COLOUR PROTECTION METHOD

Abstract

 The present invention improves dye transfer inhibition in the washing of textiles by depositing oligomeric urea or urethane derivatives comprising sulfonic or carboxylic acid groups onto the surface of the textiles.

Description

[0001] The present invention relates to the use of oligomeric urea derivatives as dye transfer-inhibiting active ingredients in the washing of textiles by depositing such compounds onto the surface of the textiles prior to the washing step.

[0002] In addition to the constituents essential for the washing process such as surfactants and builders, detergents generally contain further ingredients which may be grouped together under the heading of washing auxiliaries and thus include various groups of active ingredients such as foam regulators, greying inhibitors, bleaching agents, bleaching activators and enzymes. Such auxiliary substances also include substances which are intended to prevent dyed textiles from having a modified colour appearance after washing. This change in colour appearance of washed, i.e. clean, textiles may be due, on the one hand, to proportions of the dye being removed from the textile by the washing process ("fading"), and, on the other hand, to dyes dissolved out from differently coloured textiles being deposited on the textile ("discolouration"). Change of the discolouration kind may also involve undyed items of washing if these are washed together with coloured items of washing. In order to avoid these undesired side-effects of removing dirt from textiles by treatment with conventionally surfactant-containing aqueous systems, detergents, especially when they are intended as "colour" detergents for washing coloured textiles, contain active ingredients which are intended to prevent the dissolution of dyes from the textile or at least the deposition of dissolved-out dyes present in the washing liquor onto textiles. Many of the polymers conventionally used have such a high affinity for dyes that they draw them to a greater extent from the dyed fibre, such that greater colour losses occur.

[0003] The use of urea derivatives of general formula

         Ar-NH-C(O)-NH-Ar(A)_l-NH[-C(O)-NH-L-NH-C(O)-NH-Ar(A)_m-NH]_n-C(O)-NH-Ar

in which

Ar denotes an aromatic group or a linear, branched, or cyclic, saturated or once or several times ethylenically unsaturated hydrocarbon group with 1 to 12 carbon atoms, optionally substituted by up to 3 alkyl substituents with 1 to 4 carbon atoms,

L denotes an arylene group, optionally substituted by up to 3 alkyl substituents with 1 to 5 carbon atoms, or an alkylene group with 2 to 4 carbon atoms,

A denotes -SO₃M or -CO₂M,

M denotes H or an alkali metal atom,

l and m irrespective of each other denote 0, 1, 2 or 3, and l+m ≥ 1

n denotes a number of from 2 to 6,

for avoiding the transfer of textile dyes from dyed textiles onto undyed or differently coloured textiles when they are jointly washed in aqueous solutions, in particular surfactant-containing aqueous solutions, is known from international patent application WO 2014/187693 A1.

[0004] It has surprisingly now been found that certain urea or urethane oligomers with anionic groups give rise to unexpectedly high dye transfer inhibition in a subsequent washing step if they are deposited onto the surface of the textile to be washed prior to said washing step.

[0005] Accordingly, in a first aspect the present invention provides a method for applying a urea or urethane derivative of the general formula I,

         R(A)_l-B-C(O)-NH-Ar(A)_m-NH[-C(O)-NH-L-NH-C(O)-NH-Ar(A)_o-NH]_n-C(O)-B-R(A)_p     (I)

in which

R denotes H, Ar, or a linear, branched, or cyclic, saturated or once or several times ethylenically unsaturated hydrocarbon group with 1 to 12 carbon atoms,

Ar denotes an aromatic group, a stilbene group, both optionally substituted by up to 3 substituents selected from alkyl groups with 1 to 4 carbon atoms, NH₂ groups, and their mixtures, and mixtures thereof,

B denotes O or NH,

A denotes -SO₃M or -CO₂M,

M denotes H or an alkali metal atom,

L denotes an arylene group, optionally substituted by up to 3 alkyl substituents with 1 to 5 carbon atoms, or an alkylene group with 2 to 4 carbon atoms,

l, m, o, and p irrespective of each other denote 0, 1, 2 or 3, and l+m+o+p ≥ 1

n denotes a number of from 2 to 6,

onto the surface of a textile, by contacting said textile with an amount of 0.04 % by weight to 4.0 % by weight (% by weight of the urea derivative in relation to the weight of the textile) of said urea derivative in an aqueous system.

[0006] The concentration of said urea or urethane derivative in the aqueous system in particular is in the range of from 5 ppm by weight to 500 ppm by weight (ppm by weight of the urea derivative in relation to the weight of the aqueous system, without textile), preferably from 10 ppm by weight to 100 ppm by weight.

[0007] The time the aqueous system comprising said urea or urethane derivative stays in contact with the textile in particular is in the range of 1 minutes to 30 minutes, preferably 3 minutes to 10 minutes.

[0008] The temperature of the aqueous system comprising said urea or urethane derivative in particular is kept in the range of from 5 °C to 90 °C, preferably from 10 °C to 60 °C.

[0009] The preventive action against the staining of white or also differently coloured textiles by dyes washed out of the textiles is particularly pronounced when the textile the surface of which has been treated with the urea or urethane oligomer is made of or comprises polyamide. The urea or urethane derivatives attach themselves to the white or differently coloured textiles and have a repellent action on the dye molecules present in the liquor during a subsequent washing, stemming from coloured textiles, normally not treated with the urea or urethane oligomers.

[0010] R in the compounds of general formula I preferably is selected from C_2-5-alkyl groups and Ar, and mixtures thereof. Ar in the compounds of general formula I preferably is selected from the group encompassing phenyl, naphthyl, stilbyl, cresyl, and mixtures thereof. B in the compounds of general formula I preferably is NH. L in the compounds of general formula I preferably is selected from the group encompassing toluylene, methylenediphenylene, and mixtures thereof. The index m in the compounds of general formula I preferably is 1. The index n in the compounds of general formula I preferably is in the range of from 2 to 4.

