EP2956534B1 - Anti-greying detergent - Google Patents

Description

The invention relates to a liquid detergent which contains a specific cellulose derivative as a graying-inhibiting active ingredient.

The task of graying inhibitors is to keep the dirt detached from the fibers during the washing of textiles suspended in the liquor and thus to prevent the dirt from being drawn back onto the textile. Water-soluble colloids, mostly of an organic nature, are suitable for this purpose, for example glue, gelatin, or salts of acidic sulfuric acid esters of cellulose or starch. Water-soluble polyamides containing acidic groups are also suitable for this purpose. In addition, soluble starch preparations and starch products other than those mentioned above can be used, for example degraded starches, aldehyde starches, etc. Polyvinylpyrrolidone can also be used. Cellulose ethers such as carboxymethyl cellulose (Na salt), methyl cellulose, hydroxyalkyl cellulose and mixed ethers such as methyl hydroxyethyl cellulose, methyl hydroxypropyl cellulose, methyl carboxymethyl cellulose and mixtures thereof are also often used in amounts of normally 0.1 to 5% by weight, based on the detergent.

Although the cellulose ethers mentioned have a good graying-inhibiting effect, their use in aqueous liquid detergents is subject to such narrow limits that they cannot in practice be incorporated into them. In addition to their anti-greying effect, which is only relevant when used in the washing process, these cellulose ethers have a comparatively low solubility in surfactant-containing systems and a strong thickening effect on aqueous systems. If they are incorporated in water-based and, in particular, anionic surfactant-containing liquid detergents in the concentrations desired for the graying-inhibiting effect, the result is generally either products that are no longer flowable and pourable, and the user can only handle them with additional effort, for example making them water-soluble or water-insoluble in water-soluble tearable form packaged single dosage portions, can be achieved, or the cellulose ethers, especially after storage, are not completely dissolved in the water-containing liquid detergent or are not evenly dispersed in it, which, in addition to aesthetics that are perceived as unsatisfactory, also leads to non-uniform dosing of the graying inhibitor active ingredient when using the agent containing it leads.

The patent GB 800 705 A discloses concentrated pourable liquid detergents containing polyphosphonate, surfactant and sodium carboxymethyl cellulose. From the international patent application WO 2006/117056 A1 the use of celluloses which carry sulfoalkyl groups bonded via ether, ester or amide functions to prevent redeposition when washing textiles is known.

Surprisingly, it has now been found that a good graying-inhibiting effect can be achieved in aqueous liquid detergents without an unacceptable increase in viscosity or precipitation if sulfoethyl cellulose is used.

The invention relates to an aqueous liquid detergent containing up to about 85% by weight and in particular from 40% by weight to 85% by weight water, which can also be partially replaced with a water-soluble solvent component or a water-soluble solvent component if desired is additionally present, surfactant and other customary ingredients of detergents and cleaning agents, the agent containing sulfoethyl cellulose with a degree of substitution of 0.3 to 0.9, in particular 0.4 to 0.7 and / or salt thereof. This means that the cellulose derivative contains an average of 0.3 to 0.9, in particular 0.4 to 0.7, sulfoethyl groups per anhydroglycose monomer unit. The average molar mass (weight average) of the cellulose derivatives used according to the invention is preferably in the range from 5,000 g/mol to 3,000,000 g/mol, in particular from 20,000 g/mol to 2,000,000 g/mol, particularly preferably in the range of 70,000 g/mol to 1,500,000 g/mol and even more preferably in the range of 150,000 g/mol to 1,000,000 g/mol. The degree of polymerization or the molecular weight of the cellulose ether can be determined, for example, based on the determination of the intrinsic viscosity of sufficiently dilute aqueous solutions using an Ubbelohde capillary viscometer. From this, the degree of polymerisation and, taking into account the degrees of substitution, the corresponding molecular weight can be calculated. Alternatively, the molecular weight can be determined via size exclusion chromatography-

The sulfoethyl cellulose suitable according to the invention can be prepared in the usual way by reacting cellulose with chloroethyl sulfonic acid or ethylene sulfonic acid in the appropriate molar equivalents. Suitable salts of sulfoethyl cellulose are, in particular, the alkali metal salts, such as the sodium and potassium salts, but also the ammonium salts of sulfoethyl cellulose.

A composition according to the invention preferably contains 0.1% by weight to 5% by weight, in particular 0.5% by weight to 3% by weight, of the sulfoethyl cellulose mentioned and/or its salts.

The invention also relates to the use of the sulfoethyl cellulose mentioned and/or its salts in aqueous liquid detergents which contain from 40% by weight to 85% by weight of water, where this can also be partially replaced by a water-soluble solvent component or a water-soluble one, if desired Solvent component is also present to improve graying inhibition when washing textile fabrics with the aqueous liquid detergent.

The detergent according to the invention contains water in amounts of preferably 40% by weight to 75% by weight, based on the detergent as a whole. Non-aqueous solvents that can be used in the liquid agents come, for example, from the group of mono- or polyhydric alcohols, alkanolamines or glycol ethers, provided they are miscible with water in the specified concentration range. The solvents are preferably selected from ethanol, n- or i-propanol, the butanols, ethylene glycol, butanediol, glycerol, diethylene glycol, butyl diglycol, hexylene glycol, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol methyl ether, diethylene glycol ethyl ether, propylene glycol methyl , ethyl or propyl ether, dipropylene glycol monomethyl or ethyl ether, diisopropylene glycol monomethyl or ethyl ether, methoxy, ethoxy or butoxytriglycol, 1-butoxyethoxy-2-propanol, 3-methyl-3-methoxybutanol, propylene glycol t-butyl ether and mixtures of these. The amount of the non-aqueous, water-soluble solvent component, based on the total amount of the detergent and cleaning agent, is preferably up to 15% by weight, in particular from 0.5% by weight to 10% by weight.

