EP2134826B1 - Anti-grey detergent - Google Patents

Description

The invention relates to a surfactant-containing detergent which contains a compound with certain reactive groups as graying-inhibiting active ingredient

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. For this purpose, water-soluble colloids are usually suitable organic nature, such as glue. Gelatin, salts of starch or cellulose ether sulphonic acids or salts of acid sulphate esters of cellulose or starch. Also, water-soluble polyamides containing acidic groups are suitable for this purpose. Furthermore, soluble starch preparations and starch products other than those mentioned above can be used, for example degraded starch, strong aldehydes, 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 cellulose ethers mentioned have a good graying-inhibiting effect, their use in aqueous liquid detergents is so narrow that they are not workable in practice. 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 the desired in the graying inhibiting effect concentrations in water and in particular aniontensidhallige liquid detergent, usually obtained either no longer flowable and pourable products whose handling for the user only by zusäfzlichen effort, for example, provision in water-soluble or tear-insoluble water packaged Einzeldosierportionen, can be achieved, or the cellulose ethers are, especially after storage, not completely dissolved in aqueous liquid detergent, which in addition to poor perceived aesthetics also leads to uneven dosage of the grayness inhibitor drug in the application of the agent containing them.

EP1541568 describes the stain-resistant properties of the polyurethane and polycarbonate compounds. It discloses the surface treatment of fibers with aqueous solutions of polyurethane and polycarbonate compounds of formula IV.

Surprisingly, it has now been found that in water-containing liquid detergents a good Graying-inhibiting effect can be achieved without unreasonable viscosity increase or precipitation, if one uses certain compounds of the type of reactive carbonic carbonates

Reactive cyclic carbonates and ureas, processes for their preparation and their reaction with polymeric substrates are described in the international patent application WO 2005/058863 described. Surprisingly, it has now been found that the reactive carbonyl carbonates themselves or from these polymers obtainable by reaction with polymeric substrates have the desired effect.

worin

• R für C₁-C₁₂-Alkylen steht;
• k für eine Zahl großer als 0 steht,
• X für CO-CH=CH₂, CO-C(CH₃)=CH₂, CO-O-Aryl, C₂-C₆-Alkylen-SO₂-CH=CH₂, oder CO-NH-R¹ steht; und R¹ für C₁-C₃₀-Alkyl, C₁-C₃₀-Halogenalkyl, C₁-C₃₀-Hydroxyalkyl, C₁-C₆-Alkyloxy-C₁-C₃₀-alkyl, C₁-C₆-Alkylcarbonyloxy-C₁-C₃₀-alkyl, Amino-C₁-C₃₀-alkyl, Mono- oder Di(C₁-C₆-alkyl)amino-C₁-C₃₀-alkyl, Ammonio-C₁-C₃₀-alkyl, Polyoxyalkylen-C₁-C₃₀-alkyl, Polysiloxanyl-C₁-C₃₀alkyl, (Meth)acryloyloxy-C₁-C₃₀-alkyl, Sulfono-C₁-C₃₀-alkyl, Phosphono-C₁-C₃₀-lkyl, Di(₁-C₆-alkyl)phos phono-C₁-C₃₀alkyl, Phosphonato-C₁-C₃₀-alkyl, Di(C₁-C₆-alkyl)phosphonato-C₁-C₃₀-lkyl oder einen Saccharidrest steht, wobei X diese Bedeutung nur dann hat, wenn k für 1 steht, oder
• X für
  1. (i) den Rest eines Polyamins, an das der in Klammern stehende Formelteil über (CO)NH-Gruppen gebunden ist, oder
  2. (ii) ein polymeres Gerüst, an das der in Klammem stehende Formelteil über (CO)-, NH-C₂-C₆-Alkylen-O(CO)- oder (CO)-O-C₂-C₆-Alkylen-O(CO)-Gruppen gebunden ist, oder
  3. (iii) ein polymeres Gerüst, an das der in Klammem stehende Formelteil über (CO)-Polyslloxanyl-C₁-C₃₀-alkyl-Gruppen gebunden ist,
  steht, wenn k für eine Zahl von mehr als 1 steht,
  und/oder ein Polymer enthält, welches erhältlich ist durch Umsetzung eines polymeren Substrates, das über funktionelle Gruppen verfügt, welche unter Hydroxygruppen, primären und sekundären Aminogruppen ausgewählt sind, mit einer Verbindung der allgemeinen Formel IV.

