MXPA06012017A - Amphoteric fluorescent whitening agents in detergent formulations - Google Patents

Abstract

The present invention relates to compositions comprising specific amphoteric fluorescent whitening agents (FWA) and dyefixing, dye transfer inhibition and/or fabric softening agents, formulations for the treatment of textiles comprising such compositions, and the use of such compositions and/or formulations.

Description

ANTI-THERAPEUTIC FLUORESCENT BLEACHING AGENTS IN DETERGENT FORMULATIONS The present invention relates to compositions comprising specific amphoteric fluorescent whitening agents (FWA) and dye fixing agents, dye transfer inhibition and / or fabric softening, formulations for treatment of textiles comprising these compositions, and the use of these compositions and / or formulations. FWA, also amphoteric FWA, are often used in compositions for the treatment of textiles. These compositions, for example, are described in EP 850934. Compositions for the treatment of textiles, often comprise coloring fixing agents, inhibition of dye transfer and / or fabric softening. The disadvantage of these dye fixing agents, of dye transfer inhibition and / or fabric softening is that they drastically reduce the efficiency of the FWA. It has now been found that the use of specific amphoteric FWAs does not show this drastic efficiency loss when used in combination with dye fixing agents, dye transfer inhibition and / or fabric softening.

Therefore, the present invention relates to a composition (Cl) comprising (i) at least one compound of the formula (1) where A means the portion of the formula (2) or (3) wherein Ri represents hydrogen; C? -C? 2 straight-chain alkyl, which may be substituted by one or two groups-OH, -OC? -C4alkyl, -NH2, -NHC! -C4alkyl, -N (C? -C4alkyl) 2, -N- pyrrolidino, -N-piperidino, -N-morpholino or -N + (C? -C4alkyl) 3; branched C3-C? 2alkyl groups, which may be interrupted by one or two heteroatoms and which may be unsubstituted or substituted by one or two -OH, -OC? -C4alkyl, -NH2, -NHC? -C4alkyl, -N groups (C? -C4alkyl) 2, -N-pyrrolidino, -N-piperidino, -N-morpholino or -N + (C? -C4alkyl) 3; and R2 represents C? -C4alkyl; C2-C4hydroxyalkyl; -CH2CONH2; -CH2COOH or -CH2COO d-C4alkyl or A represents a group of the formulas wherein R3, R and R5 each independently represent hydrogen; C? -C4alkyl; C2-C4hydroxyalkyl; the group -X '-NR6R7 or the group -X' -N + RS. R6R, wherein at least one of the substituents R4 and / or R5 represents -X1-NR6R7 or -X '-N + R6' R6R7, X and X1 each independently of each other, represent a C2-C8 straight-chain alkylene, which is unsubstituted or substituted by one or two -OH; or a branched C3-C8alkylene chain, which is unsubstituted or substituted by one or two -OH; -C (= 0) -; or a cycloaliphatic ring of 5 or 6 members, Rβ / - Rd 'and R7 each independently of each other, represent hydrogen; C? -C4alkyl; or together with the nitrogen atom to which they are bound, they complete a pyrrolidino, piperidino or morpholino ring and R2 is as previously defined or A is NR8R9, wherein R8 and Rg each independently of each other, represent hydrogen; C? -C8alkyl, wherein the alkyl group may be substituted by C? -C4alkoxy, amino, mono- or di-C? -C4alkylamino or tri-C? -C4alkylammonium; C2-C4-hydroxyalkyl, wherein the alkyl group may be substituted by C? -C4alkoxy, amino, mono- or di-Ci-Calkylamino or tri- C1-C4alkylammonium; C? -C4alco iC? ~ C4alkyl; phenyl, which is unsubstituted or substituted by halogen, C? ~ C4alkoxy, C1-C4alkyl, COOM, S03M or sulfonamido, ody 9r together with the nitrogen atom to which they are connected, complete a morpholino, piperidino or pyrrolidino ring, or represents halogen, B and C independently of each other and A have the same meanings as defined for A, and D independently of A has the same meanings as defined for A except that D is not halogen, and M is hydrogen; an alkali metal atom; ammonium or a cation formed of an amine; or its quaternized form, and (ii) at least one colorant fixing agent, inhibition of dye transfer and / or fabric softening.