The liquid detergents contain surfactants, it being possible to use anionic, nonionic, cationic and/or amphoteric surfactants. The presence of anionic surfactants is preferred, with mixtures of anionic and nonionic surfactants being particularly advantageous from the application point of view. The total surfactant content of the liquid composition is preferably in the range from 10% by weight to 60% by weight, in particular 15% by weight to 50% by weight, in each case based on the total liquid composition.

The nonionic surfactants used are preferably alcohol alkoxylates, i.e. alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical is linear or preferably in 2- Position may be methyl-branched or may contain linear and methyl-branched radicals in the mixture, as they are usually present in oxo alcohol radicals. In particular, however, alcohol ethoxylates with linear radicals from alcohols of natural origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol are preferred. Preferred ethoxylated alcohols include, for example, C _12-14 alcohols with 3 EO, 4 EO or 7 EO, C _9-11 alcohol with 7 EO, C _13-15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C _12-18 alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C _12-14 alcohol with 3 EO and C _12-18 alcohol with 7 EO. The degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples of this are tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO. Nonionic surfactants which contain EO and PO groups together in the molecule can also be used according to the invention. Block copolymers with EO-PO block units or PO-EO block units can be used here, but also EO-PO-EO copolymers or PO-EO-PO copolymers. Mixed alkoxylated nonionic surfactants can also be used, in which EO and PO units are not in blocks but randomly are distributed. Such products can be obtained by the simultaneous action of ethylene and propylene oxide on fatty alcohols.

In addition, alkyl glycosides, in particular of the general formula RO(G) _x , can also be used as nonionic surfactants, in which R is a primary straight-chain or methyl-branched, in particular methyl-branched in the 2-position, aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms and G is the symbol which stands for a glycose unit with 5 or 6 carbon atoms, preferably for glucose. The degree of oligomerization x, which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; preferably x is from 1.2 to 1.4.

Another class of preferably used nonionic surfactants, which are used either as the sole nonionic surfactant or in combination with other nonionic surfactants, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably with 1 to 4 carbon atoms in the alkyl chain, especially fatty acid methyl esters.

Nonionic surfactants of the amine oxide type, for example N-cocoalkyl-N,N-dimethylamine oxide and N-tallowalkyl-N,N-dihydroxyethylamine oxide, and the fatty acid alkanolamide type can also be suitable. The amount of these nonionic surfactants is preferably not more than that of the alcohol alkoxylates, in particular not more than half thereof.

in der RCO für einen aliphatischen Acylrest mit 6 bis 22 Kohlenstoffatomen, R1 für Wasserstoff, einen Alkyl- oder Hydroxyalkylrest mit 1 bis 4 Kohlenstoffatomen und [Z] für einen linearen oder verzweigten Polyhydroxyalkylrest mit 3 bis 10 Kohlenstoffatomen und 3 bis 10 Hydroxylgruppen steht. Bei den Polyhydroxyfettsäureamiden handelt es sich um bekannte Stoffe, die üblicherweise durch reduktive Aminierung eines reduzierenden Zuckers mit Ammoniak, einem Alkylamin oder einem Alkanolamin und nachfolgende Acylierung mit einer Fettsäure, einem Fettsäurealkylester oder einem Fettsäurechlorid erhalten werden können. Zur Gruppe der Polyhydroxyfettsäureamide gehören auch Verbindungen der Formel (II),

in der R für einen linearen oder verzweigten Alkyl- oder Alkenylrest mit 7 bis 12 Kohlenstoffatomen, R¹ für einen linearen, verzweigten oder cyclischen Alkylrest oder einen Arylrest mit 2 bis 8 Kohlenstoffatomen und R² für einen linearen, verzweigten oder cyclischen Alkylrest oder einen Arylrest oder einen Oxy-Alkylrest mit 1 bis 8 Kohlenstoffatomen steht, wobei C_1-4-Alkyl- oder Phenylreste bevorzugt sind und [Z] für einen linearen Polyhydroxyalkylrest steht, dessen Alkylkette mit mindestens zwei Hydroxylgruppen substituiert ist, oder alkoxylierte, vorzugsweise ethoxylierte oder propoxylierte Derivate dieses Restes. [Z] wird vorzugsweise durch reduktive Aminierung eines Zuckers erhalten, beispielsweise Glucose, Fructose, Maltose, Lactose, Galactose, Mannose oder Xylose. Die N-Alkoxy- oder N-Aryloxy-substituierten Verbindungen können dann durch Umsetzung mit Fettsäuremethylestern in Gegenwart eines Alkoxids als Katalysator in die gewünschten Polyhydroxyfettsäureamide überführt werden.Other suitable nonionic surfactants are polyhydroxy fatty acid amides of the formula (I),

in which RCO is an aliphatic acyl radical having 6 to 22 carbon atoms, R1 is hydrogen, an alkyl or hydroxyalkyl radical having 1 to 4 carbon atoms and [Z] is a linear or branched polyhydroxyalkyl radical having 3 to 10 carbon atoms and 3 to 10 hydroxyl groups. The polyhydroxy fatty acid amides are known substances which can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride. The group of polyhydroxy fatty acid amides also includes compounds of the formula (II),

in which R is a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R ¹ is a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms and R ² is a linear, branched or cyclic alkyl radical or an aryl radical or an oxy-alkyl radical having 1 to 8 carbon atoms, with C _1-4 -alkyl or phenyl radicals being preferred and [Z] representing a linear polyhydroxyalkyl radical whose alkyl chain is substituted with at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated Derivatives of this residue. [Z] is preferably obtained by reductive amination of a sugar, for example glucose, fructose, maltose, lactose, galactose, mannose or xylose. The N-alkoxy- or N-aryloxy-substituted compounds can then be converted to the desired polyhydroxy fatty acid amides by reaction with fatty acid methyl esters in the presence of an alkoxide catalyst.

