EP1592767B1 - Bleichmittelhaltige wasch- oder reinigungsmittel mit wasserlöslichem buildersystem und schmutzablösevermögendem cellulosederivat - Google Patents

Bleichmittelhaltige wasch- oder reinigungsmittel mit wasserlöslichem buildersystem und schmutzablösevermögendem cellulosederivat Download PDF

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Publication number
EP1592767B1
EP1592767B1 EP04707148A EP04707148A EP1592767B1 EP 1592767 B1 EP1592767 B1 EP 1592767B1 EP 04707148 A EP04707148 A EP 04707148A EP 04707148 A EP04707148 A EP 04707148A EP 1592767 B1 EP1592767 B1 EP 1592767B1
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Prior art keywords
weight
alkali metal
acid
composition according
cellulose derivative
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EP04707148A
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German (de)
English (en)
French (fr)
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EP1592767A1 (de
Inventor
Josef Penninger
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Priority claimed from DE10351326A external-priority patent/DE10351326A1/de
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/22—Carbohydrates or derivatives thereof
    • C11D3/222—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
    • C11D3/225—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin etherified, e.g. CMC
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0039—Coated compositions or coated components in the compositions, (micro)capsules
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0026—Low foaming or foam regulating compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0036—Soil deposition preventing compositions; Antiredeposition agents
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3942—Inorganic per-compounds
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/01—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with natural macromolecular compounds or derivatives thereof
    • D06M15/03—Polysaccharides or derivatives thereof
    • D06M15/05—Cellulose or derivatives thereof
    • D06M15/09—Cellulose ethers
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material

Definitions

  • the present invention relates to detergents or cleaners which contain only water-soluble constituents as builder component and contain soil release-capable cellulose derivative and bleach.
  • 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.
  • 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.
  • polyphosphates in particular trisodium polyphosphate
  • zeolite Na-A is known to be capable of forming so stable complexes with especially calcium ions that their reaction with water-hard-forming anions, especially carbonate, to form insoluble compounds is suppressed.
  • 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.
  • 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.
  • detergents 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.
  • 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".
  • 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.
  • European Patent EP 0 276 977 discloses textile treatment compositions containing a combination of soap and nonionic, substituted cellulose ether derivatives. Furthermore, these textile treatment agents contain alkali metal perborate and, as the water-soluble builder block, alkali metal carbonate, alkali metal phosphate and alkali metal silicate.
  • European Patent Application EP 0 213 730 discloses textile treatment compositions containing cationic surfactants and nonionic cellulose ethers having HLB values of from 3.1 to 3.8.
  • US Pat. No. 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 consists essentially 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.
  • 4,174,305 discloses laundry 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 consists essentially of C 10 to C 12 alkylbenzenesulfonate and less than 5 wt .-% alkylbenzenesulfonate having alkyl radicals of C 13 and higher.
  • European patent application EP 0 634 481 relates to a detergent containing alkali metal percarbonate and one or more nonionic cellulose derivatives.
  • EP 0 271 312 relates to soil release agents, among these cellulose alkyl ethers and cellulose hydroxyalkyl ethers (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.
  • European Patent EP 0 948 591 B1 discloses a detergent in liquid or granular form which imparts textile appearance advantages such as pilling / lint reduction, anti-color fading, improved abrasion resistance and / or increased softness to fabrics and textiles washed therewith, and provides 1 to 80 wt .-% 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 in amounts of 0.1-5 wt .-%, based on the cellulose ether material, must be present.
  • 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.
  • acidic textile finishing agents 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 5000 and the molar ratio of ethylene terephthalate to polyethylene oxide terephthalate 50:50 to 90:10, and their use in detergents are in the German patent DE 28 57,292.
  • 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 be used in detergents according to German laid-open specification DE 33 24 258.
  • 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.
  • European Patent EP 185,427 discloses 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.
  • 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 also glycerol units.
  • polyesters which in addition to oxyethylene groups and terephthalic acid units containing 1,2-propylene, 1,2-butylene and / or 3-methoxy-1,2-propylene groups and glycerol units and with C 1 - Are end-capped to C 4 -albyl groups.
  • European Patent EP 253 567 relates to soil release polymers having a molecular weight of 900 to 9000 from 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 0.6 to 0.95.
  • European Patent Application EP 272 033 discloses, at least in part, polyesters having poly-propylene terephthalate and polyoxyethylene terephthalate units which are end-capped by C 1-4 -alkyl or acyl radicals.
