EP3167034B1 - Polyalkoxylated polyamines in laundry methods - Google Patents

Description

The present invention relates to the use of alkoxylated polyamines (also referred to below as PEI) in novel washing processes for enhancing the primary washing power of detergents when washing textile substrates in wash liquors containing such alkoxylated polyamines.

In addition to the ingredients indispensable for the washing process, such as surfactants and builders, detergents generally contain further constituents, which can be summarized under the term washing aids and which comprise such different active ingredient groups as foam regulators, grayness inhibitors, bleaching agents, bleach activators and color transfer inhibitors. Such excipients also include substances whose presence enhances the detergency of surfactants, without them usually having to have a surfactant behavior itself. The same applies mutatis mutandis to cleaners for hard surfaces. Such substances are often referred to as a detergency booster or in the case of a particularly pronounced effect against oil or fat-based stains as a "fat booster".

Alkoxylated polyamines and their use in detergents and cleaners are known, for example, from international patent applications WO 95/32272 A1 and WO 2006/108857 A1 known. From the international patent application WO 2006/108856 For example, amphiphilic water-soluble alkoxylated polyamines having an inner polyethylene block and an outer polypropylene block are known. It is in the DE 10 2011 089 948 A1 already described that certain alkoxylated polyamines with inner polypropylene block and outer polyethylene block have particularly good primary washing power enhancing properties.

US-A-2005/183206 relates to compositions and methods for cleaning textile substrates, especially carpet and upholstery fabrics. In particular, the document relates to liquid compositions containing absorbent particles in a flowable liquid dispersion resulting in a soil-loaded powder which can be removed by suction or brushing, drying and / or washing processes.

EP-A-1371718 discloses polymeric nanoparticles having an average particle diameter of 1 to 10 nm which are included as fabric care additives in detergent formulations to improve properties such as softening, wrinkle resistance, soil and stain removal, soil release, dye transfer, dye fixation, static control and anti-foaming , are suitable. The nanoparticles can be used with silicone compounds in the detergent formulation, or can be functionalized with silicone groups to extend significantly different fabric care properties of the formulations.

US-A-4655952 teaches a detergent and a process for its preparation, the detergent for textile surfaces, in particular of textile floor coverings. The product contains a powdered, porous carrier of a foamed, plasticized urea-formaldehyde resin foam enriched with detergent and contains a hydrous surfactant which adheres to the carrier material, the water in the carrier material adhering completely homogeneously.

JP-A-04241165 relates to the treatment of a dyed natural fiber material having an appearance similar to that of a stone-washed fabric while avoiding the deficiencies of the stone-wash treatment and discloses the treatment of indigo-dyed denim clothing by stirring and washing in water or in an aqueous solution of a detergent Frictional contact with solid rubber balls and 10-50 wt .-% of an abrasive such as MgO with a particle size of 60-200 mesh.

DE-A-1 900 002 discloses solid detergents, surfactants, detergents, non-surface active cleaning salts and laundry additives containing polymers of vinyl compounds having an average particle size of less than 1 mm.

WO-A-01/71083 discloses a washing machine having a drum for receiving articles to be washed, the drum having at least two rotatable drum sections and a drive, the drum comprising a plurality of different drum modes, including a mode in which the rotatable drum parts are driven to effect a relative rotation between them. A controller controls the apparatus to execute a plurality of different wash programs, each wash program having an associated drum mode.

WO 2010/094959 A1 relates to the cleaning of substrates using a solvent-free cleaning system which requires the use of only small amounts of water. In particular, the book deals with the cleaning of textile fibers with the help of such a system, and provides an apparatus for use in this context.

WO 2007/128962 enables the efficient separation of the substrate from the polymer particles upon completion of the cleaning process and describes a design for using two internal drums.

The object of the present invention is to improve the washing performance in the presence of a large number of water-insoluble solid particles, preferably polymer particles, in particular in the removal of stains from textile substrates with oily and / or fatty, proteinaceous and / or fruitaceous soils.

The invention in a first embodiment, an aqueous wash liquor is suitable for use in a device for cleaning soiled textile substrates containing a plurality of water-insoluble solid polymer particles and a liquid detergent containing polyalkoxylated polyamines and a non-aqueous solvent.

The use of PEI in combination with the water-insoluble solid particles in the wash liquor according to the invention enhances the primary washing power when washing textiles against, in particular, oil and / or greasy stains or fruit-containing soils.

PEI shows interactions with anionic surfactants such as in particular alkyl ether sulfate, which may be due to the formation of a surfactant-drug aggregate. The effect can be detected by measuring the surface or interfacial tension, the surface or interfacial tension being increased by the presence of the active ingredient. This increase may be due to the formation of a detergent-active aggregate in the solution and therefore less surfactant at the interface.