Preferred embodiments of the present invention are compositions (C2) which comprise as component (i) at least one compound of the formula (8) wherein each B is the same or different and each is -NH-ZN (Ra) (Rb) or -N- [ZN (Ra) (Rb)] 2 wherein Z is C2-C14alkylene or optionally substituted arylene, Ra and Rb are the same or different and each is C? -C12alkyl, or Ra and Rb, together with the nitrogen atom to which they are connected each form a morpholino, piperidino or piperazino ring; and A is NH2; NH (C? -Calkyl); N (C? -C4alkyl) 2; N (CH2CH2OH) 2; 0-C? -C4alkyl; where M is hydrogen; an alkali metal atom; ammonium or a cation formed of an amine; or its quaternized form, and (ii) at least one colorant fixing agent, inhibition of dye transfer and / or fabric softening. Modalities Further preferred embodiments of the present invention are compositions (C3) which comprise as component (i) at least one compound of the formula (9) where each A independently of each other, represents the portion wherein Ri represents hydrogen; a straight chain C? -C? 2alkyl group or branched chain C3-C? 2alkyl, these C2-C? 2alkyl and C3-C? 2alkyl groups, respectively, may be interrupted by one or two heteroatoms and is unsubstituted or substituted by one or two groups -OH, -OC? -C4alkyl, -NH2, -NHC1-C4alkyl, -N (C? -C4alkyl) 2, -N-pyrrolidino, -N-piperidino, -N-morpholino or -N + (C? -C4alkyl) 3 and R2 represents C1-C4alkyl; C2-C4hydroxyalkyl; -CH2C0NH2; -CH2C00H or -CH2C00 C? -C4alkyl or alternatively, each A independently from each other, represents a group of the formula iM -X R4 1 I ^ 5 (7), Hg Rs or Rj R2 where R3, R4 and R5 each independently represent hydrogen; C1-C4alkyl; C2-C4hydroxy alkyl; the group -X '-NR6R7 or the group -X' - N + R5.R6R7, wherein at least one of the substituents R4 and / or R5 represents -X 1 -NR6R7 or -X '-N + R6.R6R7, X and X 'each independently of one another, represent a straight chain C2-C8alkylene group or branched chain C3-C8alkylene, which is unsubstituted or substituted by one or two groups -OH or -C (= 0) -, Re , Re1 and R7 each, independently of each other, represents hydrogen; C? -C4alkyl or together with the nitrogen atom to which they are bound, complete a pyrrolidino, piperidino or morpholino ring, and R2 is as previously defined, and each B independently of each other, either is defined as for A or represents halogen; -NH2; C? -C4monoalkyl or dialkylamino, the alkyl groups are unsubstituted or substituted by C? -C4alkoxy, amino, mono- or di- C? ~ Cgalkylamino or tri-C? -C4alkylammonium; C2-C4hydroxyalkylamino; C2-C4di (hydroxyalkyl) amino; aniline; an aniline monosulfonic acid or sulfonamide residue or a saturated 5- or 6-membered heterocyclic ring, and (ii) at least one dye binding agent, dye transfer inhibition inhibitor and / or fabric softening. . Additional preferred embodiments of the present invention are compositions (C4) which comprise as component (i) at least one compound of formulas (10), (11), and / or (12) where E * represents a group of the formula where A 'represents X-Y-NR3R4 and C is -NRaR2 and F * represents a group of the formula wherein D 'represents -NR5R6 and B' represents -X? -Y? -NR7R8, whereby X and Xi each independently of each other, represent -O- or -NH-, Y and Yi each independently of each other, they represent a straight chain C2-C8alkylene group or branched chain C3-C8alkylene group, which may be interrupted by one or two nitrogen, oxygen or sulfur atoms or represents a 5- or 6-membered cycloaliphatic ring, preferably cyclohexyl, Ri , R2, 5 and Re each independently represent hydrogen; C? -C8 alkyl; C2- C4hydroxyalkyl; C? -Calco i C? ~ C4alcoxy; phenyl, which is unsubstituted or substituted by halogen, C? -C4alkoxy, Ci- C4alkyl or sulphonamido, or Ri and R2 and / or R5 and R6, together with the nitrogen atom to which they are connected, complete a morpholino, piperidino ring or pyrrolidino, R3, R, R7 and R8 each independently represent hydrogen; C? -C4alkyl; C2-Chydroxyalkyl or R3 and R4 and / or R7 and R8, together with the nitrogen atom to which they are connected, complete a morpholino, piperidino or pyrrolidino ring and M represents hydrogen; an alkaline or alkaline earth metal; ammonium or alkyl ammonium, and (ii) at least one dye fixing agent, color transfer inhibition inhibitor and / or fabric softening. The compounds of the formula (1) known for example from WO 03/078406, EP 413926 and EP 850943 can be produced according to known processes. As component (ii) any convenient fixative agent of. dye, inhibition of dye transfer and / or softening of fabrics can be used, for example inhibition of polymeric dye transfer and / or polymeric dye fixing agents. Preferred polymeric dye transfer inhibiting agents are polyvinylpyrrolidones, polyvinylimidazole, poly inylpyrrolidone / polyvinylimidazole copolymer or polyvinylpyridine-N-oxides which may have been modified by the incorporation of anionic or cationic substituents, especially those having a molecular weight in the range from 5'000 to 60'000, more especially from 5'000 to 50'000. These polymers are usually used in an amount of 0.01 to 5% by weight (% by weight), preferably 0.05 to 5% by weight, especially 0.01 to 2% by weight, based on the total weight of the detergent. Preferred dye fixatives are those given in WO 02/02865 (see especially page 1, last paragraph of page 2, first paragraph) and WO 03/057815 (see especially page 2, last 2 paragraphs and page 3, first paragraph) . Another preferred dye fixing agent based on basic polycondensation products of an amine of the formula (13) And a cyanamide, these polycondensation products are completely or partially neutralized with an inorganic or organic acid, R9, Ro, Rn and R12 each independently of the others is hydrogen or alkyl which are unsubstituted or substituted by amino, hydroxy, cyano or by C? -C4alkoxy and G is alkylene optionally substituted or interrupted by one or more hetero atoms. G in the formula (1) is preferably C2-C2alkylene optionally interrupted by -O-, -S-, - NH- or by -N (C? -C4alkyl) - and / or substituted by hydroxy, in especially C2 ~ C2alkylene interrupted one or more times by -NH-.