  • European Patent EP 274,907 describes sulfoethyl end-capped terephthalate-containing soil release polyesters.
  • European Patent Application EP 357,280 sulfonation of unsaturated end groups produces soil release polyesters 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 re-raising of dirt during the washing of synthetic fibers.
  • Detergents are known from German Patent DE 28 46 984, which as Schmutzablosefaresdes polymer is a reaction product of a polyester with a terminal prepolymer containing isocyanate groups, obtained from a diisocyanate and a hydrophilic nonionic macrodiol.
  • the bleaching agents are of particular importance with regard to the enhancement of the washing or cleaning performance compared to a large number of different soiling.
  • excipients include substances which assist in detergency the surfactant performance by the oxidative degradation of soils located on the textile or those that are in the fleet after detachment from the textile. The same applies mutatis mutandis to cleaners for hard surfaces.
  • inorganic peroxygen compounds particularly hydrogen peroxide and solid peroxygen compounds which dissolve in water to release hydrogen peroxide or so-called active oxygen, such as sodium perborate and sodium carbonate perhydrate, have long been used as oxidizing agents for disinfecting and bleaching purposes.
  • the latter compound which is often referred to as sodium percarbonate, is the addition compound of hydrogen peroxide to sodium carbonate (empirical formula 2 Na 2 CO 3 .3H 2 O 2 ).
  • the carbonate salts of the remaining alkali metals form H 2 O 2 - Vogelrungsberichten. Due to the often perceived as insufficient storage stability of the alkali metal percarbonate in a warm-humid environment and in the presence of other conventional detergent and cleaner components, the alkali metal percarbonate must normally be stabilized against the loss of active oxygen.
  • An essential principle for stabilization is to surround the alkali metal percarbonate particles with a shell which may be mono- or multilayered. Each shell layer may contain one or more inorganic and / or organic shell components.
  • the agent may contain all other ingredients commonly used in detergents or cleaners, unless they unduly interact negatively with them or any of them.
  • builder block is to be expressed, however, that the means do not contain other builders 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.
  • no additional bleaching agent is present in addition to the alkali metal percarbonate mentioned, although this is possible if desired.
  • 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.
  • 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 alkalipercarbonate-containing detergents containing an organic percarboxylic acid releasing compound and / or an organic percarboxylic acid and having a water-soluble builder block as described above composed of said components in the said amounts, in the washing of textiles, which in particular consist of cotton or contain cotton.
  • Another object of the invention is a process for washing textiles, wherein a Alkalipercarbonat braves detergent containing an organic percarboxylic acid-releasing compound and / or an organic percarboxylic acid, with a water-soluble builder block, as described above from said components in said And a soil release cellulosic derivative obtainable by alkylation and hydroxyalkylation of cellulose are used.
  • This method can be carried out manually or preferably by means of a conventional household washing machine. It is possible to use the bleach-containing detergent and the soil release-capable cellulose derivative simultaneously or successively. The simultaneous application can be particularly advantageous by the use of a bleach-containing detergent, which contains the soil release wealthy cellulose derivative perform.
  • 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.
  • the designated positive aspect can also be realized by a washing process in which the textile after the actual washing process, with the aid of a percarbonate-containing detergent with water-soluble builder block - which may contain a said cellulose derivative, but in In this case 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.
  • 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.
  • the detergent washing-enhancing effect of the cellulose derivatives to be used according to the invention occurs during the next washing process, even if, if desired, again no detergent is used with a cellulose derivative mentioned.
  • 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.
  • appropriate alkylating agents for example alkyl halides or alkyl sulfates
  • corresponding alkylene oxides such as, for example, ethylene oxide and / or propylene oxide.
  • 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 soil release-capable cellulose derivative is based on the determination of the limiting viscosity number of sufficiently dilute aqueous solutions by means of an 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.
  • the cellulose derivatives used according to the invention can be prepared in a simple manner and are 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 the use of compounds previously known for this purpose. Alternatively, significant amounts of surfactants can be saved while maintaining fat removal capability.
  • the use according to the invention can be carried out as part of a washing process by adding alkali percarbonate, organic percarboxylic acid releasing compound and / or organic percarboxylic acid and the cellulose derivative of a detergent-containing liquor, the cellulose derivative of a bleach and detergent-containing liquor added separately or preferably the cellulose derivative as part of a novel Bring detergent into the fleet.