In the context of the present invention and its individual aspects, the polyalkoxylated polyamine is a polymer having an N-atom-containing backbone which carries polyalkoxy groups on the N atoms. The polyamine has primary amino functions at the ends and preferably both secondary and tertiary amino functions inside; if appropriate, it may also have only secondary amino functions on the inside, so that the result is not a branched-chain but a linear polyamine. The ratio of primary to secondary amino groups in the polyamine is preferably in the range from 1: 0.5 to 1: 1.5, in particular in the range from 1: 0.7 to 1: 1. The ratio of primary to tertiary amino groups in the polyamine is preferably in the range of 1: 0.2 to 1: 1, in particular in the range of 1: 0.5 to 1: 0.8. Preferably, the polyamine has an average molecular weight in the range of 500 g / mol to 50,000 g / mol, in particular from 550 g / mol to 5000 g / mol. The mean molar masses indicated here and later, if appropriate, for other polymeric ingredients are weight-average molar masses M _w , which can in principle be determined by means of gel permeation chromatography with the aid of an RI detector, the measurement being expediently carried out against an external standard. The N atoms in the polyamine are preferably separated from one another by alkylene groups having 2 to 12 C atoms, in particular 2 to 6 C atoms, wherein not all alkylene groups must have the same C atom number. Particularly preferred are ethylene groups, 1,2-propylene groups, 1,3-propylene groups, and mixtures thereof. The primary amino functions in the polyamine can carry 1 or 2 polyalkoxy groups and the secondary amino functions 1 polyalkoxy group, with not every amino function having to be substituted by alkoxy groups. The average number of alkoxy groups per primary and secondary amino function in the polyalkoxylated polyamine is preferably 1 to 100, in particular 5 to 50. The alkoxy groups in the polyalkoxylated polyamine are preferably polypropoxy groups which are bonded directly to N atoms, and polyethoxy groups, which are bonded to the propoxy radicals and optionally to N atoms which carry no propoxy groups. The polyalkoxylated polyamines are accessible by reaction of polyamines with propylene oxide and subsequent reaction with ethylene oxide. The average number of propoxy groups per primary and secondary amino function in the polyalkoxylated polyamine is preferably 1 to 40, especially 5 to 20, and the average number of ethoxy groups per primary and secondary amino function in the polyalkoxylated polyamine is preferably 10 to 60, especially 15 to 30, if desired , the terminal OH function Polyalkoxysubstituenten in polyalkoxylated polyamine partially or completely with a C ₁ - C _10, in particular C ₁ -C ₃ - alkyl group etherified be. PEI's particularly preferred according to the invention can be selected from PEI's reacted with 43EO, PEI's reacted with 43EO, PEI's reacted with 15EO + 5PO, PEI's reacted with 15PO + 30EO, PEI's reacted with 5PO + 39.5EO, PEI's reacted with 5PO + 15EO, PEI's with 10PO + 35EO, PEI's implemented with 15PO + 30EO and PEI's implemented with 15PO + 5EO.

Furthermore, it has been found here that ethoxylated and / or propoxylated polyamines have particularly good primary laundry-enhancing properties in combination with the water-insoluble solid particles if the proportion of propoxylene groups in the entirety of the alkoxy groups does not leave a certain range. The effect is particularly pronounced if one seeks the removal of fruitous soils. Further preferred subject of the invention is the use of polyalkoxylated polyamines, which are obtainable by reacting polyamines with ethylene oxide and propylene oxide, wherein the proportion of propylene oxide in the total amount of the alkylene oxide 2 mol% to 18 mol%, especially 8 mol% to 15 mol% is in the detergents to enhance the primary washing or cleaning power when washing textiles against soiling, especially those with fruit-containing preparations.

The invention therefore also provides a combination of PEI obtainable by reacting polyamines with alkylene oxide, in particular ethylene oxide and / or propylene oxide, with water-insoluble solid particles and alkoxylated C ₈ -C ₁₈ -alcohols having an average degree of alkoxylation in the range from 1 to 5 , especially from 2 to 4, in detergents to enhance the primary washing or cleaning power when washing textile substrates against stains.

Furthermore, it has been found that alkoxylated polyamines have particularly good primary wash strength enhancing properties when combined with the water-insoluble solid particles and certain nonionic surfactants.

Preferably, the weight ratio of polyalkoxylated polyamine to alkoxylated C ₈ -C ₁₈ -alcohol having an average degree of alkoxylation of 1 to 5 is in the range of 1: 3 to 3: 1, in particular 1: 2 to 2: 1. Alkoxylated C ₈ -C ₁₈ -alcohols in the context of the present invention and their individual aspects are obtainable by reacting corresponding alcohols with alkylene oxide, preference being given to primary linear or branched-chain alcohols. Accordingly, the alkoxylates of primary alcohols having linear, in particular decyl, dodecyl, tridecyl, tetradecyl, hexadecyl or octadecyl radicals and mixtures thereof are useful. In preferred embodiments of the invention, the alcohol has a maximum of 16 C atoms, in particular 12 to 14 C atoms. The degree of alkoxylation, that is the average number of alkoxy groups per alcohol function, of the lower alkoxylated alcohol can be integer or fractional and preferably in the range from 2 to 4, in particular from 2 to 3.5. Preferred alkoxy groups are ethoxy, propoxy and butoxy groups, especially ethoxy groups and mixtures of ethoxy and propoxy groups.

