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
  • 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

Definitions

• the present invention relates to the use of certain soil release cellulosic derivatives to enhance the cleaning performance of bleach-containing laundry detergents in the washing of textiles, particularly those made of cotton or cotton, and bleach-containing detergents and cleaners containing such soil release cellulose derivatives.
• Detergents contain in addition to the indispensable for the washing process ingredients such as surfactants and builder materials usually further ingredients that can be summarized by the term washing aids and include as different drug groups such as foam regulators, grayness inhibitors, bleach, bleach activators 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 Application EP 0 213 730 discloses textile treatment compositions which contain cationic surfactants and nonionic cellulose ethers having HLB values of from 3.1 to 3.8.
• US Pat. No. 4,000,093 discloses laundry detergents which contain from 0.1% by weight to 3% by weight of alkyl cellulose, hydroxyalkyl cellulose or alkylhydroxyalkyl cellulose and from 5% by weight 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 4 alkyl sulfate and less than 5 wt .-% alkyl sulfate with alkyl radicals of C 15 and higher.
• US Pat. No. 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 2 alkylbenzenesulfonate and less than 5 wt .-% alkylbenzenesulfonate having alkyl radicals of C 13 and higher.
• European Patent Specification 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 2,000 to 100,000) such as methylcellulose and ethylcellulose, with weight percent of peroxygen bleaching agent (based on the active oxygen content of the bleaching agent ) from 10: 1 to 1:10.
• European patent application EP 0 634 481 relates to a detergent containing alkali metal percarbonate and one or more nonionic cellulose derivatives.
• the latter expressly disclose only hydroxyethylcellulose, hydroxypropylcellulose and methylcellulose and, in the examples, the methylhydroxyethylcellulose Tylose® MH50, the hydroxypropylmethylcellulose Methocel® F4M and hydroxybutylmethylcellulose.
• 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 to US Pat 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 of Cs- 24 alkyl substituents and the alkyl substituents in amounts of 0.1-5 wt .-%, based on the cellulose ether material present have to be.
• 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 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, besides oxyethylene groups and terephthalic acid units, also contains substituted ethylene units and also glycerol units.
• European patent EP 241 985 discloses polyesters which, in addition to oxyethylene groups and terephthalic acid units, contain 1,2-propylene, 1,2-butylene and / or 3-methoxy-1,2-propylene groups and also glycerol units and with Ci- to C 4 -alkyl groups are end group-capped.
• European Patent EP 253 567 relates to soil release polymers having a molecular weight of 900 to 9000 of ethylene terephthalate and polyethylene oxide terephthalate, wherein the polyethylene glycol units have molecular weights of 300 to 3000 and the molar ratio of ethylene terephthalate to polyethylene oxide terephthalate 0.6 to 0.95.
• From European patent application EP 272 033 are At least partially by Ci-4-alkyl or acyl radicals end phenomenonver claimed with poly-propylene terephthalate and polyoxyethylene terephthalate units known.
• European Patent EP 274 907 describes sulfoethyl end-capped terephthalate-containing soil release polyesters.
• the invention relates to the use of a soil release-capable cellulose derivative obtainable by alkylation and carboxyalkylation of cellulose to enhance the cleaning performance of detergents in the washing of textiles consisting of cotton or containing cotton, wherein the cellulose derivative averaged 0.4 to 2 , 7 alkyl groups and 0.001 to 0.3 carboxyalkyl groups per Anhydroglykosemonomer founded contains.
• a further subject of the invention is a process for washing textiles in which a washing agent and a corresponding soil release-capable cellulose derivative obtainable by alkylation and carboxyalkylation 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 particular 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 detergent which contains the soil release wealthy cellulose derivative perform.
• the washing performance-enhancing effect of the cellulose derivatives to be used according to the invention with repeated use, that is to say in particular for removing soiling of corresponding textiles which had already been washed and / or post-treated in the presence of the cellulose derivative before being provided with the soil.
• 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 detergent, which may contain a cellulose derivative, but in this case also free from may be 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.