  • the use according to the invention in the context of a laundering process can be carried out in such a way that the cellulose derivative is added separately to the rinsing liquor, which is used according to the washing cycle using a percarbonate-containing detergent with organic percarboxylic acid and / or organic percarboxylic acid and with a water-soluble builder block it as a component of the laundry aftertreatment, in particular a softener, brings.
  • said percarbonate-containing detergent containing organic percarboxylic acid-releasing compound and / or organic percarboxylic acid and water-soluble builder block may also contain, but may be free from, a cellulose derivative to be used in the present invention.
  • said laundry aftertreatment agent may also contain, but may be free of, and / or be a percarbonate, organic percarboxylic acid releasing compound and / or organic percarboxylic acid and / or water-soluble builder block.
  • the alkali metal percarbonate present in the compositions of the invention is preferably used in the form of coated alkali percarbonate particles comprising an alkali percarbonate core which may have been produced by any method of preparation and may also contain per se known stabilizers 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.
  • alkali metal percarbonate produced by a process comprising contacting solid alkali carbonate or a hydrate thereof with an aqueous hydrogen peroxide solution and drying may also be the core of the alkali metal percarbonate particles.
  • An alkali metal 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 alkali silicate.
  • the outer alkali silicate containing cladding layer may either be the outermost cladding layer of a cladding comprising at least two layers or a cladding layer which is not the innermost one, directly on the alkali percarbonate, which in turn may be superposed by one or more layers.
  • 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.
  • agents according to the invention contain a water-soluble builder block.
  • 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.
  • the water-soluble builder block contains at least 2 of components b), c), d) and e) in amounts greater than 0% by weight.
  • component a in a preferred embodiment of the composition according to the invention, 15% by weight to 25% by weight alkali carbonate, which may be replaced at least proportionally by alkali hydrogen carbonate, and up to 5% by weight, in particular 0.5% by weight. contain up to 2.5 wt .-% citric acid and / or alkali citrate.
  • 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 to 1: 1.
  • component b) in a preferred embodiment of the composition according to the invention, 1% by weight to 5% by weight of alkali metal silicate with a modulus in the range from 1.8 to 2.5 are contained.
  • 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 optionally Understand substituted alkylphosphonic, which may 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 metal salts, for example dimethylaminomethane diphosphonic acid, 3-aminopropane-1-hydroxy-1,1-diphosphonic acid, 1-amino-1-phenylmethane diphosphonic acid, 1-hydroxy -methane-1,1-diphosphonic acid, amino-tris (methylenephosphonic acid), N, N, N, N'-ethylenediaminetrakis (methylenephosphonic acid) and the acylated derivatives of phosphorous acid described in the German patent application DE 11 07 207, which also can be used in any mixtures.
  • dimethylaminomethane diphosphonic acid 3-aminopropane-1-hydroxy-1,1-diphosphonic acid
  • 1-amino-1-phenylmethane diphosphonic acid 1-hydroxy -methane-1,1-diphosphonic acid
  • amino-tris methylenephosphonic acid
  • 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 PO 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 their water of crystallization when heated 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 (potassium phosphate primary or monobasic potassium, 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 slightly soluble in water.
  • Disodium hydrogen phosphate (secondary sodium phosphate), Na 2 BPO 4 is a colorless, very slightly water-soluble crystalline salt.
  • 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 alkaline reaction and is prepared by evaporating 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.
  • 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.
  • 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
  • sodium tripolyphosphate potassium tripolyphosphate or mixtures of these two; It is also possible to use mixtures of sodium tripolyphosphate and sodium potassium tripolyphosphate or mixtures of halotripolyphosphate and sodium potassium tripolyphosphate or mixtures of sodium tripolyphosphate and potassium tripolyphosphate and sodium potassium tripolyphosphate according to the invention.
  • polymeric polycarboxylate in particular selected from the polymerization or copolymerization of acrylic acid, methacrylic acid and / or maleic acid contain.
  • homopolymers of acrylic acid particularly preferred are 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 or alkali metal percarbonate to be used according to the invention or are used together with it or in the process according to the invention may contain all customary other constituents of such agents which are not undesirable with the cellulose derivative of the invention.
  • the alkali percarbonate or the water-soluble builder block 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.
  • 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 .-%.
  • 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 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 Alkoxyrl istsgrad of the alcohols is usually 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.
  • alkoxylates in particular the ethoxylates, primary alcohols with linear, in particular dodecyl, tetradecyl, hexadecyl or octadecyl radicals and mixtures thereof.