An embodiment of the invention is therefore the use of the wash liquor according to the invention for the removal of proteinaceous soils, such as blood, egg, milk, or stains proteinaceous preparations, such as chocolate, latte, pudding.

The invention encompasses the removal of stains, in particular protein-containing stains or soiling of proteinaceous preparations, of textile substrates in which a wash liquor containing a combination of polyalkoxylated polyamine, water-insoluble solid particles and, optionally, low alkoxylated alcohol is used.

Fruit-containing preparations are nutritionally suitable fruit preparations, such as jams, jams and jellies. These lead due to their thickener content and their fruit content to difficult to remove stains. This wash liquor can be obtained manually or preferably by machine, for example by means of a washing machine. It is possible to apply a solid or liquid detergent beforehand, simultaneously or after use with the water-insoluble solid particles. The concentration of said polyalkoxylated polyamine in the liquid fraction of the wash liquor according to the invention including the water-insoluble solid particles is preferably 1 mg / l to 500 mg / l, in particular 5 mg / l to 100 mg / l. In this case, the liquid portion of the wash liquor is understood as the proportion of the total wash liquor including the water-insoluble solid particles obtained by centrifuging 8 kg of the wash liquor containing the solid water-insoluble particles for 5 minutes in a centrifuge with the water-insoluble solid particles separated cylindrical rotating body of 515 mm inner diameter and 370 mm internal depth at 1400 revolutions per minute from the liquid portion.

In a further preferred embodiment of the present invention, the detergent contains at least one surfactant in addition to the PEI. The PEI-containing detergent preferably contains synthetic anionic surfactants of the sulfate or sulfonate type, in amounts of preferably not more than 20 wt .-%, in particular from 0.1 wt .-% to 18 wt .-%, each based on the total agent. Suitable synthetic anionic surfactants which are particularly suitable for use in such compositions are the alkyl and / or alkenyl sulfates having 8 to 22 C atoms which carry an alkali, ammonium or alkyl or hydroxyalkyl-substituted ammonium ion as counter cation. Preference is given to the derivatives of the fatty alcohols having in particular 12 to 18 carbon atoms and their branched-chain analogs, the so-called oxo alcohols. The alkyl and alkenyl sulfates can be prepared in a known manner by reaction of the corresponding alcohol component with a conventional sulfating reagent, in particular sulfur trioxide or chlorosulfonic acid, and subsequent neutralization with alkali metal, ammonium or alkyl or hydroxyalkyl-substituted ammonium bases. The sulfate-type surfactants which can be used with particular preference include the abovementioned sulfated alkoxylation products of the alcohols mentioned, so-called ether sulfates. Such ether sulfates preferably contain 2 to 30, in particular 4 to 10 ethylene glycol groups per molecule. Suitable anionic surfactants of the sulfonate type include the α-sulfoesters obtainable by reaction of fatty acid esters with sulfur trioxide and subsequent neutralization, in particular those of fatty acids having 8 to 22 C atoms, preferably 12 to 18 C atoms, and linear alcohols having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, derivative sulfonation, as well as the formal saponification resulting from these sulfo fatty acids. The anionic surfactants which can be used also include the salts of sulfosuccinic acid esters, which are also referred to as alkylsulfosuccinates or dialkylsulfosuccinates, and which are monoesters or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and in particular ethoxylated fatty alcohols. Preferred sulfosuccinates contain C ₈ to C ₁₈ fatty alcohol residues or mixtures of these. Particularly preferred sulfosuccinates contain an ethoxylated fatty alcohol radical, which in itself is a nonionic surfactant. Sulfosuccinates, whose fatty alcohol residues are derived from ethoxylated fatty alcohols with a narrow homolog distribution, are again particularly preferred. Another synthetic anionic surfactant is alkylbenzenesulfonate in question.

A further preferred embodiment of the detergents comprises the presence of 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 their mixtures, in particular in an amount in the range of 2 wt .-% to 25 wt .-%.