[0011] Urea derivatives of the general formula I are obtainable by reacting optionally sulfonic acid and/or carboxylic acid bearing diamines with isocyanates and diisocyanates. The amines are preferably aromatic, as for example diamino benzene, diamino naphthalene, and diamino stilbene, which may bear one or more additional carboxylic and/or, preferably, sulfonic acid groups. The isocyanates are preferably aromatic, as for example phenyl isocyanate, naphthyl isocyanate, and stilbenyl isocyanate. The diisocyanates are also preferably aromatic, as for example toluene diisocyanate (TDI), 4,4' methylene diphenyl diisocyanate (MDI), and phenyldisocyanate. Mixtures of the stated substances may also be used. Urethane derivatives of general formula I with B = O are obtainable by reacting a isocyanate group with an alcohol R(A)_l-OH; in such alcohols R preferably is selected from an ethyl group, a propyl group, a hexyl group, and mixtures thereof.

[0012] Preferably the average molecular weight (here and in the following: weight average) of the oligomers according to general formula I is in the range of from 1000 g/mol to 4000 g/mol, in particular in the range of from 1000 g/mol to 2000 g/mol.

[0013] Preferred urea derivatives according to general formula I are those of formula II,

in which Ph is a phenyl group optionally substituted by -SO₃M, n is 2, 3, or 4, the substituent -SO₃M is in ortho position, the substituent -CH₃ is in ortho position, and M is hydrogen or an alkali metal atom.

[0014] The compounds of the general formula I make a contribution to both of the above-mentioned aspects of colour consistency, i.e. they reduce both discolouration and fading, although the staining prevention effect, in particular when washing white textiles, is most pronounced. The present invention accordingly also provides the use of a compound defined above for avoiding the modification of the colour appearance of textiles when they are washed in aqueous solutions, in particular in surfactant-containing aqueous solutions. A modification of the colour appearance should not be taken to mean the difference between the dirty and the clean textile, but instead the difference between the clean textile in each case before and after the washing operation.

[0015] Accordingly, a second aspect of the present invention is a method for washing a textile in a surfactant-containing aqueous system, wherein the surfactant-containing aqueous system is prepared by dissolving a detergent which is free from a urea or urethane derivative defined above, and in which the textile comprises at its surface a urea or urethane derivative as defined above.

[0016] In such a washing method, it is possible to wash the textile that comprises at its surface a urea or urethane derivative as defined above, which may for example be dyed, white, or undyed, together with coloured or differently coloured textiles without said textile being stained. Preferably the textile that comprises at its surface the urea or urethane derivative is washed in the presence of a differently coloured textile that had been dyed with acid dyes, direct dyes, disperse dyes, reactive dyes, or mixtures thereof.

[0017] Said urea or urethane derivative may most conveniently have been applied to the textile surface by the method according to the invention, described in the first aspect of the invention. It may also have been applied to the textile surface in the final rinse step of a prior washing process, preferably by the use of a rinse-cycle fabric softener that comprises a urea or urethane derivative as defined above. Accordingly, still another aspect of the invention is a fabric softener composition, suitable to be used in the rinse step of a process employing a laundry washing machine, comprising a urea or urethane derivative as defined above.

[0018] A fabric softener composition according to the invention comprises, preferably, from 0.05 % by weight to 5 % by weight, in particular from 0.2 % by weight to 3 % by weight, of the urea or urethane derivative defined above; here and elsewhere in the text, "% by weight" or "wt.%" are relative to the entire product, unless stated differently.

[0019] It additionally comprises preferably a fabric softening compound. Especially preferred fabric softening compounds include fabric softening clays, monomeric and polymeric cationic compounds, and mixtures thereof.

[0020] A suitable fabric softening clay is for example a smectite clay. Preferred smectite clays include beidellite clays, hectorite clays, laponite clays, montmorillonite clays, nontronite clays, saponite clays, sauconite clays, and mixtures thereof. Montmorillonite clays are the preferred softening clays. Bentonites contain mainly montmorillonites and may be used as preferred source for the fabric softening clay. Suitable bentonites include, for example, those distributed by the brand names Laundrosil® by the company Süd-Chemie or by the trademark Detercal® by the company Laviosa. It is preferable for the fabric softener to contain a powdered bentonite.

[0021] Most suitable among cationic compounds are those having two hydrophobic residues, for example distearyldimethylammonium chloride, although because of its insufficient biodegradability the latter is increasingly being replaced by quaternary ammonium compounds that contain ester groups in their hydrophobic residues as defined break points for biodegradation. Preferred cationic compounds are of the following formulae





in which each group R¹ is selected mutually independently from C_1-6 alkyl, alkenyl, or hydroxyalkyl groups; each group R² is selected mutually independently from C_8-28 alkyl or alkenyl groups; R³ = R¹ or (CH₂)_n-T-R²; R⁴ = R¹ or R² or (CH₂)_n-T-R²; T = -CH₂-, -O-CO-, or -CO-O-, and n is an integer from 0 to 5, in particular 1 to 4.

[0022] Preferred "Esterquats" (with T = -O-CO-, or -CO-O-) of this kind having improved biodegradability are obtainable, for example, by esterifying mixtures of methyl diethanolamine and/or triethanolamine with fatty acids and then quaternizing the reaction products in known fashion with alkylating agents.

[0023] Suitable cationic polymers comprise in particular those summarized under the term "polyquaternium."

[0024] A fabric softener composition according to the invention comprises, preferably, from 1 % by weight to 20 % by weight, in particular from 3 % by weight to 8 % by weight, of fabric softening compound.

[0025] A fabric softener composition according to the invention preferably is liquid at room temperature and comprises water and/or water miscible solvents, preferably in amounts from 25 % by weight to 98 % by weight, in particular from 30 % by weight to 95 % by weight. It may comprise additional ingredients normally found in fabric softeners, such as for example fragrants, preservatives, and/or ironing aids.