The content of nonionic surfactants in the liquid detergents is preferably 5% by weight to 30% by weight, in particular 7% by weight to 20% by weight and particularly preferably 9% by weight to 15% by weight, in each case based on the total mean. In a preferred embodiment, the nonionic surfactant is selected from alcohol alkoxylate and alkyl polyglycoside and mixtures thereof.

Examples of anionic surfactants that can be used are those of the sulfonate and sulfate type. Surfactants of the sulfonate type are preferably C _9-13 -alkylbenzene sulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkane sulfonates and disulfonates, such as those obtained, for example, from C _12-18 -monoolefins with a terminal or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products. Also suitable are alkanesulfonates obtained from C _12-18 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization. Also suitable are the esters of α-sulfofatty acids (ester sulfonates), for example the α-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids.

Other suitable anionic surfactants are sulfonated fatty acid glycerol esters. Fatty acid glycerol esters are to be understood as meaning the mono-, di- and triesters and mixtures thereof as are obtained in the production by esterification of a monoglycerol with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerol. Preferred sulfonated fatty acid glycerol esters are the sulfonation products of saturated fatty acids having 6 to 22 carbon atoms, for example caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid.

Alk(en)yl sulfates are the alkali and in particular the sodium salts of the sulfuric acid half esters of the _C12 - _C18 fatty alcohols, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the _C10 - _C20 oxo alcohols and those half esters of secondary alcohols of these chain lengths are preferred. Also preferred are alk(en)yl sulfates of the chain length mentioned which contain a synthetic, straight-chain alkyl radical produced on a petrochemical basis, which have a degradation behavior analogous to that of the appropriate compounds based on oleochemical raw materials. C ₁₂ -C ₁₆ -alkyl sulfates and C ₁₂ -C ₁₅ -alkyl sulfates and also C ₁₄ -C ₁₅ -alkyl sulfates are preferred for reasons of washing technology. 2,3-Alkyl sulfates, which can be obtained, for example, as commercial products from the Shell Oil Company under the name ^DAN® , are also suitable anionic surfactants.

The sulfuric acid monoesters of the alcohol alkoxylates mentioned above, for example the straight-chain or branched C _7-21 alcohols ethoxylated with 1 to 6 moles of ethylene oxide, such as 2-methyl-branched C _9-11 alcohols with an average of 3.5 moles of ethylene oxide (EO) or C _{C 12-18} fatty alcohols with 1 to 4 EO are suitable. These are also often referred to as ether sulfates.

Other suitable anionic surfactants are also the salts of alkyl sulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and are monoesters and/or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and in particular ethoxylated fatty alcohols. Preferred sulfosuccinates contain C _8-18 fatty alcohol residues or mixtures thereof. Particularly preferred sulfosuccinates contain a fatty alcohol residue which is derived from ethoxylated fatty alcohols which, considered on their own, are nonionic surfactants (see description below). In this context, sulfosuccinates whose fatty alcohol radicals are derived from ethoxylated fatty alcohols with a narrow homolog distribution are particularly preferred. It is also possible to use alk(en)ylsuccinic acid preferably having 8 to 18 carbon atoms in the alk(en)yl chain or salts thereof.

Preferred anionic surfactants are soaps. Saturated and unsaturated fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, (hydrogenated) erucic acid and behenic acid, and in particular soap mixtures derived from natural fatty acids, for example coconut, palm kernel, olive oil or tallow fatty acids, are suitable. In a preferred embodiment, the detergent contains 2% by weight to 20% by weight, in particular 3% by weight to 15% by weight and particularly preferably 5% by weight to 10% by weight of fatty acid soap. Fatty acid soaps are an important component for the detergency of a liquid, in particular aqueous, detergent and cleaning agent. Surprisingly, it has been found that when the low-methylated carboxymethyl cellulose ether is used, clear and stable liquid detergents are obtained even in the presence of large amounts of fatty acid soap. The use of high amounts (≥2% by weight) of fatty acid soap in such systems usually leads to cloudy and/or unstable products.

The anionic surfactants, including soaps, can be in the form of their sodium, potassium or ammonium salts, as well as soluble salts of organic bases such as mono-, di- or triethanolamine. The anionic surfactants are preferably in the form of their sodium or potassium salts, in particular in the form of the sodium salts.

The content of anionic surfactants in preferred liquid detergents is 5% by weight to 35% by weight, in particular 8% by weight to 30% by weight and particularly preferably 10% by weight to 25% by weight, based in each case on the entire mean. It is particularly preferred that the amount of fatty acid soap is at least 2% by weight, more preferably at least 3% by weight and especially from 4% to 10% by weight. In a further preferred embodiment, the agents contain at least 2, in particular 3, different anionic surfactants selected from alkyl benzene sulfonate, ether sulfate and fatty acid soap.