Suitable nonionic surfactants include the alkoxylates, in particular the ethoxylates and / or propoxylates of saturated or mono- to polyunsaturated linear or branched-chain alcohols having 10 to 22 C atoms, preferably 12 to 18 C atoms. The degree of alkoxylation of the alcohols is generally between 1 and 20, preferably between 3 and 10. They can be prepared in a known manner by reacting the corresponding alcohols with the corresponding alkylene oxides. Particularly suitable are the derivatives of fatty alcohols, although their branched-chain isomers, in particular so-called oxo alcohols, can be used for the preparation of usable alkoxylates. Useful are accordingly the alkoxylates, in particular the ethoxylates, primary alcohols with linear, in particular dodecyl, tetradecyl, hexadecyl or octadecyl radicals and mixtures thereof. In addition, suitable alkoxylation products of alkylamines, vicinal diols and carboxamides, which correspond to the said alcohols with respect to the alkyl part, usable. In addition, the ethylene oxide and / or propylene oxide insertion products come of fatty acid alkyl esters and Fettsäurepolyhydroxyamiden into consideration. So-called alkylpolyglycosides which are suitable for incorporation in the compositions according to the invention are compounds of the general formula (G) _n -OR ¹² , in which R ^{12 is} an alkyl or alkenyl radical having 8 to 22 C atoms, G is a glycose unit and n is a number between 1 and 10 mean. 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 Oligomerisierungsgrad. The degree of oligomerization n assumes as the value to be determined analytically generally broken numerical values; it is between 1 and 10, with the glycosides preferably used below a value of 1.5, in particular between 1.2 and 1.4. Preferred monomer building block is glucose because of its good availability. The alkyl or alkenyl moiety R ^{12 of} the glycosides preferably also originates from readily available derivatives of the raw materials, in particular fatty alcohols, although their branched-chain isomers, in particular so-called oxo alcohols, can be used to prepare useful glycosides. Accordingly, the primary alcohols having linear octyl, decyl, dodecyl, tetradecyl, hexadecyl or octadecyl radicals and mixtures thereof are particularly suitable. Particularly preferred alkyl glycosides contain a Kokosfettalkylrest, that is, mixtures having substantially R ¹² = dodecyl and R ¹² = tetradecyl.

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

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

If desired, the detergents may contain peroxygen bleaching agents, in particular in amounts ranging from 5% by weight to 70% by weight, and optionally bleach activator, especially in amounts ranging from 2% to 10% by weight. The bleaches in question are preferably the peroxygen compounds generally used in detergents, such as percarboxylic acids, for example 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. Such bleaching agents are in detergents containing an active ingredient 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 .-%, each based on total agent, present, in particular percarbonate is used. 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 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. The bleach activators may have been coated and / or granulated in a known manner with coating substances in order to avoid the interaction with the per compounds, granulated tetraacetylethylenediamine having mean particle sizes of from 0.01 mm to 0.8 mm, granulated 1, with the aid of carboxymethylcellulose. 5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine, and / or in particulate form, trialkylammonium acetonitrile is particularly preferred. 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 case on the total agent.

In a further embodiment, the detergent 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 .-%.

The detergent preferably contains from 20% by weight 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, as well as the polymeric (poly) carboxylic acids, in particular the polycarboxylates obtainable by oxidation of polysaccharides, polymeric acrylic acids, methacrylic acids, maleic acids and mixed polymers thereof, which also small proportions of polymerizable substances without carboxylic acid functionality may contain polymerized. The relative molecular mass of the homopolymers of unsaturated carboxylic acids is generally between 5000 g / mol and 200,000 g / mol, that of the copolymers between 2000 g / mol and 200,000 g / mol, preferably 50,000 g / mol to 120,000 g / mol, based on the free acid , A particularly preferred acrylic acid-maleic acid copolymer has a molecular weight of 50,000 g / mol to 100,000 g / mol. 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. It is also possible to use as water-soluble organic builder substances terpolymers which contain two carboxylic acids and / or salts thereof as monomers and vinyl alcohol and / or a vinyl alcohol derivative or a carbohydrate as the third monomer. 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. In particular, preferred are vinyl alcohol derivatives which are an ester of short-chain carboxylic acids, for example 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 and / or (meth) acrylate, particularly preferably acrylic acid and / or acrylate, and maleic acid and / or maleate and 5 wt .-% to 40 wt .-%, preferably 10 wt .-% to 30 wt .-% of vinyl alcohol and / or vinyl acetate. Very particular preference is given to terpolymers in which the weight ratio of (meth) acrylic acid and / or (meth) acrylate to maleic acid and / or maleate is between 1: 1 and 4: 1, preferably between 2: 1 and 3: 1 and in particular 2: 1 and 2.5: 1. Both the amounts and the weight ratios are based on the acids. 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, of (meth) acrylic acid and / or (meth) acrylate, particularly preferably acrylic acid and / or acrylate, 10% by weight to 30 wt .-%, preferably 15 wt .-% to 25 wt .-% methallylsulfonic acid and / or Methallylsulfonat and as the third monomer 15 wt .-% to 40 wt .-%, preferably 20 wt .-% to 40 wt. % 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 generally have a molecular weight between 1000 g / mol and 200000 g / mol, preferably between 2000 g / mol and 50,000 g / mol and in particular between 3000 g / mol and 10,000 g / mol. 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 particularly suitable as water-insoluble, water-dispersible inorganic builder materials. used. Among these, 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. In particular, suitable aluminosilicates have no particles with a particle size greater than 30 .mu.m and preferably consist of at least 80% by weight of particles having a size of less than 10 .mu.m. Their calcium binding capacity, according to the information of the German Patent DE 24 12 837 can be determined ranges from 100 to 200 mg CaO per gram. Suitable substitutes or partial substitutes for the said aluminosilicate are crystalline alkali metal 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 of Na ₂ O: SiO ₂ of 1: 1.9 to 1: 2.8 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 + 1} · are used yH ₂ O, in which x, the so-called module, 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 the European patent application EP 0 164 514 A described. Preferred crystalline phyllosilicates are those in which x in the abovementioned general formula assumes the values 2 or 3. In particular, both β- and δ-sodium disilicates are (Na ₂ Si ₂ O ₅ .yH ₂ O) is preferred. Also prepared from amorphous alkali metal silicates, practically anhydrous crystalline alkali silicates of the above general formula in which x is a number from 1.9 to 2.1, can be used in agents which contain an active ingredient to be used according to the invention. In a further preferred embodiment of the composition according to the invention, a crystalline sodium layer silicate with a modulus of 2 to 3 is used, as can be prepared from sand and soda. Crystalline sodium silicates with a modulus in the range from 1.9 to 3.5 are used in a further preferred embodiment of detergents containing an active ingredient used according to the invention. 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. If alkali metal aluminosilicate, in particular zeolite, is present as an additional builder substance, the content of alkali 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. In agents containing both amorphous and crystalline alkali metal silicates, 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.

