contain microfine, optionally silanized or otherwise hydrophobized silica. For use in particle-shaped agents, such foam inhibitors are preferably bound to granular, water-soluble carrier substances, as described, for example, in German patent application DE 34 36 194, European patent applications EP 262 588, EP 301 414, EP 309 931 or European patent EP 150 386.

It is also possible to use a combination of the above-mentioned tree-active, dirt-releasing cellulose derivative with a polyester-active dirt-releasing polymer made from a dicarboxylic acid and a given polymeric diol to enhance the cleaning performance when washing textiles. Such combinations of the aforementioned tree-active, dirt-releasing, CeUulose derivative with a polyester-active, dirt-releasing polymer are also possible within the scope of agents according to the invention and the method according to the invention.

The known polyester-active dirt-releasing polymers which can be used in addition to the CeUulose 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. The preferred dirt-releasing polyesters include those compounds which are formally accessible by esterification of two monomer units, the first monomer being a dicarboxylic acid HOOC-Ph-COOH and the second monomer being a diol HO- (CHR ^π -) _a OH, which is also a polymer Diol can contain H- (O- (CHKπ-) _a ) bOH. Therein, Ph represents an o-, m- or p-phenylene radical, which can carry 1 to 4 substituents selected from alkyl radicals having 1 to 22 carbon atoms, sulfonic acid groups, carboxyl groups and mixtures thereof, R ^{11 is} hydrogen, an alkyl radical having 1 to 22 carbon atoms and their mixtures, a a number from 2 to 6 and b a number from 1 to 300. Preferably, both monomer diol units -O- (CHRπ-) _a O- and polymer diol units - (O - (CHR ^π -) _a ) bO- before. The molar The 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 from 4 to 200, in particular from 12 to 140. The molecular weight or the average molecular weight or the maximum molecular weight distribution of preferred dirt-releasing polyesters is in the range from 250 to 100,000, in particular from 500 to 50,000 The acid on which the rest Ph is based is preferably selected from terephthalic acid, isophthalic acid, phthalic acid, trimellitic acid, meulitic 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 an alkali or ammonium salt. Among them, the sodium and potassium salts are particularly preferred. If desired, instead of the HOOC-Ph-COOH monomer, small amounts, in particular not more than 10 mol%, based on the amount of Ph with the meaning given above, of other acids which have at least two carboxyl groups can be present in the dirt-releasing polyester. 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 ^π -) _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 carbon atoms is selected. Among the latter diols, those of the formula HO-CH ₂ -CHR ^π -OH, in which R ^{11 has} the meaning given above, 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 with an average molecular weight in the range from 1000 to 6000.

If desired, the polyesters composed as described above can also be end group-closed, alkyl groups with 1 to 22 C atoms and esters of monocarboxylic acids being suitable as end groups. The end groups bonded via ester bonds can be alkyl, alkenyl and aryl monocarboxylic acids with 5 to 32 carbon atoms, in particular 5 to 18 carbon atoms, are the basis. These include valeric acid, caproic acid, oenanthic acid, caprylic acid, pelargonic acid, capric acid, undecanoic acid, undecenoic acid, lauric acid, lauroleic acid, tridecanoic acid, myristic acid, myristoleic acid, pentadecanoic acid, palmitic acid, stearic acid, petroselinic acid, petroselaidic acid, linoleic acid, linoleic acid, linoleic acid, oleolic acid, oleol acid , Arachidic acid, gadoleic acid, arachidonic acid, behenic acid, erucic acid, brassidic acid, clupanodonic acid, lignoceric acid, cerotic acid, melissic acid, benzoic acid, which can carry 1 to 5 substituents with a total of up to 25 C atoms, in particular 1 to 12 C atoms, for example tert. -Butylbenzoesäure. The end groups can 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 hydroxy monocarboxylic acids can in turn be linked to one another via their hydroxyl group and their carboxyl group and can therefore be present several times in an end group. The number of hydroxymonocarboxylic acid units per end group, that is to say their degree of oligomerization, is preferably 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 CeUulosederivaten.

The dirt-releasing polymers are preferably water-soluble, the term “water-soluble” being understood to mean 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. So. Preferred polymers have under these conditions however, a solubility of at least 1 g per liter, in particular at least 10 g per liter.

