WO2015155194A1

WO2015155194A1 - Glyceride derivatives as active substances with dirt removing properties

Info

Publication number: WO2015155194A1
Application number: PCT/EP2015/057538
Authority: WO
Inventors: Frank Janssen; Christa JUNKES; Stefanie Juntermanns; Sofia Mandikos
Original assignee: Henkel Ag & Co. Kgaa
Priority date: 2014-04-11
Filing date: 2015-04-08
Publication date: 2015-10-15
Also published as: DE102014206987A1

Abstract

The aim of the invention is to improve the cleaning performance of washing agents during the laundering of textiles. This is achieved essentially by the use of ethoxylated glycerides.

Description

Glycerolesterderivate as Schmutzablösvermögende agents

The present invention relates to the use of certain ethoxylated glycerol esters as soil release-modifying agents for enhancing the cleaning performance of laundry detergents in the washing of textiles.

In addition to the ingredients indispensable for the washing process, such as surfactants and builder materials, laundry detergents generally comprise further constituents which can be summarized under the term laundry detergents and which comprise such different active ingredient groups as foam regulators, grayness inhibitors, bleaches, bleach activators and color transfer inhibitors. Such adjuvants also include substances which impart soil repellency properties to the laundry fiber and, if present during the wash, aid the soil release properties of the remaining detergent ingredients. The same applies mutatis mutandis to cleaners for hard surfaces. Such soil release agents are often referred to as "soil release" agents or because of their ability to render the treated surface, e.g., fiber, soil repellent, "soil repellents." For example, U.S. Patent No. 4,136,038 discloses U.S. Pat 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.

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

These polymers known from the prior art have the disadvantage that they have no or only insufficient effectiveness, in particular for textiles which are not or at least not predominantly made of polyester. However, a large part of today's textiles consists of cotton or cotton-polyester blend fabrics, so that there is a need for especially greasy soiling on especially such textiles more effective soil release agents. Surprisingly, it has been found that this object can be achieved by the use of certain carboxylic acid derivatives.

The invention relates to the use of α-hydroxy-hydroxy (1-oxy-1,2-ethanediyl) _n- ether of 1, 2,3-propanetriol mono-C8-22-alkanoates, wherein the degree of ethoxylation n is a number in Range of 4 to 16, in particular 6 to 12 and particularly preferred 8, which may also have broken values as an average, for enhancing the cleaning performance of detergents in the washing of textiles.

The substances used according to the invention are glycerol monoesters of linear or mono- or polysubstituted carboxylic acids having 8 to 22, in particular 16 to 20, carbon atoms which have been reacted in a known manner with ethylene oxide. In the context of the invention, the carboxylic acid is preferably selected from caprylic acid, pelargonic acid, capric acid, lauric acid, myristic acid, palmitic acid, isostearic acid, stearic acid, arachic acid and behenic acid and mixtures thereof; Stearic acid (n-octadecanoic acid) and isostearic acid (16-methylheptadecanoic acid) and mixtures thereof are particularly preferred. For example, the α-hydroxy-hydroxy-octa (oxy-1,2-ethanediyl) ether of 1,2,3-propanetriol mono (16-methylheptadecanoate) is available under the name Cirrasol Expel® LQ.

A further subject matter of the invention is a process for washing textiles, in which a detergent and a soil release agent in the form of an above-defined alkanoate polyether are used. Under this procedure, soiled textiles are brought in contact with water and the substances mentioned in order to remove the soiling of the textiles, in whole or at least to a satisfactory extent. These methods can be carried out manually or optionally with the aid of a conventional household washing machine. It is possible to use the detergent and soil release agent simultaneously or sequentially. The simultaneous application can be particularly advantageous by the use of a detergent containing the soil release agent, perform.

The effect of the active substance to be used according to the invention is particularly pronounced when used repeatedly, that is to say in particular for removing soiling of textiles which had already been washed and / or post-treated in the presence of the active substance before they were provided with the soiling to be removed. In connection with the aftertreatment it should be pointed out that the designated positive aspect can also be realized by a washing process in which the textile after the actual washing process, with the help of a detergent which may contain a named active ingredient, but in this case also free may be carried out with an aftertreatment agent. For example, in the context of a fabric softening step, which contains an inventively used active ingredient is brought into contact. In this procedure as well, if desired again a detergent without an active ingredient to be used according to the invention is used in the next washing process, the washing performance-enhancing effect of the active ingredients to be used according to the invention occurs. This is significantly higher than that resulting from the use of a conventional soil release agent. In a particularly preferred embodiment, the addition of the active ingredient essential to the invention takes place in the fabric softening cycle of the textile washing.