In addition to the said inorganic builder, other water-soluble or water-insoluble inorganic substances may be contained in the detergents which contain an active substance to be used according to the invention, used together with the latter 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.

In addition, the detergents may contain other usual in detergents or cleaning ingredients. These optional ingredients 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. Preferably, in agents which contain an active substance 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 wt .-%, in particular 0.1 wt .-% to 2 wt .-% complexing agent for Heavy metals, in particular aminoalkylenephosphonic acids and their salts and up to 2% by weight, in particular 0.1% by weight contain up to 1 wt .-% foam inhibitors, wherein said weight fractions each refer to the total agent.

The nonaqueous solvents are preferably those nonaqueous solvents that are water miscible. These include the lower alcohols, for example, ethanol, propanol, isopropanol, and the isomeric butanols, glycerol, lower glycols, such as ethylene and propylene glycol, and the derivable from said classes of compounds ether. In such liquid agents, the active compounds used in the invention are usually dissolved or in suspended form.

Optionally present enzymes are preferably selected from the group comprising protease, amylase, lipase, cellulase, hemicellulase, oxidase, peroxidase, pectinase and mixtures thereof. First and foremost, proteases derived from microorganisms, such as bacteria or fungi, come into question. It can be obtained in a known manner by fermentation processes from suitable microorganisms. Proteases are commercially available, for example, under the names BLAP®, Savinase®, Esperase®, Maxatase®, Optimase®, Alcalase®, Durazym® or Maxapem®. The lipase which can be used can be obtained, for example, from Humicola lanuginosa, from Bacillus species, from Pseudomonas species, from Fusarium species, from Rhizopus species or from Aspergillus 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 commercially available under the names Celluzyme®, Carezyme® and Ecostone®. Suitable pectinases are, for example, under the names Gamanase®, Pektinex AR®, X-Pect® or Pectaway® from Novozymes, under the name Rohapect UF®, Rohapect TPL®, Rohapect PTE100®, Rohapect MPE®, Rohapect MA plus HC, Rohapect DA12L ®, Rohapect 10L®, Rohapect B1L® from AB Enzymes and available under the name Pyrolase® from Diversa Corp., San Diego, CA, USA.

To the optionally present in particular liquid detergents usual enzyme stabilizers include amino alcohols, for example mono-, di-, triethanol- and -propanolamine and mixtures thereof, lower carboxylic acids, boric acid, alkali metal borates, boric acid-carboxylic acid combinations, boric acid esters, boronic acid derivatives, calcium salts, for example Ca-formic acid combination, magnesium salts, and / or sulfur-containing reducing agents.

Suitable foam inhibitors include long-chain soaps, especially behenic soap, fatty acid amides, paraffins, waxes, microcrystalline waxes, organopolysiloxanes and mixtures thereof, which moreover can contain microfine, optionally silanated or otherwise hydrophobicized silica. For use in particulate agents, such foam inhibitors are preferably bound to granular, water-soluble carrier substances.

