MXPA98007313A - Method for caring for te - Google Patents

Abstract

The present invention provides a method for inhibiting the reabsorption of dyes migrating in the washing liquid, comprising introducing into the washing liquid containing a detergent containing peroxide, between 0.5 to 150, preferably between 1.5 to 75, especially between 7.5 to 40 mg, per liter of the washing liquid of one or more compounds having the formula (1), wherein n is 1, 2 or 3; A is an anion, R1 is hydrogen or C1-6alkyl; C4, Y is - (CH2) m where m is an integer within a range between 1 and 8; (CH2) p-CH (R1) - where p is an integer within a range between 1 and 7 and R1 is a linear or branched C 1 -C 4 alkyl, preferably methyl; -CX = CX- where X is cyano, C 1 -C 8 alkyl (linear or branched C 1 -C 8 alkyl) -amino;-( CH 2) q-NR 1 - ( CH2) q- wherein R1 has the above meaning and q is 1,2,34 or a residue of 1,2-cyclohexylene having the formula (see formula) and R is cyano, halogen, hydroxy, OR 1 where R 1 has the previous meaning, C O 2 R 2 where R 2 is hydrogen or straight or branched C 1 -C 4 alkyl, nitro, straight or branched C 1 -C 8 alkyl, di- (C 1 -C 12 alkyl) amino, NR 3 R 4 where R 3 and R 4 are the same or different and each is a C 1 -C 12 straight or branched alkyl, N + R 1 R 3 R 4 where R 1, R 3 and R 4 have their meanings

Description

METHOD FOR CARE OF THE FABRICS The present invention relates to a process for inhibiting the reabsorption of the dyes that migrate in the liquid for washing. It is known that various metal compounds, for example, manganese complexes, are useful in detergents as catalysts for oxidation with peroxide compounds. It is also known that other manganese complexes cause improved cleaning effects on dirt or dyes in the washing liquid. Moreover, these manganese complexes do not exhaust themselves at all on cotton, polyamide or polyester fibers in such a way that the complexes can not cause fiber discoloration problems. A problem associated with the evaluation of a compound as a candidate for use in a process to inhibit the reabsorption of the dyes that migrate in the wash liquid is the lack of a reliable and broad classification technique. This technique has now been developed and used to quantify the performance in the inhibition of dye transfer of potential substances. This classification procedure comprises a variety of tests that make it possible to determine the utility / damage balance of any of the candidates on a quantitative basis. The product is characterized in terms of its specific effectiveness, range of use, compatibility with the most important system components, oxygen demand and its potential degradation of fiber and pigment. Moreover, the accuracy of the data is such that a relationship between structure and effect can develop. The application of a new evaluation technique for manganese complexes has resulted in the identification of other manganese complexes that exhibit excellent performance as dye transfer inhibitors, which have a relatively low molecular weight and whose effectiveness is substantial even at of low addition.

Accordingly, the present invention provides a process for inhibiting the reabsorption of dyes that migrate in the wash liquor, comprising introducing into the wash liquid containing a peroxide detergent, between 0.5 to 150, preferably between 1, 5 to 75, especially between 7.5 to 40 mg, per liter of the liquid for washing, of one of the compounds having the formula: or wherein n is 1, 2 or 3; A is an anion; Ri is hydrogen or C? -C4 alkyl? Y is a linear or branched alkylene of the formula - [C (R?) 2] m wherein m is an integer within a range between 1 and 8 and each R ^ independently the other has its previous meaning; -CX = CX- wherein X is cyano, linear or branched C? -C8 alkyl or di (linear or branched C? -C8 alkyl amino), in which Ri has the above meaning and q is 1, 2 , 3 or 4; or a 1,2-cyclohexylene or phenylene residue having the formula: wherein R7 is hydrogen, CH2OH or CH2NH2 or SO3M, where M is hydrogen, an alkali metal atom, ammonium or a cation formed from an amine, R and R 'are each independently of another cyano; Halogen, Hydroxy; ORi or COOR-i, in which Ri has the previous meaning; nitro; linear or branched partial or fully fluorinated CrC8 alkyl; NR3R4 where R3 and R are the same or different and each is hydrogen or straight or branched C1-C12 alkyl; -N + R- | R3R4 where R1, R3 and R4 have their previous meaning or straight or branched C1-C13-R2 alkylene where R2 is OR-i, COOR1 or NR3R4, R5 and Re are independent of the other hydrogen; linear or branched C1-C4 alkyl; unsubstituted aryl or aryl that is substituted with cyano, halogen, OR1 or COOR-i, nitro, straight or branched CrC8 alkyl, NR3R where R3 and R4 are the same or different and each is hydrogen or C1-C-12 alkyl linear or branched; -N + R1R3R where R1, R3 and R4 have their previous meaning or straight or branched C? -CB-R2 alkylene where R2 is OR1, COOR1 or NR3R4, with the proviso that each n is 1, if R and R ' they are both C1-C4 alkyl.

Where Y is a 1,2-cyclohexylene residue, this residue can have any of its cis / trans stereoisomeric forms. And preferably it is - [C (R8) 2] 2 where Rβ is hydrogen or methyl, -CX = CX- where X is cyano, - (CH2) q-NR8- (CH2) q- where R8 has its previous meaning and q is 1, 2, 3 or 4; a 1,2-cyclohexylene or phenylene residue having the formula: The halogen atoms R or R 'are chlorine, bromine or fluorine atoms. Where n is 1, preferably the group R or R 'respectively is in the 4-position of the respective benzene ring, with the exception that when R or R' is nitro or CO2R2l the group R or R 'is preferably in the 5-position. of the respective benzene ring. When n is 2, preferably the R or R 'groups are in the 4,6 positions of the respective benzene ring, with the exceptions that when R or R' is nitro or CO2R2. the R or R 'groups are preferably in the 3,5- positions of the respective benzene ring. When R or R 'is the di (C? -C? 2) amino group, the alkyl portion may be a branched or unbranched chain alkyl portion, and preferably contains between 1 and 8, more preferably between 1 and 4 and, especially between 1 and 2 carbon atoms. The preferred R and R groups are dimethylamino, diethylamino, hydroxy, methoxy, ethoxy, chlorine or nitro. The anions A include the halide, especially chloride, perchlorate, sulfate, nitrate, hydroxide, BF 4", PF 6", carboxylate, especially acetate, triflate or tosylate.

