EP1989282B1 - Graying-inhibiting liquid washing composition - Google Patents

Description

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

Graying inhibitors have the task of keeping the fabric removed from the fiber during washing of the fiber suspended in the liquor and thus prevent the re-raising of the dirt on the textile. Water-soluble colloids of mostly organic nature are suitable for this purpose, for example glue, gelatine, salts of ether sulfonic acids or cellulose or salts of acidic sulfuric acid esters of cellulose or starch. Also, water-soluble polyamides containing acidic groups are suitable for this purpose. It is also possible to use soluble starch preparations and starch products other than those mentioned above, for example degraded starch, aldehyde starches, etc. Polyvinylpyrrolidone is also useful. Often, cellulose ethers such as carboxymethylcellulose (Na salt), methylcellulose, hydroxyalkylcellulose and mixed ethers such as methylhydroxyethylcellulose, methylhydroxypropylcellulose, methyl-carboxymethylcellulose and mixtures thereof in amounts of normally 0.1 to 5 wt .-%, based on the detergent used.

Although the mentioned cellulose ethers have a good graying-inhibiting effect, their use in water-based liquid detergents is so narrow that in practice they can not be incorporated into them. In addition to their graying inhibitor effect relevant only when used in the washing process, these cellulose ethers have a comparatively low solubility in surfactant-containing systems and a strongly thickening effect on aqueous systems. When incorporated into desired for the graying-inhibiting effect concentrations in water and especially anionic surfactant liquid detergent, usually either no longer flowable and pourable products, their handling for the user only by additional effort, such as providing water-soluble or auflassbar water insoluble packaged Einzeldosierportionen, can be achieved, or the cellulose ethers are, especially after storage, not completely dissolved in aqueous liquid detergent, which in addition to perceived as poor aesthetics too non-uniform dosage of the grayness inhibitor drug in the application of the agent containing it.

Surprisingly, it has now been found that a good graying-inhibiting effect can be achieved in water-containing liquid detergents without unreasonable viscosity increase or precipitation, if methyl-carboxymethylcellulose with a low degree of methylation is used.

The invention relates to an aqueous liquid detergent containing surfactant and optionally further conventional ingredients of detergents and cleaners, wherein the agent methyl-carboxymethylcellulose having a degree of methylation in the range of 0.01 to 0.3, in particular 0.05 to 0.2 , contains. This means that in the cellulose derivative averaged 0.01 to 0.3, in particular 0.05 to 0.2 methyl groups per Anhydroglykosemonomereinheit are included. The degree of carboxymethylation, which accordingly indicates the average number of carboxymethyl groups per anhydroglycosyl monomer unit, is preferably in the range of 0.3 to 1, in particular 0.4 to 0.8. The average molar mass of the cellulose derivatives used according to the invention is preferably in the range from 80,000 D to 300,000 D, in particular from 100,000 D to 280,000 D and particularly preferably in the range from 150,000 D to 250,000 D. The determination of the degree of polymerization or of the molecular weight of the cellulose ether can be carried out based on the determination of the intrinsic viscosity of sufficiently dilute aqueous solutions by means of a Ubbelohde capillary viscometer (eg capillary 0c). From this, the degree of polymerization and, taking into account the degrees of substitution, the corresponding molecular weight can be calculated.

The present invention suitable methyl-carboxymethylcellulose can be prepared in the usual way by reacting cellulose with methylating agents, such as chloromethane, and subsequent reaction with Carboxymethylierungsagenzien, such as chloroacetic acid, in the corresponding molar equivalents.

An inventive composition preferably contains 0.1 wt .-% to 2 wt .-%, in particular 0.3 wt .-% to 1.5 wt .-% of said methyl-carboxymethylcellulose.

The invention also relates to the use of said low methylated methyl carboxymethylcellulose in aqueous liquid detergents for improving the grayness inhibition in the washing of textile fabrics with the aqueous liquid detergent.