  • suitable alkoxylation products of alkylamines, vicinal diols and carboxamides, which correspond to the said alcohols with respect to the alkyl part usable.
  • the ethylene oxide and / or propylene oxide insertion products of fatty acid alkyl esters as can be prepared according to the process disclosed in International Patent Application WO 90/13533, and fatty acid polyhydroxyamides, as prepared according to the processes of US Pat. Nos. 1,985,424, US 2 016 962 and US 2 703 798 and international patent application WO 92/06984.
  • 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.
  • R 12 is an alkyl or alkenyl radical having 8 to 22 C atoms
  • G is a glycose unit
  • n is a number between 1 and 10 mean.
  • Such compounds and their preparation 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 are oligomers or polymers of naturally occurring aldose or ketose monomers, in particular glucose, mannose, fructose, galactose, talose, gulose, altrose, allose, idose, ribose, arabinose, Include 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 Oligomermaschinesgrad.
  • 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.
  • Nonionic surfactant is used according to the invention in agents which contain a soil-release agent used according to the invention, or used in the process according to the invention, preferably in amounts of 1 wt .-% to 30 wt .-%, in particular from 1 wt .-% to 25 Wt .-%, with 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.
  • 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.
  • 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 ⁇ -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.
  • 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.
  • those soap mixtures are preferred which are composed of 50% to 100% by weight of saturated C 12 -C 18 fatty acid soaps and up to 50% by weight of oleic acid soap.
  • soap is included in amounts of from 0.1% to 5% by weight.
  • higher amounts of soap of, as a rule, up to 20% by weight may be present.
  • compositions may also contain betaines and / or cationic surfactants, which, if present, are preferably used in amounts of from 0.5% by weight to 7% by weight.
  • betaines and / or cationic surfactants which, if present, are preferably used in amounts of from 0.5% by weight to 7% by weight.
  • esterquats discussed below are particularly preferred.
  • compositions contain, in addition to the percarbonate, an organic percarboxylic acid releasing compound (i.e., a so-called bleach activator) under perhydrolysis conditions, and / or an already formed organic percarboxylic acid, especially in amounts of from 0.5% to 6% by weight.
  • an organic percarboxylic acid releasing compound i.e., a so-called bleach activator
  • 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 isononanoyl-phenolsulfonate, and acylated sugar derivatives, in particular pentaacetylglucose, as well as cationic nitrile derivatives such as trimethylammoniumacetonitrile salts.
  • N- or O-acyl compounds for example polyacylated alkylenediamines, in particular tetraacety
  • 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 granulated 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine, as can be prepared according to the process described in German Patent DD 255,884 , and / or according to the in particulate form described in International Patent Applications WO 00/50553, WO 00/50556, WO 02/12425, WO 02/12426 or WO 02/26927 described method trialkylammoniumacetonitrile is particularly preferred.
  • 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.
  • 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.
  • 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% by weight, in particular from 0.1% by weight to 1% by weight, of foam inhibitors, wherein said parts by weight each refer to total means.
  • 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% by weight, in particular from 0.1% by weight to 1% by weight, of foam inhibitors, wherein said parts by weight each refer to total means.
  • 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.
  • the cellulose derivatives used in the invention are usually dissolved or in suspended form.
  • present enzymes are preferably selected from the group comprising protease, amylase, lipase, cellulase, hemicellulase, oxidase, peroxidase or mixtures thereof.
  • 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 German Offenlegungsschriften DE 19 40 488, DE 20 44 161, 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 are described.
  • Proteases are commercially available, for example, under the names BLAP ®, Savinase ®, Esperase ®, Maxatase ®, Optimase.RTM ®, Alcalase ®, ® or Durazym Maxapem ®.
  • the lipase which can be used can be prepared from Humicola lanuginosa, as described, for example, in European Patent Applications EP 258 068, EP 305 216 and EP 341 947, from Bacillus species, as described, for example, in International Patent Application WO 91/16422 or European Patent Application EP 384 717 , from Pseudomonas species, as for example 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 international patent application WO 90/10695, from Fusarium species, as described for example in European patent application EP 130 064, from Rhizopus species, as described, for example, in European patent application EP 117 553, or from Aspergillus species, as described, for example, in European patent application EP 167 309.
  • 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.