R_ > / io / Rn and R12 preferably each independently of the others are hydrogen or Ca-C4alkyl. Examples of suitable compounds of the formula (13) are 1, -butanediamine, 1,6-hexanediamine, dipropylenetriamine, N- (2-aminoethyl) -1,3-propanediamine, N, N-bis (2-aminopropyl) methyl amine, polyethylene imines and polyethylene polyamines such as diethylenetriamine, triethylenetetramine, tetraethylenepentamine and pentamethyleneteamine. Preferred compounds of the formula (13) are polyethylene polyamines and among those, especially diethylenetrinamine. The number of repeating monomer units of the formula (13) in the basic polycondensation products is, for example, from 4 to 100, in particular from 4 to 50. Suitable cyanamides are, for example, cyanamide, dicyandiamide, guanidine and biguanidine. Preference is given to dicyandiamide. The aforementioned dye fixing agents are known, for example, from EP-A-692 511, WO 99/64550, EP-A-1303665, WO 03/057815 and WO 01/74982 and can be obtained by the method described therein. The softening compounds may be any common softening compound as well as mixtures of fabric softening compounds.

Fabric softening components, especially hydrocarbon fabric softening components, suitable for use herein, are chosen from the following classes of compounds: (i) cationic quaternary ammonium salts. The counter ion of these cationic quaternary ammonium salts can be a halide, such as chloride or bromide, methyl sulfate or other ions well known in the literature. Preferably, the counter ion is methyl sulfate or any alkyl sulfate or any halide, methyl sulfate is most preferred for the articles added to the dryer of the present invention. Examples of cationic quaternary ammonium salts include but are not limited to: (1) Acyclic quaternary ammonium salts having at least two C8-C30-, preferably C? 2-C22-alkyl or alkenyl chains, such as: Disodbodimethyl ammonium, methylsulfate di (hydrogenated tallow) dimethyl ammonium, di methylchloride (hydrogenated tallow) dimethyl ammonium, distearyldimethyl ammonium methylsulfate, dicocodimethyl ammonium methylsulfate and the like. It is especially preferred if the fabric softening compound is a water-soluble quaternary ammonium material comprising a compound having two C ?2-C18-alkyl or alkenyl groups connected to the molecule by at least one ester linkage. It is more preferred if the quaternary ammonium material has two ester linkages present. An ester-bound quaternary ammonium material especially preferred for use in the invention can be represented by the formula: wherein each R13 group is independently chosen from Ci to C4 alkyl, hydroxyalkyl or C2-C4-alkenyl groups; T is ether -O-C (O) - or -C (0) -0-, and wherein each R14 group is independently chosen from C8-C8-alkyl or alkenyl groups; and e is an integer from 0 to 5. A second preferred type of quaternary ammonium material can be represented by the formula: 0-G. { 0) -RM (R13) 3N - (CH2) -CH T I CHz-0-C. { 0) -Rt4 wherein R13, e and R14 are as defined above. (2) Cyclic quaternary ammonium salts of the imidazolinium type such as metal sulphate di (hydrogenated tallow) dimethyl imidazolinium, methyl sulfate of 1-ethylene-bis (2-tallow-1-methyl) imidazolinium and the like; (3) Quaternary ammonium diamido salts such as: methyl bis (hydrogenated tallow amidoethyl) -2-hydroxyethyl ammonium methylsulfate methyl methylsulfate (tallow amidoethyl) -2-hydroxypropyl ammonium and the like; (4) Biodegradable quaternary ammonium salts such as N, N-di (sebooyl-oxy-ethyl) -N, N-dimethyl ammonium methyl sulfate and N, N-di (sebooyl-oxy-ethyl) -N methyl sulfate , N-dimethyl ammonium. Biodegradable quaternary ammonium salts are described, for example, in U.S. Pat. Nos. 4,137,180, 4,767,547 and 4,789,491 incorporated herein by reference. Preferred biodegradable quaternary ammonium salts include the biodegradable cationic diester compounds as described in US Pat. No. 4,137,180, incorporated herein by reference. (ii) Tertiary fatty amines having at least one and preferably two C8 to C30 chains, preferably C? 2 to C22 alkyl. Examples include hardened tallow-di-methylamine amines and cyclics such as 1- (hydrogenated tallow) amidoethyl-2- (hydrogenated tallow) imidazoline. Cyclic amines, which can be used for the present compositions, are described in US Pat. No. 4,806,255 here incorporated by reference. (iii) Carboxylic acids having 8 to 30 carbon atoms and one carboxylic group per molecule. The alkyl portion has 8 to 30, preferably 12 to 22, carbon atoms. The alkyl portion may be linear or branched, saturated or unsaturated, with preferred linear saturated alkyl. Stearic acid is preferably a fatty acid for use in the present composition. Examples of these carboxylic acids are commercial grades of stearic acid and palmitic acid and their mixtures, which may contain small amounts of other acids. (iv) Esters of polyhydric alcohols such as sorbitan esters or glycerol stearate. Sorbitan esters are the condensation products of sorbitol or iso-sorbitol with fatty acids such as stearic acid. Sorbitan preferred esters are monoalkyl. A common example of sorbitan ester is SPANMR 60 (ICI) which is a mixture of sorbitan e-isosorburo stearates. (v) Fatty alcohols, ethoxylated fatty alcohols, alkylphenols, ethoxylated alkylphenols, ethoxylated fatty amines, ethoxylated monoglycerides and ethoxylated diglycerides. (vi) Mineral oils, and polyols such as polyethylene glycol.