The detergent according to the invention contains, in addition to the stated cellulose ether derivative and surfactants which are explained in more detail below, water in amounts, based on the total agent, of preferably up to about 85% by weight and in particular from 40% by weight to 75% by weight, which, if desired, may also be partially exchanged for a water-soluble solvent component. Non-aqueous solvents that can be used in the liquid agents, for example, from the group of monohydric or polyhydric alcohols, alkanolamines or glycol ethers, provided that they are miscible in the specified concentration range with water. The solvents are preferably selected from ethanol, n- or i-propanol, the butanols, ethylene glycol, butanediol, glycerol, diethylene glycol, butyldiglycol, 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 butoxy triglycol, 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 cleaner is preferably up to 15% by weight, especially 0.5% by weight to 10% by weight.

The liquid detergents contain surfactant, wherein anionic, nonionic, cationic and / or amphoteric surfactants can be used. Preference is given to the presence of anionic surfactants, mixtures of anionic and nonionic surfactants being particularly advantageous from an application point of view. The total surfactant content of the liquid agent is preferably in the range from 10% by weight to 60% by weight, in particular from 15% by weight to 50% by weight, in each case based on the total liquid agent.

The nonionic surfactants used are preferably alcohol alkoxylates, ie alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and on average 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical is linear or preferably 2- Position may be methyl branched or contain linear and methyl-branched radicals in the mixture, as they are usually present in Oxoalkoholresten. In particular, however, alcohol ethoxylates with linear residues of alcohols of native origin having 12 to 18 carbon atoms, for example coconut, palm, tallow or oleyl alcohol, and on average 2 to 8 EO per mole of alcohol are preferred. The preferred ethoxylated alcohols include, for example, C _12-14 alcohols with 3 EO, 4 EO or 7 EO, C _9-11 alcohols 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 _2-18 -alcohol with 7 EO. The degrees of ethoxylation given represent statistical means which, for a particular product, may be an integer or a fractional number. 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 include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO. Nonionic surfactants containing EO and PO groups together in the molecule can also be used according to the invention. Here, block copolymers with EO-PO block units or PO-EO block units can be used, but also EO-PO-EO copolymers or PO-EO-PO copolymers. It is also possible to use mixed alkoxylated nonionic surfactants in which EO and PO units are not distributed in blocks, but statistically distributed. Such products are available by the simultaneous action of ethylene and propylene oxide on fatty alcohols.

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

Another class of preferred nonionic surfactants 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 having from 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-tallow alkyl N, N-dihydroxyethyl amine oxide, and the fatty acid alkanolamides may also be suitable. The amount of these nonionic surfactants is preferably not more than that of the alcohol alkoxylates, especially 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.Further suitable nonionic surfactants are polyhydroxy fatty acid amides of the formula (I)

wherein RCO is an aliphatic acyl group having 6 to 22 carbon atoms, R ^{1 is} hydrogen, an alkyl or hydroxyalkyl group having 1 to 4 carbon atoms and [Z] is a linear or branched polyhydroxyalkyl group 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 the 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 oxyalkyl radical having 1 to 8 carbon atoms, with C _1-4 alkyl or phenyl radicals being preferred and [Z] for a linear polyhydroxyalkyl radical whose alkyl chain is substituted with at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated derivatives of this radical. [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 into the desired polyhydroxy fatty acid amides by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst.

The content of nonionic surfactants in the liquid detergents is preferably 5 wt .-% to 30 wt .-%, in particular 7 wt .-% to 20 wt .-% and particularly preferably 9 wt .-% to 15 wt .-%, 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.

As anionic surfactants, for example, those of the sulfonate type and sulfates can be used. When. Surfactants of the sulfonate type are preferably C _9-13 alkylbenzenesulfonates, olefinsulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates, such as those of C _12-18 monoolefins having terminal or internal double bond by sulfonating with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation obtained. Also suitable are alkanesulfonates which are obtained from C _12-18 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization. Likewise suitable are the esters of α-sulfo fatty acids (ester sulfonates), for example the α-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids.