Some of the compounds of the formula (1) and the ligands from which they are derived are known compounds. For example, US Pat. No. 5,281,578 describes the preparation of N, N-bis (4-dimethylaminosalicylidene) diiminoethylene; EP-A-0 693 550 describes the production of the manganese complex of N, N-bis (4-diethylaminosalicilidenojdiiminoethylene, and in Bernardo et al., Inorganic Chemistry 35 (2) 387 (1996), the production is described of N, N-bis (4-diethylaminosalicilidene) diminocyclohexylene as well as the production of the manganese complex N, Nb.sup. (4-diethylaminosalicilidene) diiminocyclohexylene The new compounds of the formula (1) and the novel ligands of the which derive form other aspects of the present invention.

Furthermore, the use, as dye transfer inhibitors of these compounds of the formula (1) wherein A is an anion already) Y is -CH2CH2- each R is di- (Ct-Czjamino alkyl; is cyclohexylene and each R is di- (alkyl d-C2) amine, has been indicated generally, but has not been specifically described in GB-A-2,296.015. On the other hand, it is believed that the use as dye transfer inhibitors of these compounds of the formula (1) in which A is an anion, Y is -CH2CH2- and each R is hydroxy is completely new.

Those compounds of the following formulas are of particular interest for the method of the present invention: The present invention also provides a detergent composition comprising: i) 5-90%, preferably 5-70% of A) an anionic surfactant and / or B) a nonionic surfactant; ü) 5-70%, preferably 5-50%, especially 5-40% of C) a reinforcer; Ii) 0.1-30%, preferably 1-12% of D) a peroxide; and iv) 0.005-2%, preferably 0.02-1%, especially 0.1-0.5% E) a compound of the formula (1) or (2) as defined above, each by weight, based on in the total weight of the detergent. The detergent can be formulated as a solid; or as a non-aqueous liquid detergent, containing not more than 5, preferably 0-1% by weight of water, and based on a suspension of a reinforcer in a non-ionic surfactant, as described for example in GB- A-2158454. Preferably, the detergent has the form of powder or granulate. These powdered or granulated forms can be produced by first forming a base powder by spray drying an aqueous paste containing all of these components, in addition to components D) and E); then adding the components D) and E) by means of dry mixing in a base powder. In another process, component E) can be added to the aqueous paste containing components A), B) and C), followed by spray drying of the aqueous paste prior to dry mixing of component D) in the mixture . Even in other processes, component B) is not present, or is only partially present in an aqueous paste containing components A) and C); component E) is incorporated in component B), which is then added to the spray-dried base powder; and finally component D) is mixed dry with the mixture. Component A) of the anionic surfactant may be, for example, a sulfate, sulfonate or carboxylate surfactant, or a mixture thereof. Preferred sulfates are alkyl sulfates having 12-22 carbon atoms in the alkyl radical, optionally in combination with the alkyl ethoxy sulfates having 10-20 carbon atoms in the alkyl radical. Preferred sulfates include alkyl benzene sulphonates having 9-15 carbon atoms in the alkyl radical. In each case, the cation is preferably an alkali metal, especially sodium. Preferred carboxylates are the alkali metal sarcosinates of the formula R-CO-N (R1) -CH2COOM1 wherein R is alkyl or alkenyl containing 9-17 carbon atoms in the alkyl or alkenyl radical, R1 is hydrogen or alkyl of C? -C4 and M1 is an alkali metal. Component B) of the nonionic surfactant can be, for example, a condensate of ethylene oxide with a C9-C5 primary alcohol having 3-8 moles of ethylene oxide per mole. The reinforcing component C) can be an alkali metal phosphate, especially a tripolyphosphate; a carbonate or bicarbonate, especially sodium salts; a silicate; an aluminosilicate; a polycarboxylate; a polycarboxylic acid; an organic phosphonate; or an aminoalkylene poly (alkylene phosphonate); or a mixture of them. The preferred silicates are the sodium silicates in crystalline layers of the formula NaHSimOüm + i.pH? O where m is a number between 1, 9 and 4 and p is between 0 and 20. Preferred aluminosilicates are the commercially available synthetic materials designated as Zeolites A; B, X and HS, or their mixtures. Zeolite A is the preferred one. Preferred polycarboxylates include the hydroxypolycarboxylates, in particular the citrates, polyacrylates and their copolymers with maleic anhydride. Preferred polycarboxylic acids include nitrilotriacetic acid and ethylene diamine tetraacetic acid, ethylenediamine adisuccinate in its racemic form as well as the S, S enantiomeric form. Preferred organic phosphonates or aminoalkylene poly (alkylene phosphonates) are alkali metal ethane-1-hydroxy diphosphonates, nitrile trimethylene phosphonates, ethylene diamide tetramethylene phosphonates and diethylene triamine penta methylene phosphonates. The component D of peroxide can be an inorganic peroxide compound, described in the literature or commercially available, which whitens the fabrics at conventional washing temperatures such as, for example, temperatures within a range between 30CC to 90 ° C. In particular, organic peroxides are, for example, monoperoxides or polyperoxides having alkyl chains of at least 3, preferably between 6 and 20, carbon atoms; in particular, diperoxydicarboxylates having between 6 and 12 carbon atoms, such as, for example, diperoxyperazelates, diperoxypersebacates, diperoxyphthalates and / or diperoxydedecanedioates, especially their corresponding free acids are of interest. It is preferred, however, to use very active inorganic peroxides, such as, for example, persulfate, perborate and / or percarbonate. Of course, it is also possible to use mixtures of organic and / or inorganic peroxides. The peroxides can have different crystalline forms and / or different degrees of hydration. They can be used mixed with other organic or inorganic salts, thus improving their stability during storage. The addition of the peroxides in the detergent is carried out, in particular, by mixing the components, for example, by means of screw measuring systems and / or fluidized bed mixers. The detergents may contain, in addition to the combination according to the invention, one or more of the fluorescent whitening agents, such as, for example, bis-triazinylamino-stilbene-disulfonic acid, a bis-triazolyl-stilbene-disulphonic acid, a derivative of bis-styryl-biphenyl, bis-benzofuranyl biphenyl, bis-benzoxalyl, bis-benzimidazolyl, a coumarin derivative or a pyrazoline derivative; stain suspending agents, for example, sodium carboxymethyl cellulose; salts for adjusting the pH, for example, alkali metal or alkaline earth metal silicates; foam regulators, for example, soap; salts for adjusting spray drying and granulation properties, for example, sodium sulfate; perfumes; and in addition, if appropriate, anti-static agents and softening agents, such as, for example, smectite clays; enzymes such as, for example, amylases; photobleaching agents; pigments; and / or matting agents. These constituents must of course be stable in the bleaching system used. A particularly preferred detergent co-additive is a polymer known to be useful in preventing the transfer of labile dyes between the fabrics during the wash cycle. Preferred examples of these polymers are polyvinyl pyrrolidones, optionally modified by means of the inclusion of an anionic or cationic substituents, especially those having a molecular weight in the range between 5,000 and 60,000, in particular between 10,00 and 50,000. Preferably, this polymer is used in an amount within a range between 0.05 and 5%, preferably between 0.2-1.7% by weight, based on the passage of the detergent. The detergents may additionally contain so-called perborate activators, for example, TAGU or, preferably, TAED. This is preferably used in an amount between 0.05 to 5% by weight, especially between 0.2 to 1.7% by weight, based on the total weight of the detergent. The manganese complexes of the formula (2) are new compounds and some of the manganese complexes of the formula (1) are also new.