These softeners are described more definitively in U.S. Pat. No. 4,134,838 the description of which is incorporated herein by reference. Preferred fabric softeners for use herein are acyclic quaternary ammonium salts. Mixtures of the fabric softeners mentioned above can also be used. The compositions described above (Cl), (C2), (C3) or (C4) may be in solid or liquid form. Preferably the compositions are in solid form. A further embodiment of the present invention relates to detergent formulations (DF1) comprising (a) at least one composition (Cl), (C2), (C3) or (C4), (b) at least one surfactant and ( c) optionally at least one additional auxiliary. The surfactant (b) can be anionic or non-ionic. Examples of suitable anionic surfactants are sulfate, sulfonate or carboxylate surfactant or a mixture of these surfactants. Preferred sulfates are those having from 12 to 22 carbon atoms in the alkyl radical, when appropriate in combination with alkyl ethoxy sulfates having from 10 to 20 carbon atoms in the alkyl radical. Preferred sulfonates are, for example, alkylbenzenesulfonates having from 9 to 20 carbon atoms in the alkyl radical and / or alkylnaphthalenesulfonates having from 6 to 20 carbon atoms in the alkyl radical. The cation in the anionic surfactant is preferably an alkali metal cation, especially sodium. Preferred carboxylates are alkali metal sarcosinates of the formula R 5 -CO-N (R 5) -CH 2 COOM ?, wherein. R15 is alkyl or alkenyl having 8 to 20 carbons in the alkyl or alkenyl radical, R16 is C? -C4alkyl and Mi is an alkali metal. Examples of suitable nonionic surfactants are condensation products of 3 to 8 moles of ethylene oxide with 1 mole of primary alcohol containing from 9 to 20 carbon atoms. Additional auxiliaries (c) for the examples are reinforcing substances; peroxides; slurry suspension agents, for example sodium carboxymethyl cellulose; pH regulators, for example alkali metal or alkaline earth metal silicates; foam regulators, for example soap; salts for regulating the properties of spray drying and granulation, for example sodium sulfate; fragrances; . antistatic agents; fabric conditioners; enzymes such as amylase, cellulase and protease; bleaching agents; pigments and / or toning agents. In addition, the washing agent compositions according to the invention may also comprise perborate activators so named, such as for example -TAED or TAGU. Preference is given to TAED, which is preferably used in an amount of 0.05 to 5% by weight, especially 0.2 to 1.7% by weight, based on the total weight of the detergent formulation. Suitable reinforcing substances are, for example, alkali metal phosphates, in particular tripolyphosphates, carbonates or hydrogen carbonates, in particular sodium salts, silicates, aluminum silicates, polycarboxylates, polycarboxylic acids, organic phosphonates, aminoalkylene poly (alkylene phosphonates) or mixtures thereof. of those compounds. Especially suitable silicate are sodium salts of crystalline silicates having layered structures of the formula NaHSit02t +? PH20 or a2Sit? 2t +? _ PH2 ?, where t is a number from 1.9 to 4 and p is a number from 0 to 20. Among the aluminum silicates, preference is given to those which are commercially obtained by the names zeolite A, B, X and HS, and also to mixtures comprising two or more of these components. Among the polycarboxylates, preference is given to polyhydroxycarboxylates, especially citrates and acrylates and also their copolymers with maleic anhydride. Preferred polycarboxylic acids are nitrilotriacetic acid, ethylenediaminetetraacetic acid and ethylenediamine disuccinate either in racemic form or in the enantiomerically pure S, S form. Phosphonates and aminoalkylene poly (alkylene phosphonates) which are particularly suitable are alkali metal salts of 1-hydroxyethane-1,1-diphosphonic acid, nitrile-tris (methylene phosphonic acid), ethylene diamine tetra-methylene phosphonic acid and diethylenetriamine pentamethylene phosphonic acid. They come into consideration as the peroxide component, for example the organic and inorganic peroxides known in the literature and commercially available whitening textiles at conventional washing temperatures, for example from 10 to 95 degrees C. The peroxides. organic compounds are, for example, mono- or poly-peroxides, in particular organic peroxides or their salts, such as phthalimidoperoxycaproic acid, peroxybenzoic acid, diperoxydodecanoic diacid, diperoxynonanoic acid, diperoxydecanoic acid, diperoxyphthalic acid or their salts. Preferably, however, inorganic peroxides are used, such as, for example, persulfates, perborates, percarbonates and / or persilicates. It will be understood that mixtures of inorganic and / or organic peroxides can also be employed. The peroxides may be in a variety of crystalline forms and have different water contents, and may also be used in conjunction with other organic or inorganic compounds in order to improve their storage stability. The peroxides are added to the washing agent composition, preferably when mixing the components, for example using a dosing system with spindle and / or fluidized bed mixer. Preferred enzymes are cellulases, proteases, amylases and lipases. Preferred enzymes are cellulases and proteases, especially proteases. Celluloses are enzymes that act on cellulose and its derivatives and the threads hydrolyze into glucose, cellobiose, cellooligosaccharides. Cellulases eliminate dirt and have the effect of mitigating roughness or roughness to the touch. Examples of enzymes to be used include but are by no means limited to the following: proteases as given in US-B-6, 242, 405, column 14, lines 21 to 32; lipases as given in US-B-6, 242, 405, column 14, lines 33 to 46; amylases as given in US-B-6, 242, 405, column 14, lines 47 to 56; and cellulases as given in US-B-6, 242, 405, column 14, lines 57 to 64. Enzymes may optionally be present in the