[0026] A detergent for use in the method according to the second aspect of the invention is free from urea or urethane derivatives defined above and may comprise any ingredients usually found in laundry detergents. It may contain known dye transfer inhibitors, preferably in quantities of 0.1 wt.% to 2 wt.%, in particular 0.2 wt.% to 1 wt.%, said inhibitor being for example a polymer of vinylpyrrolidone, vinylimidazole, vinylpyridine N-oxide or a copolymer thereof. Usable compounds are not only the polyvinylpyrrolidones with a molecular weight of for example 15,000 g/mol to 50,000 g/mol but also the polyvinylpyrrolidones with a molecular weight of above 1,000,000 g/mol, in particular of 1,500,000 g/mol to 4,000,000 g/mol, N-vinylimidazole/N-vinylpyrrolidone copolymers, polyvinyl-oxazolidones, copolymers based on vinyl monomer and carboxamides. Preferred copolymers are those prepared from vinylpyrrolidone and vinylimidazole in molar ratios from 5:1 to 1:1 having an average molar mass in the range from 5,000 g/mol to 50,000 g/mol, in particular from 10,000 g/mol to 20,000 g/mol.

[0027] The detergents may in particular contain builder substances, surfactants, bleaching agents based on organic and/or inorganic peroxy compounds, bleaching activators, water-miscible organic solvents, enzymes, sequestering agents, electrolytes, pH regulators and further auxiliary materials, such as optical brighteners, greying inhibitors, foam regulators together with colorants and fragrances.

[0028] The detergents may contain surfactants, it being possible in particular to consider not only anionic surfactants, nonionic surfactants and mixtures thereof, but also cationic, zwitterionic and amphoteric surfactants.

[0029] Suitable nonionic surfactants are in particular alkylglycosides and ethoxylation and/or propoxylation products of alkylglycosides or linear or branched alcohols in each case having 12 to 18 C atoms in the alkyl moiety and 3 to 20, preferably 4 to 10, alkyl ether groups. Corresponding ethoxylation and/or propoxylation products of N-alkylamino, vicinal diols, fatty acid esters and fatty acid amides, which correspond with regard to the alkyl moiety to the stated long-chain alcohol derivatives, and of alkylphenols having 5 to 12 C atoms in the alkyl residue may furthermore be used.

[0030] Preferably used nonionic surfactants are alkoxylated, advantageously ethoxylated, in particular primary alcohols with preferably 8 to 18 C atoms and on average 1 to 12 mol of ethylene oxide (EO) per mol of alcohol, in which the alcohol residue may be linear or preferably methyl-branched in position 2 or may contain linear and methyl-branched residues in the mixture, as are conventionally present in oxo alcohol residues. In particular, however, alcohol ethoxylates with linear residues prepared from alcohols of natural origin with 12 to 18 C atoms, for example from coconut, palm, tallow fat or oleyl alcohol, and on average 2 to 8 EO per mol of alcohol are preferred. Preferred ethoxylated alcohols include, for example, C₁₂-C₁₄ alcohols with 3 EO or 4 EO, C₉-C₁₁ alcohols with 7 EO, C₁₃-C₁₅ alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C₁₂-C₁₈ alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C₁₂-C₁₄ alcohol with 3 EO and C₁₂-C₁₈ alcohol with 7 EO. The stated degrees of ethoxylation are statistical averages which, for a specific product, may be an integer or a fractional number. Preferred alcohol ethoxylates have a narrow homologue distribution (narrow range ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO may also be used. Examples of these are (tallow) fatty alcohols with 14 EO, 16 EO, 20 EO, 25 EO, 30 EO or 40 EO. In particular in products for use in machine washing, extremely low-foam compounds are conventionally used. These preferably include C₁₂-C₁₈ alkylpolyethylene glycol/polypropylene glycol ethers in each case having up to 8 mol of ethylene oxide and propylene oxide units per molecule. It is, however, also possible to use other nonionic surfactants which are known to be low-foaming, such as for example C₁₂-C₁₈-alkyl polyethylene glycol/polybutylene glycol ethers with in each case up to 8 mol ethylene oxide and butylene oxide units per molecule and end group-terminated alkylpolyalkylene glycol mixed ethers. Alkoxylated alcohols containing hydroxyl groups, or "hydroxy mixed ethers", are also particularly preferred. Alkylglycosides of the general formula RO(G)_x, in which R means a primary linear or methyl-branched aliphatic residue, in particular methyl-branched in position 2, with 8 to 22, preferably 12 to 18 C atoms, and G denotes a glycose unit with 5 or 6 C atoms, preferably glucose, may also be used as nonionic surfactants. The degree of oligomerization x, which indicates the distribution of monoglycosides and oligoglycosides, is any desired number and, being an analytically determined variable, may also assume fractional values between 1 and 10; x is preferably 1.2 to 1.4. Polyhydroxyfatty acid amides of the formulae