Accordingly, the invention also relates to the manganese complexes of the formula (3) or the formula (2) where n is 1, 2 or 3; A is an anion; R and R 'are independently of each other, cyano; halogen; hydroxy; ORi COORi where R1 has the above meaning; nitro; linear C-C8 alkyl partially branched or fully fluorinated; NR3R3 where R3 and R4 s' are the same or different and each is hydrogen or branched linear C? -C? 2 alkyl; -N + R? R3R-? where R ^ R3 and R4 have the above meaning or rent of d-Cß-R? linear or branched where R2 is OR1, COOR1 or NR3R4, R is hydrogen or alkyl of d-C4l Yi is -CX = CX- where X is cyano, - (CHzJq-NRHCH? Jq- where R ^ has earlier meaning and q is 1 , 2, 3 or 4; linear or branched alkylene of the formule [C (R?) 2] m where m is an integer in the range between 1 and 8 and each independently has the above meaning, with the proviso that less an R1 is alkyl of C-rC4, or a residue of 1,2-cyclohexylene or phenylene having the formula: wherein R7 is hydrogen, CH2OH or CH2NH2 or SO3M, wherein M is hydrogenating an alkali metal atom, ammonium or a cation formed from an amine, with the proviso that each n is 1 if R and R 'are both d-C4 alkyl and Y1 be 1. residue 1, 2-cyclohexylene, Y is a linear or branched alkylene of the formula? [C (R?) 2] m where m is an integer in the range between 1 and 8 and each independently has its previous meaning; -CX = CX- where X is linear or branched C1-C8 alkyl or di (linear or branched alkyl) -amino; - (CH2) q-NR? - (CH2) q- where Ri has the above meaning and q is 1, 2, 3 or 4; a 1,2-cyclohexylene or phenylene residue having the formula: wherein R7 is hydrogen, CH2OH or CH2NH2 or SO3M, where M is hydrogen, an alkali metal atom, ammonium or a cation formed of an amine. R5 and Rβ are independent of the other hydrogen; linear or branched C? -C4 alkyl; unsubstituted aryl or aryl substituted by cyano, halogen, ORi or COORi, nitro, straight or branched C? -C8 alkyl, NR3R4 where R3 and R4 are the same or different and each is hydrogen or linear C ^ C ^ alkyl or branched -N + R 1 R 3 R 4 where R 1 (R 3 and R 4 have the above meaning or straight or branched C 1 -C 8 -R 2 alkylene where R 2 is OR 1, COOR 1 or NR 3 R 4 The ligands of the formulas (4) or (5) which are contained in The manganese complexes are new in themselves and these ligands are also part of the present invention The invention consequently also relates to compounds of the formula (4). or of the formula (5) where n is 1, 2 or 3; R and R 'are each independent of the other cyano; halogen; hydroxy; ORÍ or COORi, where R has the previous meaning; nitro; linear or partially branched or fully fluorinated C? -C8 alkyl; NR3R4 wherein R3 and R4 are the same or different and each is hydrogen or straight or branched C1-C12 alkyl; -N + R1R3R4 where R t R3 and R4 have the above meaning or straight or branched C1-C8-R2 alkylene where R2 is OR1, COOR1 or NR3R4r Ri is hydrogen or C? -C4 alkyl, YI is -CX = CX - where X is cyano, - (CH2) q-NR1- (CH2) q- where R has the above meaning and q is 1, 2, 3 or 4; linear or branched alkylene of the formula - [C (R?) 2] m where m is an integer within a range between 1 and 8 and each R1 independently has the above meaning, with the proviso that at least one R is alkyl of C? -C4; or a 1,2-cyclohexylene or phenylene residue having the formula: where R7 is hydrogen, CH2OH or CH2NH2 or SO3M, where M is hydrogen, an alkali metal atom, ammonium or a cation formed from an amine, with the proviso that each n is 1 if R and R 'are both C-alkyl; ? -C4 and Y is a residue of 1, 2-unsubstituted cyclohexylene, Y is a linear or branched alkylene of the formula - [C (R?) 2] m where m is an integer in the range between 1 and 8 and each Ri independently has the above meaning; -CX = CX- where X is cyano, linear or branched C? -C alkyl or di (linear or branched alkyl d-C8) -amino; - (CH2) q-NRr (CH2) q- where R ^ has the above meaning and q is 1, 2, 3 or 4; or a residue of 1,2-cyclohexylene or phenylene having the formula: wherein R7 is hydrogen, CH2OH or CH2NH2 or SO3M, where M is hydrogen, an alkali metal atom, ammonium or a cation formed from an amine, R5 and R6 they are independent of the other hydrogen; linear or branched C? -C4 alkyl; unsubstituted aryl or aryl that is substituted by cyano, halogen, ORi or COORi, nitro, straight or branched C? -C8 alkyl, NR3R4 where R3 and R4 are the same or different and each is hydrogen or a linear Ci.sub.2 alkyl or branched; -N + R1R3R4 where R1t R3 and R4 have the above meaning or C1-C & -R2 linear or branched alkylene where R2 is ORi, COOR, or NR3R4. The preferred compounds of the formula (4) are the following: The preferred compounds of the formula (5) are The following Examples serve to illustrate the invention; the parts and percentages are by weight, unless otherwise specified. Preparation of the new ligands: Ligand 2a: a) Preparation of the corresponding aldehyde. In the first instance, the starting compound N, N-dibutyl-4-amino-2-hydroxy-benzaldehyde had to be prepared by means of the Vilsmeyer formulation of N, N-dibutyl-3-amino-phenol. The Vilsmeyer reagent was prepared by the slow addition of 4.7 ml (0.0497 mol) of phosphorus oxychloride to 15 ml (0.189 mol) of N, N-dimethyl formamide with a stirring of 15 minutes at room temperature . Stirring was continued for a further 30 minutes before using this Vilsmeyer reagent. 11 g of (0.497 mol) of N, N-dibutyl-3-amino-phenol were prepared by alkylation of 3-aminophenol after the procedure described in EP 0356173 were dissolved in 13 ml of N, N-dimethyl formamide This solution was added dropwise at room temperature to the Vilsmeyer reagent described above. The solution was stirred for 3 hours, heated to 50 ° C for 10 minutes. The solution was cooled to room temperature and stirred for another 2 hours. Then, the reaction mixture was poured onto 70 g of ice and stirred for 1 hour. The aqueous layer was extracted three times with 100 ml of chloroform. The combined organic layers were evaporated in vacuo. The crude product was purified by column chromatography (450 g of silica gel, eluent hexane / ethyl acetate : 1, volume ratio). 3.2 g (26%) of N, N-d-butyl-4-amino-2-hydroxy-benzaldehyde were obtained as an oily orange compound. b) Preparation of ligand 2a To a solution of 1 g (0.004 mol) of 4 N, N-dibutyl-4-amino-2-hydroxy-benzaldehyde in 2 ml of ethanol at 55 ° C was added in the form of drops 0.13 ml (0.00191 mol) of ethylene diamine. The resulting clear solution was kept under stirring for 4 hours between 60-65 ° C. The solution was cooled and the formed precipitate was filtered and dried to give 540 g (54%) of a slightly brown solid. 3 C NMR (CDCl 3): d = 14.0 (alif CH 3), 20.2, 29.5, 50.8, 58.2 (alif.CH2), 98.2, 103.1, 132.9 ( aryl-C tere), 108.2, 151, 9, 165.7 (aryl-C cuart), 164.3 (C = N). Calculated: C 73.52 H 9.65 N 10.72 Found C 73.14 H 9.34 N 10.55. Ligand 2b Preparation of the corresponding aldehyde: A solution of 13 g (0.04255 mol) of N, N-heptyl-3-amino-phenoxy, prepared after the procedure in EP 0356173, in 30 ml of chloroform was treated with 6.7 g (0.04255 mol) ) of phosphorus oxychloride and 12.4 g (0.169 mol) of N, N-dimethyl formamide and worked in the manner described for compound 2a. Purification was achieved by column chromatography of a mixture of chlorobenzene / ethyl acetate / ethanol (90: 5: 5, volume ratio). 1.78 g (13%) of N, N-heptyl-4-amino-2-hydroxybenzaldehyde were obtained as a green oily compound. A solution of 0.8 g (0.0024 mol) of N, N-heptyl-4-amino-2-hydroxy-benzaldehyde in 1 ml of ethanol was worked up and worked up as described for compound 2a. 720 mg (92%) of the ligand was obtained as a brown oil that crystallized slowly when stored at 5 ° C for three days. 13 C NMR (CDCl 3): d = 14, 0 (CH3 alif.), 22.6, 27.1, 27.5, 29.2, 31, 9, 51, 0, 57.7 (aliphat CH2), 98.3, 103.2, 133 , 0 (aryl-C tere), 108.2, 152.1, 166.5 (aryl-C quart), 164.2 (C = N). Calculated: C 76.47 H 10.79 N 8.11 Found: C 76.18 H 10.60 N 7.95. Ligand 2c To a stirred solution of 2 g (0.0121 mol) of 5-dimethylamino-2-hydroxy-benzaldehyde [prepared according to Bull. Chem. Soc. Jpn 51 (1978) 2433] in 6 ml of ethanol at 50 ° C was added in the form of drops 0.35 g (0.0058 mol) of ethylene diamine. An orange suspension was formed which was stirred at 60 ° C for 4 hours. The suspension was cooled to room temperature, filtered and dried under vacuum at 30 ° C. The pure ligand was obtained as a yellow solid (1.77 g, 87%). 3 C NMR (CDCl 3): d = 45.0 (NCH3 alif.), 60.0 (aliphat CH2), 116.2, 117.2 119.6 (aryl-C tere), 118.4, 144.2 , 153.3 (aryl-C quart), 166.8 (C = N). Calculated: C 67.77 H 7.39 N 15.81 Found: C67.56 H 7.35 N 15.25. Ligand 2d To a solution of 2.5 g (0.015 mol) was added N, N-dimethyl-4-amino-2-hydroxy-bepzaldehyde in 7 ml of ethanol for 2 minutes to a solution of 0.82 g. (0.00721 mol) of diamino maleic acid dinitrile in 14 ml of methanol. The reaction mixture was heated for 5 hours to give a brown solid (2.03 g, 70%). 13 C NMR (CDCl 3): d = 40.0 (NCH 3 alif.), 110.4, 115.1 (O alif. Quart.), 98.2, 105.8, 133.0 (aryl-C tere), 110.4 115.1, 161.2 (aryl-C quart), 156.2 (C = N). Ligand 2e A solution of 5.0 g (0.0259 mol) of 4-diethylamino-2-hydroxy-benzaldehyde in 12 ml of ethanol was treated with 1.66 g (0.0123 mol) of bis- (3- aminopropyl) amine and worked in the manner described for ligand 2a. The crude product was dried under high vacuum to give 5.7 g (98%) of a red oil. 13 C NMR (CDCl 3): d = 12.8 (CH3 alif.), 31.1, 44.5, 47.2, 53.6 (aliphat CH2), 98.7, 103.1, 133.2 ( aryl-C tere), 108.2, 152.2, 169.0 (aryl-C quart), 162.5 (C = N). Calculated: C 68.77 H 9.00 N 14.32 Found: C67.09 H 8.66 N 13.38 (The substance contains 1.51% water) Ligand 2f A solution of 0.81 g (0.00517 mol) 4-chloro-2-hydroxy-benzaldehyde prepared according to Beilstein (E IV, col 8, 223) in ethanol was treated with 0.29 g (0, 00246 mol) trans-1, 2-diaminohexane and worked in the manner described for ligand 2a. The ligand was obtained as a yellow oil (0.96 g, 100%) which upon crystallization slowly crystallized. 13 C NMR (CDCl 3): d = 24.1, 32.9 (CH 2), 54.6, 72.4 (CH), 117.0, 130.1, 1G2, (aryl-C quart), 117, 2, 118.9 (Aryl-C tere), 164.0 (C = N).