Preferred laundry aftertreatment agents have a so-called ester quat as the fabric softening active ingredient, that is to say a quaternized ester of carboxylic acid and amino alcohol. These are known substances that can be obtained using the relevant methods of preparative organic chemistry. In this Reference is made to the international patent application WO 91/01295, according to which triethanolamine is partially esterified with fatty acids in the presence of hypophosphorous acid, air is passed through and then quaternized with dimethyl sulfate or ethylene oxide. German patent DE 43 08 794 also discloses a process for the preparation of solid ester quats, in which the quaternization of triethanolamine esters is carried out in the presence of suitable dispersants, preferably fatty alcohols. Overviews on this topic have been published, for example, by R.Puchta et al. in Tens.Surf.Det, 30, 186 (1993), M.Brock in Tens.Surf.Det. 30: 394 (1993) RXagerman et al. in J.Am.Oil.Chem.Soc, 71, 97 (1994) and I.Shapiro in Cosm.Toü. 109, 77 (1994) appeared.

Ester quats preferred in the compositions are quaternized fatty acid triethanolamine ester salts which follow the formula (I)

(I)

in which R * CO stands for an acykest with 6 to 22 carbon atoms, R ² and R ³ independently of one another for hydrogen or R ^x CO, R ⁴ for an alkyl radical with 1 to 4 carbon atoms or a (CH ₂ CH ₂ O) _q H- Group, m, n and p in total for 0 or numbers from 1 to 12, q for numbers from 1 to 12 and X for a charge-balancing anion such as halide, alkyl sulfate or alkyl phosphate. Typical examples of ester quats that can be used in the context of the invention are products based on caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, isostearic acid, stearic acid, oleic acid, elaidic acid, arachic acid, behenic acid and erucic acid and their technical mixtures, such as they occur, for example, when pressure is released from natural fats and oils. Technical Cπ / is coconut fatty acids and, in particular, cost-hardened cig / is tallow or palm fatty acids as well as elaidic acid-rich Ci6 / i8 fatty acid cuts are preferably used. The fatty acids and the triethanolamine can generally be used in a molar ratio of 1.1: 1 to 3: 1 to produce the quaternized esters become. With regard to the technical application properties of the ester quats, an application ratio of 1.2: 1 to 2.2: 1, preferably 1.5: 1 to 1.9: 1, has proven to be particularly advantageous. The preferred esterquats are technical mixtures used of mono-, di- and triesters having a degree of esterification of durchschnittUchen 1.5 to 1.9 and are derived from technical Cι ₆ / I8- tallow or palm fatty acid (iodine value from 0 to 40) from , Quaternized fatty acid triethanolamine esters of the formula (I) in which R ^! CO for an acyl radical with 16 to 18 carbon atoms, R ² for R ^ O, R ³ for hydrogen, R ⁴ for a methyl group, m, n and p for 0 and X for methyl sulfate have proven to be particularly advantageous.

In addition to the quaternized carboxylic acid triethanol amine ester salts, quaternized ester salts of carboxylic acids with di-ethanol alkyl amines of the formula (II) are also suitable as ester quats,

R ⁴ [R ¹ CO- (OCH ₂ CH ₂ ) _m OCH2CH ₂ -N ⁺ -CH ₂ CH2θ- (CH2CH ₂ O) _n R ² ] (II)

J in the R CO for an acyl radical with 6 to 22 carbon atoms, R ² for hydrogen or R CO, R ⁴ and R ⁵ independently of one another for alkyl radicals with 1 to 4 carbon atoms, m and n in total for 0 or numbers from 1 to 12 and X represents a charge-balancing anion such as halide, alkyl sulfate or alkyl phosphate.

Finally, the quaternized ester salts of carboxylic acids with 1,2-dydroxypropyldialkylanines of the formula (III) should be mentioned as a further group of suitable ester quats.