are likewise suitable, in which R¹ and R³ denote linear or branched alkyl or alkenyl residues with 7 to 12 carbon atoms, R² denotes hydrogen, an alkyl or hydroxyalkyl residue with 1 to 4 carbon atoms, R⁴ denotes a linear, branched or cyclic alkylene residue or an arylene residue with 2 to 8 carbon atoms, R⁵ denotes a linear, branched or cyclic alkyl residue or an aryl residue or an oxyalkyl residue with 1 to 8 carbon atoms, C₁-C₄ alkyl or phenyl residues being preferred, and [Z] denotes a linear or branched polyhydroxyalkyl residue with 3 to 10 carbon atoms, the alkyl chain of which is substituted with at least two hydroxyl groups, or its alkoxylated, preferably ethoxylated or propoxylated, derivatives. The polyhydroxyfatty acid amides, especially those of the second formula given above, may preferably be derived from reducing sugars with 5 or 6 carbon atoms. [Z] is also preferably obtained by reductive amination of a sugar such as glucose, fructose, maltose, lactose, galactose, mannose or xylose. The N-alkoxy- or N-aryloxy-substituted compounds may then be converted into the desired polyhydroxyfatty acid amides by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst. A further class of preferably used nonionic surfactants, which are used either as sole nonionic surfactant or in combination with other nonionic surfactants, in particular together with alkoxylated fatty alcohols and/or alkyl glycosides, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably with 1 to 4 carbon atoms in the alkyl chain, in particular fatty acid methyl esters. Nonionic surfactants of the amine oxide type, for example N-coconut alkyl-N,N-dimethylamine oxide and N-tallow alcohol-N,N-dihydroxyethylamine oxide, and the fatty acid alkanolamide type may also be suitable. The quantity of these nonionic surfactants preferably amounts to no more than that of the ethoxylated fatty alcohols, in particular no more than half the quantity thereof. "Gemini" surfactants may also be considered as further surfactants. These are generally taken to mean such compounds as have two hydrophilic groups per molecule. These groups are generally separated from one another by a "spacer". This spacer is generally a carbon chain which should be long enough for the hydrophilic groups to be sufficiently far apart that they can act mutually independently. Such surfactants are in general distinguished by an unusually low critical micelle concentration and the ability to bring about a great reduction in the surface tension of water. In exceptional cases, gemini surfactants include not only such "dimeric" surfactants, but also corresponding "trimeric" surfactants. Suitable gemini surfactants are, for example, sulfated hydroxy mixed ethers or dimer alcohol bis- and trimer alcohol tris-sulfates and -ether sulfates. End group-terminated dimeric and trimeric mixed ethers are in particular distinguished by their di- and multifunctionality. The stated end group-terminated surfactants accordingly exhibit good wetting characteristics and are low-foaming, such that they are in particular suitable for use in machine washing or cleaning processes. Gemini polyhydroxyfatty acid amides or poly-polyhydroxyfatty acid amides may, however, also be used.

[0031] Suitable anionic surfactants are in particular soaps and those which contain sulfate or sulfonate groups. Surfactants of the sulfonate type which may preferably be considered are C₉-C₁₃ alkyl benzene sulfonates, olefin sulfonates, i.e. mixtures of alkene and hydroxyalkane sulfonates and disulfonates, as are obtained, for example, from C₁₂-C₁₈ monoolefins with a terminal or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products. Alkane sulfonates which are obtained from C₁₂-C₁₈ alkanes for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization are also suitable. The esters of α-sulfofatty acids (ester sulfonates), for example the α-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids, which are produced by α-sulfonation of the methyl esters of fatty acids of vegetable and/or animal origin with 8 to 20 C atoms in the fatty acid molecule and subsequent neutralization to yield water-soluble mono salts, may also be considered suitable. The α-sulfonated esters of hydrogenated coconut, palm, palm kernel or tallow fatty acids are here preferred, it also being possible for sulfonation products of unsaturated fatty acids, for example oleic acid, also to be present in small quantities, preferably in quantities of no more than approx. 2 to 3 wt.%. Preferred α-sulfofatty acid alkyl esters are in particular those which comprise an alkyl chain with no more than 4 C atoms in the ester group, for example methyl ester, ethyl ester, propyl ester and butyl ester. The methyl esters of α-sulfofatty acids (MES), and the saponified disalts thereof too, are particularly advantageously used. Further suitable anionic surfactants are sulfated fatty acid glycerol esters, which are mono-, di- and triesters and mixtures thereof, as are obtained during production by esterification by a monoglycerol with 1 to 3 mol of fatty acid or on transesterification of triglycerides with 0.3 to 2 mol of glycerol. Preferred alk(en)yl sulfates are the alkali metal and in particular sodium salts of sulfuric acid semi-esters of C₁₂-C₁₈ fatty alcohols for example prepared from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl- or stearyl alcohol or C₁₀-C₂₀ oxo alcohols and those semi-esters of secondary alcohols of this chain length. Alk(en)yl sulfates of the stated chain length which contain a synthetic linear alkyl residue produced on a petrochemical basis and which exhibit degradation behaviour similar to that of the appropriate compounds based on fatty chemical raw materials are also preferred. In particular, C₁₂-C₁₆ alkyl sulfates and C₁₂-C₁₅ alkyl sulfates and C₁₄-C₁₅ alkyl sulfates are preferred because of their washing characteristics. The sulfuric acid monoesters of linear or branched C₇-C₂₁ alcohols ethoxylated with 1 to 6 mol of ethylene oxide are also suitable, such as 2-methyl-branched C₉-C₁₁ alcohols with on average 3.5 mol of ethylene oxide (EO) or C₁₂-C₁₈ fatty alcohols with 1 to 4 EO. Preferred anionic surfactants also include the salts of alkylsulfosuccinic acid, which are also known as sulfosuccinates or sulfosuccinic acid esters, and are the monoesters and/or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and in particular ethoxylated fatty alcohols. Preferred sulfosuccinates contain C₈ to C₁₈ fatty alcohol residues or mixtures thereof. Particularly preferred sulfosuccinates contain a fatty alcohol residue which is derived from ethoxylated fatty alcohols, which are in themselves nonionic surfactants. Sulfosuccinates whose fatty alcohol residues are derived from ethoxylated fatty alcohols with a narrow homologue distribution are here particularly preferred. It is likewise also possible to use alk(en)ylsuccinic acid with preferably 8 to 18 carbon atoms in the alk(en)yl chain or the salts thereof. Further anionic surfactants which may be considered are fatty acid derivatives of amino acids, for example of N-methyltaurine (taurides) and/or of N-methylglycine (sarcosides). Sarcosides or sarcosinates are particularly preferred here and most especially sarcosinates of higher and optionally mono- or polyunsaturated fatty acids such as oleyl sarcosinate. Further anionic surfactants which may in particular be considered are soaps. Saturated fatty acid soaps are in particular suitable, 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 or tallow fatty acids. Known alkenylsuccinic acid salts may also be used together with these soaps or as substitutes for soaps.