The detergent can contain a polyacrylate which acts as a cobuilder and optionally also as a thickener. The polyacrylates include polyacrylate or polymethacrylate thickeners, such as the high molecular weight homopolymers of acrylic acid crosslinked with a polyalkenyl polyether, in particular an allyl ether of sucrose, pentaerythritol or propylene (INCI designation according to the "International Dictionary of Cosmetic Ingredients" of "The Cosmetic, Toiletry and Fragrance Association (CTFA)": carbomers), also known as carboxyvinyl polymers. Such polyacrylic acids are available, inter alia, from 3V Sigma under the trade name ^Polygel® , eg Polygel DA, and from Noveon under the trade name ^Carbopol® , eg Carbopol 940 (molecular weight approx. 4,000,000), Carbopol 941 (molecular weight approx 1,250,000) or Carbopol 934 (molecular weight ca. 3,000,000). Also included are the following acrylic acid copolymers: (i) Copolymers of two or more monomers from the group consisting of acrylic acid, methacrylic acid and their simple esters, preferably formed with C _1-4 alkanols (INCI acrylates copolymer), which include, for example, the copolymers of methacrylic acid, butyl acrylate and methyl methacrylate ( CAS designation according to Chemical Abstracts Service: 25035-69-2 ) or of butyl acrylate and methyl methacrylate ( CAS 25852-37-3 ) belong and which are available, for example, from Rohm & Haas under the trade names ^Aculyn® and ^Acusol® and from Degussa (Goldschmidt) under the trade name ^Tego® Polymer, for example the anionic nonassociative polymers Aculyn 22, Aculyn 28, Aculyn 33 (crosslinked), Acusol 810, Acusol 823 and Acusol 830 ( CAS 25852-37-3 ); (ii) Crosslinked high molecular weight acrylic acid copolymers, which include, for example, the copolymers crosslinked with an allyl ether of sucrose or pentaerythritol of C _10-30 -alkyl acrylates with one or more monomers from the group of acrylic acid, methacrylic acid and their simple, preferably with C _{1 -4} -Alkanols formed, esters (INCI Acrylates/C10-30 Alkyl Acrylate Crosspolymer) belong and which are available, for example, from Noveon under the trade name ^Carbopol® , for example the hydrophobicized Carbopol ETD 2623 and Carbopol 1382 (INCI Acrylates/C10- 30 Alkyl Acrylate Crosspolymer) and Carbopol Aqua 30 (formerly Carbopol EX 473). Preferred liquid detergents contain the polyacrylate in an amount up to 5% by weight, in particular from 0.1% to 2.5% by weight. It is advantageous if the polyacrylate is a copolymer of an unsaturated mono- or dicarboxylic acid and one or more C ₁ -C ₃₀ -alkyl esters of (meth)acrylic acid.

The viscosity of the liquid detergents and cleaning agents can be measured using customary standard methods (for example Brookfield viscometer LVT-II at 20 rpm and 20° C., spindle 3) and is preferably in the range from 150 mPas to 5000 mPas. Preferred agents have viscosities of 500 mPas to 4000 mPas, values of 1000 mPas to 3500 mPas being particularly preferred.

In addition, the liquid detergents can contain other ingredients that further improve their performance and/or aesthetic properties. In the context of the present invention, preferred agents contain one or more substances from the group of builders, bleaches, bleach activators, enzymes, electrolytes, pH adjusters, fragrances, perfume carriers, fluorescent agents, dyes, hydrotopes, foam inhibitors, additional antiredeposition agents or graying inhibitors, optical brighteners, Shrink inhibitors, anti-crease agents, color transfer inhibitors, antimicrobial agents, germicides, fungicides, antioxidants, corrosion inhibitors, antistatic agents, ironing aids, repellents and impregnating agents, swelling and non-slip agents and UV absorbers.

In particular, silicates, aluminum silicates (particularly zeolites), carbonates, salts of organic di- and polycarboxylic acids and mixtures of these substances are to be mentioned as builders which can be contained in the liquid compositions.

Suitable crystalline, layered sodium silicates have the general formula NaMSi _x O _{2x + 1} H ₂ O, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20 and preferred values for x are 2 , 3 or 4 are. Preferred crystalline sheet silicates of the given formula are those in which M is sodium and x is 2 or 3. In particular, both β- and δ-sodium disilicates Na ₂ Si ₂ O ₅ .yH ₂ O are preferred.

Amorphous sodium silicates with an Na ₂ O:SiO ₂ modulus of 1:2 to 1:3.3, preferably of 1:2 to 1:2.8 and in particular of 1:2 to 1:2.6, can also be used are delayed in dissolving and have secondary washing properties. The delay in dissolving compared to conventional amorphous sodium silicates can have been brought about in various ways, for example by surface treatment, compounding, compacting/densification or by overdrying. In the context of this invention, the term "amorphous" also means "X-ray amorphous". This means that the silicates in X-ray diffraction experiments do not produce any sharp X-ray reflections, as are typical for crystalline substances, but at most a or multiple peaks of scattered X-ray radiation having a width of several degrees of diffraction angle. However, it can very well even lead to particularly good builder properties if the silicate particles provide blurred or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted in such a way that the products have microcrystalline areas with a size of 10 to a few hundred nm, with values up to a maximum of 50 nm and in particular up to a maximum of 20 nm being preferred. Such so-called X-ray amorphous silicates also have a delay in dissolving compared to conventional water glasses. Densified/compacted amorphous silicates, compounded amorphous silicates and overdried X-ray amorphous silicates are particularly preferred.

The finely crystalline, synthetic zeolite containing bound water used is preferably zeolite A and/or P. Zeolite P is particularly preferably zeolite ^MAP® (commercial product from Crosfield). However, zeolite X and mixtures of A, X and/or P are also suitable. A co-crystallizate of zeolite X and zeolite A (approx. 80% by weight of zeolite X ), which is sold by the company SASOL under the brand name VEGOBOND AX ^® and by the formula

nNa ₂ O ˙ (1-n)K ₂ O ˙ Al ₂ O ₃ ˙ (2 - 2.5)SiO ₂ ˙ (3.5 - 5.5) H ₂ O

can be described with n = 0.90 - 1.0. The zeolite can be used as a spray-dried powder or as an undried, stabilized suspension that is still moist from its production. If the zeolite is used as a suspension, this can contain small additions of nonionic surfactants as stabilizers, for example 1 to 3% by weight, based on zeolite, of ethoxylated C ₁₂ -C ₁₈ fatty alcohols having 2 to 5 ethylene oxide groups , C ₁₂ -C ₁₄ fatty alcohols having 4 to 5 ethylene oxide groups or ethoxylated isotridecanols. Suitable zeolites have an average particle size of less than 10 μm (volume distribution; measurement method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water.