Further suitable anionic surfactants are sulfated fatty acid glycerol esters. Fatty acid glycerol esters are to be understood as meaning the mono-, di- and triesters and mixtures thereof, as obtained in the preparation 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 sulfated fatty acid glycerol esters are the sulfonation products of saturated fatty acids containing 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) ylsulfates are the alkali metal salts and in particular the sodium salts of the sulfuric monoesters of C ₁₂ -C ₁₈ fatty alcohols, for example coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C ₁₀ -C ₂₀ oxo alcohols and those half-esters of secondary alcohols of these chain lengths are preferred. Also preferred are alk (en) ylsulfates of said chain length, which contain a synthetic, produced on a petrochemical basis straight-chain alkyl radical, which have an analogous degradation behavior as the adequate compounds based on oleochemical raw materials. Of washing technology interest, the C ₁₂ -C ₁₆ alkyl sulfates and C ₁₂ -C ₁₅ alkyl sulfates and C ₁₄ -C ₁₅ alkyl sulfates are preferred. 2,3-alkyl sulfates, which may for example be obtained as commercial products from Shell Oil Company under the name DAN ^®, are suitable anionic surfactants.

Also the sulfuric acid monoesters of the above-mentioned alcohol alkoxylates, for example the straight-chain or branched C _7-21 -alcohols ethoxylated with 1 to 6 mol of ethylene oxide, such as 2-methyl-branched C _9-11- alcohols having on average 3.5 mol of ethylene oxide (EO) or C _12-18 fatty alcohols containing 1 to 4 EO are suitable. These are often referred to as ether sulfates.

Further suitable anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and the 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 of these. Particularly preferred sulfosuccinates contain a fatty alcohol residue derived from ethoxylated fatty alcohols, which in themselves constitute nonionic surfactants (see description below). Sulfosuccinates, whose fatty alcohol residues are derived from ethoxylated fatty alcohols with a narrow homolog distribution, are again particularly preferred. Likewise, it is also possible to use alk (en) ylsuccinic acid having preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.

Preferred anionic surfactants are soaps. Suitable are 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. In a preferred embodiment, the detergent contains 2 wt .-% to 20 wt .-%, in particular 3 wt .-% to 15 wt .-% and particularly preferably 5 wt .-% to 10 wt .-% fatty acid soap. Fatty acid soaps are an important ingredient for the detergency of a liquid, especially aqueous, detergent and cleaning agent. Surprisingly, it has been shown that clear and stable liquid detergents are obtained when using the low-methylated carboxymethylcellulose also in the presence of high amounts of fatty acid soap. Typically, the use of high levels (≥2 wt.%) Of fatty acid soap in such systems results in cloudy and / or unstable products.

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

The content of preferred liquid detergents to anionic surfactants is 5 wt .-% to 35 wt .-%, in particular 8 wt .-% to 30 wt .-% and particularly preferably 10 wt .-% to 25 wt .-%, each based on the entire remedy. 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 in particular from 4% by weight to 10% by weight. In a further preferred embodiment, the compositions contain at least 2, in particular 3, different anionic surfactants selected from alkylbenzenesulfonate, ether sulfate and fatty acid soap.