An object of the invention is therefore a detergent which is liquid and contains up to 85 wt .-% water containing surfactant and optionally other conventional ingredients of detergents and cleaners, wherein the agent contains a graying-inhibiting compound of general formula IV.

wherein

• R is C ₁ -C ₁₂ alkylene;
• k is a number greater than 0,
• X is CO-CH = CH ₂ , CO-C (CH ₃ ) = CH ₂ , CO-O-aryl, C ₂ -C ₆ -alkylene-SO ₂ -CH = CH ₂ , or CO-NH-R ¹ ; and R ^{1 is} C ₁ -C ₃₀ -alkyl, C ₁ -C ₃₀ -haloalkyl, C ₁ -C ₃₀ -hydroxyalkyl, C ₁ -C ₆ -alkyloxy-C ₁ -C ₃₀ -alkyl, C ₁ -C ₆ - Alkylcarbonyloxy-C ₁ -C ₃₀ -alkyl, amino-C ₁ -C ₃₀ -alkyl, mono- or di (C ₁ -C ₆ -alkyl) amino-C ₁ -C ₃₀ -alkyl, ammonio-C ₁ -C ₃₀ -alkyl, polyoxyalkylene-C ₁ -C ₃₀ -alkyl, polysiloxanyl-C ₁ -C ₃₀ -alkyl, (meth) acryloyloxy-C ₁ -C ₃₀ -alkyl, sulfono-C ₁ -C ₃₀ -alkyl, phosphono-C ₁ - C ₃₀ -lkyl, di (C ₁ -C ₆ alkyl) phos phono-C ₁ -C ₃₀ alkyl, phosphonato-C ₁ -C ₃₀ alkyl, di (C ₁ -C ₆ alkyl) phosphonato-C ₁ -C ₃₀ -alkyl or a saccharide radical, wherein X has this meaning only when k is 1, or
• X for
  1. (i) the residue of a polyamine to which the parenthesized part of the formula is linked via (CO) NH groups, or
  2. (ii) a polymeric backbone to which the formula part in parentheses is replaced by (CO) -, NH-C ₂ -C ₆ -alkylene-O (CO) - or (CO) -OC ₂ -C ₆ -alkylene-O ( CO) groups, or
  3. (iii) a polymeric backbone to which the formula part in parentheses is attached via (CO) polysoloxanyl-C ₁ -C ₃₀ alkyl groups is bound
  stands if k stands for a number of more than 1,
  and / or a polymer which is obtainable by reacting a polymeric substrate which has functional groups which are selected from hydroxy groups, primary and secondary amino groups, with a compound of general formula IV.

The polymeric substrates suitable in connection with the latter aspect of the invention include in particular polyvinyl alcohols, polyalkyleneamines such as polyethyleneimines, polyvinylamines, polyallylamines, polyethylene glycols, chitosan, polyamide-epichlorohydrin resins, polyamino-styrenes, aminoalkyl-terminated or pendant polysiloxanes such as polydimethylsiloxanes, peptides, Polypeptides, and proteins and mixtures thereof. Particularly preferred polymeric substrates are selected from
Polyethyleneimines having molecular weights in the range of 5,000 to 100,000, in particular 15,000 to 50,000,
Compounds of the formula NH ₂ - [CH ₂ ] _m - (Si (CH ₃ ) ₂ O) _n -Si (CH ₃ ) ₂ - [CH ₂ ] _o -R ', where m = 1 to 10, preferably 1 to 5 , particularly preferably 1 to 3, where n = 1 to 50, preferably 30 to 50, where o = 0 to 10, preferably 1 to 5, particularly preferably 1 to 3 and wherein R '= H, C _1-20 -Alkyl, an amino or ammonium group, and / or
Compounds of the formula NH ₂ - [CH (CH ₃ ) -CH ₂ O] ₁ - [CH ₂ -CH ₂ O] _m - [CH ₂ -CH (CH ₃ ) O] _n -R "where I, m and n independently represent numbers from 0 to 50 with the proviso that the sum of I + m + n = 5 to 100, in particular 10 to 50, preferably 10 to 30, particularly preferably 10 to 20, and R "= H, a C _1-22 alkyl, C _1-21 aminoalkyl or C _1-22 ammonium alkyl group, and mixtures thereof.