[0032] Anionic surfactants, including soaps, may be present in the form of the sodium, potassium or ammonium salts, and as soluble salts of organic bases, such as mono-, di- or triethanolamine. Anionic surfactants are preferably present in the form of the sodium or potassium salts thereof, in particular in the form of the sodium salts.

[0033] Surfactants are present in detergents in amounts of preferably 5 wt.% to 50 wt.%, in particular of 8 wt.% to 30 wt.%.

[0034] A detergent preferably contains at least one water-soluble and/or water-insoluble, organic and/or inorganic builder. The water-soluble organic builder substances include polycarboxylic acids, in particular citric acid and saccharic acids, monomeric and polymeric aminopolycarboxylic acids, in particular methylglycinediacetic acid, nitrilotriacetic acid and ethylenediaminetetraacetic acid and polyaspartic acid, polyphosphonic acids, in particular aminotris(methylenephosphonic acid), ethylenediaminetetrakis(methylenephosphonic acid) and 1-hydroxyethyl-1,1-diphosphonic acid, polymeric hydroxy compounds such as dextrin and polymeric (poly)carboxylic acids, in particular polycarboxylates obtainable by oxidation of polysaccharides or dextrins, polymeric acrylic acids, methacrylic acids, maleic acids and copolymers thereof, which may also contain small proportions of polymerizable substances without carboxylic acid functionality incorporated therein by polymerization. The relative molecular mass of the homopolymers of unsaturated carboxylic acids is in general between 3,000 and 200,000, that of the copolymers between 2,000 and 200,000, preferably 30,000 to 120,000, in each case relative to free acid. One particularly preferred acrylic acid/maleic acid copolymer has a relative molecular mass of 30,000 to 100,000. Conventional commercial products are for example Sokalan® CP 5, CP 10 and PA 30 from BASF. Suitable, albeit less preferred, compounds of this class are copolymers of acrylic acid or methacrylic acid with vinyl ethers, such as vinyl methyl ethers, vinyl esters, ethylene, propylene and styrene, the acid fraction of which amounts to at least 50 wt.%. Terpolymers containing as monomers two unsaturated acids and/or the salts thereof and, as third monomer, vinyl alcohol and/or an esterified vinyl alcohol or a carbohydrate may also be used as water-soluble organic builder substances. The first acidic monomer or the salt thereof is derived from a monoethylenically unsaturated C₃-C₈-carboxylic acid and preferably from a C₃-C₄-monocarboxylic acid, in particular from (meth)acrylic acid. The second acidic monomer or the salt thereof may be a derivative of a C₄-C₈-dicarboxylic acid, maleic acid being particularly preferred, and/or a derivative of an allylsulfonic acid which is substituted in position 2 with an alkyl or aryl residue. Such polymers generally have a relative molecular mass of between 1,000 and 200,000. Further preferred copolymers are those which comprise acrolein and acrylic acid/acrylic acid salts or vinyl acetate as monomers. The organic builder substances may be used, in particular for producing liquid products, in the form of aqueous solutions, preferably in the form of 30 to 50 wt.% aqueous solutions. All the stated acids are generally used in the form of the water-soluble salts, in particular the alkali metal salts, thereof.

[0035] Such organic builder substances may, if desired, be present in quantities of up to 40 wt.%, in particular of up to 25 wt.% and preferably of 1 wt.% to 8 wt.%. Quantities close to the stated upper limit are preferably used in pasty or liquid, in particular water-containing, detergents.

[0036] Water-soluble inorganic builder materials which may in particular be considered are alkali metal silicates, alkali metal carbonates and alkali metal phosphates, which may be present in the form of the alkaline, neutral or acidic sodium or potassium salts thereof. Examples of these are trisodium phosphate, tetrasodium diphosphate, disodium dihydrogendiphosphate, pentasodium triphosphate, "sodium hexametaphosphate", oligomeric trisodium phosphate with degrees of oligomerization of 5 to 1000, in particular 5 to 50, and the corresponding potassium salts or mixtures of sodium and potassium salts. Water-insoluble, water-dispersible inorganic builder materials which are used are in particular crystalline or amorphous alkali metal aluminosilicates, in quantities of up to 50 wt.%, preferably of no more than 40 wt.% and, in liquid products, in particular from 1 wt.% to 5 wt.%. Preferred such materials are crystalline sodium aluminosilicates of detergent grade, in particular zeolite A, P and optionally X, alone or in mixtures, for example in the form of a co-crystallization product of zeolites A and X (Vegobond® AX, a commercial product of Condea Augusta S.p.A.). Quantities close to the stated upper limit are preferably used in solid, particulate products. Suitable aluminosilicates in particular comprise no particles with a grain size of above 30 µm and preferably consist to an extent of at least 80 wt.% of particles with a size below 10 µm. Their calcium binding capacity, which may be determined as stated in German patent DE 24 12 837, is generally in the range from 100 to 200 mg of CaO per gram.

[0037] Suitable substitutes or partial substitutes for the stated aluminosilicates are crystalline alkali metal silicates, which may be present alone or mixed with amorphous silicates. The alkali metal silicates usable as builders preferably have a molar ratio of alkali metal oxide to SiO₂ of below 0.95, in particular of 1:1.1 to 1:12 and may be in amorphous or crystalline form. Preferred alkali metal silicates are sodium silicates, in particular amorphous sodium silicates, with a Na₂O:SiO₂ molar ratio of 1:2 to 1:2.8. Preferably used crystalline silicates, which may be present alone or mixed with amorphous silicates, are crystalline phyllosilicates of the general formula Na₂Si_xO_2x1 · y H₂O, in which x, or "modulus", is a number from 1.9 to 22, in particular 1.9 to 4 and y is a number from 0 to 33 and preferred values for x are 2, 3 or 4. Preferred crystalline phyllosilicates are those in which x in the stated general formula assumes the values 2 or 3.