The detergent may contain a polyacrylate acting as a cobuilder and optionally also as a thickener. The polyacrylates include polyacrylate or polymethacrylate thickeners, such as the high molecular weight crosslinked with a polyalkenyl polyether, in particular an allyl ether of sucrose, pentaerythritol or propylene Homopolymers of acrylic acid (INCI name according to "International Dictionary of Cosmetic Ingredients" of "The Cosmetic, Toiletry and Fragrance Association (CTFA)": Carbomer), which are also referred to as Carboxyvinylpolymere. Such polyacrylic acids are available, inter alia, from 3V Sigma under the trade name Polygel®, for example Polygel DA, and from Noveon under the trade name Carbopol®, for example Carbopol 940 (molecular weight about 4,000,000), Carbopol 941 (molecular weight approx 1. 250,000) or Carbopol 934 (molecular weight about 3,000,000). Furthermore, the following acrylic acid copolymers are included: (i) Copolymers of two or more monomers from the group of acrylic acid, methacrylic acid and their simple ester, preferably formed with C _1-4 -alkanols (INCI acrylates copolymer), such as 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) and which are available, for example, from Rohm & Haas under the trade names Aculyn® and Acusol®, as well as from the company Degussa (Goldschmidt) under the trade name Tego® polymer, for example the anionic non-associative polymers Aculyn 22, Aculyn 28, Aculyn 33 (cross-linked), Acusol 810, Acusol 823 and Acusol 830 (CAS 25852 -37-3); (ii) crosslinked high molecular weight acrylic acid copolymers, such as those crosslinked with an allyl ether of sucrose or pentaerythritol copolymers 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, esters (INCI acrylates / C10-30 alkyl acrylate crosspolymer) and which are available, for example, from Noveon under the trade name Carbopol®, for example the hydrophobic Carbopol ETD 2623 and Carbopol 1382 (INCI Acrylates / C 10 -30 alkyl acrylate crosspolymer) and Carbopol Aqua 30 (former Carbopol EX 473). Preferred liquid detergents contain the polyacrylate in an amount of up to 5 wt .-%, in particular from 0.1 wt .-% to 2.5 wt .-%. It is advantageous if the polyacrylate is a copolymer of an unsaturated mono- or dicarboxylic acids and one or more C ₁ -C ₃₀ -alkyl esters of (meth) acrylic acid.

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

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

As builder, which may be contained in the liquid agents, in particular silicates, aluminum silicates (especially zeolites), carbonates, salts of organic di- and polycarboxylic acids and mixtures of these substances may be mentioned.

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 2, 3 or 4 are. Preferred crystalline layered silicates of the formula given are those in which M is sodium and x assumes the values 2 or 3. In particular, both β- and δ-sodium disilicates Na ₂ Si ₂ O ₅ .yH ₂ O are preferred.

It is also possible to use amorphous sodium silicates with a Na ₂ O: SiO ₂ modulus of from 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2.6, which Delayed and have secondary washing properties. The dissolution delay compared to conventional amorphous sodium silicates may have been caused in various ways, for example by surface treatment, compounding, Kmmpaktierung / compression or by overdrying. In the . For the purposes of this invention, the term "amorphous" also includes "X-ray amorphous" Understood. This means that the silicates do not yield sharp X-ray reflections typical of crystalline substances in X-ray diffraction experiments, but at most one or more maxima of the scattered X-rays which have a width of several degrees of diffraction angle. However, it may 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 as meaning that the products have microcrystalline regions of size 10 to a few hundred nm, with values of 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 dissolution delay compared to the conventional water glasses. Particularly preferred are compacted / compacted amorphous silicates, compounded amorphous silicates and overdried X-ray amorphous silicates.

The finely crystalline, synthetic and bound water-containing zeolite used is preferably zeolite A and / or P. As zeolite P, zeolite ^MAP® (commercial product from Crosfield) is particularly preferred. Also suitable, however, are zeolite X and mixtures of A, X and / or P. Commercially available and preferably usable in the context of the present invention is, for example, a cocrystal of zeolite X and zeolite A (about 80% by weight of zeolite X) which is sold by 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

with n = 0.90 - 1.0 can be described. The zeolite can be used as a spray-dried powder or else as undried, still moist, stabilized suspension of its preparation. In the event that the zeolite is used as a suspension, it may contain minor additions of nonionic surfactants as stabilizers, for example 1 to 3 wt .-%, 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, measuring method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight. on bound water.

It is also possible to use the generally known phosphates as builders, if such use is not to be avoided for ecological reasons. Particularly suitable are the sodium salts of orthophosphates, pyrophosphates and in particular tripolyphosphates.

Among the compounds serving as bleaches in water H ₂ O ₂ , sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance. Other useful bleaching agents are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H ₂ O ₂ -producing peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid. If present, they are preferably used in encased form to protect against disintegration upon 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 detergents and cleaners. As bleach activators, it is possible to use compounds which, under perhydrolysis conditions, give aliphatic peroxycarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid. Suitable substances are those which carry O- and / or N-acyl groups of the stated C atom number and / or optionally substituted benzoyl groups. 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 in their place may also so said bleach catalysts are incorporated into the liquid detergents and cleaners. These substances are bleach-enhancing transition metal salts or transition metal complexes such as, for example, Mn, Fe, Co, Ru or Mo saline 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.