Preferred polymers are those which are obtainable by reacting the polymeric substrate with a compound of general formula IV where k = 1. Preference is furthermore given to those polymers which are obtainable by reaction of the polymeric substrate with equal molar amounts of compound of the general formula IV where k = 1, based on the content of hydroxyl groups, primary and secondary amino groups.

The compound of formula IV is preferably selected from
4-phenyloxycarbonyloxymethyl-2-oxo-1,3-dioxolane,
4- (4-Phenyloxycarbonyloxy) butyl-2-oxo-1,3-dioxolane,
2-oxo-1,3-dioxolan-4-yl-methyl,
2-oxo-1,3-dioxolan-4-yl-methyl,
4- (2-oxo-1,3-dioxolan-4-yl) butyl acrylate,
4- (2-oxo-1,3-dioxolan-4-yl) -butyl methacrylate and
4- (Vinylsulfonylethyloxy) butyl-2-oxo-1,3-dioxolane.

An agent of the invention preferably contains from 0.01% to 5%, more preferably from 0.1% to 1% by weight of the graying-inhibiting active ingredient described herein.

The invention also relates to the use of said active substances in detergents, in particular in aqueous liquid detergents, for improving the grayness inhibition when washing textile fabrics with the detergent.

A liquid detergent according to the invention contains, in addition to said graying-inhibiting active ingredient or mixtures thereof and surfactants described in more detail below, water in amounts of up to 85% by weight, and in particular from 40% by weight to 75%, of the total composition. %, which, if desired, can also be exchanged proportionally 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 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 cleaning agent is preferably up to 15% by weight, especially 0.5% by weight to 10% by weight.

The detergents according to the invention contain at least one 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 particular liquid agent is preferably in the range of 10 wt .-% to 60 wt .-%, in particular 15 wt .-% to 50 wt .-%, each 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 having linear radicals 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 among the 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 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-dimethyl-amine oxide and N-tallow alkyl-N, N-dihydroxyethylamine 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 R-CO 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 öder einem Fettsäurechlorid erhalten werden können. Zur Gruppe der Polyhydroxyfettsäureamide gehören auch Verbindungen der Formel (VII),

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 Alköxids als Katalysator in die gewünschten Polyhydroxyfettsäureamide überführt werden.Further suitable nonionic surfactants are polyhydroxy fatty acid amides of the formula (VI)

in the R-CO for an aliphatic acyl radical having 6 to 22 carbon atoms, R ^{1 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 stands. 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 (VII)

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] being a linear polyhydroxyalkyl radical whose alkyl chain is substituted by 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 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 particularly 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. The surfactants of the sulfonate type are preferably C _9-13 -alkylbenzenesulfonates, olefinsulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates, as are obtained, for example, from C _12-18 -monoolefins having terminal or internal double bonds by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acid hydrolysis of the sulfonation products into consideration. Also suitable are alkanesulfonates from C _12-18 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization can be recovered. 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 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) 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 moles of ethylene oxide (EO) or C. _12-18 fatty alcohols with 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 in particular an important constituent for the washing power of a liquid, in particular aqueous, washing 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% by weight) 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 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 co-builder and optionally also a thickener-acting polyacrylate. These polyacrylates include polyacrylate or polymethacrylate thickeners, such as, for example, the high molecular weight homopolymers of acrylic acid crosslinked with a polyalkenyl polyether, in particular an allyl ether of sucrose, pentaerythritol or propylene (INCI name according to the International Dictionary of Cosmetic Ingredients, The Cosmetic, Toiletry and Fragrance Association (CTFA) ": carbomer), also referred to as carboxyvinyl polymers. 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, esters (INCI Acrylates Copolymer) preferably formed with C _1-4 -alkanols, 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) 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 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 / C10). 30 alkyl acrylate crosspolymer) and Carbopol Aqua 30 (formerly Carbopol EX 473). Preferred detergents, in particular those in liquid form, contain the polyacrylate in an amount of up to 5% by weight, in particular from 0.1% by weight to 2.5% by weight. 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 liquid detergents and cleaning agents 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 liquid agents have viscosities in the range from 500 mPas to 4000 mPas, with values in the range from 1000 mPas to 3500 mPas being particularly preferred.

In addition, the 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, hydrotopes, foam inhibitors, additional antiredeposition agents or grayness inhibitors, optical brighteners, Anti-shrinkage agents, anti-wrinkling 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.