Calculated: C 61, 39, H 5.15 N 7.16 Cl 18.12 Found: C61.50 H 5.34 N 7.70 Cl 17.26 Ligand 2g To a stirred solution of 2 g (0.013 mol) 2 -hydroxy-4-methoxy-benzaldehyde in 10 ml of ethanol at room temperature was added in one portion 579 mg (0.0065 mol) 1,2-diethylamino-2-methylpropane. The solution was heated at 60 ° C for 3 hours and cooled to room temperature. The clear solution was evaporated and dried under high vacuum to give the ligand as a red-brown oil (2.58 g, 100%). 13 C NMR (CDCl 3): d = 25.3 ((CH 3) 2 C-), 55.3 (OCH 3), 59.2 (C alif. Cuart.), 69.2 (NCH 2), 101, 2, 101, 4 (Aryl-C tere), 106.3, 106.4 (Aryl-C tere), 112.2, 112.3 (Aryl-C quart), 132.9 133.1 (Aryl-C tere), 160.3, 165.6 (C = N), 163.7, 163.9 (Aryl-C quart), 165.0 166.7 (Aryl-C quart). Calculated: C 67.39 H 6.79 N 7.86 Found: C 67.51 H 6.91 N 7.69 Ligand 2h 2 g (0.0103 mol) 4-diethylamino-2-hydroxy-benzaldehyde and 456 mg (0.00517 mol) 1, 2-diethylamino-2-methylpropane were treated and worked in the manner described for the 2g ligand. The ligand was obtained as a red-brown solid (1.9 g, 84%). 13 C NMR (CDCl 3): d = 12.7 (CH 3 CH 2 N), 25.4 ((CH 3) 2 C), 44.4 (NCH 2 CH 3), 58.4 (C quart), 68.6 (NCH 2), 98 , 1, 98.6 (Aryl-C tere), 103.0, 103.1 (Aryl-C tere), 108.3, 108.4 (Aryl-C quart), 133.1, 133.4 ( Aryl-C tere), 151, 6, 151, 9 (Aryl-C quart), 158.9, 164.5 (C = N), 166.0, 168.4 (A-C-quart). Calculated: C 71, 91 H 8.74 N 12.72 Found: C 70.88 H 8.65 N 12.35 Ligand 2i 1, 21 g (0.006 mol) of 4-diethylamino-2-hydroxy-benzaldehyde was dissolved with stirring in 2 ml of ethanol at 50 ° C. At this temperature, a solution of 2,3-dipane-2,3-dimethyl-butane (prepared according to Beilstein E IV, vol 4, 1354) in 2 ml of ethanol in 30 minutes was added. The reaction mixture was heated to 70 C for 3 hours and stirred at room temperature for another 8 hours. The resulting suspension was filtered and the precipitate was washed with cold ethanol and dried under high vacuum to give a brown solid (890 mg, 66%). 13 C NMR (CDCl 3): d = 12.8, 23.0 (CH 3), 63.3 (C quarter alif), 98.6, 103.0, 133.5 (Aryl-C tere), 108.2 , 152.1, 169.1 (Aryl C cuart), 158.9 (C = N). Calculated: C 72.07, H 9.07 N 12.01 Found C 71, 78 H 9.03 N 11.88 Linked 2j To a solution of 974 mg (0.0045 mol) of 2,3,6,7 -tetrahydro-8-hydroxy-1 H, 5H-benzo [ij] quinolicine-9-carboxaldehyde in 30 ml of methanol was added a solution of 148 mg (0.0025 mol) of ethylene diamine. The reaction mixture was heated under reflux for 2 h. The formed precipitate was filtered and crystallized from 100 ml of methanol to give 590 mg (29%) of yellow crystals. 13 C NMR (CDCl 3): d = 20, 4, 21, 3, 22.2, 27.2 49.8, 50.1.2.2 (CH2), 106.8, 107.9, 112.2, 129.0, 146.4, 164, 3 (C = N). Calculated: C 73.33 H 7.47 N 12.22 Found: C 73.37, H 7.54 N 12.22 Ligand 2k A solution of 1.95 g (0.00714 mol) of 8-hydroxy-1 , 1, 7,7-tetramethyljulolidine-9-carboxaldehyde in 60 ml of methanol was reacted with 236 mg (0.0393 mmol) of ethylene diamine as described for ligand 2j. The precipitate was filtered and washed with methanol to give 1.52 g (75%). 13 C NMR (CDCl 3): d = 28.5 (C prim.), 31, 2 (C prim.), 31, 7, 32.2, 36.6, 40.1, 47.0, 47.4, 58.9, 108.7, 114.8, 121, 6, 127.5, 145.7, 161, 2, 165.4 (C = N). Ligand 21 A solution of 5.0 g (0.0355 mol) of 2,4-dihydroxybenzaldehyde in 17 ml of ethanol was treated with 1.97 g (0.0169 mol) of trans-1,2-diaminocyclohexane and it was heated at 65 ° C for 5 hours. A yellow suspension formed which was cooled to 2 ° C. The precipitate was filtered, washed with ethanol and dried to give 5.9 g (99%) of a yellow solid. 13 C NMR (CDCl 3): d = 24.9, 33.6 (CH 2), 71.3 (CH), 103.3, 107.8, 134.1 (Aryl-C tere), 112.0, 162, 6 (Aryl-C quart), 164.9 (C = N). Ligand 2m A solution of 5 g (0.025 mol) of 4-diethylamino-2-hydroxy-benzaldehyde in 12 ml of ethanol was treated with 0.92 g (0.0123 mol) of 1,2-diaminopropane and heated to 65 ° C for 5 hours. The solution was cooled and stirred for 8 hours. The solution was concentrated to give 4.68 g (90%) of a brown solid. 3 C NMR (CDCl 3): d = 12.7, 20.3 (CH 3), 44.5, 63.8 (CH 2), 98.2, 103.1, 133.1 (Aryl-C tere), 108, 3, 151, 5, 165.5 (Aryl-C quart), 162.5 (C = N). The following ligands are known compounds.