R ^δ O- (CH ₂ CH ₂ O) _m OCR ¹ [R ⁴ -N ⁺ -CH ₂ CHCH ₂ O- (CH ₂ CH ₂ θ) _n R ² ] (HI)

in the ^ O for an acyl residue with 6 to 22 carbon atoms, R ² for hydrogen or ^ O, R ⁴ , R ⁶ and R ⁷ independently of one another for alkyl residues with 1 to 4 carbon atoms Substance atoms, m and n in total for 0 or numbers from 1 to 12 and X for 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 information given for (I) also applies analogously to the esterquats of the formulas (II) and (ILI). The esterquats are usually commercially available in the form of 50 to 90 percent by weight alcoholic solutions, which can also be diluted with water, ethanol, propanol and isopropanol being the usual alcoholic solvents.

Ester quats are preferably used in amounts of 5% by weight to 25% by weight, in particular 8% by weight to 20% by weight, in each case based on the total laundry aftertreatment agent. If desired, the laundry aftertreatment agent can additionally contain detergent ingredients listed above, provided that they do not unreasonably interact negatively with the esterquat. It is preferably a liquid, water-containing agent.

Solid agents are preferably manufactured in such a way that a tissue containing cellulose derivative which is capable of removing dirt is mixed with other detergent ingredients which are present in solid form, in particular the constituents of the water-soluble broth block. A spray-drying step is preferably used to produce the tissue which contains the cellulose derivative which is capable of removing dirt. Alternatively, it is also possible to use a compacting compounding step to produce this particle and, if appropriate, also to produce the finished agent.

example

Containing a detergent (VI)

ABS 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 bicarbonate 5 parts by weight

Sokalan® CP 5 ^a) 3 parts by weight sodium sulfate 27 parts by weight

Tinopal® DMS-X ^b) 0.2 part by weight

a) Polymeric polycarboxylate, HersteUer BASF AG b) Optical brightener, HersteUer Ciba

0.5 parts by weight of methyl hydroxyethyl cellulose (DS 1.89; MS 0.15; average poppy mass 100,000) (Wl) was added. Fabrics made from pure cotton, finished cotton, and polyester / cotton blend 50/50 were treated as follows:

Washing machine: Miele W 918 Novotronic®

Primary washing performance: normal program single-washing process

Washing temperature: 40 ° C

Determination: 5 times

Fleet volume: 18 1

Water hardness: 16 ° dH

Filling laundry: 3.5 kg clean laundry

The fabrics were washed uncontaminated three times with the detergent to be tested under the conditions specified above and dried after each wash. After prewashing three times, the fabrics were soiled with the following standardized soiling by hand: 0.10 g lipstick

0.10 g black shoe polish

0.10 g dust / skin fat

The soiled tissues were measured with a Minolta CR 200 and then aged at RT for 7 days. The soiled tissues were then stapled onto towels and washed under the conditions specified above.

The tissues were dried and measured again with a Minolta CR 200. The following washing results (dde values) resulted:

Table 1: pure cotton

Table 2: Cotton grafted

Table 3: Cotton / polyester

It can be seen that when the detergent is used with the CeUulose derivative to be used according to the invention, the washing performance is significantly better than when the detergent lacking the cellulose derivative is used.

Claims

claims

1. Buüder-containing washing or cleaning agent, containing a water-soluble broth block, alkali percarbonate and dirt-releasing cellulose derivative, which is obtainable by alkylation and hydroxyalkylation of cellulose.

2. Composition according to claim 1, characterized in that the CeUulosivativ is alkylated with Ci- to Cio groups, in particular Ci- to C ₃ groups and additionally carries Gabis Cio-hydroxyalkyl groups, in particular C2- to C ₃ -hydroxyalkyl groups.

3. Composition according to claim 1 or 2, characterized in that averaged in the cellulose derivative 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 anhydroglycose monomer unit are included.

4. Composition according to one of claims 1 to 3, characterized in that the average molecular weight of the CeUulosederivats in the range of 10,000 D to 150,000 D Hegen.

5. Composition according to one of claims 1 to 4, characterized in that the average poppy mass of CeUulosederivates in the range of 40,000 D to 120,000 D, in particular from 80,000 D to 110,000 D.

6. Composition according to one of claims 1 to 5, characterized in that it contains 0.1% by weight to 5% by weight, in particular 0.5% by weight to 2.5% by weight, of the dirt-releasing cellulose derivative ,

7. Composition according to one of claims 1 to 6, characterized in that the content of alkali percarbonate is 6% by weight to 30% by weight, in particular 10% by weight to 25% by weight.