The active ingredient used according to the invention leads to a significantly better detachment of, in particular, fatty and cosmetic stains on textiles, in particular those made of cotton or cotton-containing fabric, than is the case when compounds previously known for this purpose are used. Alternatively, surfactants can be saved with constant fat removal capacity.

The use according to the invention can be carried out as part of a washing process by adding the soil release agent to a detergent-containing liquor, or preferably introducing the active ingredient as a component of a detergent into the liquor containing the object to be cleaned or contacted with it.

The use according to the invention within the scope of a laundry aftertreatment process can be carried out in such a way that the rinse liquor 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 a component of the laundry aftertreatment agent, in particular a softener. In this aspect of the invention, the laundry detergent used before the laundry aftertreatment agent may also contain, but may be free from, an active ingredient to be used according to the invention.

The washing process is preferably carried out at a temperature of 15 ° C to 60 ° C, more preferably at a temperature of 20 ° C to 40 ° C. The washing process is preferably carried out at a pH of 6 to 1 1, more preferably at a pH of 7.5 to 9.5. The use concentration of the carboxylic acid ester defined above in the washing or laundry aftertreatment liquor is preferably in the range from 0.0001 g / l to 10 g / l, in particular from 0.005 g / l to 1 g / l.

Compositions which contain an active substance to be used according to the invention in the form of said alkanoate polyether or which are used together or in which Ssen methods are used, may contain all the usual other ingredients of such agents, which do not interact in an undesirable manner with the essential ingredient of the invention, in particular surfactant. Preferably, the above-defined active ingredient in amounts of 0.01 wt .-% to 10 wt .-%, particularly preferably from 0, 1 wt .-% to 5 wt .-%, is used, with these and the following amounts refer to the total amount, unless stated otherwise.

Surprisingly, it has been found that the active ingredient used according to the invention has a positive effect on the action of certain other detergent ingredients and conversely that the effect of the soil release active ingredient essential to the invention is additionally enhanced by certain other detergent ingredients. These effects occur in particular with bleaches, with enzymatic active substances, in particular proteases and lipases, with water-soluble inorganic and / or organic builders, in particular based on oxidized carbohydrates or polymeric polycarboxylates, with synthetic anionic surfactants of the sulphate and sulphonate type, and with color transfer inhibitors, for example Vinylpyrrolidone, vinylpyridine or vinylimidazole polymers or copolymers or corresponding polybetaines, for which reason the use of at least one of the further ingredients mentioned together with the active ingredient to be used according to the invention is preferred.

An agent which contains or is used together with an active substance to be used according to the invention or which is used in the process according to the invention preferably contains peroxygen-based bleaching agents, in particular in amounts ranging from 5% by weight to 70% by weight, and optionally However bleach activator, especially in amounts ranging from 0.3% to 10% by weight, may in another preferred embodiment also be free of bleach and bleach activator. The bleaching agents which may be used are preferably the peroxygen compounds generally used in detergents, such as percarboxylic acids, for example dodecanedioic acid or phthaloylaminoperoxicaproic acid, hydrogen peroxide, alkali perborate, which may be present as tetra- or monohydrate, percarbonate, perpyrophosphate and persilicate, which are generally 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 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, as well as carboxylic anhydrides, in particular phthalic anhydride, carboxylic acid esters, in particular sodium nonanopyl and isononanoylphenolsulfonate, and acylated sugar derivatives, in particular penicylic anhydride. taacetylglucose, and cationic nitrile derivatives such as trimethylammonium acetonitrile salts. To avoid interaction with the peroxygen compounds, the bleach activators may have been coated or granulated in known manner with encapsulating substances, granulated tetraacetylethylenediamine having weight-average particle sizes of 0.01 mm to 0.8 mm, granulated 1, 5 with the aid of carboxymethylcellulose. Diacetyl-2,4-dioxohexahydro-1, 3,5-triazine, and / or formulated in particulate Trialkylammoniumaceto- nitrile 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 preferred embodiment, an 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 .-%.