Particularly suitable enzymes are those from the classes of hydrolases such as the proteases, esterases, lipases or lipolytic enzymes, amylases, cellulases or other glycosyl hydrolases and mixtures of the enzymes mentioned. All of these hydrolases in the wash contribute to the removal of stains such as proteinaceous, greasy or starchy stains and graying. In addition, cellulases and other glycosyl hydrolases may contribute to color retention and to enhancing the softness of the fabric by removing pilling and microfibrils. Oxireductases can also be used for bleaching or inhibiting color transfer. Particularly suitable are bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis, Streptomyceus griseus and Humicola insolens derived enzymatic agents. Preference is given to the use of subtilisin-type proteases and in particular proteases derived from Bacillus lentus. In this case, enzyme mixtures, for example from protease and amylase or protease and lipase or lipolytic enzymes or protease and cellulase or from cellulase and lipase or lipolytic enzymes or from 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 proved suitable in some cases. Suitable amylases include in particular α-amylases, iso-amylases, pullulanases and pectinases. As cellulases are preferably cellobiohydrolases, endoglucanases and β-glucosidases, which are also called cellobiases, or mixtures thereof used. Since different cellulase types differ by their CMCase and avicelase activities, targeted mixtures of the Cellulases the desired activities are set.

The bleach activators, catalysts and / or enzymes may be adsorbed and / or coated on carriers to protect them from premature decomposition. The proportion of enzymes, enzyme liquid formulations, enzyme mixtures or enzyme granules may, for example, about 0.1 wt .-% to 5 wt .-%, preferably 0.12 wt .-% to about 2.5 wt .-%, each based on the total agent , amount.

As electrolytes from the group of inorganic salts, a wide number of different salts can be used. 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 compositions is preferred. The proportion of electrolytes in the compositions is usually not more than 8% by weight, in particular from 0.5% by weight to 5% by weight.

To bring the pH of the liquid agents within the desired range, the use of pH adjusters may be indicated. Can be used here are all known acids or alkalis, unless their use is not for technical application or environmental reasons or for reasons of consumer protection prohibited. Usually, the amount of these adjusting agents does not exceed 10% by weight of the total formulation.

Another optional component of the agent according to the invention is a hydrotrope. Preferred hydrotropes include the sulfonated hydrotropes, such as the alkylarylsulfonates or alkylarylsulfonic acids. Preferred hydrotropes are selected from xylene, toluene, cumene, naphthalenesulfonate or sulfonic acid and mixtures thereof. Counterions are preferably selected from sodium, calcium and ammonium. Optionally, the liquid agents may comprise up to 20% by weight of a hydrotrope, in particular from 0.05% to 10% by weight.

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

Suitable foam inhibitors which 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 support materials.

Suitable antiredeposition agents, which are also referred to as "soil repellents", are, for example, the polymers of phthalic acid and / or terephthalic acid known from the prior art or derivatives thereof, in particular polymers of ethylene terephthalates and / or polyethylene glycol terephthalates or anionic and / or nonionic modified Derivatives of these. Especially preferred of these are the sulfonated derivatives of the phthalic and terephthalic acid polymers.

Optical brighteners can be added to the liquid detergents and cleaners to eliminate yellowing of the treated fabrics. These fabrics attract and cause lightening by converting ultraviolet radiation invisible to the human eye into visible longer wavelength light, emitting the ultraviolet light absorbed from the sunlight as faint bluish fluorescence and turning the yellowish yellowed laundry to pure white. Suitable compounds are derived, for example, from the substance classes of 4,4'-diamino-2,2'-stilbenedisulfonic acids (flavonic acids), 4,4'-distyrylbiphenyls, methylumbelliferones, coumarins, dihydroquinolinones, 1,3-diarylpyrazolines, naphthalimides, benzoxazole , Benzisoxazole and benzimidazole systems as well as heterocyclic substituted pyrene derivatives. Optical brighteners are usually available in quantities up to. 0.5 wt .-%, in particular from 0.03 wt .-% to 0.3 wt .-%, based on the finished composition used.