• Preferred cellulose derivatives are those which are alkylated with Ci to Cio groups, in particular C 1 to C 3 groups and additionally Ci to Cio-Carboxyalkyl phenomenon, in particular Ci to C 4 -Carboxyalkyl phenomenon and particularly prefers C 2 - or C 3 -Carboxyalkyl- groups, carry (at the indicated C numbers is not counted in the carboxyalkyl carboxyl-C-atom).
• cellulose derivatives can be obtained in a known manner by reacting cellulose with appropriate alkylating agents, for example alkyl halides or alkyl sulfates, and subsequent reaction with corresponding haloalkyl carboxylic acids, such as, for example, chloroacetic acid, 3-chloropropionic acid and / or 4-chlorobutyric acid.
• alkylating agents for example alkyl halides or alkyl sulfates
• corresponding haloalkyl carboxylic acids such as, for example, chloroacetic acid, 3-chloropropionic acid and / or 4-chlorobutyric acid.
• a mean of 0.5 to 2.5, in particular 1 to 2 alkyl groups and 0.002 to 0.2, in particular 0.005 to 0.1, carboxyalkyl groups per anhydroglycose monomer 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 70,000 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 soiling on cotton or cotton-containing fabrics than when used so far for this purpose known compounds is the case. Alternatively, significant amounts of surfactants can be saved while maintaining fat removal capability.
• the use according to the invention can be carried out in the context of a washing process in such a way that the cellulose derivative is added to a detergent-containing liquor or, preferably, the cellulose derivative is introduced into the liquor as a constituent of a washing agent.
• Another object of the invention is therefore a detergent containing a cellulose derivative described above.
• cellulose derivative is added separately to the rinse liquor which is used after the wash cycle using a particular bleach-containing detergent, or it is incorporated as part of the laundry aftertreatment agent, in particular a softener.
• said detergent may also contain, but may be free of, a cellulose derivative to be used in accordance with the invention.
• Detergents containing a cellulose derivative to be used according to the invention or used together with it or used in the process according to the invention may contain all customary other constituents of such agents which do not interact in an undesired manner with the cellulosic derivative essential to the invention.
• the cellulose derivative in amounts of from 0.1 wt .-% to 2 wt .-%, in particular 0.5 wt .-% to 1 wt .-% is incorporated in detergent.
• the bleaches in question are preferably the peroxygen compounds generally used in detergents, such as percarboxylic acids, for example dodecanedioic acid or phthaloylaminoperoxicaproic acid, hydrogen peroxide, alkali metal perborate, which may be present as tetra- or monohydrate, percarbonate, perpyrophosphate and persilicate, which are generally used as alkali metal salts, in particular as sodium salts.
• percarboxylic acids for example dodecanedioic acid or phthaloylaminoperoxicaproic acid
• hydrogen peroxide alkali metal perborate
• percarbonate percarbonate
• perpyrophosphate and persilicate which are generally used as alkali metal salts, in particular as sodium salts.
• Such bleaching agents are in detergents which contain a cellulose derivative used according to the invention, preferably in amounts of up to 25 wt .-%, in particular up to 15 wt .-% and particularly preferably from 5 wt .-% to 15 wt -.%, In each case on total agent, present, in particular percarbonate is used.
• the optionally present component of the bleach activators comprises the conventionally 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, also carboxylic acid anhydrides, in particular phthalic anhydride, carboxylic acid esters, in particular sodium isononanoyl-phenolsulfonate, and acylated sugar derivatives, in particular penta-acetylglucose, 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 mean particle sizes of from 0.01 mm to 0.8 mm, as can be prepared, for example, according to the process described in the European patent EP 37,026 granulated l, 5-diacetyl-2,4-dioxohexahydro-l, 3,5-triazine, as described in the German Patent DD 255 884 and / or is particularly preferred according to the particulate form of trialkylammonium acetonitrile as described in international patent applications WO 00/50553, WO 00/50556, WO 02/12425, WO 02/12426 or WO 02/26927.