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

Suitable nonionic surfactants include the alkoxylates, in particular the ethoxylates and / or propoxylates of saturated or mono- to polyunsaturated linear or branched-chain alcohols having 10 to 22 C atoms, preferably 12 to 18 C atoms. The degree of alkoxylation of the alcohols is generally between 1 and 20, preferably between 3 and 10. They can be prepared in a known manner by reacting the corresponding alcohols with the corresponding alkylene oxides. Particularly suitable are the derivatives of fatty alcohols, although their branched-chain isomers, in particular so-called oxo alcohols, can be used for the preparation of usable alkoxylates. Useful are accordingly the alkoxylates, in particular the ethoxylates, primary alcohols with linear, in particular dodecyl, tetradecyl, hexadecyl or octadecyl radicals and mixtures thereof. In addition, suitable alkoxylation products of alkylamines, vicinal diols and carboxylic acid amides, which correspond to the said alcohols with respect to the alkyl moiety, are usable. Moreover, the ethylene oxide and / or propylene oxide insertion products of fatty acid alkyl esters and also fatty acid polyhydroxy amides are suitable. So-called alkylpolyglycosides which are suitable for incorporation in the compositions are compounds of the general formula (G) n-OR ¹² in which R ^{2 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 , 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 Oligomerisierungsgrad. The mean degree of oligomerization n assumes as the value to be determined analytically generally broken numerical values; it is between 1 and 10, with the preferably used glycosides below a value of 1, 5, in particular in the range of 1, 2 to 1, 4. Preferred monomer building block is glucose because of its good availability. The alkyl or alkenyl moiety R ^{2 of} the glycosides preferably also originates from readily available derivatives of renewable raw materials, in particular from fatty alcohols, although their branched-chain isomers, in particular so-called oxoalcohols, can 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 coconut oil alkyl radical, ie mixtures with essentially R ² = dodecyl and R ² = tetradecyl.

Nonionic surfactant is used in compositions which comprise a soil release active substance used according to the invention, used according to the invention or used in the process according to 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 .-%.

The agents may instead or additionally contain other surfactants, preferably synthetic anionic surfactants of the sulfate or sulfonate type, such as alkylbenzenesulfonates, in amounts of preferably not more than 20 wt .-%, in particular from 0.1 wt .-% to 18 wt .-%, in each case relative to 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 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 customary sulfating reagent, in particular sulfur trioxide or chlorosulfonic acid, and subsequent neutralization with alkali metal, ammonium or alkyl or hydroxyalkyl substituted ammonium bases are produced. Sulfur-type surfactants which can be used also include the sulfated alkoxylation products of the alcohols mentioned, known as ether sulfates. Such ether sulfates preferably contain from 2 to 30, in particular from 4 to 10, ethyleneglycol groups per molecule. Suitable anionic surfactants of the sulfonate type include the α-sulfoesters obtainable by reaction of fatty acid esters with sulfur trioxide and subsequent neutralization, in particular those of fatty acids having 8 to 22 C atoms, preferably 12 to 18 C atoms, and linear alcohols having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, derivative sulfonation, as well as the formal saponification resulting from these sulfo fatty acids.

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

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

In a further embodiment, 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 .-%.