detergent compositions. When used, the enzymes are usually present in an amount of 0.01-5% by weight, preferably 0.05-5% by weight and more preferably 0.1-4% by weight, based on the total weight of the detergent composition. A preferred detergent formulation (DF2) consists of (i) from 0.01 to 10% by weight, preferably 0.01 to 5% by weight, based on the total weight of the detergent formulation, of at least one composition (Cl), (C2), (C3) or (C4) and ii) from 5 to 70% by weight, based on the total weight of the detergent formulation, of at least one anionic surfactant from the group consisting of alkylbenzene sulfonates having from 9 to 20 carbon atoms in the alkyl radical; alkylnaphthalenesulfonates having from 6 to 20 carbon atoms in the alkyl radical; and alkali metal sarcosinates of the formula R15-C0-N (R16) -CH2COOM ?, wherein R15 is alkyl or alkenyl having from 8 to 20 carbon atoms in the alkyl or alkenyl radical, R16 is C? -C4alkyl and -Mi is an alkali metal and / or at least one nonionic surfactant of the group consisting of condensation products of 3 to 8 moles of ethylene oxide with 1 mole of primary alcohol containing from 9 to 20 carbon atoms, iiia) of 5 to 60% by weight, based on the total weight of the detergent formulation, of a reinforcing substance, of the group consisting of alkali metal phosphates; carbonates; hydrogen carbonates; silicates; alumino silicates; polycarboxylates; polycarboxylic acids; organic phosphonates and aminoalkylene poly (alkylene phosphonates), and iiib) from 0 to 30% by weight, based on the total weight of the detergent formulation, of a peroxide from the group consisting of organic mono- or poly-peroxides; organic perishes and their salts; persulphates; perborates; percarbonates and persilicates, iiic) from 0 to 60% by weight, based on the total weight of the detergent formulation, of additional additives from the group consisting of optical brighteners; slurry suspension agents; pH regulators; foam regulators; salts to regulate the application properties by spraying and granulation; fragrances; antistatic agents; fabric conditioners; enzymes; bleaching agents; pigments; toning agents; and perborate activators, and i) from 0 to 5% by weight, based on the total weight of the detergent formulation, water. The detergent formulations (DF1) and (DF2) according to the invention can be in solid, liquid, gel or paste-like form, for example in the form of a liquid, non-aqueous washing agent composition containing no more than 5% by weight, preferably 0 to 1% by weight of, water and based on a suspension of a reinforcing substance in a non-ionic surfactant, for example as described in GB-A-2 158 454 '. The detergent formulations (DF1) and (DF2) according to the invention can also be in the form of (super) compact powders or powders, in the form of single or multi-layer tablets (tabs), in the form of bars of washing agent, washing agent blocks, washing agent sheets, washing agent pastes or washing agent gels, or in the form of powders, pastes, gels or liquids used in capsules or in bags (sachets) . A further embodiment of the present invention relates to the use of the compositions (Cl), (C2), (C3) and (C4) or the formulations (DF1), (DF2) for the treatment of textiles. This detergent treatment of textiles can be conducted as a domestic treatment in normal washing machines. The treated textile fibers can be natural or synthetic fibers or their mixtures. Examples of natural fibers include vegetable fibers such as cotton, viscose, linen, rayon, preferably cotton and animal fibers such as wool, camel hair (mohair), cashmere, angora and silk, preferably wool. Synthetic fibers include polyester, polyamide and polyacrylonitrile fibers. Preferred textile fibers are cotton, polyamide and wool fibers, especially cotton fibers. Preferably, textile fibers treated in accordance with the method of the present invention have a density of less than 1000 g / m2, especially less than 500 g / m2 and more preferably less than 250 g / m2. The process is usually carried out in the temperature range of 5 to 100 degrees C, especially to 60 degrees C. A temperature range of 5 to 40 degrees C is preferred, especially 5 to 35 degrees C and more preferably 5 to 30 degrees C. The detergent compositions present preferably will be formulated such that during For use in aqueous cleaning operations, the wash water will have a pH between about 6.5 and about 11, preferably between about 7.5 and 11. Laundry products are typically at pH 9-11. Techniques for controlling pH at recommended levels of use include the use of buffers, alkalis, acids, etc., and are well known to those skilled in the art. Machine laundry methods here typically comprise treating the soiled laundry articles with an aqueous washing solution, in a washing machine having dissolved or dispersed an effective amount of a machine laundry detergent composition according to the invention. For an effective amount of the detergent composition is meant, for example, 10 g to 300 g of product dissolved or dispersed in a volume washing solution of 5 to 85 liters, as typical product doses and volumes of washing solution commonly used in conventional machine laundry methods. Examples are automatic washing machines of the US type, vertical axis, top loading, which use approximately 45 to 83 liters of water in the wash bath, a wash cycle of approximately 10 to approximately 14 minutes and a wash water temperature of about 10 to about 50 degrees C; automatic washing machines of European type with horizontal axis, loading by the front, approximately 8 to 15 liters of water are used in the washing bath, a washing cycle of approximately 10 to approximately 60 minutes and a washing water temperature from about 30 to about 95 degrees C; Japanese-type automatic top-loading, vertical-load washing machines that use approximately 26 to 52 liters of water in the wash bath, a