It is also possible to use the generally known phosphates as builder substances, provided such use is not to be avoided for ecological reasons. The sodium salts of orthophosphates, pyrophosphates and, in particular, tripolyphosphates are particularly suitable.

Among the compounds serving as bleaching agents and yielding H ₂ O ₂ in water, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance. Examples of other bleaching agents that can be used are sodium percarbonate, peroxypyrophosphates, citrate perhydrates and peracid salts or peracids which supply H ₂ O ₂ , such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloimino peracid or diperdodecanedioic acid. If present, these are preferably used in coated form to protect them from deterioration during storage.

In order to achieve an improved bleaching effect when washing at temperatures of 60°C and below, bleach activators can be incorporated into the washing and cleaning agents. Bleach activators which can be used are compounds which, under perhydrolysis conditions, produce aliphatic peroxocarboxylic acids having preferably 1 to 10 carbon atoms, in particular 2 to 4 carbon atoms, and/or optionally substituted perbenzoic acid. Substances which carry O- and/or N-acyl groups with the number of carbon atoms mentioned and/or optionally substituted benzoyl groups are suitable. Preference is given to polyacylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), N- Acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic anhydrides, in particular phthalic anhydride, acylated polyhydric alcohols, in particular triacetin, ethylene glycol diacetate and 2,5-diacetoxy 2,5-dihydrofuran.

In addition to the conventional bleach activators or instead of them, so-called bleach catalysts can also be incorporated into the liquid detergents and cleaning agents. These substances are bleach-boosting transition metal salts or transition metal complexes such as, for example, Mn, Fe, Co, Ru or Mo salen complexes or carbonyl complexes. Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with nitrogen-containing tripod ligands and Co, Fe, Cu and Ru ammine complexes can also be used as bleach catalysts.

Suitable enzymes are in particular those from the classes of hydrolases such as proteases, esterases, lipases or lipolytic enzymes, amylases, cellulases or other glycosyl hydrolases and mixtures of the enzymes mentioned. All of these hydrolases contribute to the removal of stains such as protein, fat or starchy stains and graying in the wash. Cellulases and other glycosyl hydrolases can also help to retain the color and increase the softness of the textile by removing pilling and microfibrils. Oxyreductases can also be used to bleach or to inhibit color transfer. Enzymatic active ingredients obtained from bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis, Streptomyceus griseus and Humicola insolens are particularly suitable. Proteases of the subtilisin type and in particular proteases which are obtained from Bacillus lentus are preferably used. Here, enzyme mixtures, for example of protease and amylase or protease and lipase or lipolytic enzymes or protease and cellulase or of cellulase and lipase or lipolytic enzymes or of protease, amylase and lipase or lipolytic enzymes or protease, Lipase or lipolytic enzymes and cellulase, but in particular protease and/or lipase-containing mixtures or mixtures with lipolytic enzymes of particular interest. Examples of such lipolytic enzymes are the known cutinases. Peroxidases or oxidases have also proven to be suitable in some cases. Suitable amylases include in particular α-amylases, iso-amylases, pullulases and pectinases. Cellobiohydrolases, endoglucanases and β-glucosidases, which are also called cellobiases, or mixtures of these are preferably used as cellulases. Since different cellulase types differ in their CMCase and Avicelase activities, the desired activities can be set by mixing the cellulases in a targeted manner.

The bleach activators, catalysts and/or enzymes can be adsorbed and/or coated on carriers in order to protect them against premature decomposition. The proportion of the enzymes, enzyme liquid formulations, enzyme mixtures or enzyme granules can be, for example, about 0.1% by weight to 5% by weight, preferably 0.12% by weight to about 2.5% by weight, based in each case on the entire composition , amount.

A large number of the most varied salts can be used as electrolytes from the group of inorganic salts. Preferred cations are the alkali and alkaline earth metals, preferred anions are the halides and sulfates. From a manufacturing point of view, the use of NaCl or MgCl ₂ in the agents is preferred. The proportion of electrolytes in the agents is usually not more than 8% by weight, in particular 0.5% by weight to 5% by weight.

In order to bring the pH value of the liquid agent into the desired range, the use of pH adjusters can be indicated. All known acids or bases can be used here, provided their use is not prohibited for technical or ecological reasons or for reasons of consumer protection. The amount of these extenders does not usually exceed 10% by weight of the total formulation.

A further component of agents according to the invention which is optionally present is a hydrotrope. Preferred hydrotropes include the sulfonated hydrotropes such as the alkyl aryl sulfonates or alkyl aryl sulfonic acids. Preferred hydrotropes are selected from xylene, toluene, cumene, naphthalene sulfonate or sulfonic acid and mixtures thereof. Counterions are preferably selected from sodium, calcium and ammonium. If appropriate, the liquid agents can comprise up to 20% by weight of a hydrotrope, in particular 0.05% by weight to 10% by weight.

In order to improve the aesthetic impression of the liquid agents, they can be colored with suitable dyes. Preferred dyes, the selection of which presents no difficulty to the person skilled in the art, have a high storage stability and are insensitive to the other ingredients of the agent and against light and no pronounced substantivity to textile fibers in order not to stain them.

Foam inhibitors that can be used in the liquid detergents and cleaning agents are, for example, soaps, paraffins or silicone oils, which may also have been applied to carrier materials.

Suitable additional anti-redeposition agents, which are also referred to as "soil repellents", are, for example, the polymers of phthalic acid and/or terephthalic acid or derivatives thereof known from the prior art, in particular polymers of ethylene terephthalates and/or polyethylene glycol terephthalates or anionically and/or nonionically modified derivatives of these. Particularly preferred of these are the sulfonated derivatives of the phthalic and terephthalic acid polymers.