8. Composition according to one of claims 1 to 7, characterized in that the alkali percarbonate is particulate and has at least two coating layers, an innermost layer at least one hydrate-bonding inorganic salt and contains an outer layer of alkali silicate.

9. Composition according to one of claims 1 to 8, characterized in that it additionally contains a compound which cleaves an organic percarboxylic acid under perhydrolysis conditions and / or an organic percarboxylic acid, in particular in amounts of 0.5% by weight to 6% by weight ,

10. Composition according to one of claims 1 to 9, characterized in that the amount of the Buüderblock is at least 15 wt .-%.

11. Agent according to one of claims 1 to 10, characterized in that the amount of the Buüderblocks is up to 55 wt .-%, in particular 25 wt .-% to 50 wt .-%.

12. Composition according to one of claims 1 to 11, characterized in that the water-soluble Buüderblock (A) is composed of the components a) 5 wt .-% to 35 wt .-% citric acid, alkali citrate and / or alkali carbonate, which is at least expensive can be replaced by alkali hydrogen carbonate, b) up to 10% by weight of alkali silicate with a modulus in the range from 1.8 to 2.5, c) up to 2% by weight of phosphonic acid and or alkali metal phosphonate, d) up to 50% by weight .-% alkali phosphate, and e) up to 10 wt .-% polymeric polycarboxylate.

13. Composition according to one of claims 1 to 12, characterized in that the Buüderblock contains at least 2 of components b), c), d) and e) in amounts greater than 0 wt .-%.

14. Composition according to one of claims 1 to 13, characterized in that as component a) 15 wt .-% to 25 wt .-% alkali carbonate, which can be at least partially replaced by alkali hydrogen carbonate, and up to 5 wt .-%, in particular 0.5 wt .-% to 2.5 wt .-% citric acid and / or alkali citrate are included.

15. Composition according to one of claims 1 to 13, characterized in that as component a) 5 wt .-% to 25 wt .-%, in particular 5 wt .-% to 15 wt .-% citric acid and / or alkali citrate and up 5% by weight, in particular 1% by weight to 5% by weight, of alkali carbonate, which can be replaced at least in part by alkali hydrogen carbonate, are present.

16. Agent according to one of claims 1 to 15, characterized in that component a) has alkali carbonate and alkali hydrogen carbonate in a weight ratio of 10: 1 to 1: 1.

17. Composition according to one of claims 1 to 16, characterized in that as component b) 1 wt .-% to 5 wt .-% AlkaHsilikat with a module in the range of 1.8 to 2.5 is included.

18. Composition according to one of claims 1 to 17, characterized in that as component c) 0.05 wt .-% to 1 wt .-% phosphonic acid and / or alkali metal phosphonate, in particular selected from the hydroxy- and / or aminoalkylphosphonic acid and / or their alkali salts is contained.

19. Composition according to one of claims 1 to 18, characterized in that as component d) 15 wt .-% to 35 wt .-% alkali phosphate, in particular trisodium polyphosphate, is contained.

20. Composition according to one of claims 1 to 19, characterized in that as component e) 1.5 wt .-% to 5 wt .-% polymeric polycarboxylate, in particular selected from the polymerization or copolymerization products of acrylic acid, methacrylic acid and / or Maleic acid is included.

21. Use of a dirt-releasing CeUulose derivative, which is obtained by alkylation and hydroxyalkylation of CeUulose, to enhance the cleaning performance of detergents that contain alkali percarbonate and have a water-soluble broth block, when washing textiles that consist in particular of cotton or contain cotton.

22. A process for washing textiles, in which an alkali-percarbonate-containing detergent with a water-soluble builder block and a dirt-releasing cellulose derivative, which is obtained by alkylation and hydroxyalkylation of cellulose, are used.

23. A process for the production of solid agents according to one of claims 1 to 20, characterized in that a particle which contains cellulose derivative which is capable of removing dirt is mixed with further detergent ingredients present in solid form.

24. The method according spoke 21, characterized in that a spray drying step is used to manufacture the tissue, which contains dirt-releasing cellulose derivative.

25. The method according spoke 21, characterized in that a compacting compounding step is used to manufacture the tissue which contains dirt-releasing ceululose derivative.