These ligands were prepared according to procedures known in the literature. All the described ligands were transformed into their manganese complexes. The synthesis of these complexes was carried out according to the literature as described by E. N. Jacobsen et al., J. Org. Chem., 59 (1994) 1939 or as described in GB-A 2,296,015. As an example for the standard procedure, we describe the synthesis of the manganese complex 1b: to a stirred solution of 667 mg of the 3f ligand dissolved in 10 ml of ethanol was added 465 g of manganese tetrahydrate-tetrahydrate-ll. The reaction solution was heated at 65-70 ° C for 4 hours. Then, the solution was evaporated and the residue was dissolved in 40 ml of water. The solution was treated with 3.7 g of sodium chloride. The resulting precipitate was filtered and dried in vacuo. The manganese complex was obtained as a red-brown powder (820 mg, 86%). Example 1 Each of the test compounds was then evaluated for activity as a dye transfer inhibitor according to the following method. 7.5 g of white cotton was washed in 80 ml of the washing liquid. The washing liquid contains 8.6 mmol / l H2O2, a solution of a test pigment and 7.6 g / l of the standard phosphate-free ECE detergent (456 IEC) EMPA, Switzerland: 9.74% linear sodium alkylbenzenesulfonate (Marion A375) .19% Ethoxylated C? 2-C? 8 fatty alcohol (7 moles of EO) 3.64% sodium soap 6.49% silicone foam inhibitor 32.47% Zeolite 4A sodium aluminum silicate 11, 82% sodium carbonate 5.19% sodium salt of an acrylic acid / maleic acid copolymer (Sokolan CP 5) 3.38% sodium silicate (SiO2: Na2O = 3.3: 1) 1, 30% carboxymethylcellulose 0.26% EDTA 7.40% sodium sulfate 12.21% water 0.65% pill of proteolytic enzyme 0.26% fluorescent whitening agent 20.0% sodium percarbonate and 3.0% TAED The washing was carried out in whisks in a LINITEST apparatus at 40 ° C for 30 minutes. The test dye transfer inhibitor was added at a level of 50 μmol / L. The commercially available test dye is both Cuprofenil Brown 2GL (Cuprophenyl Brown 2GL) (Tincture 1) used at a level of mg / L of the 250% formulation, or Blue Reagent 238 (Reactive Blue 238) (Dye 2) used at a level of 6 mg / L of the 100% formulation. The reflection spectrum of the respective test samples was measured with a SPECTRAFLASH 2000 instrument and transformed into brightness values according to the standard CIÉ procedure. The effectiveness of ITT (percentage dye transfer inhibition) (a) is then calculated according to the following equation: a =. { [Y (E) - Y (A)] / [Y (W) - Y (A)]} x 100 where Y (W), Y (A) and Y (E), respectively, are the brightness values CIÉ of the white material before the treatment, of the fabric obtained when it is washed without a dye transfer inhibitor and of the fabric obtained by washing it with a dye transfer inhibitor. A zero percent value of the value a denotes a completely ineffective dye transfer inhibitor, this is a compound, whose addition to the washing liquid allows the complete transfer of dye onto the white material. In contrast, a percentage value of 100 denotes a perfect dye transfer inhibitor, this is a compound, whose addition to the washing liquid does not allow the transfer of dye on the white material. The results obtained are determined in the following Table 1.