  • Such cellulases are known, for example, from German Offenlegungsschriften DE 31 17 250, 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 known and the international patent applications WO 95/02675 and WO 97/14804 and commercially available under the name Celluzyme ®, ® and Carezyme Ecostone® ®.
  • customary enzyme stabilizers include amino alcohols, for example 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 known boric acid or Alkali borates, boric acid-carboxylic acid combinations, as known for example from the European patent application EP 451 921, boric acid esters, as known for example from the international patent application WO 93/11215 or the European patent application EP 511 456, boronic acid derivatives, as for example from the European patent application EP 533 536 known, calcium salts, for example, the known from European Patent EP 28 865 Ca-formic acid combination, magnesium salts, as known for example from European Patent Application EP 378 262, and / or sulfur-containing reducing agents, such as from European patent applications EP 080 748 or EP 080 223.
  • lower carboxylic acids such as from the European patent applications EP 376 705 and EP 378 261 known boric acid or Alkali bor
  • 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.
  • foam inhibitors are preferably bound to granular, water-soluble carrier substances, as described, for example, in German Offenlegungsschrift DE 34 36 194, European patent applications EP 262 588, EP 301 414, EP 309 931 or European patent EP 150 386.
  • 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.
  • dicarboxylic acids for example adipic acid, phthalic acid or terephthalic acid
  • diols for example ethylene glycol or propylene glycol
  • polydiols for example polyethylene glycol or polypropylene glycol.
  • Preferred soil release polymers include those compounds which are formally accessible by esterification of two monomeric moieties, wherein the first monomer is a dicarboxylic acid HOOC-Ph-COOH and the second monomer is a diol HO- (CHR 11 -) a OH, also known as polymeric Diol H- (O- (CHR 11 -) a ) b OH may be present.
  • 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
  • a is a number from 2 to 6
  • b is a number from 1 to 300.
  • 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.
  • 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.
  • acids having at least two carboxyl groups may be included in the soil release-capable 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 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.
  • R 11 is hydrogen and a is a number from 2 to 6
  • R 11 is hydrogen and the alkyl radicals 1 to 10, in particular 1 to 3 C-atoms is selected.
  • those of the formula HO-CH 2 -CHR 11 -OH in which R 11 has the abovementioned meaning are particularly preferred.
  • 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 neopentylglycol.
  • Particularly preferred among the polymeric diols is polyethylene glycol having an average molecular weight in the range of 1000 to 6000.
  • 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.
  • 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-butyl
  • 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.
  • the number of hydroxymonocarboxylic acid units per end group is in the range from 1 to 50, in particular from 1 to 10.
  • polymers of ethylene terephthalate and polyethylene 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 in combination with the cellulose derivatives.
  • the soil release 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.
  • 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.
  • ester quat that is a quaternized ester of carboxylic acid and aminoalcohol
  • these are known substances that can be obtained by the relevant methods of preparative organic chemistry.
  • German Patent DE 43 08 794 moreover discloses a process for preparing solid ester quats, in which the quaternization of triethanolamine esters is carried out in the presence of suitable dispersants, preferably fatty alcohols.
  • 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.
  • 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
  • esterquats which can be used in the context of the invention are products based on caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, isostearic acid, stearic acid, oleic acid, elaidic acid, arachidic acid, behenic acid and erucic acid and their technical mixtures, such as They occur, for example, in the pressure splitting of natural fats and oils. It is preferred to use technical C 12/18 coconut fatty acids and in particular partially hydrogenated C 16/18 tallow or palm oil fatty acids and also elaidic acid-rich C 16/18 fatty acid cuts.
  • the fatty acids and the triethanolamine can generally be used in a molar ratio of 1.1: 1 to 3: 1 become.
  • 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.
  • quaternized ester salts of carboxylic acids with diethanolalkylamines of the formula (II) are also suitable as esterquats.
  • 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
  • X is a charge-balancing anion such as halide, alkyl sulfate or alkyl phosphate.
  • R 1 CO for an acyl radical having 6 to 22 carbon atoms
  • R 2 is hydrogen or R 1 is CO
  • R 4 , R 6 and R 7 are independently of one another alkyl radicals having 1 to 4 carbon atoms
  • m and n in total are 0 or numbers from 1 to 12
  • X is a charge-balancing anion such as halide, alkyl sulfate or alkyl phosphate.
  • esterquats of the formulas (II) and (III).
  • 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.
  • 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 further detergent ingredients present in solid form, especially the components of the water-soluble builder block.