• Such bleach activators are preferably contained in detergents in amounts of up to 8% by weight, in particular from 2% by weight to 6% by weight, based in each
• an inventive agent used according to the invention or used in the process 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, 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 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.
• 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 such as may 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.
• alkylpolyglycosides which are suitable for incorporation into 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, Include arabinose, xylose and lyxose.
• the oligomers consisting of such glycosidically linked monomers are characterized not only by the nature of the sugars contained in them by their number, the so-called 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.
• the alkyl or alkenyl part R 12 of the glycosides also preferably originates from readily available derivatives of renewable raw materials, in particular from fatty alcohols, although also their branched-chain isomers, in particular so-called oxo alcohols, can be used for the preparation of useful glycosides. Accordingly, the primary alcohols having linear octyl, decyl, dodecyl, tetradecyl, hexadecyl or octadecyl radicals and mixtures thereof are particularly suitable.
• Nonionic surfactant is used in accordance with the invention or used in the process according to the invention in compositions which comprise a soil release active ingredient used in accordance with the invention, preferably in amounts of from 1% by weight to 30% by weight, in particular from 1% by weight 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 .-%.
• compositions 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.
• a conventional sulfating reagent in particular sulfur trioxide or chlorosulfonic acid
• the sulfate-type surfactants which can be used also include the sulfated alkoxylation products of the alcohols mentioned, so-called 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 include the sulfonate type Reaction of fatty acid esters with sulfur trioxide and subsequent neutralization obtainable ⁇ -sulfoester, 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 C-atoms, preferably 1 to 4 C. -Atomen, derivative sulfonation products, as well as the formal saponification resulting from these sulfo fatty acids.
• soaps suitable being saturated 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% by weight 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 as a rule up to 20% by weight, can also 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.
• the composition contains water-soluble and / or water-insoluble builder, in particular selected from alkali metal aluminosilicate, crystalline alkali metal silicate with modulus above 1, monomeric polycarboxylate, polymeric polycarboxylate and mixtures thereof, in particular in amounts ranging from 2.5 wt .-% to 60 wt .-%.
• water-soluble and / or water-insoluble builder in particular selected from alkali metal aluminosilicate, crystalline alkali metal silicate with modulus above 1, monomeric polycarboxylate, polymeric polycarboxylate and mixtures thereof, in particular in amounts ranging from 2.5 wt .-% to 60 wt .-%.
• the agent preferably contains from 20% to 55% by weight of water-soluble and / or water-insoluble, organic and / or inorganic builders.
• the water-soluble organic builder substances include, in particular, those from the class of polycarboxylic acids, in particular citric acid and sugar acids, and also the polymeric (poly) carboxylic acids, in particular the polycarboxylates of international patent application WO 93/16110 obtainable by oxidation of polysaccharides, polymeric acrylic - acids, methacrylic acids, maleic acids and copolymers thereof, which are also low Particles of polymerizable substances without carboxylic acid functionality may contain polymerized.
• the molecular weight of the homopolymers of unsaturated carboxylic acids is generally between 5000 and 200,000, that of the copolymers between 2000 and 200,000, preferably 50,000 to 120,000, based on the free acid.
• a particularly preferred acrylic acid-maleic acid copolymer has a molecular weight of 50,000 to 100,000.
• Suitable, although less preferred, compounds of this class are copolymers of acrylic or methacrylic acid with vinyl ethers, such as vinylmethyl ethers, vinyl esters, ethylene, propylene and styrene, in which the acid content is at least 50% by weight.
• the first acidic monomer or its salt is derived from a monoethylenically unsaturated C 3 -C 8 -carboxylic acid and preferably from a C 3 -C 4 -monocarboxylic acid, in particular from (meth) acrylic acid.
• the second acidic monomer or its salt may be a derivative of a C 4 -C 8 -dicarboxylic acid, with maleic acid being particularly preferred.
• the third monomeric unit is formed in this case of vinyl alcohol and / or preferably an esterified vinyl alcohol.