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

If desired, these polyesters composed as described above may also be end-capped, alkyl groups having from 1 to 22 carbon atoms and esters of monocarboxylic acids being suitable as end groups. The ester groups bound by end groups alkyl, alkenyl and Arylmonocarbonsäuren with 5 to 32 carbon atoms, in particular 5 to 18 carbon atoms, based. These include valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, undecanoic acid, undecenoic acid, lauric acid, lauroleinic acid, tridecanoic acid, myristic acid, myristoleic acid, pentadecanoic acid, palmitic acid, stearic acid, petroselinic acid, petroselaidic acid, oleic acid, linoleic acid, linolaidic acid, linolenic acid, levostearic acid, arachidic acid , Gadoleic acid, arachidonic acid, behenic acid, erucic acid, brassidic acid, clupanodonic acid, lignoceric acid, cerotic acid, melissic acid, benzoic acid, which may carry 1 to 5 substituents having a total of up to 25 carbon atoms, in particular 1 to 12 carbon atoms, for example tert-butylbenzoic acid , The end groups may also be based on hydroxymonocarboxylic acids having 5 to 22 carbon atoms, which include, for example, hydroxyvaleric acid, hydroxycaproic acid, ricinoleic acid, their hydrogenation product hydroxystearic acid, and o-, m- and p-hydroxybenzoic acid. The hydroxymonocarboxylic acids may in turn be linked to one another via their hydroxyl group and their carboxyl group and thus be present several times in an end group. Preferably, the number of hydroxymonocarboxylic acid units per end group, that is to say their degree of oligomerization, is in the range from 1 to 50, in particular from 1 to 10. In a preferred embodiment of the invention, polymers of ethylene terephthalate and polyethylene oxide terephthalate in which the polyethylene glycol units have molar weights of 750 g / mole to 5000 g / mol and the molar ratio of ethylene terephthalate to polyethylene oxide terephthalate is 50:50 to 90:10, used in combination with an essential ingredient of the invention. The soil release polymers are preferably water-soluble, wherein the term "water-soluble" has a solubility of at least 0.01 g, preferably at least 0.1 g, of the polymer per liter of water Room temperature and pH 8 should be understood. However, preferred polymers have a solubility of at least 1 g per liter, in particular at least 10 g per liter, under these conditions.

The preparation of solid detergents presents no difficulties and can be carried out in a known manner, for example by spray-drying or granulation, with enzymes and any other thermally-sensitive ingredients such as, for example, bleaching agents optionally being added separately later. To produce the detergents with an increased bulk density, in particular in the range from 650 g / l to 950 g / l, a process comprising an extrusion step is preferred.

In a preferred embodiment, a PEI-containing liquid detergent contains 1 wt .-% to 15 wt .-%, in particular 2 wt .-% to 10 wt .-% of nonionic surfactant, 2 wt .-% to 30 wt .-%, in particular from 5% by weight to 20% by weight of synthetic anionic surfactant, up to 15% by weight, in particular from 2% by weight to 12.5% by weight, of soap, from 0.5% by weight to 5% by weight. -%, In particular 1 wt .-% to 4 wt .-% organic builder, in particular polycarboxylate such as citrate, up to 1.5 wt .-%, in particular 0.1 wt .-% to 1 wt .-% complexing agent for heavy metals such as phosphonate, and optionally enzyme, enzyme stabilizer, color and / or perfume, water and / or water-miscible solvent.

In a further preferred embodiment, the detergent 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, of up to 15% by weight, in particular 1% by weight. to 10% by weight of bleach activator, 20% by weight to 55% by weight of inorganic builder, up to 10% by weight, in particular 2% by weight to 8% by weight, of water-soluble organic builder, 10% by weight % 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 .-% to 25 wt .-% of inorganic salts, in particular Alkali carbonate and / or bicarbonate.

Another aspect of the present invention includes a method of cleaning a soiled textile substrate, the method including treating the wet substrate with the above formulation comprising a plurality of water-insoluble solid polymer particles, wherein the polymer particles are optionally regenerated with or be reused without the use of the detergent in further purification processes according to the method.

The PEI-containing detergent can be introduced into the device before the polymer particles are brought into contact with the soiled textile substrate (wetting with water) during, before or after contacting the polymer particles with the substrate. Of course, it is also possible to introduce the detergent or the water-insoluble solid particles in incremental steps.

The substrate to be cleaned according to the invention comprises textile substrates, each optionally of a variety of materials, which may be either a natural fiber such as cotton or synthetic textile fibers such as nylon 6,6 or a polyester.

Particularly preferred as polymer particles are polyalkenes such as polyethylene and polypropylene, polyesters and polyurethanes. However, preferred are the polymer particles of polyamide, more particularly particles of nylon, most preferably in the form of nylon chips. The polyamides are particularly effective for aqueous stain / soil removal, while polyalkenes are particularly useful for removing oily stains. Optionally, copolymers of the above polymeric materials may be used for the purposes of the invention.