Since fabrics, especially those of rayon, rayon, cotton and their blends, may tend to wrinkle because the individual fibers are susceptible to flexing, kinking, squeezing and squeezing across the grain, the compositions may contain synthetic crease inhibitors. These include, for example synthetic products based on fatty acids, fatty acid esters, fatty acid amides, alkylol esters, 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 may contain antimicrobial agents. Depending on the antimicrobial spectrum and mechanism of action, a distinction is made between bacteriostatic agents and bactericides, fungistatics and fungicides, etc. Important substances from these groups are, for example, benzalkonium chlorides, alkylarylsulfonates, halophenols and phenolmercuric acetate, and the compounds according to the invention can be completely dispensed with.

To prevent undesirable changes to the liquid detergents and cleaners and / or the treated fabrics caused by oxygen and other oxidative processes, the agents may 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 using such antioxidants, the agents according to the invention are naturally free of oxidizing bleaches.

Increased comfort may result from the additional use of antistatic agents added to the compositions. Antistatic agents increase the surface conductivity and thus allow an improved drainage of formed charges. External antistatic agents are generally substances with at least one hydrophilic molecule ligand and give a more or less hygroscopic film on the surfaces. These mostly surface-active antistatic agents can be subdivided into nitrogen-containing (amines, amides, quaternary ammonium compounds), phosphorus-containing (phosphoric acid esters) and sulfur-containing (alkyl sulfonates, alkyl sulfates) antistatic agents. External antistatic agents are, for example, lauryl (or stearyl) dimethylbenzyl ammonium chlorides, which are suitable as antistatic agents for textile fabrics or as an additive to detergents, in which case additionally a softening effect is achieved.

To improve the water absorbency, the rewettability of the treated fabrics and to facilitate the ironing of the treated fabrics, for example, silicone derivatives can be used in the liquid detergents and cleaners. These additionally improve the rinsing behavior of the agents by 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 completely or partially fluorinated. Preferred silicones are polydimethylsiloxanes, which may 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 are in the range between 100 and 100,000 mPas at 25 ° C, wherein the silicones in amounts between 0.2 and 5 wt .-%, based on the total agent can be used.

Finally, the liquid detergents and cleaners may also contain UV absorbers that wick onto the treated fabrics and improve the lightfastness of the fibers. Compounds having these desired properties include, for example, the non-radiative deactivating compounds and derivatives of benzophenone having substituents in the 2- and / or 4-position. Also suitable are substituted benzotriazoles, in the 3-position phenyl-substituted acrylates (cinnamic acid derivatives), optionally with cyano groups in the 2-position, salicylates, organic Ni complexes and natural substances such as umbelliferone and urocanic acid.

In order to avoid the catalyzed by heavy metals decomposition of certain detergent ingredients, substances that complex heavy metals can be used. 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 complexing agents are the phosphonates, which are preferred liquid agents in amounts of from 0.01% to 2.5%, preferably from 0.02% to 2%, by weight, and especially from 0.03 wt .-% to 1.5 wt .-% are. These preferred compounds include in particular organophosphonates such as 1-hydroxyethane-1,1-diphosphonic acid (HEDP), aminotri (methylenephosphonic acid) (ATMP), diethylenetriamine penta (methylenephosphonic acid) (DTPMP or DETPMP) and 2-phosphonobutane-1,2 , 4-tricarboxylic acid (PBS-AM), which are used mostly 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. The liquid detergents and cleaners without addition of a dye preferably have a transmission of the visible light (410 to 800 nm) of at least 30%, preferably at least 50% and especially preferably at least 75%.

In addition to the constituents mentioned, however, a liquid washing and cleaning agent may also contain particles dispersed therein whose diameter along their greatest spatial extent is, for example, 0.01 μm to 10,000 μm. Such particles may be microcapsules or speckles as well as granules, compounds and fragrance beads, with microcapsules or speckles being preferred.