[0038] In particular, both β- and δ-sodium disilicates (Na₂Si₂O₅ · y H₂O) are preferred. Virtually anhydrous crystalline alkali metal silicates of the above-stated general formula in which x means a number from 1.9 to 2.1, which are produced from amorphous alkali metal silicates, may be used. A crystalline sodium phyllosilicate with a modulus of 2 to 3, as may be produced from sand and soda, is used in a further preferred embodiment of detergents. Crystalline layered silicates of the above-stated formula are commercially available from Clariant GmbH under the trade name Na-SKS, for example Na-SKS-1 (Na₂Si₂₂O₄₅×H₂O, kenyaite), Na-SKS-2 (Na₂Si₁₄O₂₉×H₂O, magadiite), Na-SKS-3 (Na₂Si₈O₁₇×H₂O) or Na-SKS-4 (Na₂Si₄O₉×H₂O, makatite). Suitable representatives of these are primarily Na-SKS-5 (α-Na₂Si₂O₅), Na-SKS-7 (β-Na₂Si₂O₅, natrosilite), Na-SKS-9 (NaHSi₂O₅ · 3H₂O), Na-SKS-10 (NaHSi₂O₅ 3H₂O, kanemite), Na-SKS-11 (t-Na₂Si₂O₅) and Na-SKS-13 (NaHSi₂O₅), but in particular Na-SKS-6 (δ-Na₂Si₂O₅). In preferred detergents, a granular compound is used which is prepared from crystalline phyllosilicate and citrate, from crystalline phyllosilicate and above-stated (co)polymeric polycarboxylic acid, or from alkali metal silicate and alkali metal carbonate, as is commercially available for example under the name Nabion® 15.

[0039] Builder substances are preferably present in detergents in quantities of up to 75 wt.%, in particular of 5 wt.% to 50 wt.%.

[0040] Peroxy compounds suitable for use in detergents which may in particular be considered are organic peracids or peracid salts of organic acids, such as phthalimidopercaproic acid, perbenzoic acid or salts of diperdodecanedioic acid, hydrogen peroxide and inorganic salts which release hydrogen peroxide under washing conditions, which latter include perborate, percarbonate, persilicate and/or persulfate such as caroate. Where solid peroxy compounds are to be used, they may be used in the form of powders or granules, which may also in principle be encapsulated in known manner. If a detergent contains peroxy compounds, these are preferably present in quantities of up to 50 wt.%, in particular of 5 wt.% to 30 wt.%. It may be appropriate to add relatively small quantities of known bleaching agent stabilizers, such as for example phosphonates, borates or metaborates and metasilicates and magnesium salts such as magnesium sulfate.

[0041] Bleaching activators which may be used are compounds which, under perhydrolysis conditions, yield aliphatic peroxycarboxylic acids with preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and/or optionally substituted perbenzoic acid. Suitable substances are those which bear O- and/or N-acyl groups having the stated number of C atoms and/or optionally substituted benzoyl groups. Preferred substances are repeatedly acylated 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, 2,5-diacetoxy-2,5-dihydrofuran and enol esters and acetylated sorbitol and mannitol, or the mixtures thereof (SORMAN), acylated sugar derivatives, in particular pentaacetyl glucose (PAG), pentaacetyl fructose, tetraacetyl xylose and octaacetyl lactose and acetylated, optionally N-alkylated glucamine and gluconolactone, and/or N-acylated lactams, for example N-benzoylcaprolactam. Such bleaching activators may be present, in particular in the presence of the above-stated hydrogen peroxide-releasing bleaching agents, in a conventional quantity range, preferably in quantities of from 0.5 wt.% to 10 wt.%, in particular from 1 wt.% to 8wt.%, but are preferably entirely absent when percarboxylic acid is used as the sole bleaching agent.

[0042] In addition to or instead of the above listed conventional bleaching activators, sulfone imines and/or bleach-boosting transition metal salts or transition metal complexes may be present as "bleach catalysts".

[0043] Enzymes usable in the products which may be considered are those from the class of amylases, proteases, lipases, cutinases, pullulanases, hemicellulases, cellulases, oxidases, laccases and peroxidases and mixtures thereof. Particularly suitable enzymatic active ingredients are those obtained from fungi or bacteria, such as Bacillus subtilis, Bacillus licheniformis, Bacillus lentus, Streptomyces griseus, Humicola lanuginosa, Humicola insolens, Pseudomonas pseudoalcaligenes, Pseudomonas cepacia or Coprinus cinereus. The enzymes may be adsorbed onto carrier substances and/or be embedded in encapsulating substances in order to protect them from premature inactivation. They are present in detergents preferably in quantities of up to 5 wt.%, in particular of 0.2 wt.% to 4 wt.%. If the detergent contains protease, it preferably exhibits a proteolytic activity in the range from approx. 100 PU/g to approx. 10,000 PU/g, in particular 300 PU/g to 8000 PU/g. If two or more enzymes are to be used in the detergent, this may be achieved by incorporating the two or more separate enzymes or enzymes which are separately formulated in known manner or by two or more enzymes jointly formulated in a granular product.

[0044] Organic solvents other than water which may be used in detergents, or in fabric softening compositions according to the invention, in particular if those are in liquid or pasty form, include alcohols with 1 to 4 C atoms, in particular methanol, ethanol, isopropanol and tert.-butanol, diols with 2 to 4 C atoms, in particular ethylene glycol and propylene glycol, and mixtures thereof and the ethers derivable from the stated classes of compounds. Such water-miscible solvents are preferably present in quantities of no more than 30 wt.%, in particular of 6 wt.% to 20 wt.%.