Various nylon homo- or co-polymers can be used, including nylon 6 and nylon 6,6. Preferably, the polyamide comprises nylon 6,6 homopolymer having an average molecular weight in the range of 5,000 to 30,000 daltons, preferably 10,000 to 20,000 daltons, most preferably 15,000 to 16,000 daltons.

The water-insoluble solid particles or granules, particles or moldings are of such a shape and size that enables good flowability and close contact with the textile substrate. Preferred forms of the particles include spheres and cubes, but the preferred particle shape is cylindrical. The particles are preferably sized to each have an average weight in the range of 20-50 mg, preferably 30-40 mg. In the case of the most preferred cylindrically shaped particles, the preferred average particle diameter is 1.5 to 6.0 mm, more preferably 2.0 to 5.0 mm, most preferably 2.5 to 4.5 mm, while the length of the cylindrical particles is preferably in the range of 2.0 to 6.0 mm, more preferably 3.0 to 5.0 mm, and most preferably in the range of 4.0 mm.

Prior to cleaning, the textile substrate is preferably moistened by wetting with water to provide additional enhancement to the wash liquor thereby allowing for an improvement in transport properties within the system (Pretreatment). Thus, more efficient transfer from the detergent to the substrate and the removal of soils and stains from the substrate is facilitated. Most conveniently, the substrate can be wetted by contact with tap water. Preferably, the wetting treatment is carried out to achieve a substrate to water weight ratio of 1: 0.1 to 1: 5; more preferably the ratio is between 1: 0.2 and 1: 2, with particularly favorable results being achieved in ratios such as 1: 0.2, 1: 1 and 1: 2. However, in some cases, successful results with the substrate can be achieved to water ratios of up to 1:50, although such ratios are not preferred in view of the significant amounts of wastewater that are generated.

In the method according to this aspect of the invention, which can be regarded as an interstitial process between cleaning and scrubbing, a weight ratio of textile substrate to water-insoluble solid particles in the range of 1: 1 to 1:30, in particular from 1: 1.5 to 1: 2.5, especially set by 1: 2. The proportion of the water-insoluble solid particles as the weight of the particles in the dry state, i. after 24 hours storage at 21 ° C and a relative humidity of 65%.

According to the invention, the water-insoluble solid particles can be coated prior to use with the detergent according to known methods.

In addition, it has been found that the regeneration of the water-insoluble solid particles is possible, and the particles are satisfactorily reused in the purification process, although some deterioration in performance is generally observed with three uses of the particles. Re-use of the particles will give optimum results when re-coated with the detergent before reuse.

The regeneration of the water-insoluble solid particles can be carried out in a conventional manner, as described for example in the WO 2012/035342 A1 is described. In the present invention, the regeneration is carried out by contacting the particles with the detergent, for example by coating the particles with the agent, for example in a separate rinse, optionally by adding further cleaning agents, which may also be aggressive in nature. The temperature of the regeneration step is independent of the washing temperature when the textile substrate has been removed from the washing machine before regeneration. Furthermore, the usual detergent raw materials can be used.

Another embodiment of the invention involves the regeneration of the water-insoluble, solid polymer particles as described in claim 14.

A further embodiment of the invention comprises the use of a plurality of water-insoluble solid particles as defined above, and a PEI-containing detergent for cleaning textile substrates by contacting the detergent and the particles with the textile substrate as described in claim 12.

A device for cleaning soiled textile substrates comprising a plurality of water-insoluble solid particles, a reservoir for receiving the particles inside or outside the device, and a detergent containing polyalkoxylated polyamines is also disclosed.

An essential feature of the device is the presence of the above water-insoluble solid particles, a reservoir for the particles and the polyalkoxylated polyamine-containing detergent as described above.

The apparatus typically includes a trap door in a housing to allow access to the interior of the washing tub to provide a substantially closed system. Preferably, the door includes a window of the stationary cylindrical drum rotatably supported in another drum while the rotatably supported cylinder drum is mounted vertically inside the housing. Consequently, a front loading device is preferred. Alternatively, the stationary cylindrical drum may be mounted vertically within the housing and the access device located in the top of the device.

The device is suitable for providing contact of the particles with the soiled substrate. Ideally, these particles should be efficiently circulated to promote effective purification.

The apparatus comprises at least one reservoir, in particular with a corresponding control, for the water-insoluble solid particles, for example located inside the washing machine, which contains particles for regeneration and is suitable for controlling the flow of particles within the washing machine.