wash cycle of about 8 to about 15 minutes and a water temperature of about 5 to about 25 degrees C. The preferred liquor ratio is 1: 3 to 1:40, especially 1: 3 to 1:30. A liquor ratio of 1: 3 to 1:25 is particularly preferred. The following examples serve to illustrate the invention but do not limit the invention to them. Parts and percentages refer to weight, unless otherwise indicated. The temperatures are given in degrees Celsius, unless otherwise indicated. Examples of Application: Detergent formulation comprising dye fixing or dye transfer inhibiting agents. For Examples 1-4 the following detergent formulations are used: Detergent 1 (Di): 8.0% Sodium alkyl benzoyl sulfonate 2.9% Alcohol-tetradecan-ethylene glycol tallow ether (14 moles EO) 3.5% Sodium soap 43.8% Sodium triphosphate 7.5% Sodium silicate 1.9% Magnesium silicate 1.2% Carboxymethylcellulose 0.2% EDTA 21.2% Sodium sulphate 9.8% Water Detergent 2 (D2): 9.7% Sodium linear alkyl benzene sulfonate (average chain length Cu ^) 5.2% ethoxylated fatty alcohol C? 2-C? 8 (7 EO) 3.6% Sodium soap (chain length Ca2-C8: 65% and C20-C22"35%) 6.5% SIK (Foam inhibitor) 32.5% Aluminum sodium silicate (zeolites 4A) 11.8% Sodium carbonate 5.2% Sodium salt of a copolymer of acrylic and maleic acids (Sokalan CP5 (BASF)) 3.4% Sodium silicate 1.3% Carboxymethylcellulose 0.8% Diethylene triamine penta (methylene phosphonic acid) (Dequest 2060 (Monsanto)) 7.8% Sodium sulphate 12.2% Water Detergent 3 (liquid detergent formulation) (D3): 2. 5% Sodium alkyl benzene sulfonate 20% Ethoxylated fatty alcohol 13% Soap 2.5% Citric acid Remainder Water Detergent 4 (D4): 3% Sodium alkylbenzene sulfonate 8% Ethoxylated fatty alcohol 3% Soap 44% Sodium tripolyphosphate (STPP) Silicate rest, Sodium Sulfate In Examples 2-4, 0.75% by weight of the following dye binding or dye transfer inhibiting agents (a) Tinofix CLMR (Ciba Specialty Chemicals) (b) Sokalan HP 53MR (BASF) (c) Sokalan HP 56MR (BASF) (d) Chromabond S-100MR (1SP) (e) Chromabond S-400MR (ISP) are added to detergent formulations. The percentages by weight refer to the active material of these compounds and are based on the total weight of the detergent formulation. The following washing procedure is used for Examples 1-4 5 g of bleached (woven) cotton cloth are washed / rinsed in a Linitest machine applying the following conditions: Main wash: Detergent formulation dose: 2.5 g / 1 Proportion of liqueur: 1:10 Duration: 15 minutes Temperature: 30 degrees C The cloth is dried by centrifugation at 60 degrees C; wash cycles 1 and 3. In all the Examples, whiteness is measured by the Ganz / Griesser method. Example 1: Detergent formulation comprising FWA of the formula (I), (II) or (III) but without the dye fixing or dye transfer inhibiting agent A to the detergent formulations DI, D2, D3 and D4, 0. 1% by weight of 0. 2% by weight of 0. 2% by weight of are added to the detergent formulation. The percentages by weight refer to the active material of these compounds and are based on the total weight of the detergent formulation. Table 1: Degree of whiteness after 3 washing cycles Example 2: Detergent formulation comprising an FWA of the formula (I) and dye binding or dye transfer inhibiting agents (Comparative Example) To the detergent formulations DI, D2, D3 and D4, 0. 1% by weight of is added to the detergent formulation. The percentages by weight refer to the active material of these compounds and are based on the total weight of the detergent formulation.

Table 2: Degree of whiteness after 3 wash cycles Table 3: Difference between the whiteness obtained by the detergent with FWA alone and the whiteness obtained by the detergent with FWA and the coloring fixing agents or dye transfer inhibition after 3 washing cycles Example 3: Detergent formulation comprising an FWA of the formula (II) and a dye transfer inhibitor or dye transfer inhibitor (Comparative Example) To the detergent formulations DI, D2, D3 and D4, 0.2% by weight they are added to the detergent formulation. The percentages by weight refer to the active material of these compounds and are based on the total weight of the detergent formulation. Table: Degree of whiteness after 3 wash cycles Table 5: Difference between the whiteness obtained by the detergent with FWA alone and the whiteness obtained by the detergent with FWA and coloring fixing agents or dye transfer inhibition after 3 washing cycles Example 4: Detergent formulation comprising an FWA of formula (III) and dye transfer inhibitor or dye transfer inhibitor. Table 6: Degree of whiteness after 3 wash cycles Table 7: Difference between the whiteness obtained by the detergent with FWA alone and the whiteness obtained by the detergent with FWA and the dye fixing or dye transfer inhibiting agents after 3 washing cycles Application Example 5: Detergent formulation comprising fabric softening agents In Example 5, the following Softergent SI (a detergent formulation comprising a softening agent): Softergent SI: 20% by weight of ethoxylated fatty alcohol 54% Zeolite A 20% by weight of Sodium Carbonate 6% Arquat 2HT-75 (softening agent) In Example 5, the following washing procedure is used: 5 g of bleached cotton fabric (fabric) are washed / rinsed in Linitest machine applying the following conditions : Main wash: Softergent dose: 0.83 g / 1 Liquor proportion: 1:30 Washing temperature: 25 degrees C; Water hardness: 3 dH approx. 50 ppm CaC03 Duration: 12 minutes Rinse bath: Liquor ratio: 1:30 Temperature: 25 degrees C; Water hardness: 3 ° dH approx. 50 ppm of CaCO3 Duration: 4 minutes The fabric is washed with (a) a softergent formulation (SI) as such, (b) the softergent formulation (SI) comprising 0.2% by weight of an FWA of the formula (I) = Comparative Test (c) the softergent formulation (SI) comprising 0.2% by weight of an FWA of the formula (III) The whiteness of the fabric was measured after 1 and after 3 washing cycles.