[0045] In order to establish a desired pH value which is not automatically obtained by mixing the remaining components, detergents or the fabric softening compositions according to the invention may contain acids which are compatible with the system and are environmentally compatible, in particular citric acid, acetic acid, tartaric acid, malic acid, lactic acid, glycolic acid, succinic acid, glutaric acid and/or adipic acid, as well as mineral acids, in particular sulfuric acid, or bases, in particular ammonium or alkali metal hydroxides. Such pH regulators are present in detergents in quantities of preferably no more than 20 wt.%, in particular of 1.2 wt.% to 17 wt.%.

[0046] Greying inhibitors have the task of keeping dirt which has been dissolved away from the textile fibres suspended in the liquor. Water-soluble colloids of a mainly organic nature are suitable for this purpose, for example starch, size, gelatine, salts of ether carboxylic acids or ether sulfonic acids of starch or cellulose or salts of acidic sulfuric acid esters of cellulose or starch. Water-soluble polyamides containing acidic groups are also suitable for this purpose. Derivatives of starch other than those stated above, for example aldehyde starches, may further be used. Cellulose ethers, such as carboxymethylcellulose (Na salt), methylcellulose, hydroxyalkylcellulose and mixed ethers, such as methylhydroxyethylcellulose, methylhydroxypropylcellulose, methylcarboxymethylcellulose and mixtures thereof, are preferably used, for example in quantities of 0.1 to 5 wt.%, relative to the detergent.

[0047] Textile detergents may for example contain derivatives of diaminostilbene disulfonic acid or the alkali metal salts thereof as optical brighteners, although they preferably contain no optical brightener for use as a colour detergent. Suitable compounds are, for example, salts of 4,4'-bis(2-anilino-4-morpholino-1,3,5-triazinyl-6-amino)stilbene 2,2'-disulfonic acid or compounds of similar structure which, instead of the morpholino group, bear a diethanolamino group, a methylamino group, an anilino group or a 2-methoxyethylamino group. Brighteners of the substituted diphenylstyryl type may furthermore be present, for example the alkali metal salts of 4,4'-bis(2-sulfostyryl)-diphenyl, 4,4'-bis(4-chloro-3-sulfostyryl)-diphenol, or 4-(4-chlorostyryl)-4'-(2-sulfostyryl)-diphenyl. Mixtures of the above-stated optical brighteners may also be used.

[0048] Especially for use in machine washing, it may be advantageous to add conventional foam inhibitors to the products. Suitable foam inhibitors are, for example, soaps of natural or synthetic origin, which comprise an elevated proportion of C₁₈-C₂₄ fatty acids. Suitable non-surfactant foam inhibitors are, for example, organopolysiloxanes and mixtures thereof with microfine, optionally silanized silica as well as paraffins, waxes, microcrystalline waxes and mixtures thereof with silanized silica or bistearylethylenediamides. Mixtures of different foam inhibitors are also advantageously used, for example mixtures of silicones, paraffins or waxes. The foam inhibitors, in particular foam inhibitors containing silicone and/or paraffin, are preferably bound to a granular carrier substance which is soluble or dispersible in water. Mixtures of paraffins and bistearylethylenediamide are particularly preferred here.

[0049] The production of solid detergents presents no difficulties and may proceed in known manner, for example by spray drying or granulation, with enzymes and any further thermally sensitive constituents such as for example bleaching agents optionally subsequently being separately added. Products with an elevated bulk density, in particular in the range from 650 g/l to 950 g/l, may preferably be produced by a method comprising an extrusion step. A further preferred production process is using a granulation method.

[0050] Liquid or pasty detergents in the form of solutions containing conventional solvents are generally produced by simply mixing the ingredients, which may be introduced into an automatic mixer as an undissolved material or as a solution.

Examples

Example 1: Synthesis of urea derivative A

[0051] 2,5-Diaminobenzenesulfonic acid (28.2 g, 0.15 mol) was dissolved in water (400 ml) by the addition of sodium bicarbonate (12.6 g, 0.15 mol). Acetone (200 ml) was added followed by phenyl isocyanate (11.9 g, 0.10 mol) and the mixture was stirred for 16 h. The mixture was clarified through a glass fiber filter to remove a small amount of insoluble white solid and gave a clear pale yellow solution. Further acetone (200 ml) was added followed by tolylene-2,4-diisocyanate (15.7 g, 0.09 mol) and the mixture was stirred for 24 h. The mixture was again filtered to remove insoluble solids and the filtrate was concentrated in vacuo to leave a viscous brown liquid.

Example 2: Dye transfer inhibition

[0052] 5 g/l of otherwise identical liquid aqueous detergents comprising compound A produced according to the preceding example 1 in the amounts (% by weight; different amounts were compensated by the content of water) given in the following table were added to water of hardness 16 °dH. White textiles made of polyamide were treated therein for 30 minutes at 60 °C and dried thereafter. The white textiles made of polyamide (PA, acceptor) so treated and a poorly dyed textile (bleeder) were put into a wash liquor comprising 5 g/l of the liquid detergent (LD) without dye transfer inhibitor and washed therein at 60°C for 30 minutes, using water of hardness 16 °dH. Staining of the white textile was measured according to ISO 105 A04 and rated on a scale from 1 (= severely stained) to 5 (= no discernible staining), as also given in the following table. As comparatives the results of the use of the wash liquor comprising LD on the textile pre-treated with the wash liquor comprising LD instead of the liquor comprising the compound according to the invention, and of the use of the wash liquor comprising LD on the untreated textile (-) are also given in the table.