• vinyl alcohol derivatives which are an ester of short-chain carboxylic acids, for example of C 1 -C 4 -carboxylic acids, with vinyl alcohol.
• Preferred terpolymers contain from 60% by weight to 95% by weight, in particular from 70% by weight to 90% by weight of (meth) acrylic acid or (meth) acrylate, more preferably acrylic acid or acrylate, and maleic acid or Maleinate and 5 wt .-% to 40 wt .-%, preferably 10 wt .-% to 30 wt .-% of vinyl alcohol and / or vinyl acetate.
• the second acidic monomer or its salt may also be a derivative of an allylsulfonic acid which is in the 2-position with an alkyl radical, preferably with a C 1 -C 4 -alkyl radical, or an aromatic radical which is preferably derived from benzene or benzene derivatives, is substituted.
• Preferred terpolymers contain from 40% by weight to 60% by weight, in particular from 45 to 55% by weight.
• (Meth) acrylic acid or (meth) acrylate more preferably acrylic acid or acrylate, 10 wt .-% to 30 wt .-%, preferably 15 wt .-% to 25 wt .-% methallylsulfonic acid or methallylsulfonate and as a third monomer 15 wt % to 40% by weight, preferably 20% to 40% by weight of a carbohydrate.
• This carbohydrate may be, for example, a mono-, di-, oligo- or polysaccharide, mono-, di- or oligosaccharides being preferred, sucrose being particularly preferred.
• the use of the third monomer presumably incorporates predetermined breaking points in the polymer which are responsible for the good biodegradability of the polymer.
• These terpolymers can be prepared in particular by processes which are described in German Patent DE 42 21 381 and German Patent Application DE 43 00 772, and generally have a molecular weight between 1000 and 200,000, preferably between 200 and 50,000 and in particular between 3000 and 10000 on. They can be used, in particular for the preparation of liquid agents, in the form of aqueous solutions, preferably in the form of 30 to 50 percent by weight aqueous solutions. All the polycarboxylic acids mentioned are generally used in the form of their water-soluble salts, in particular their alkali metal salts.
• Such organic builder substances are preferably present in amounts of up to 40% by weight, in particular up to 25% by weight and particularly preferably from 1% by weight to 5% by weight. Quantities close to the stated upper limit are preferably used in pasty or liquid, in particular hydrous, agents.
• crystalline or amorphous alkali metal aluminosilicates in amounts of up to 50% by weight, preferably not more than 40% by weight and in liquid agents, in particular from 1% by weight to 5% by weight, are used as water-insoluble, water-dispersible inorganic builder materials.
• the detergent-grade crystalline aluminosilicates especially zeolite NaA and optionally NaX, are preferred. Amounts near the above upper limit are preferably used in solid, particulate agents.
• suitable aluminosilicates have no particles with a particle size greater than 30 mm and preferably consist of at least 80% by weight of particles having a size of less than 10 mm.
• Suitable substitutes or partial substitutes for the said aluminosilicate are crystalline alkali silicates which may be present alone or in a mixture with amorphous silicates.
• the alkali metal silicates useful as builders in the compositions preferably have a molar ratio of alkali metal oxide to SiO 2 below 0.95, in particular from 1: 1.1 to 1:12, and may be present in amorphous or crystalline form.
• Preferred alkali metal silicates are the sodium silicates, in particular the amorphous sodium silicates, with a molar ratio of Na 2 O: SiO 2 of 1: 2 to 1: 2.8.
• Such amorphous alkali silicates are commercially available, for example, under the name Portil®.
• Those with a molar ratio Na 2 O: SiO 2 of 1: 1, 9 to 1: 2.8 can be prepared by the process of European Patent Application EP 0 425 427. They are preferably added in the course of the production as a solid and not in the form of a solution.
• the crystalline silicates which may be present alone or in admixture with amorphous silicates, are crystalline layer silicates with the general formula Na 2 Si x O 2x + I y H 2 O used in the x, the so-called module is a number from 1.9 to 4 and y is a number from 0 to 20 and preferred values for x are 2, 3 or 4.