The term "microcapsule" is understood to mean aggregates which contain at least one solid or liquid core which is enclosed by at least one continuous shell, in particular a shell of polymer (s). These are usually finely dispersed liquid or solid phases coated with film-forming polymers, during the production of which the polymers precipitate on the material to be enveloped after emulsification and coacervation or interfacial polymerization. The microscopic capsules can be dried like powder. Besides mononuclear microcapsules, multinuclear aggregates, also called microspheres, are known, which contain two or more cores distributed in the continuous shell material. Mono- or polynuclear microcapsules can also be enclosed by an additional second, third, etc., sheath. Preferred are mononuclear microcapsules with a continuous shell. The shell may be made of natural, semi-synthetic or synthetic materials. Naturally, shell materials are, for example, gum arabic, agar agar, agarose, maltodextrins, alginic acid or its salts, for example sodium chloride. or calcium alginate, fats and fatty acids, cetyl alcohol, collagen, chitosan, lecithins, gelatin, albumin, shellac, polysaccharides such as starch or dextran, sucrose and waxes. Semi-synthetic shell materials include chemically modified celluloses, in particular cellulose esters and ethers, for example cellulose acetate, ethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose and carboxymethylcellulose, and also starch derivatives, in particular starch ethers and esters. Synthetic envelope materials are, for example, polymers such as polyacrylates, polyamides, polyvinyl alcohol or polyvinylpyrrolidone.

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

The microcapsules may have any shape in the production-related framework, but they are preferably approximately spherical. Their diameter along their largest spatial extent, depending on the components contained in their interior and the application between 0.01 microns (not visually recognizable as a capsule) and 10,000 microns. Preference is given to visible microcapsules having a diameter in the range from 100 μm to 7000 μm, in particular from 400 μm to 5000 μm. The microcapsules are accessible by methods known in the art, with coacervation and interfacial polymerization being the most important. As microcapsules, all surfactant-stable microcapsules available on the market can be used, for example the commercial products (in each case the shell material is indicated in parentheses) Hallcrest Microcapsules (gelatin, gum Arabicum), Coletica thalaspheres (marine collagen), Lipotec millicapsules (alginic acid, agar-agar), induchem unispheres (lactose, microcrystalline cellulose, hydroxypropylmethylcellulose); Unicerin C30 (lactose, microcrystalline cellulose, hydroxypropyl methylcellulose), 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 have no 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. For producing alginate-based speckles is an aqueous alginate solution which also contains the entrapped active ingredient or active ingredients to be entrapped, and then dripped cured ³⁺ ions precipitation bath containing ions in a Ca ²⁺ or Al. It may be advantageous that the alginate-based speckles are subsequently washed with water and then washed in an aqueous solution with a complexing agent to free Ca ²⁺ ions or free Al ³⁺ ions, which undesirable interactions with ingredients of the liquid wash - And detergent, such as the fatty acid soaps, can go out, wash out. Subsequently, the alginate-based speckles are 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, hydroxyethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, hyaluronic acid, Carboxymethylcellulose, carboxymethylcellulose, deacetylated chitosan, dextran sulfate and derivatives of these materials. The matrix formation in these materials takes place, for example, via gelation, polyanion-polycation interactions or polyelectrolyte-metal ion interactions and is well-known in the art as well as the production of particles with these matrix-forming materials. The particles can be stably dispersed in the aqueous liquid detergent and cleaner. Stable means that the agent is at room temperature and at 40 ° C over a period of time of at least 4 weeks, and preferably of at least 6 weeks, without the means creaming or sedimenting.

The release of the active ingredients from the microcapsules or speckles is usually carried out during the application of the agents containing them by destruction of the shell or the matrix due to 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 wt .-%, in particular 0.2 to 8 wt .-% and most preferably 0.5 to 5 wt .-%.