Table 1b: TTI efficiency of manganese complexes derived from known ligands.

The results in Table 1 clearly demonstrate that the claimed manganese complexes exhibit excellent performance as dye transfer inhibitors. Example 2 The procedure of Example 1 was repeated with the exception that only inhibitors 1 (A) and 1 (B) were used and that the amounts used of these inhibitors varied over a wide range. The results obtained were determined in the following Table 2.

Table 2 The results in Table 2 show that the manganese complexes of the formula (1) exhibit excellent performance as transfer dye inhibitors at very low levels of aggregate. Example 3: The procedure of Example 1 was repeated with the exception that only inhibitors 1 (A) and 1 (B) were used and that their effectiveness for controlling the transfer of a wide range of dye was examined, Various levels of dye aggregate.

Table 3 The results in Table 3 show that the manganese complexes of the formula (1) exhibit excellent performance as dye transfer inhibitors against the migration of a wide range of dyes, at various levels of dye aggregate. Example 4: The procedure in Example 1 was repeated for a washing temperature of 20 ° C. The results obtained are determined in the following Table 4.

The results in Table 4 show that the manganese complexes of the formula (1) exhibit excellent performance as dye transfer inhibitors at wash temperatures as low as 20 ° C. Example 5 The procedure was repeated in Example 1 with the exception that only inhibitors 1 (A) and 1 (B) were used and that the detergent composition used was modified by the addition of 4% by weight of TAED, as bleach activator. The results obtained are determined in the following Table 5. Table 5 The results in Table 5 show that the manganese complexes of formula (1) exhibit excellent performance as dye transfer inhibitors and that their effectiveness is not impaired by use with activated bleaching systems. Moreover, the compatibility between the manganese complexes of the formula (1) and the activated bleaching systems has reciprocal benefits. In particular, under the conditions described in Example 1, the promoter action of the bleaching of the TAED is maintained, even in the presence of 20μM of a manganese complex of the formula (1). In this way, the increase in brightness (? Y) obtained with the tea-stained cotton test matepal is 24 when no dye transfer inhibitor is present (control test); is 23 when inhibitor 1 (A) is used; and 24 when the inhibitor 1 (B) is used. Example 6 The procedure in Example 1 was repeated with the exception that only inhibitors 1 (A) and 1 (B) were used and that the detergent composition used was modified by the addition of 100 μM DEQUEST 2041 [acid ethylenediamine-tetra- (methylene phosphonic), as a sequestering agent. The results obtained are determined in Table 6. Table 6 The results of Table 6 show that the manganese complexes of formula (1) exhibit excellent performance as dye transfer inhibitors and that their effectiveness is not impaired by their use with a sequestering agent. Sequestering agents are generally present in detergent formulations and their presence often leads to the observation of higher values. This is because the heavy metal ones are masked and, therefore, the peroxidic oxygen reserve is not degraded by useless degradation processes. Example 7 The procedure of Example 1 is repeated with the exception that only inhibitors 1 (A) and 1 (B) are used and the amounts of H2O2 used in the detergent are varied. The results obtained are determined in the following Table 7.

The results in Table 7 show that, even when the conventional amount of H2O2 present in the detergent formulation is reduced by a factor of 4, the effectiveness of the manganese complexes of the formula (1) is retained as dye transfer inhibitors. . Example 8 The procedure was repeated in Example 1 with the exception that only inhibitors 1 (A) and 1 (B) were used and that a series of dyed cotton fabrics known to be sensitive to bleaching systems were used. aggressive For the purpose of comparison, an analogous test was carried out using TAED instead of inhibitor 1 (A) or 1 (B). The washing treatment was carried out five times with each respective detergent composition and, after completing the respective fifth wash, the percentage loss of dyeing was determined. The results were determined in the following Table 8.

Table 8 The results in Table 8 show that the loss of pigment observed when a detergent containing a manganese complex of the formula (1) is used as a dye transfer inhibitor, is of the same order as experienced when a detergent containing a detergent is used. a whitening system activated by TAED. This latter detergent composition represents the state of the art for oxygen bleaches, and its damage / utility balance in dyeing is accepted in the industry. Using the same test conditions, after completing the fifth respective wash, the percentage relative reduction of DP was determined (average degree of polymerization, in order to classify the damage in the fiber.) The results are determined in the following Table 9. Table 9 The results in Table 9 show that the damage observed on the fiber on the cotton material dyed when a detergent containing a manganese complex of the formula (1) is used as a dye transfer inhibitor, is of the same order as the experienced one. When a detergent is used it contains a bleaching system activated by TAED.