Optical brighteners can be added to the liquid detergents and cleaning agents in order to eliminate yellowing of the treated textile fabrics. These substances are absorbed by the fibers and cause a lightening effect by converting ultraviolet radiation that is invisible to the human eye into visible longer-wave light, with the ultraviolet light absorbed from the sunlight being emitted as a weak bluish fluorescence and resulting in pure white with the yellow hue of yellowed laundry. Suitable compounds come, for example, from the classes of 4,4'-diamino-2,2'-stilbenedisulfonic acids (flavonic acids), 4,4'-distyrylbiphenyls, methylumbelliferones, coumarins, dihydroquinolinones, 1,3-diarylpyrazolines, naphthalimides, benzoxazole and benzisoxazole - and benzimidazole systems and substituted by heterocycles pyrene derivatives. Optical brighteners are normally used in amounts of up to 0.5% by weight, in particular from 0.03% by weight to 0.3% by weight, based on the finished agent.

Since textile fabrics, especially those made of rayon, rayon, cotton and their blends, can tend to wrinkle because the individual fibers are sensitive to bending, kinking, pressing and squeezing transversely to the fiber direction, the agents can contain synthetic anti-crease agents. These include, for example, synthetic products based on fatty acids, fatty acid esters, fatty acid amides, fatty acid alkylol esters, fatty acid alkylolamides or fatty alcohols, which are usually reacted with ethylene oxide, or products based on lecithin or modified phosphoric acid esters.

To combat microorganisms, the liquid detergents and cleaning agents can contain antimicrobial active ingredients. Depending on the antimicrobial spectrum and mechanism of action, a distinction is made between bacteriostatics and bactericides, fungistatics and fungicides, etc. Important substances from these groups are, for example, benzalkonium chlorides, alkylaryl sulfonates, Halophenols and phenolmercuric acetate, although these compounds can also be dispensed with entirely in the agents according to the invention.

In order to prevent undesirable changes in the liquid detergents and cleaning agents and/or the treated textile fabrics caused by the action of oxygen and other oxidative processes, the agents can contain antioxidants. This class of compounds includes, for example, substituted phenols, hydroquinones, catechols and aromatic amines, as well as organic sulfides, polysulfides, dithiocarbamates, phosphites and phosphonates. When such antioxidants are used, the agents according to the invention are naturally free from oxidizing bleaching agents.

Increased wearing comfort can result from the additional use of antistatic agents, which are also added to the agents. Antistatic agents increase the surface conductivity and thus enable an improved flow of charges that have formed. External antistatic agents are generally substances with at least one hydrophilic molecular ligand and form a more or less hygroscopic film on the surface. These mostly surface-active antistatic agents can be divided into nitrogen-containing (amines, amides, quaternary ammonium compounds), phosphorus-containing (phosphoric esters) and sulfur-containing (alkyl sulfonates, alkyl sulfates) antistatic agents. External antistatic agents are, for example, lauryl (or stearyl)dimethylbenzylammonium chlorides, which are suitable as antistatic agents for textile fabrics or as an additive to detergents, with an additional finishing effect being achieved.

Silicone derivatives, for example, can be used in the liquid detergents and cleaning agents to improve the water absorption capacity, the rewettability of the treated textile fabrics and to facilitate ironing of the treated textile fabrics. These also improve the rinsing behavior of the agents due to their foam-inhibiting properties. Preferred silicone derivatives are, for example, polydialkyl or alkylaryl siloxanes in which the alkyl groups have one to five carbon atoms and are wholly or partially fluorinated. Preferred silicones are polydimethylsiloxanes, which can optionally be derivatized and are then amino-functional or quaternized or have Si-OH, Si-H and/or Si-Cl bonds. The viscosities of the preferred silicones at 25° C. are in the range between 100 and 100,000 mPas, and the silicones can be used in amounts of between 0.2 and 5% by weight, based on the composition as a whole.

Finally, the liquid detergents and cleaning agents can also contain UV absorbers, which are absorbed by the treated textile fabrics and improve the lightfastness of the fibers. Compounds which have these desired properties are, for example, the compounds and derivatives of benzophenone having substituents in the 2- and/or 4-position which are active by radiationless deactivation. Furthermore, substituted benzotriazoles, acrylates phenyl-substituted in the 3-position (cinnamic acid derivatives), optionally with cyano groups in the 2-position, salicylates, organic Ni complexes and natural substances such as umbelliferone and urocanic acid.

Substances that complex heavy metals can be used to prevent the decomposition of certain detergent ingredients catalyzed by heavy metals. Suitable heavy metal complexing agents are, for example, the alkali metal salts of ethylenediaminetetraacetic acid (EDTA) or nitrilotriacetic acid (NTA) and alkali metal salts of anionic polyelectrolytes such as polymaleates and polysulfonates.

A preferred class of chelating agents are the phosphonates, which are present in preferred liquid compositions in amounts of from 0.01% to 2.5%, preferably from 0.02% to 2%, and most preferably from 0.02% to 2% by weight from 0.03% to 1.5% by weight. These preferred compounds include, in particular, organophosphonates such as 1-hydroxyethane-1,1-diphosphonic acid (HEDP), aminotri(methylenephosphonic acid) (ATMP), diethylenetriaminepenta(methylenephosphonic acid) (DTPMP or DETPMP) and 2-phosphonobutane-1,2 ,4-tricarboxylic acid (PBS-AM), which are mostly used in the form of their ammonium or alkali metal salts.

The liquid detergents are preferably clear, ie they have no sediment and are transparent or at least translucent. Without the addition of a dye, the liquid detergents preferably have a transmission of visible light (410 to 800 nm) of at least 10%, in particular at least 15% and particularly preferably at least 25%.

In addition to the components mentioned, a liquid washing and cleaning agent can also contain particles dispersed therein, the diameter of which is, for example, 100 μm to 10,000 μm along their greatest spatial extent. Such particles can be either microcapsules or speckles or granules, compounds and scented pearls, microcapsules or speckles being preferred.