Aqueous detergents and cleaners can be inexpensively and easily produced in conventional mixing and bottling plants. For the preparation of the liquid agents, 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 introduced. The solvent component is preferably also added at this time, but the addition may also be made at a later time. To these components, if present, the complexing agent is added. Subsequently, a base such as NaOH, KOH, triethanolamine or monoethanolamine followed by the fatty acid, if present, is added. Subsequently, the remaining ingredients and optionally the remaining solvents of the aqueous liquid agent 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, in each case based on the total agent) of inventive detergents M1 and M2. Table 1: M1 M2 C _9-13 Alkylbenzenesulfonate, Na salt 10 10 Sodium lauryl ether sulfate with 2 EO 5 5 C _12-14 fatty alcohol with 7 EO 10 10 C _12-14 alkyl glucoside 2 2 C _12-18 fatty acid, Na salt 8th 8th glycerin 5 5 trisodium citrate 1 1 polyacrylate 2 2 Me-CMC I ^a) 1 - Me-CMC II ^b) - 1 Enzymes, dye, opt. brighteners + + water Ad 100 Ad 100 a) degree of methylation 0.09, degree of carboxymethylation 0.56, molecular weight 218,000
b) degree of methylation 0.14, degree of carboxymethylation 0.73, molecular weight 198,000

The funds were tested under the following conditions: Washer: Launderometer, Fa. Atlas balls: 10 Washing temperature: 40 ° C, 60 min. Determination: 3 times Number of washes: 5 Liquor ratio: 1:12 Water hardness: 16 ° dH Soil carrier: 6.7 g Greying Swatch Dosage: 1 g of the agent / 200 ml

The following materials were used: A 65% polyester / 35% cotton, WFK 20A B 100% cotton Trigema® Jerzey, pink C 100% cotton, Trigema® pique, light yellow D 100% cotton, Zwir-terry cloth, 1.1.04, white with opt. brighteners e 100% cotton, knitted cotton 1.1.27, double rib knit, bleached, with opt. brighteners F 100% cotton, cotton fabric, WFK 10A, without opt. brighteners

Table 2 gives the percent improvement in grayness inhibition that results from the use of the low methylated carboxymethylcelluloses (compared to an otherwise equal composition lacking this agent). Table 2: M1 M2 A 5.5 4.6 B 5.6 7.3 C 12.0 10.1 D 10.4 10.5 e 17.4 13.6 F 11.4 11.3

Claims (10)

1. An aqueous liquid laundry detergent containing surfactant as well as further usual ingredients of laundry detergents and cleaning agents, the detergent containing methylcarboxymethyl cellulose having a degree of methylation in the range from 0.01 to 0.3.
2. The detergent according to Claim 1, wherein the methylcarboxymethyl cellulose has a degree of carboxymethylation in the range from 0.3 to 1, in particular 0.4 to 0.8.
3. The detergent according to Claim 1 or 2, wherein the methylcarboxymethyl cellulose has a degree of methylation in the range from 0.05 to 0.2.
4. The detergent according to one of Claims 1 to 3, wherein it contains 0.1 to 2 wt%, in particular 0.3 wt% to 1.5 wt%, of the methylcarboxymethyl cellulose.
5. The detergent according to one of Claims 1 to 4, wherein it contains 10 wt% to 60 wt%, in particular 15 wt% to 50 wt%, surfactant.
6. The detergent according to one of Claims 1 to 5, wherein it contains anionic surfactant and in particular fatty acid soap.
7. The detergent according to one of Claims 1 to 6, wherein it contains at least two different anionic surfactants, selected from alkylbenzenesulfonate, ether sulfate, and soap.
8. The detergent according to one of Claims 1 to 7, wherein it contains nonionic surfactant, selected in particular from alcohol alkoxylate and alkylpolyglycoside and mixtures thereof.
9. The detergent according to one of Claims 1 to 8, wherein it contains up to 85 wt%, in particular from 40 wt% to 75 wt%, water.
10. Use of methylcarboxymethyl cellulose having a degree of methylation in the range from 0.01 to 0.3 in aqueous liquid laundry detergents in order to improve graying inhibition when washing textile fabrics.