Table 8: Degree of whiteness after 1 or 3 wash cycles

Claims (14)

1. CLAIMS 1. A composition comprising (i) at least one compound of the formula (1) wherein A means the portion of formula (2) or (3; wherein Ri represents hydrogen; C? -C? Straight chain alkyl, which may be substituted by one or two groups -OH, -OC? -C4alkyl, -NH2, -NHC? -C4alkyl, -N (C? -C4alkyl) 2, -N- pyrrolidino, -N-piperidino, -N-morpholino or -N + (C? -C4alkyl) 3; branched C3-C? 2alkyl groups, which may be interrupted by one or two heteroatoms and which may be unsubstituted or substituted by one or two -OH, -OC? -C4alkyl, -NH2, -NHC? -C4alkyl, -N groups (C? -C4alkyl) 2 / -N-pyrrolidino, -N-piperidino, -N-morpholino or -N + (C? -C4alkyl) 3; and R2 represents C-C4alkyl; C2-C4hydroxyalkyl; -CH2CONH2; -CH2COOH or -CH2COO C? -C4alkyl or, A represents a group of the formulas where 3? R4 and R5 each independently of each other 10 represent hydrogen; C? ~ C4alkyl; C2-C4hydroxyalkyl; the group -X'-NR6R7 or the group -X'-N + R6.R6R7r wherein at least one of the substituents R4 and / or R5 represents -X'- NR6R7 or -X'-N + R6'R6R7, X and X 'each independently of each other, 15. represent a straight chain C2-C8alkylene, which is unsubstituted or substituted by one or two -OH; or a branched C3-C8alkylene chain, which is unsubstituted or substituted by one or two -OH; -C (= 0) -; or a cycloaliphatic ring of 5 or 6 members, 20 R ?, Re1 and R? each independently of each other, represent hydrogen; C? -C4alkyl; or together with the nitrogen atom to which they are bound, they complete a pyrrolidino, piperidino or morpholino ring and R2 is as previously defined or A is NR8R9, wherein R8 and Rg each independently of each other, represent hydrogen; C? -C8alkyl, wherein the alkyl group may be substituted by C? -C4alkoxy, amino, mono- or di-C? -C4alkylamino or tri-C? -C4alkylammonium; C2-C4-hydroxyalkyl, wherein the alkyl group may be substituted by C? -Calkoxy, amino, mono- or di-Ci-C4alkylamino or tri- C? -C4alkylammonium; C? -C4alkoxyC? -C4alkyl; phenyl, which is unsubstituted or substituted by halogen, C? -C4alkoxy, C? -C4alkyl, COOM, S03M or sulfonamido, or R8 and R? together with the nitrogen atom to which they are connected, complete a morpholino, piperidino or pyrrolidino, or A represents halogen, B and C have independently of each other and of A the same meanings that are defined for A, and D has independently of Á the same meanings that are defined for A except that D is not halogen, and « M is hydrogen; an alkali metal atom; ammonium or a cation formed of an amine; or its quaternized form, and (ii) at least one colorant fixing agent, inhibition of dye transfer and / or fabric softening. 2. One according to claim 1 comprising (i) at least one compound of the formula (8) wherein each B is the same or different and each is -NH-ZN (Ra) (Rb) or -N- [ZN (Ra) (Rb)] 2 wherein Z is optionally substituted C2-C? alkylene or arylene, Ra and b are the same or different and each is C? -C? 2alkyl, or Ra and - together with the nitrogen atom to which they are connected each form a morpholino, piperidino or piperazino ring; and A is NH2; NH (C1-C4alkyl); N (C? -C4alkyl) 2; N (CH2CH2OH) 2; 0-C? -C4alkyl;
2. MH- - - "CO > • aN! .. N.H., _- r (Aísv W -N p where it is hydrogen; an alkali metal atom; ammonium or a cation formed of an amine; or its quaternized form.
3. 3. A composition according to claim 1, comprising at least one compound of the formula (9) where each A independently of each other, represents the portion wherein Ri represents hydrogen; a straight chain C? -C? 2alkyl or branched chain C3-C? 2alkyl group, these C2-C? 2alkyl and C3-C? 2alkyl groups, respectively, may be interrupted by one or two heteroatoms and is unsubstituted or substituted by one or two groups -OH, -0C? -C4alkyl, -NH2, -NHC? -C4alkyl, -N (C? -C4alkyl) 2, -N-pyrrolidino, -N-piperidino, -N-morpholino or - N + (C? -C4alkyl) 3 and R2 represents C? -C4alkyl; C2-Chydroxyalkyl; -CH2C0NH2; -CH2C00H or -CH2C00 C? -C4alkyl or alternatively, each A independently from each other, represents a group of the formula wherein R3, R4 and R5 each independently represent hydrogen; C? -C4alkyl; C2-C4hydroxyalkyl; the group -X'-NR6R7 or the group -X'- + R6.ReR7, wherein at least one of the substituents R4 and / or R5 represents -X'-NR6R7 or -X'-N + R6.R6R7, X and X 'each independently from each other, represent a straight chain C2-C8alkylene group or branched chain C3-C8alkylene, which is unsubstituted or substituted by one or two -OH or -C (= 0) -, R- groups e 'and R7 each, independently of each other, represents hydrogen; C? -Calkyl or together with the nitrogen atom to which they are bound, they complete a pyrrolidino, piperidino or morpholino ring, and R2 is as previously defined, and each B independently of each other, either is defined as for A or represents halogen; -NH2; C? -C4monoalkyl or dialkylamino, the alkyl groups are unsubstituted or substituted by C? -Calkoxy, amino, mono- or di- C? -C4alkylamino or tri-C? -C4alkylammonium; C2-Chidroxyalkylamino; C2-C4di (hydroxyalkyl) amino; aniline; an aniline monosulfonic acid or a sulfone ida residue or a saturated 5- or 6-membered heterocyclic ring.