Example 1:

Table 1: Detergent compositions (in% by weight) A B C D e F G H C9-13-Alkylbenzenesulfonate, Na salt 9 10 6 7 5 15 15 9 C12-18 fatty alcohol with 7 EO 8th 9 6 7 5 6 11 10 C12-14 fatty alcohol sulfate with 2EO - - 8th 7 10 2 2 5 C12-18 fatty acid, Na salt 4 3 3 3 4 2 4 7 citric acid 2 3 3 2 2 2 2 3 Sodium hydroxide, 50% 3 3 2 3 3 3 3 4 boric acid 1 1 1 1 1 1 1 1 enzymes + + + + + + + + Perfume 1 0.5 0.5 0.5 1 1 1 1 propanediol - - - - - 5 5 - ethanol 1.5 1.5 1.5 1.5 1.5 1.5 1.5 5 PVA / maleic acid copolymer 0.1 - 0.1 - - - - - Optical brightener - 0.1 - 0.1 0.2 0.2 0.2 0.2 opacifiers 0.2 - - - - - - - Phosphonic acid, Na salt 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 PEI 2 2 2 2 2 2 2 2 water on 100

• PEI umgesetzt mit 45EO
• PEI umgesetzt mit 43EO
• PEI umgesetzt mit 15EO + 5PO
• PEI umgesetzt mit 15PO + 30EO
• PEI umgesetzt mit 5PO + 39,5EO
• PEI umgesetzt mit 5PO + 15EO
• PEI umgesetzt mit 10PO + 35EO
• PEI umgesetzt mit 15PO + 30EO
• PEI umgesetzt mit 15PO + 5EO

In Examples A to H, the following PEIs in the stated amounts can be used individually or in combination:

• PEI implemented with 45EO
• PEI implemented with 43EO
• PEI implemented with 15EO + 5PO
• PEI implemented with 15PO + 30EO
• PEI implemented with 5PO + 39.5EO
• PEI implemented with 5PO + 15EO
• PEI implemented with 10PO + 35EO
• PEI implemented with 15PO + 30EO
• PEI implemented with 15PO + 5EO

Claims (14)

1. An aqueous washing liquor suitable for use in an apparatus for cleaning soiled textile substrates, containing a plurality of water-insoluble solid polymer particles and a liquid detergent containing polyalkoxylated polyamines and a non-aqueous solvent.
2. The washing liquor according to claim 1, characterized in that the polyalkoxylated polyamines can be obtained by reacting polyamines with alkylene oxide, in particular ethylene oxide and/or propylene oxide.
3. The washing liquor according to one of claims 1 to 2, characterized in that it comprises polyalkoxylated polyamines in combination with alkoxylated C₈-C₁₈ alcohols having an average degree of alkoxylation in the range of from 1 to 5.
4. The washing liquor according to one of claims 1 to 3, characterized in that the polyalkoxylated polyamine has an average molar mass in the range of from 500 g/mol to 50,000 g/mol, in particular from 550 g/mol to 5,000 g/mol.
5. The washing liquor according to one of claims 1 to 4, characterized in that the average number of alkoxy groups per primary and secondary amino function in the polyalkoxylated polyamine is preferably from 1 to 100, in particular from 10 to 50.
6. The washing liquor according to one of claims 1 to 5, characterized in that the average number of propoxy groups per primary or secondary amino function in the polyalkoxylated polyamine is from 1 to 40, in particular from 5 to 20, and the average number of ethoxy groups per primary or secondary amino function in the polyalkoxylated polyamine is from 10 to 60, in particular from 15 to 30.
7. The washing liquor according to one of claims 1 to 6, characterized in that the terminal OH function of the polyalkoxy substituents in the polyalkoxylated polyamine can be partially or completely etherified with a C₁-C₁₀ alkyl group, in particular a C₁-C₃ alkyl group.
8. The washing liquor according to one of claims 1 to 7, characterized in that the concentration of the polyalkoxylated polyamine in the liquid fraction of the washing liquor is from 1 mg/l to 500 mg/l, in particular from 5 mg/l to 100 mg/l.
9. The washing liquor according to one of claims 1 to 8, characterized in that the polymer particles contain polyalkanes, polyesters, polyurethanes and/or polyamides including their copolymers, in particular a nylon 6.6 homopolymer having an average molar mass of from 5,000 to 30,000 daltons.
10. The washing liquor according to one of claims 1 to 9, characterized in that the water-insoluble solid particles are in the form of spheres, cubes and/or cylinders.
11. The washing liquor according to one of claims 1 to 10, characterized in that each of the water-insoluble solid particles has an average weight in the range of from 20 to 50 mg.
12. The use of a plurality of water-insoluble solid polymer particles and of a liquid detergent containing polyalkoxylated polyamines and a non-aqueous solvent for cleaning soiled textile substrates, in particular textile substrates having oil- and/or fat-containing, protein-containing and/or fruit-containing stains, by bringing the detergent and the polymer particles into contact with the textile substrate.
13. A method for cleaning soiled textile substrates using a washing liquor according to one of claims 1 to 11.
14. The regeneration of a plurality of soiled water-insoluble solid polymer particles as defined in one of claims 1 to 11 using a washing liquor, as defined in one of claims 1 to 11, by bringing the polymer particles into contact with the liquid detergent containing the polyalkoxylated polyamines and a non-aqueous solvent.