The term “microcapsule” is understood to mean aggregates which contain at least one solid or liquid core which is surrounded by at least one continuous shell, in particular a shell made of polymer(s). These are usually finely dispersed liquid or solid phases coated with film-forming polymers, during the production of which the polymers are deposited on the material to be coated after emulsification and coacervation or interfacial polymerization. The microscopically small capsules can be dried like powder. In addition to mononuclear microcapsules, multinuclear aggregates, also called microspheres, are known, which contain two or more cores distributed in the continuous shell material. Single-core or multi-core microcapsules can also be surrounded by an additional second, third, etc. shell.

Mononuclear microcapsules with a continuous shell are preferred. The shell can be made of natural, semi-synthetic or synthetic materials. Natural coating materials are, for example, gum arabic, agar agar, agarose, maltodextrins, alginic acid or its salts, e.g. sodium or calcium alginate, fats and fatty acids, cetyl alcohol, collagen, chitosan, lecithin, gelatin, albumin, shellac, polysaccharides such as starch or dextran , sucrose and waxes. Semi-synthetic casing materials include chemically modified celluloses, particularly cellulose esters and ethers, e.g., cellulose acetate, ethyl cellulose, hydroxypropyl cellulose, hydroxypropylmethyl cellulose and carboxymethyl cellulose, and starch derivatives, particularly starch ethers and esters. Synthetic shell materials are, for example, polymers such as polyacrylates, polyamides, polyvinyl alcohol or polyvinylpyrrolidone.

Inside the microcapsule, sensitive, chemically or physically incompatible and volatile components (= active ingredients) of the liquid agent can be enclosed in a stable manner for storage and transport. In the microcapsules, for example, optical brighteners, surfactants, complexing agents, bleaches, bleach activators, dyes and fragrances, antioxidants, builders, enzymes, enzyme stabilizers, antimicrobial agents, antiredeposition agents, pH adjusters, electrolytes, foam inhibitors and / or UV absorbers condition. In addition to the components mentioned above as ingredients of the aqueous liquid agents according to the invention, the microcapsules can contain, for example, vitamins, proteins, preservatives, detergent boosters or pearlescent agents. The fillings of the microcapsules can be solids or liquids in the form of solutions or emulsions or suspensions.

The microcapsules can have any shape within the production-related scope, but they are preferably approximately spherical. Its diameter along its greatest spatial extent can range from 0.01 µm (not visually recognizable as a capsule) to 10,000 µm, depending on the components it contains and the application. Visible microcapsules with a diameter in the range from 100 μm to 7000 μm, in particular from 400 μm to 5000 μm, are preferred. The microcapsules can be obtained by methods known in the art, the most important being coacervation and interfacial polymerisation. All surfactant-stable microcapsules available on the market can be used as microcapsules, for example the commercial products (the shell material is given in brackets) Hallcrest Microcapsules (gelatine, gum arabic), Coletica Thalaspheres (maritime collagen), Lipotec millicapsules (alginic acid, agar-agar) , Induchem Unispheres (lactose, microcrystalline cellulose, hydroxypropyl methyl cellulose); Unicerin C30 (lactose, microcrystalline cellulose, hydroxypropylmethylcellulose), Kobo Glycospheres (modified starch, fatty acid esters, phospholipids), Softspheres (modified agar agar) and Kuhs Probiol Nanospheres (phospholipids).

Alternatively, it is also possible to use particles which do not have a core-shell structure but in which the active substance is distributed in a matrix of a matrix-forming material. Such particles are also referred to as "speckles". A preferred matrix-forming material is alginate. To produce alginate-based speckles, an aqueous alginate solution, which also contains the active ingredient or ingredients to be included, is added dropwise and then hardened in a precipitation bath containing Ca ²⁺ ions or Al ³⁺ ions. It can be advantageous that the alginate-based speckles are subsequently washed with water and then washed in an aqueous solution with a complexing agent in order to avoid free Ca ²⁺ ions or free Al ³⁺ ions, which have undesirable interactions with ingredients in the liquid detergent , for example the fatty acid soaps. The alginate-based speckles are then washed with water to remove excess complexing agent. Alternatively, other matrix-forming materials can be used instead of alginate. Examples of matrix-forming materials include polyethylene glycol, polyvinylpyrrolidone, polymethacrylate, polylysine, poloxamer, polyvinyl alcohol, polyacrylic acid, polyethylene oxide, polyethoxyoxazoline, albumin, gelatin, acacia, chitosan, cellulose, dextran, Ficoll ^® , starch, hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxypropylmethyl cellulose, hyaluronic acid, carboxymethyl cellulose, carboxymethyl cellulose, deacetylated chitosan, dextran sulfate and derivatives of these materials. In the case of these materials, matrix formation takes place, for example, via gelation, polyanion-polycation interactions or polyelectrolyte-metal ion interactions and is well known in the prior art, as is the production of particles with these matrix-forming materials. The particles can be stably dispersed in the aqueous liquid detergents and cleaning agents. Stable means that the agents are stable at room temperature and at 40° C. over a period of at least 4 weeks and preferably at least 6 weeks without the agents creaming or sedimenting.

The release of the active ingredients from the microcapsules or speckles usually takes place during the application of the agents containing them by destruction of the shell or the matrix as a result of mechanical, thermal, chemical or enzymatic action. In a preferred embodiment of the invention, the liquid detergents contain identical or different particles in amounts of 0.01 to 10% by weight, in particular 0.2 to 8% by weight and extremely preferably 0.5 to 5% by weight.