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 building substances include, in particular, those from the class of the 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 these, which may also contain small amounts of polymerizable substances without carboxylic acid functionality in copolymerized form. 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, albeit less preferred, compounds of this class are copolymers of acrylic acid or methacrylic acid with vinyl ethers, such as vinylmethyl ethers, vinyl esters, ethylene, propylene and styrene, in which the proportion of the acid is at least 50% by weight. Terpolymers which contain two carboxylic acids and / or salts thereof as monomers and also vinyl alcohol and / or a vinyl alcohol derivative or a carbohydrate as the third monomer may also be used as water-soluble organic builder substances. The first acidic monomer or its salt is derived from a monoethylenically unsaturated C 3 -C 5 -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 C4-Cs-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 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 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 substituted 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. 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 3000 g / mol and 10000 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 μm, and preferably consist of at least 80% by weight of particles having a size of less than 10 μm. Their calcium binding capacity, which can be determined according to the specifications of the German patent DE 24 12 837, is in the range of 100 to 200 mg CaO per gram. 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 from 1: 2 to 1: 2.8. Such amorphous alkali silicates are commercially available, for example, under the name Portil®. They are preferably added in the course of the production as a solid and not in the form of a solution. Crystalline silicates which may be present alone or in a mixture with amorphous silicates are preferably crystalline phyllosilicates of the general formula Na.sub.2SixO.sub.2 O.sub.x + VH.sub.2O, in which x, the so-called modulus, is a number from 1.9 to 4 and y is a number from 0 is up to 20 and preferred values for x are 2, 3 or 4. Preferred crystalline phyllosilicates are those in which x in the abovementioned general formula assumes the values 2 or 3. In particular, both .beta. And .delta.-sodium disilicates (Na.sub.2Si.sub.20.sup.yH.sub.2O.sub.2) are 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 compositions 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 also present as an additional builder substance, the content of alkali metal silicate is preferably 1% by weight to 15% by weight and, in particular, particular 2 wt .-% to 8 wt .-%, 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 compositions which contain an active substance to be used according to the invention together with it or used in the process 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 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. 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 Aminoalkylenphosphonsäuren and their salts and up to 2 wt .-%, in particular 0.1 wt .-% to 1 wt .-% foam inhibitors, wherein said weight percentages in each case refer to the total agent.

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, for example ethylene and propylene glycol, and the ethers derivable from the classes of compounds mentioned. 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 or mixtures thereof. First and foremost, proteases derived from microorganisms, such as bacteria or fungi, come into question. It can be obtained in a known manner by fermentation processes from suitable microorganisms. Proteases are in the trade, for example, under the name 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 Dionys®-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®.

The customary enzyme stabilizers present, if appropriate, in particular in liquid agents include amino alcohols, for example mono-, di-, triethanol- and -propanolamine and mixtures thereof, lower carboxylic acids, boric acid or alkali 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, in particular behenose, 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.

In a preferred embodiment, an agent to which the active ingredient to be used according to the invention is incorporated is particulate and contains up to 25% by weight, in particular from 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% by weight to 25% by weight of synthetic anionic surfactant, 1% by weight to 5% by weight of nonionic surfactant and up to 25% by weight, in particular 0.1% by weight to 25 wt .-% of inorganic salts, in particular alkali carbonate and / or bicarbonate.

In a further preferred embodiment, an agent in which the active ingredient to be used according to the invention is incorporated is liquid and contains from 1% by weight to 25% by weight, in particular from 5% by weight to 15% by weight, of nonionic surfactant, up to 10 wt .-%, in particular 0.5 wt .-% to 8 wt .-% of synthetic anionic surfactant, 3 wt .-% to 15 wt .-%, in particular 5 wt .-% to 10 wt .-% soap, 0 , 5 wt .-% to 5 wt .-%, in particular 1 wt .-% to 4 wt .-% organic builder, especially 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 in addition to optionally contained enzyme, enzyme stabilizer, dye and / or perfume, water and / or water-miscible solvent.

It is also possible to use a combination of an active substance suitable for removing soil according to the invention with a soil release polymer from a dicarboxylic acid and an optionally polymeric diol for enhancing the cleaning performance of washing agents when washing textiles. Also within the scope of the invention used agent and the method according to the invention such combinations with a particular polyester-active soil release wealthy polymer are possible.