Suitable builders which may be present in the compositions are, for example, aluminum silicates (in particular zeolites), carbonates, salts of organic di- and polycarboxylic acids and mixtures of these substances.

The usable finely crystalline, synthetic and bound water-containing zeolite 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, in particular in water-containing liquid agents, also 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, of 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.

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. Preferably, subtilisin-type proteases and in particular proteases derived from Bacillus lentus are used. 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 Cellobiohydrolaseh, endoglucanases and β-glucosidases, which are also called cellobiases, or mixtures thereof used. Since different cellulase types differ by their CMCase and avicelase activities, the desired activities can be set by targeted mixtures of the cellulases.

The enzymes can be adsorbed and / or coated on carriers to protect against premature degradation. 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 particular liquid agents is usually not more than 8 wt .-%, in particular 0.5 wt .-% to 5 wt .-%.

In order to bring the pH of liquid agents in 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 liquid agents of 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 agents, they or at least one of their components can be dyed with suitable dyes. Preferred dyes, the selection of which presents no difficulty to the skilled person, have a high storage stability and insensitivity to the other ingredients of the agents and to light and no pronounced substantivity to textile fibers so as not to stain them.

Suitable foam inhibitors which can be used in the detergents and cleaners are, for example, soaps, paraffins or silicone oils which, if appropriate, may 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 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 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 composition.

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 ester.

To combat microorganisms, 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.

In order to prevent undesirable changes to the detergents and cleaners and / or the treated fabrics caused by oxygen and other oxidative processes, the compositions 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 such antioxidants are used, the agents according to the invention are free from 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) dimethylbenzylammonium chlorides, which are suitable as antistatic agents for textile fabrics or as an additive to detergents, in which case additionally a finishing 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 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 detergents and cleaners may also contain UV absorbers which 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 in preferred compositions are present in amounts of from 0.01% to 2.5%, preferably from 0.02% to 2%, by weight, and most preferably 0.03 wt .-% to 1.5 wt .-% are included. 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.

Liquid detergents according to the invention 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%.

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, adding the remaining solvents of the aqueous liquid agent to the mixture and adjusting the pH 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 a detergent M1 according to the invention. Table 1: M1 C _9-13 alkyl benzene sulfonate, Na salt 10 Sodium lauryl ether sulfate with 2 EO 5 C _12-18 fatty alcohol with 7 EO 10 C _12-14 alkyl polyglycoside 2 C _12-18 fatty acid, Na salt 8th glycerin 5 trisodium citrate 1 polyacrylate 2 active substance 1 Enzymes, dye, opt. brighteners + water Ad 100

The agent was tested under the following conditions: Washer: Washing machine Washing temperature: 40 ° C Number of washes: 10 Water hardness: 16 ° dH Soil carrier: 6,7 g mixed dirt (eg clay, dust-skin fat, soot) Dosage: 75 g of the medium / 17L

1. A Polyester / Baumwolle Mischgewebe
2. B 100% Baumwolle
3. C 100% Baumwolle, Zwirn-Frottiergewebe
4. D 100% Baumwolle, Baumwoll-Gewirke

The following materials were used:

1. A polyester / cotton blended fabric
2. B 100% cotton
3. C 100% cotton, twisted terry cloth
4. D 100% cotton, cotton knit

The use of the active ingredient used according to the invention resulted in an improvement in the grayness inhibition in all materials in comparison with an otherwise equally composed composition which lacked the active ingredient.

Claims (7)

1. Washing agent, which is liquid and contains up to 85% by weight water, containing a surfactant and optionally additional conventional ingredients of washing and cleaning agents, wherein the agent contains a graying inhibiting compound of the general formula IV

   

   where

   R stands for C₁-C₁₂ alkylene;

   k stands for a number greater than 0;