Dye Transfer Inhibition		SSR value, after pre-treatment with
acceptor	Bleeder with	-	LD	1 % A	3 times 1 % A	3 % A	5 % A
PA	Acid blue 113	1.5	1.4	2.0	3.6	3.3	3.6
	Direct black 22	2.6	2.4	3.3	3.6	3.6	3.6
	Direct orange 39	2.7	2.7	4.2	4.7	4.5	4.7
	Disperse blue 79	2.7	2.7	3.2	4.1	3.9	4.1

Claims

1. Method for applying a urea or urethane derivative of the general formula I,

         R(A)_l-B-C(O)-NH-Ar(A)_m-NH[-C(O)-NH-L-NH-C(O)-NH-Ar(A)_o-NH]_n-C(O)-B-R(A)_p     (I)

in which

R denotes H, Ar, or a linear, branched, or cyclic, saturated or once or several times ethylenically unsaturated hydrocarbon group with 1 to 12 carbon atoms,

Ar denotes an aromatic group, a stilbene group, both optionally substituted by up to 3 substituents selected from alkyl groups with 1 to 4 carbon atoms, NH₂ groups, and their mixtures, and mixtures thereof,

B denotes O or NH,

A denotes -SO₃M or -CO₂M,

M denotes H or an alkali metal atom,

L denotes an arylene group, optionally substituted by up to 3 alkyl substituents with 1 to 5 carbon atoms, or an alkylene group with 2 to 4 carbon atoms,

l, m, o, and p irrespective of each other denote 0, 1, 2 or 3, and l+m+o+p ≥ 1

n denotes a number of from 2 to 6,

onto the surface of a textile, by contacting said textile with an amount of 0.04 % by weight to 4.0 % by weight (% by weight of the urea derivative in relation to the weight of the textile) of said urea derivative in an aqueous system.

2. Method according to claim 1, characterized in that the concentration of the urea or urethane derivative of formula I in the aqueous system is in the range of from 5 ppm by weight to 500 ppm by weight (ppm by weight of the urea derivative in relation to the weight of the aqueous system, without textile), preferably from 10 ppm by weight to 100 ppm by weight.

3. Method according to claim 1 or 2, characterized in that the time the aqueous system comprising the urea or urethane derivative of formula I stays in contact with the textile is in the range of 1 minutes to 30 minutes, preferably 3 minutes to 10 minutes.

4. Method according to any of claims 1 to 3, characterized in that the temperature of the aqueous system comprising the urea derivative of formula I is kept in the range of from 5 °C to 90 °C, preferably from 10 °C to 60 °C.

5. Method for washing a textile in a surfactant-containing aqueous system, wherein the surfactant-containing aqueous system is prepared by dissolving a detergent which is free from a urea or urethane derivative of the general formula I,

         R(A)_l-B-C(O)-NH-Ar(A)_m-NH[-C(O)-NH-L-NH-C(O)-NH-Ar(A)_o-NH]_n-C(O)-B-R(A)_p     (I)

in which

R denotes H, Ar, or a linear, branched, or cyclic, saturated or once or several times ethylenically unsaturated hydrocarbon group with 1 to 12 carbon atoms,

Ar denotes an aromatic group, a stilbene group, both optionally substituted by up to 3 substituents selected from alkyl groups with 1 to 4 carbon atoms, NH₂ groups, and their mixtures, and mixtures thereof,

B denotes O or NH,

A denotes -SO₃M or -CO₂M,

M denotes H or an alkali metal atom,

L denotes an arylene group, optionally substituted by up to 3 alkyl substituents with 1 to 5 carbon atoms, or an alkylene group with 2 to 4 carbon atoms,

l, m, o, and p irrespective of each other denote 0, 1, 2 or 3, and l+m+o+p ≥ 1

n denotes a number of from 2 to 6,

in water, and in which the textile comprises at its surface a urea or urethane derivative of said formula (I).

6. Method according to claim 5, characterized in that the urea derivative of said formula (I) was applied to the textile surface by a method according to any of claims 1 to 4.

7. Method according to claim 5 or 6, characterized in that the textile that comprises at its surface a urea or urethane derivative is washed in the presence of a differently coloured textile that had been dyed with acid dyes, direct dyes, disperse dyes, reactive dyes, or mixtures thereof.

8. Method according to any of claims 1 to 7, characterized in that the textile that comprises at its surface a urea or urethane derivative is made of or comprises polyamide.

9. Method according to any of claims 1 to 8, characterized in that the urea derivative of general formula I is of formula II,

in which Ph is a phenyl group optionally substituted by -SO₃M, n is 2, 3, or 4, the substituent - SO₃M is in ortho position, and the substituent -CH₃ is in ortho position, and M is hydrogen or an alkali metal atom.

10. Fabric softener composition, comprising a urea or urethane derivative of the general formula I,

         R(A)_l-B-C(O)-NH-Ar(A)_m-NH[-C(O)-NH-L-NH-C(O)-NH-Ar(A)_o-NH]_n-C(O)-B-R(A)_p     (I)

in which

R denotes H, Ar, or a linear, branched, or cyclic, saturated or once or several times ethylenically unsaturated hydrocarbon group with 1 to 12 carbon atoms,

Ar denotes an aromatic group, a stilbene group, both optionally substituted by up to 3 substituents selected from alkyl groups with 1 to 4 carbon atoms, NH₂ groups, and their mixtures, and mixtures thereof,

B denotes O or NH,

A denotes -SO₃M or -CO₂M,

M denotes H or an alkali metal atom,

L denotes an arylene group, optionally substituted by up to 3 alkyl substituents with 1 to 5 carbon atoms, or an alkylene group with 2 to 4 carbon atoms,

l, m, o, and p irrespective of each other denote 0, 1, 2 or 3, and l+m+o+p ≥ 1

n denotes a number of from 2 to 6.

11. Fabric softener composition according to claim 10, characterized in that it comprises 0.05 % by weight to 5 % by weight, in particular 0.2 % by weight to 3 % by weight, of the urea or urethane derivative.

12. Fabric softener composition according to claim 10 or 11, characterized in that it additionally comprises a fabric softening compound, preferably in amounts of from 1 % by weight to 20 % by weight, in particular from 3 % by weight to 8 % by weight.