Claims (31)

CLAIMS Having thus specially described and determined the nature of the present invention and the way it has to be put into practice, it is claimed to claim as property and exclusive right:

1. A process for inhibiting the reabsorption of dyes migrating in the washing liquid, comprising introducing into the washing liquid a detergent containing peroxide, between 0.5 and 150 mg, per liter of the washing liquid, of one or more compounds which has the formula: or where n is 1, 2 or 3; A is an anion; R is hydrogen or C4 alkyl, and is a linear or branched alkylene of the formula - [C (R?) 2] m wherein m is an integer within a range between 1 and 8 and each R independently of the other it has its previous meaning; -CX = CX- where X is cyano, linear or branched C? -C8 alkyl or di (straight or branched C8 alkyl amino), - (CH2) q-NR1- (CH2) q- in the that Ri has the above meaning and q is 1, 2, 3 or 4; or a 1,2-cyclohexylene or phenylene residue having the formula: wherein R7 is hydrogen, CH2OH or CH2NH2 or SO3M, where M is hydrogen, an alkali metal atom, ammonium or a cation formed from an amine, R and R 'are each independently of another cyano; halogen, hydroxy; ORi or COORi, in which Ri has the previous meaning; nitro; linear or branched C? -C8 alkyl partially or completely fluorinated; NR3R4 wherein R3 and R4 are the same or different and each is hydrogen or straight or branched C1-C12 alkyl; -N + R? R3R4 where R ^ R3 and have their previous meaning or straight or branched C? -C8-R2 alkylene where R2 is OR1, COOR1 or NRsR- ,, R5 and R6 are independent of the other hydrogen; linear or branched C? -C4 alkyl; unsubstituted aryl or aryl that is substituted with cyano, halogen, OR1 or COOR1, nitro, straight or branched C? -C8 alkyl, NR3R4 where R3 and R4 are identical or different and each is hydrogen or d-Ci2 alkyl linear or branched; -N + R? R3R4 where R1 f R3 and RÜ have their previous meaning or straight or branched C? -C8-R2 alkylene where R2 is OR1, COOR1 or NRaR ^ with the proviso that each n is 1, if R and R 'are both CC alkyl.

2. A process according to Claim 1 wherein between 1.5 to 75 mg, per liter of washing liquid, is introduced from one or more compounds having the formula (1) or (2) into the washing liquid.

3. A process according to claim 2 wherein between 7.5 to 40 mg, per liter of washing liquid, of one or more compounds having the formula (1) or (2) is introduced into the liquid of washed.

4. A process according to any of the preceding claims wherein the anion A is a halide, perchlorate, sulfate, nitrate, hydroxide, BF4", PF6" or a carboxylate.

5. A process according to Claim 4 wherein the halide anion is chloride.

6. A process according to Claim 4 wherein the carboxylate anion is acetate, triflate or tosylate.

7. A process according to any of the preceding claims wherein Y is - [C (Rβ) 2] 2 where R8 is hydrogen or methyl, -CX = CX- where X is cyano, - (CH2) q-NR8- ( CH2) q- where R8 has the above meaning and q is 1, 2, 3 or 4; or a 1,2-cyclohexylene residue or phenylene residue having the formula:

8. A process according to any of the preceding claims wherein R and R 'are dimethylamino, diethylamino, hydroxy, methoxy, ethoxy, chloro or nitro.

9. A process according to any one of the preceding claims wherein n is 1, the group R or R 'is in the 4-position of the respective benzene ring, with the exceptions that when R or R' is nitro or CO2R2, the Group R or R1 is in the 5-position of the respective benzene ring.

10. A process according to any of Claims 1 to 8 wherein when n is 2, the R or R 'groups are in the 4,6 positions of the respective benzene ring, with the exceptions that when R or R 'is nitro or CO2R2 the groups R or R' are in positions 3, 5 of the respective benzene ring.

11. A process according to any one of the preceding Claims wherein R or R 'is di- (alky) C? -C? 2) amino, preferably di- (alkyl d-C8) amine.

12. A process according to Claim 11 wherein the alkyl portion in the di-C 1 -C 2 alkylamino group contains between 1 and 4 carbon atoms.

13. A process according to Claim 12 wherein the alkyl portion in the di- (C 1 -C 2 alkyl) amino group contains between 1 and 2 carbon atoms.

A process according to any one of the preceding Claims wherein the compound of the formula (1) is one or more of the compounds of the formulas: (1A)

15. A detergent composition comprising: i) 5-90% of A) an anionic surfactant and / or B) a nonionic surfactant; ii) 5-70% of C) a reinforcer; iii) 0.1-30% of D) a peroxide; and iv) 0.005-2% of E) a compound of formula (1) or (2) as defined in Claim 1, each by weight, based on the total weight of the detergent.

16. A composition according to Claim 15 comprising: i) 5-70% of A) an anionic surfactant and / or B) a nonionic surfactant; I) 5-50% of C) a reinforcer; Ii) 1-12% of D) a peroxide; and iv) 0.02-1% of E) a compound of the formula (1) or (2) as defined in Claim 1, each by weight based on the total weight of the detergent.

17. A composition according to Claim 16 comprising: i) 5-70% of A) an anionic surfactant and / or B) a nonionic surfactant; ii) 5-40% of C) a reinforcer; iii) 1-12% of D) a peroxide; and iv) 0.1-0.5% of E) a compound of the formula (1) or (2) as defined in Claim 1, each by weight based on the total weight of the detergent.

18. A composition according to Claim 15 comprising a combination of two or more of the compounds of the formula (1) or (2) as defined in Claim 1.

19. A composition according to any of the Claims. 15 to 18 comprising between 0.5-5% by weight of a polymer useful for preventing the transfer of labile dyes between the fabrics during a wash cycle.

20. A composition according to Claim 19 comprising between 0.2-1.7% of the polymer.

21. A composition according to Claim 19 or 20 wherein the polymer is a polyvinylpyrrolidone which optionally contains an anionic or cationic substituent.

22. A composition according to any of Claims 15 to 21 wherein the detergent has the powder or granular form.

23. A composition according to any of Claims 15 to 21 wherein the detergent has the liquid form and contains between 0-5% of water.

24. A composition according to Claim 23 wherein the detergent has the liquid form and contains between 0-1% water.

25. A composition according to Claim 15, which additionally contains TAGU or TAED.

26. A process for the production of a detergent as claimed in Claim 22 wherein the detergent components are mixed in the dry form.

27. A process for the production of a detergent as claimed in Claim 22 wherein a base powder is produced by spray-drying an aqueous paste containing all of the components defined in Claim 22, in addition to the D components ) and E); and then adding the components D) and E) by mixing them dry in the base powder.