• Crystalline layered silicates which fall under this general formula are described, for example, in European Patent Application EP 0 164 514.
• Preferred crystalline phyllosilicates are those in which x in the abovementioned general formula assumes the values 2 or 3.
• both .beta.- and ⁇ -sodium are preferred, with beta-sodium disilicate being obtainable, for example, by the method described in International Patent Application WO 91/08171.
• beta-Sodium silicates with a modulus between 1.9 and 3.2 can be prepared according to Japanese patent applications JP 04/238 809 or JP 04/260 610.
• Crystalline sodium silicates with A module in the range from 1.9 to 3.5 as obtainable by the methods of European patents EP 0 164 552 and / or the European patent application EP 0 294 753, in a further preferred embodiment of detergents which are in accordance with the invention used cellulose derivative used.
• Their content of alkali metal silicates is preferably 1 wt .-% to 50 wt .-% and in particular 5 wt .-% to 35 wt .-%, based on anhydrous active substance.
• alkali metal silicate in particular zeolite
• the content of alkali metal silicate is preferably 1% by weight to 15% by weight and in particular 2% by weight to 8% by weight, based on anhydrous active substance.
• the weight ratio of aluminosilicate to silicate, in each case based on anhydrous active substances, is then preferably 4: 1 to 10: 1.
• the weight ratio of amorphous alkali metal silicate to crystalline alkali metal silicate is preferably 1: 2 to 2: 1 and especially 1: 1 to 2: 1.
• inorganic builder In addition to the mentioned inorganic builder, other water-soluble or water-insoluble inorganic substances may be contained in the compositions which contain a cellulose derivative to be used according to the invention together with it or used in processes according to the invention. Suitable in this context are the alkali metal carbonates, alkali metal bicarbonates and alkali metal sulfates and mixtures thereof. Such additional inorganic material may be present in amounts up to 70% by weight.
• the agents may contain other ingredients customary in detergents and cleaners.
• These optional constituents include, in particular, enzymes, enzyme stabilizers, complexing agents for heavy metals, for example aminopolycarboxylic acids, aminohydroxypolycarboxylic acids, polyphosphonic acids and / or aminopolyphosphonic acids, 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, up to 5% by weight, especially 0.1% by weight to 2 wt .-% complexing agent for heavy metals, in particular Aminoalkylenphosphon- acids and their salts and up to 2 wt .-%, in particular 0.1 wt .-% to 1 wt .-% foam inhibitors, wherein said weight fractions in each case to total Obtain funds.
• 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
• up to 5% by weight especially 0.1% by weight to 2 wt
• 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.
• Proteases are commercially available, for example, under the names BLAP®, Savinase®, Esperase®, Maxatase®, Optimase®, Alcalase®, Durazym® or Maxapem®.
• the lipase which can be used can be 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 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
• 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 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 and international patent applications WO 95/02675 and WO 97/14804 and commercially available under the names Celluzyme®, Carezyme® and Ecostone®.
• the customary enzyme stabilizers present in particular, if appropriate, 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 376 705 and EP 378 261, Boric acid or alkali metal borates, boric acid-carboxylic acid combinations, as known for example from European patent application EP 451 921, boric acid esters, such as from the international patent application WO 93/11215 or European patent application EP 511 456 known boronic acid derivatives, such as from the European patent application EP 583 536 known, calcium salts, for example, 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 de n European patent applications EP 080 748 or EP 080 223.
• amino alcohols for example mono-, di-, triethanol- and -propanol
• Suitable foam inhibitors include long-chain soaps, in particular heel soap, fatty acid amides, paraffins, waxes, microcrystalline waxes, organopolysiloxanes and mixtures thereof, which moreover are microfine, optionally silanated or otherwise hydrophobized silica may contain.
• 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.
• an agent which is incorporated into the cellulose derivative to be used according to the invention is particulate and contains up to 25% by weight, in particular 5% by weight to 20% by weight, of bleaching agent, in particular alkali percarbonate, up to 15% by weight.