The well-known polyester-active soil release polymers that can be used in addition to the essential ingredients 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, the first monomer being a dicarboxylic acid HOOC-Ph-COOH and the second monomer being a diol HO- (CHR-) _a OH, also known as a polymeric diol H- (O- (CHR -) _a ) t _> OH may be present. Therein, Ph is an o-, m- or p-phenylene radical which may carry 1 to 4 substituents selected from alkyl radicals having 1 to 22 C atoms, sulfonic acid groups, carboxyl groups and mixtures thereof, R is 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 -0- (CHR -) _a O- and also polymeric diol units - (O- (CHR -) _a ) bO-. 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 from 4 to 200, in particular from 12 to 140. The molecular weight or the average molecular weight or the maximum of the molecular weight distribution of preferred soil release polymers is in the range from 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, metilitic 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, instead 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 present 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. Preferred diols HO- (CHR-) _a OH include those in which R is hydrogen and a is a number from 2 to 6, and those in which a is 2 and R is hydrogen and the alkyl radicals have from 1 to 10 , in particular 1 to 3 C-atoms is selected. Among the latter diols, those of the formula HO-CH 2 -CHR-OH, in which R 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-group-capped, alkyl groups having from 1 to 22 carbon atoms and esters of monocarboxylic acids being suitable as end groups. The ester groups bonded via end groups can be based on alkyl, alkenyl and aryl monocarboxylic acids having 5 to 32 carbon atoms, in particular 5 to 18 carbon atoms. 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, brasidoside 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, the hydrogenation product of which includes hydroxystearic acid and o-, m- and p-hydroxybenzoic acid. The hydroxymonocarboxylic acids may in turn be linked to one another via their hydroxyl group and their carboxyl group and thus be present several times in an end group. Preferably, the number of hydroxymonocarboxylic acid units per end group, that is to say their degree of oligomerization, is in the range from 1 to 50, in particular from 1 to 10. In a preferred embodiment of the invention, polymers of ethylene terephthalate and polyethylene oxide terephthalate in which the polyethylene glycol units have molecular weights of 750 to 5000 g / mol and the molar ratio of ethylene terephthalate to polyethylene oxide terephthalate 50:50 to 90:10, used in combination with a combination with an essential ingredient of the invention.

The polyester-active 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. that should. However, preferred polymers have a solubility of at least 1 g per liter, in particular at least 10 g per liter, under these conditions.

Preferred laundry aftertreatment compositions which comprise an active substance 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. These are known substances which can be obtained by the relevant methods of preparative organic chemistry, for example by partially esterifying triethanolamine in the presence of hypophosphorous acid with fatty acids, passing air through and then quaternizing with dimethyl sulfate or ethylene oxide. The preparation of solid ester quats is also known, in which the quaternization of triethanolamine esters is carried out in the presence of suitable dispersants, preferably fatty alcohols.

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

R ⁴

X ^" (IV)

in which R is CO for an acyl radical having 6 to 22 carbon atoms, R ² and R ^{3 are} independently hydrogen or R is CO, R ^{4 is} an alkyl radical having 1 to 4 carbon atoms or a

(CH 2 CH 2 O) qH group, m, n and p in total are 0 or numbers from 1 to 12, q is numbers from 1 to 12 and X is a charge-balancing anion such as halide, alkyl sulfate or alkyl phosphate. Typical examples of esterquats which can be used in the context of the invention are products based on caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, isostearic acid, stearic acid, oleic acid, elaidic acid, arachidic acid, behenic acid and erucic acid and their technical mixtures, such as They occur, for example, in the pressure splitting of natural fats and oils. Preference is given to using technical C 12 / Cis coconut fatty acids and, in particular, partially hydrogenated cis / tallow or palm oil fatty acids and C 16/18 fatty acid cements rich in elaidic acid. For the preparation of the quaternized esters, the fatty acids and the triethanolamine can generally be used in a molar ratio of 1, 1: 1 to 3: 1. With regard to the performance properties of the esterquats, an employment ratio of 1.2: 1 to 2.2: 1, preferably 1.5: 1 to 1.9: 1, has proven particularly advantageous. The preferred esterquats used are technical mixtures of mono-, di- and triesters with an average degree of esterification of 1.5 to 1.9 and are derived from technical C 16/18 tallow or palm oil fatty acid (iodine number 0 to 40). from. Quaternized fatty acid triethanolamine ester salts of the formula (IV) in which R is CO for an acyl radical having 16 to 18 carbon atoms, R ^{2 is} R is CO, R ^{3 is} hydrogen, R ^{4 is} a methyl group, m, n and p are 0 and X is methyl sulfate, have proven to be particularly advantageous.