28. A process for the production of a detergent as claimed in Claim 22 wherein the component E) is added to the aqueous paste containing components A), B) and C), whose aqueous paste is then spray dried. before component D) is mixed dry in the mixture.

29. A process for the production of a detergent as claimed in Claim 22 wherein component B) is not present, or is present only partially in an aqueous paste containing components A) and C); component E) is incorporated into component B), which is then added to the spray-dried base powder; and finally component D) is mixed dry in the mixture.

30. The manganese complexes of the formula (3). or of the formula (2) where A is an anion; R and R 'are independently of each other, cyano; halogen; hydroxy; ORi or COOR! where R has the previous meaning; nitro; linear or partially branched or fully fluorinated d-C8 alkyl; NR3R3 where R3 and R4 are identical or different and each is hydrogen or a straight or branched dC12 alkyl; -N + R1R3R4 where R1f R3 and R4 have the above meaning or alkylene of straight or branched d-C8-R2 where R is OR1, COORi or NR3R4, R1 is hydrogen or C1-C4 alkyl, Y! is -CX = CX- where X is cyano, - (CH2) q-NR? - (CH2) q- where RT has the above meaning and q is 1, 2, 3 or 4; linear or branched alkylene of the formula - [C (R?) 2] m where m is an integer in the range between 1 and 8 and each R independently has the above meaning, with the proviso that at least one Ri is alkyl CrC4; or a residue of 1,2-cyclohexylene or phenylene having the formula: where R7 is hydrogen, CH2OH or CH2NH2 or SO3M, where M is hydrogen, an alkali metal atom, ammonium or a cation formed from an amine, with the proviso that each n is 1 if R and R 'are both C-alkyl; ? -C4 and Y1 is a 1,2-cyclohexylene residue, Y is a linear or branched alkylene of the formula - [C (R?) 2] m where m is an integer in the range between 1 and 8 and each R independently have its previous meaning; -CX = CX- where X is cyano, linear or branched C.sub.1 -C.sub.8 alkyl or di (linear or branched C? -C8 alkyl) -amino; has the above meaning and q is 1, 2, 3 or 4; or a 1,2-cyclohexylene or phenylene residue having the formula: where R7 is hydrogen, CH2OH or CH2NH2 or SO3M, where M is hydrogen, an alkali metal atom, ammonium or a cation formed of an amine. R5 and Re are independent of the other hydrogen; linear or branched C1-C4 alkyl; unsubstituted aryl or aryl substituted by cyano, halogen, OR1 or COORi, nitro, straight or branched C? -C8 alkyl, NR3R where R3 and R4 are the same or different and each is hydrogen or straight or branched dCi2 alkyl; -N + R? R3R-t where R1 t R3 and R4 have the above meaning or alkylene of linear or branched C? -C8-R2 where R2 is ORi, COORt or NR3R4.

31. The compounds of the formula (4) or of the formula (5) where n is 1, 2 or 3; R and R 'are each independent of the other cyano; halogen; hydroxy; ORi or COOR-i, where Ri has the previous meaning; nitro; linear or partially branched or fully fluorinated C? -C8 alkyl; NR3R4 wherein R3 and R4 are the same or different and each is hydrogen or straight or branched C1-C12 alkyl; -N * R? RsR4 where R ^ R3 and R "have the above meaning or straight or branched alkylene-C? -C8-R2 where R2 is OR1, COOR1 or NR3R4, R1 is hydrogen or CrC4l Y alkyl; is -CX = CX- where X is cyano, - (CH2) q-NR? - (CH2) q- where Rt has the above meaning and q is 1, 2, 3 or 4; linear or branched alkylene of the formula - [C (R?) 2] m where m is an integer within a range between 1 and 8 and each R ^ independently has the above meaning, with the proviso that at least one Ri is dd alkyl; or a 1,2-cyclohexylene or phenylene residue having the formula: where R7 is hydrogen, CH2OH or CH2NH2 or SO3M, where M is hydrogen, an alkali metal atom, ammonium or a cation formed from an amine, with the proviso that each n is 1 if R and R 'are both C1-alkyl -C4 and Y is an unsubstituted 1,2-cyclohexylene residue, Y is a linear or branched alkylene of the formula - [C (R?) 2] m where m is an integer in the range between 1 and 8 and each R1 independently has the above meaning; -CX = CX- where X is cyano, linear or branched C? -C8 alkyl or di (linear or branched C? -C8 alkyl) -amino; - (CH2) q-NR1- (CH2) q- where Ri has the above meaning and q is 1, 2, 3 or 4; or a 1,2-cyclohexylene or phenylene residue having the formula: where R7 is hydrogen, CH2OH or CH2NH2 or SO3M, where M is hydrogen, an alkali metal atom, ammonium or a cation formed of an amine, R5 and R8 are independent of the other hydrogen; linear or branched C1-C4 alkyl; unsubstituted aryl or aryl that is substituted by cyano, halogen, OR1 or COOR1, nitro, straight or branched C? -C8 alkyl, NR3R4 where R3 and R4 are the same or different and each is hydrogen or a CC? linear or branched; -N + R! R3R4 where R1 (R3 and R4 have the above meaning or alkylene of straight or branched C1-CB-R2 where R2 is OR1, COORi or NR3R4. omitted from the formula: 2m or SUMMARY OF THE DESCRIPTION The present invention provides a method for inhibiting the resorption of dyes that migrate in the washing liquid, comprising introducing into the washing liquid containing a peroxide-containing detergent, between 0.5 to 150, preferably between 1, 5 to 75, especially between 7.5 to 40 mg, per liter of the washing liquid of one or more compounds having the formula: where n is 1, 2 or 3; A is an anion; Ri is hydrogen or C 1 -C 4 alkyl, Y is - (CH 2) m wherein m is an integer within a range between 1 and 8; - (CH2) P-CH (Ri) - where p is an integer within a range between 1 and 7 and Ri is a linear or branched C? -C4 alkyl, preferably methyl; -CX = CX- where X is cyano, d-C8 alkyl or di (linear or branched alkyl) -amino; - (CH2) q-NR? - (CH2) q- in which Ri has the above meaning and q is 1, 2, 3 or 4; or a 1,2-cyclohexylene residue having the formula: R is cyano; halogen; hydroxy; ORi where Ri has the previous meaning; CO2R2 wherein R2 is hydrogen or linear or branched d-d alkyl; nitro; linear or branched C? -C8 alkyl; di- (C 1 -C 2 alkyl) amino; NR3R4 where R3 and R4 are the same or different and each is a straight or branched C1-C12 alkyl; or -N + R? R3R4 where R1t R3 and R4 have their previous meaning.