• % in particular from 1% by weight to 10% by weight of bleach activator, from 20% by weight to 55% by weight of inorganic builder, up to 10% by weight, in particular from 2% by weight to 8% by weight % water-soluble organic builder, 10 wt.% to 25 wt.% of synthetic anionic surfactant, 1 wt.% to 5 wt.% of nonionic surfactant and up to 25 wt.%, in particular 0.1 wt 25 wt .-% of inorganic salts, in particular alkali carbonate and / or bicarbonate.
• an agent which is incorporated into the cellulose derivative to be used according to the invention is liquid and contains 10% by weight to 25% by weight, in particular 12% by weight to 22.5% by weight, of nonionic surfactant, 2 wt .-% to 10 wt .-%, in particular 2.5 wt .-% to 8 wt .-% synthetic anionic surfactant, 3 wt .-% to 15 wt .-%, in particular 4.5 wt .-% bis 12.5 wt .-% soap, 0.5 wt .-% to 5 wt .-%, in particular 1 wt .-% to 4 wt .-% organic builder, in particular polycarboxylate such as citrate, up to 1.5 wt.
• nonionic surfactant 2 wt .-% to 10 wt .-%, in particular 2.5 wt .-% to 8 wt .-% synthetic anionic surfactant, 3 wt
• wt .-% In particular 0.1 wt .-% to 1 wt .-% complexing agent for heavy metals, such as phosphonate, and in addition to optionally contained enzyme, enzyme stabilizer, color and / or fragrance water and / or water-miscible solvent.
• heavy metals such as phosphonate
• 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- (CHRi i-) a ) b 0H 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.
• acids having at least two carboxyl groups be contained in the soil release-capable polyester.
• 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 1 ⁇ 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 neopentyl glycol.
• 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.
• the ester groups bound by end groups alkyl, alkenyl and Arylmonocarbonklaren with 5 to 32 carbon atoms, in particular 5 to 18 carbon atoms, based.
• 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, petroseic 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-butylbenzo
• 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, the hydrogenation product of which includes hydroxystearic acid and also o-, m- and p-hydroxybenzoic acid.
• the hydroxy-monocarboxylic acids can in turn via their hydroxyl group and its carboxyl group be connected to each other and thus present multiple 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.
• 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.
• Preferably used polymers have these conditions However, a solubility of at least 1 g per liter, in particular at least 10 g per liter.
• Preferred laundry aftertreatment compositions containing a cellulose derivative to be used according to the invention have, as a laundry softening active ingredient, a so-called esterquat, that is to say a quaternized ester of carboxylic acid and aminoalcohol.
• esterquat that is to say a quaternized ester of carboxylic acid and aminoalcohol.
• 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.
• suitable dispersants preferably fatty alcohols.
• Reviews on this topic are, for example, by R. Puchta et al. in Tens.Surf.Det, 30, 186 (1993), M.Brock in Tens.Surf.Det. 30, 394 (1993), R. Lagerman et al. in J.Am.Oil.Chem.Soc, 7I 3 97 (1994) and I.Shapiro in Cosm. 109, 77 (1994).
• Ester quats preferred in the compositions are quaternized fatty acid triethanolamine ester salts which follow formula (I), R 4
• 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 for O 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.
• 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.
• industrial Ci 2 / is-coconut fatty acids and in particular partly hydrogenated C 16A8 -TaIg- or palm fatty acids, as well as elaidic-rich C 16/18 are - fatty cuts used.
• the fatty acids and the triethanolamine can generally be used in a molar ratio of 1.1: 1 to 3: 1.
• 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 esterquats are preferably 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 fatty acid (iodine value O to 40) from , 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 O 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 CO
• R 4 , R 6 and R 7 are independently alkyl radicals having 1 to 4 carbon atoms
• 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 laundry aftertreatment agents used according to the invention may additionally contain detergent ingredients listed above, Unless they interact unacceptably with the esterquat. It is preferably a liquid, water-containing agent.
• Tinopal® DMS-X a 0.2% by weight
• the soiled tissues 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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• 2006
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