4. 4. A composition according to claim 1, comprising at least one compound of the formulas (10), (11) and / or (12) where E * represents a group of the formula where A 'represents X-Y-NR3R4 and C is -NRaR2 and F * represents a group of the formula where D 'represents -R5R6 and B' represents -X? -Y? -NR7R8, whereby X and Xi each independently of one another, represent -O- or -NH-, Y and Yi each independently of each other, they represent a straight chain C-C8 alkylene or branched chain C3-C8 alkylene group, which may be interrupted by one or two nitrogen, oxygen or sulfur atoms or represents a 5- or 6-membered cycloaliphatic ring, preferably cyclohexyl, Ri , R2, R5 and Re each independently represent hydrogen; C? -C8alkyl; C2- C4hydroxyalkyl; C? -C4alkoxy C? -C4alkoxy; phenyl, which is unsubstituted or substituted by halogen, C? -C4alkoxy, C? ~ C4alkyl or sulphonamido, oiy R2 and / or R5 and R6, together with the nitrogen atom to which they are connected, complete a ring morpholino, piperidino or pyrrolidino, R3, R, R and R8 each independently represent hydrogen; C? -C4alkyl; C2 ~ C4hydroxyalkyl or R3 and R4 and / or R7 and Rs / - together with the nitrogen atom to which they are connected complete a morpholino, piperidino or pyrrolidino ring and M represents hydrogen; an alkaline or alkaline earth metal; ammonium or alkyl ammonium.
5. 5. A composition according to any of the preceding claims, characterized in that it comprises (ii) at least one polymeric dye transfer inhibiting agent.
6. 6. A composition according to claim 5, characterized in that the polymeric dye transfer inhibitor is selected from the group consisting of polyvinylpyrrolidones, polyvinyl imidazole or polyvinylpyridine-N-oxides which may have been modified by the incorporation of anionic or cationic substituents. .
7. 7. A composition according to any of claims 1-4, characterized in that it comprises (ii) at least one colorant fixing agent based on basic polycondensation products of an amine of the formula (13)
8. And a cyanamide, these polycondensation products are completely or partially neutralized with an inorganic or organic acid, Rg, Rio, Rn and R12 each independently of the others is hydrogen or alkyl which are. unsubstituted or substituted by amino, hydroxy, cyano or by C-C4alkoxy and G is alkylene optionally substituted or interrupted by one or more hetero atoms. 8. A composition according to claim 7, wherein G is C2-C2oalkylene optionally interrupted by -O-, -S-, -NH- or by -N (C? -Calkyl) - and / or substituted by hydroxy .
9. 9. A composition according to claim 7 or 8, characterized in that Rg, Rio, Rp and R12 each independently of the others is hydrogen or C? -C4alkyl.
10. 10. A composition according to claim 7, 8 or 9, characterized in that the cyanamides are cyanamide, dicyandiamide, guanidine and / or biguanidine.
11. 11. A detergent formulation comprising (i) at least one composition according to any of the preceding claims, (ii) at least one surfactant and (iii) optionally at least one additional auxiliary.
12. 12. A detergent formulation according to claim 11, characterized in that it comprises (i) from 0.01 to 10% by weight, preferably 0.01 to 5% by weight, based on the total weight of the detergent formulation, of at least one composition according to claims 1 - 10 and ii) from 5 to 70% by weight, based on the total weight of the detergent formulation, of at least one anionic surfactant from the group consisting of alkylbenzene sulfonates having from 9 to 20 atoms of carbon in the alkyl radical; alkylnaphthalenesulfonates having from 6 to 20 carbon atoms in the alkyl radical; and alkali metal sarcosinates of the formula R15-CO-N (R? S) -CH2C00M ?, wherein R15 is alkyl or alkenyl having from 8 to 20 carbon atoms in the alkyl or alkenyl radical, Ri6 is C? C4alkyl and Mi is an alkali metal and / or at least one nonionic surfactant of the group consisting of condensation products of 3 to 8 moles of ethylene oxide with 1 mole of primary alcohol containing from 9 to 20 carbon atoms, iiia) from 5 to 60% by weight, based on the total weight of the detergent formulation, of a reinforcing substance, from the group consisting of alkali metal phosphates; carbonates; hydrogen carbonates; silicates; alumino silicates; polycarboxylates; acids, polycarboxylics; organic phosphonates and aminoalkylene poly (alkylene phosphonates), and iiib) from 0 to 30% by weight, based on the total weight of the detergent formulation, of a peroxide from the group consisting of organic mono- or poly-peroxides; organic perishes and their salts; persulphates; perborates; percarbonates and persilicates, iiic) from 0 to 60% by weight, based on the total weight of the detergent formulation, of additional additives from the group consisting of optical brighteners; slurry suspension agents; pH regulators; foam regulators; salts to regulate the application properties by spraying and granulation; fragrances; antistatic agents; fabric conditioners; enzymes; bleaching agents; pigments; toning agents; and perborate activators, and iv) from 0 to 5% by weight, based on the total weight of the detergent formulation, of water.
13. 13. The use of compositions according to any of claims 1-10 for the treatment of textiles.
14. 14. The use of formulations according to any of claims 11-12 for the treatment of textiles.