  • a spray-drying step it is preferable to use a spray-drying step to produce the particle which contains the soil release-capable cellulose derivative.
  • a compacting compounding step for producing this particle and optionally also for producing the finished product.
  • 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.

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EP04707148A 2003-02-10 2004-01-31 Bleichmittelhaltige wasch- oder reinigungsmittel mit wasserlöslichem buildersystem und schmutzablösevermögendem cellulosederivat Revoked EP1592767B1 (de)

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JP2006517245A (ja) * 2003-02-10 2006-07-20 ヘンケル・コマンディットゲゼルシャフト・アウフ・アクチエン 発泡調節剤としてのセルロース誘導体の使用
DE10351321A1 (de) * 2003-02-10 2004-08-26 Henkel Kgaa Verstärkung der Reinigungsleistung von Waschmitteln durch eine Kombination von Cellulosderivaten
JP4578465B2 (ja) * 2003-02-10 2010-11-10 ヘンケル・アクチェンゲゼルシャフト・ウント・コムパニー・コマンディットゲゼルシャフト・アウフ・アクチェン 繊維製品の水吸収力の増大
ES2286602T3 (es) * 2003-02-10 2007-12-01 Henkel Kommanditgesellschaft Auf Aktien Antecedentes de la invencion.
DE10351325A1 (de) * 2003-02-10 2004-08-26 Henkel Kgaa Wasch- oder Reinigungsmittel mit wasserlöslichem Buildersystem und schmutzablösevermögendem Cellulosederivat
US9376648B2 (en) 2008-04-07 2016-06-28 The Procter & Gamble Company Foam manipulation compositions containing fine particles
EP2135932B1 (en) * 2008-06-20 2012-03-21 The Procter & Gamble Company Laundry composition
EP2135933B1 (en) * 2008-06-20 2013-04-03 The Procter and Gamble Company Laundry composition
WO2012022034A1 (en) 2010-08-18 2012-02-23 Unilever Plc Improvements relating to fabric treatment compositions comprising targeted benefit agents
CN103747772B (zh) * 2011-08-24 2016-03-16 荷兰联合利华有限公司 包含非离子多糖的有益剂递送颗粒
CN103781460B (zh) 2011-08-24 2016-05-18 荷兰联合利华有限公司 包含右旋糖酐的有益剂递送颗粒
JP6126605B2 (ja) * 2011-08-24 2017-05-10 ユニリーバー・ナームローゼ・ベンノートシヤープ 非イオン性多糖を含む有益剤送達粒子
DE102015205799A1 (de) * 2015-03-31 2016-10-06 Henkel Ag & Co. Kgaa Waschmittelzusammensetzung mit verbesserter Fleckentfernung
CN109403036B (zh) * 2018-10-24 2020-01-03 武汉纺织大学 一种用于棉质鞋垫防臭整理液的制备方法及应用
WO2024257963A1 (ko) * 2023-06-13 2024-12-19 주식회사 엘지생활건강 시트형 표백제

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ATE342953T1 (de) * 2003-02-10 2006-11-15 Henkel Kgaa Bleichmittelhaltiges waschmittel mit baumwollaktivem schmutzablösevermögendem cellulosederivat
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JP2006517245A (ja) * 2003-02-10 2006-07-20 ヘンケル・コマンディットゲゼルシャフト・アウフ・アクチエン 発泡調節剤としてのセルロース誘導体の使用
DE10351321A1 (de) * 2003-02-10 2004-08-26 Henkel Kgaa Verstärkung der Reinigungsleistung von Waschmitteln durch eine Kombination von Cellulosderivaten
ES2286602T3 (es) * 2003-02-10 2007-12-01 Henkel Kommanditgesellschaft Auf Aktien Antecedentes de la invencion.
JP4578465B2 (ja) * 2003-02-10 2010-11-10 ヘンケル・アクチェンゲゼルシャフト・ウント・コムパニー・コマンディットゲゼルシャフト・アウフ・アクチェン 繊維製品の水吸収力の増大

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DE502004003835D1 (de) 2007-06-28
EP1592767A1 (de) 2005-11-09
JP4519122B2 (ja) 2010-08-04
US20060035801A1 (en) 2006-02-16
US7375072B2 (en) 2008-05-20
ATE362511T1 (de) 2007-06-15
ES2285421T3 (es) 2007-11-16
WO2004069978A1 (de) 2004-08-19
JP2006517265A (ja) 2006-07-20

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