Aqueous detergents and cleaning agents can be produced inexpensively and easily in conventional mixing and filling plants. If present, the acidic components such as, for example, the linear alkyl sulfonates, citric acid, boric acid, phosphonic acid, the fatty alcohol ether sulfates, and the nonionic surfactants are preferably initially initially introduced for the production of the liquid compositions. The solvent component is preferably added at this time as well, but it can be added at a later time. If present, the complexing agent is added to these components. Then a base such as NaOH, KOH, triethanolamine or monoethanolamine is added followed by the fatty acid if present. Subsequently, the remaining ingredients and optionally the remaining solvents of the aqueous liquid composition are added to the mixture and the pH is adjusted to the desired value. Finally, if desired, the particles to be dispersed can be added and distributed homogeneously in the aqueous liquid agent by mixing.

examples

Table 1 shows the composition (ingredients in percent by weight, based in each case on the detergent as a whole) of detergent M1 according to the invention and of detergents C1, C2, C3 and C4 not according to the invention produced for comparison. The agent M1 had a transmission of 18% at 550 nm, whereas the agents V3 and V4 had transmissions of only 1% and 7% at the same light wavelength, and the agent V1 had a transmission of 81%. Table 1: V1 M1 v2 V3 V4 C ₉ - ₁₃ alkyl benzene sulfonate, Na salt 6 6 6 6 6 Sodium Lauryl Ether Sulfate with 2 EO 8th 8th 8th 8th 8th C _12-14 fatty alcohol with 7 EO 6 6 6 6 6 C _12-18 fatty acid, Na salt 3 3 3 3 3 NaOH 2 2 2 2 2 citric acid 2 2 2 2 2 phosphonate 0.2 0.2 0.2 0.2 0.2 Na-Sulfoethylcellulose ^a) - 1 - - - Na-Sulfoethylcellulose ^b) - - 1 - - Na-Sulfoethylcellulose ^c) - - - 1 - carboxymethyl cellulose - - - - 1 Water to 100 a) degree of substitution 0.51; _Mw 792 670 g/mol
b) degree of substitution 0.21; _Mw 539,000 g/mol
c) degree of substitution 1.14; _Mw 639 650 g/mol

1. A 100% Baumwolle, Baumwoll-Gewebe WFK 10A, ohne opt. Aufheller
2. B 100% Baumwolle, Baumwoll-Gewebe WFK 12A Frottier, ohne opt. Aufheller
3. C 100% Baumwolle, Frottierhandtuch
4. D 100% Baumwolle, Bleichnesselgewebe
5. E 100% Baumwolle, Krefelder Standardtextil, ohne opt. Aufheller
6. F 100% Baumwolle, Doppelrippware
7. G 100% Baumwolle, Baumwoll-Gewebe EMPA 221

The detergents were tested in a ^Miele® W 1714 washing machine (cotton washing program, 40° C.; water hardness 16° dH; Greying Swatch dirt carrier; dosage 66 ml of the respective detergent per wash cycle). In addition to filling laundry for a load of 3.5 kg, the following materials were used (each 8 pieces of textile measuring 20 x 40 cm):

1. A 100% cotton, cotton fabric WFK 10A, without opt. brightener
2. B 100% cotton, cotton fabric WFK 12A terry, without opt. brightener
3. C 100% cotton, terry towel
4. D 100% cotton, bleach nettle fabric
5. E 100% cotton, Krefeld standard textile, without opt. brightener
6. F 100% cotton, double rib fabric
7. G 100% cotton, cotton fabric EMPA 221

Table 2 shows the change in brightness (ΔY value) of the materials after 3 washes with the respective agent. Table 2: M1 V1 v2 V3 V4 A -4.8 -9.3 -6.9 -6.1 -5.1 B -8.6 -16.4 -9.2 -9.1 -7.8 C -6.7 -15.0 -10.9 -10.3 -8.4 D -5.8 -9.7 -6.9 -6.8 -5.7 E -6.9 -10.7 -8.7 -7.9 -6.7 f -6.6 -15.7 -9.6 -10.8 -6.6 G -9.0 -16.0 -12.4 -10.2 -9.1

The superiority of the agent according to the invention over agents with Na-sulfoethylcellulose of other degrees of substitution can be seen.

Claims (9)

1. Aqueous liquid detergent composition containing up to about 85% by weight and in particular from 40% by weight to 85% by weight of water, it also being possible, if desired, to exchange this proportionally for a water-soluble solvent component or a water-soluble solvent component being additionally present, surfactant and other customary ingredients of detergents and cleaning compositions, the composition containing sulphoethylcellulose with a degree of substitution of 0.3 to 0.9 and/or its salt.
2. Composition according to claim 1, characterized in that the sulfoethylcellulose and/or its salt has a degree of substitution of 0.4 to 0.7.
3. Composition according to claim 1 or 2, characterized in that it contains 0.1% by weight to 5% by weight, in particular 0.5% by weight to 3% by weight, of sulfoethylcellulose and/or its salt.
4. Composition according to any one of claims 1 to 3, characterized in that it contains 10% by weight to 60% by weight, in particular 15% by weight to 50% by weight, of surfactant.
5. Composition according to any one of claims 1 to 4, characterised in that it contains anionic surfactant and in particular fatty acid soap.
6. Composition according to any one of claims 1 to 5, characterized in that it contains at least 2 different anionic surfactants selected from alkyl benzene sulphonate, ether sulphate and soap.
7. Composition according to any one of claims 1 to 6, characterized in that it contains non-ionic surfactant, in particular selected from alcohol alkoxylate and alkyl polyglycoside and mixtures thereof.
8. Composition according to any one of claims 1 to 7, characterized in that it contains from 40% to 75% by weight of water.
9. The use of sulfoethyl cellulose having a degree of substitution of from 0.3 to 0.9, in particular from 0.4 to 0.7, and/or a salt thereof in aqueous liquid detergents containing from 40% to 85% by weight of water, which, if desired, may also be replaced proportionally by a water-soluble solvent component or a water-soluble solvent component is additionally present, for improving the inhibition of greying during the washing of textile fabrics.