   X stands for CO-CH=CH₂, CO-C(CH₃)=CH₂, CO-O-aryl, C₂-C₆-alkylene-SO₂-CH=CH₂ or CO-NH-R¹ and R¹ for C₁-C₃₀ alkyl, C₁-C₃₀ haloalkyl, C₁-C₃₀ hydroxyalkyl, C₁-C₆-alkyloxy-C₁-C₃₀-alkyl, C₁-C₆-alkylcarbonyloxy-C₁-C₃₀-alkyl, amino-C₁-C₃₀-alkyl, mono- or di(C₁-C₆-alkyl)-amino-C₁-C₃₀-alkyl, ammonio-C₁-C₃₀-alkyl, polyoxyalkylene-C₁-C₃₀-alkyl, polysiloxanyl-C₁-C₃₀-alkyl, (meth)acryloyloxy-C₁-C₃₀-alkyl, sulfono-C₁-C₃₀-alkyl, phosphono-C₁-C₃₀-alkyl, di(C₁-C₆-alkyl)phosphono-C₁-C₃₀-alkyl), phosphonato-C₁-C₃₀-alkyl, di(C₁-C₆-alkyl)phosphonato-C₁-C₃₀-alkyl or a saccharide radical, where X has this meaning only when k stands for 1 or

   X stands for

   (i) the radical of a polyamine, to which the part of the formula in parentheses is bound by (CO)NH groups, or

   (ii) a polymer structure, to which the part of the formula in parentheses is bound by (CO), NH-C₂-C₅-alkylene-O(CO) or (CO)-O-C₂-C₆-alkylene-O(CO) groups, or

   (iii) a polymer structure, to which the part of the formula in parentheses is bound by (CO)-polysiloxanyl-C₁-C₃₀-alkyl groups,

   when k stands for a number of more than 1,
   and/or a polymer, which can be obtained by reacting a polymeric substrate having functional groups, which are selected from hydroxyl groups, primary and secondary amino groups, with a compound of general formula IV.
2. Agent according to claim 1, characterized in that it contains 10% by weight to 60% by weight, in particular 15% by weight to 50% by weight surfactant.
3. Agent according to claim 1 or 2, characterized in that it contains anionic surfactant and in particular fatty acid soap.
4. Agent according to any one of claims 1 to 3, characterized in that it contains at least two different anionic surfactants selected from alkylbenzene sulfonate, ether sulfate and soap.
5. Agent according to any one of claims 1 to 3, characterized in that it contains nonionic surfactant, in particular selected from alcohol alkoxylate and alkyl polyglycoside and mixtures thereof.
6. Agent according to any one of claims 1 to 3, characterized in that it contains 40% by weight to 75% by weight water.
7. Use of compounds of general formula IV

   

   where

   R stands for C₁-C₁₂ alkylene;

   k stands for a number greater than 0;

   X stands for CO-CH=CH₂, CO-C(CH₃)=CH₂, CO-O-aryl, C₂-C₆-alkylene-SO₂-CH=CH₂ or CO-NH-R¹ and R¹ for C₁-C₃₀ alkyl, C₁-C₃₀ haloalkyl, C₁-C₃₀ hydroxyalkyl, C₁-C₆-alkyloxy-C₁-C₃₀-alkyl, C₁-C₆-alkylcarbonyloxy-C₁-C₃₀-alkyl, amino-C₁-C₃₀-alkyl, mono- or di(C₁-C₆-alkyl)-amino-C₁-C₃₀-alkyl, ammonio-C₁-C₃₀-alkyl, polyoxyalkylene-C₁-C₃₀-alkyl, polysiloxanyl-C₁-C₃₀-alkyl, (meth)acryloyloxy-C₁-C₃₀-alkyl, sulfono-C₁-C₃₀-alkyl, phosphono-C₁-C₃₀-alkyl, di(C₁-C₆-alkyl)phosphono-C₁-C₃₀-alkyl), phosphonato-C₁-C₃₀-alkyl, di(C₁-C₆-alkyl)phosphonato-C₁-C₃₀-alkyl or a saccharide radical, where X has this meaning only when k stands for 1 or

   X stands for

   (i) the radical of a polyamine, to which the part of the formula in parentheses is bound by (CO)NH groups, or

   (ii) a polymer structure, to which the part of the formula in parentheses is bound by (CO), NH-C₂-C₆-alkylene-O(CO) or (CO)-O-C₂-C₆-alkylene-O(CO) groups, or

   (iii) a polymer structure, to which the part of the formula in parentheses is bound by (CO)-polysiloxanyl-C₁-C₃₀-alkyl groups,

   when k stands for a number of more than 1,
   and/or a polymer, which can be obtained by reacting a polymeric substrate having functional groups, which are selected from hydroxyl groups, primary and secondary amino groups, with a compound of general formula IV, in detergents, in particular aqueous liquid detergents, to improve the graying inhibition in washing textile fabrics.