In addition to the quaternized carboxylic acid triethanolamine ester salts, suitable esterquats are quaternized ester salts of carboxylic acids with diethanolalkylamines of the formula (V),

R ⁴

I

[R CO- (OCH2CH2) mOCH2CH2-N ⁺ -CH2CH20- (CH2CH ₂ 0) n R ^2]

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

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

[R ⁴ -N ⁺ -CH ₂ CHCH ₂ - (CH ₂ CH ₂ O) n R ² ] X ^" (VI)

I

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

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

Esterquats are preferably used in amounts of from 5% by weight to 25% by weight, in particular from 8% by weight to 20% by weight, in each case based on the total laundry aftertreatment agent. If desired, the laundry aftertreatment agents used according to the invention can additionally The above detergent ingredients are included unless they unduly interact negatively with the ester quat. It is preferably a liquid, water-containing agent.

Examples

example 1

Washing machine: Miele W 918 Novotronic®

Temperature: 40 ° C

Wash volume: 17 l

Water hardness: 16 ° dH (German hardness)

Ballast laundry: clean laundry (pillows, tricot, kitchen towel); 3.5 kg minus weight of the test textiles

Cotton test fabrics were washed three times in the presence of ballast scrubbing with laundry detergent as described above containing 66 ml of Detergent V1 or Detergent E1 composition shown in Table 1). After the wash, the laundry was air dried.

Table 1: Detergent compositions [wt. %]:

V1 E1

C12-14 fatty alcohol with 7 EO 7 7

C12-18 fatty acid, sodium salt 10 10

Boric acid 4 4

Citric acid 2 2

Propanediol 6 6

NaOH 3 3

Protease 0.6 0.6

Amylase 0.1 0.1

Cirrasol Expel LQ (MV) - 1

Water at 100 Subsequently, the test textiles were provided with standardized stains and kept for 7 days at room temperature. The test fabrics were then rinsed together with the ballast wash in wash liquor containing 66 ml of the previously used detergent composition under the conditions described. The remaining spot intensity was determined with DATA-COLOR Spectra Flash SF500 reflectance spectrometer.

The washing performance with the use of the agent E1 was improved in the sum of more than 30 stains from the areas of fat, pigment, cosmetics compared to the use of the agent V1 by the relative factor of 308.1.

Claims

claims

1. Use of α-hydroxy-hydroxy (1-oxy-1,2-ethanediyl) _n- ethers of 1,3,3-propanetriol mono- C 8-22-alkanoates, wherein the degree of ethoxylation n is a number in the range of 4 to 16, which may also have broken values as an average, to enhance the detergency of laundry detergents when washing textiles.

2. Use according to claim 1, characterized in that the textiles were already washed and / or post-treated in the presence of the alkanoate polyether before they were provided with soils to be removed.

3. A process for laundering textiles which comprises a detergent and an α-hydroxy-hydroxy (1,2-ethanediyl) _n -ether of 1,2,3-propanetriol mono-C8-22 alkanoates, where n is a number in the range of 4 to 16, which may also have broken values as average.

4. The method according to claim 3, characterized in that the use concentration of the alkanoate polyether in the wash liquor in the range of 0.0001 g / l to 10 g / l, in particular from 0.005 g / l to 1 g / l.

5. The method according to claim 3 or 4, characterized in that it is carried out using a detergent containing the alkanoate polyether.

6. A process for washing textiles according to one of claims 3 to 5, characterized in that it is carried out using a Wäschenachbehandlungsmittels, in particular fabric softener, containing the alkanoate polyether.

7. The method according to any one of claims 3 to 6, characterized in that the agent is the alkanoate polyether in amounts of 0.01 wt .-% to 10 wt .-%, in particular from 0, 1 wt .-% to 5 wt .-% contains.

8. Use according to claim 1 or 2 or method according to one of claims 3 to 7, characterized in that the carboxylic acid in the alkanoate polyether is linear or mono- or polysubstituted and / or 16 to 20 carbon atoms.

9. Use or method according to one of the preceding claims, characterized in that the carboxylic acid in the alkanoate polyether is selected from caprylic acid, pelargonic acid, capric acid, lauric acid, myristic acid, palmitic acid, isostearic acid, stearic acid, arinic acid, arachidic acid and behenic acid and mixtures thereof, in particular of stearic acid (n-octadecanoic acid) and isostearic acid (16-methylheptadecanoic acid) and mixtures thereof.

Use or method according to one of the preceding claims, characterized in that the degree of ethoxylation n in the alkanoate polyether is a number in the range of 6 to 12, in particular 8.