MXPA97003799A - Compounds of estilben and its - Google Patents

Abstract

The present invention relates to novel stilbene compounds which are useful as fluorescent whitening agents (FWAs) which impart high levels of whiteness to the textile fiber material treated therewith, and which also impart a high sun protection factor (SPF) to the textile fiber materials treated therewith. The present invention also relates to a method for imparting a high level of whiteness and a high sun protection factor to textile fiber materials, especially cotton, polyamide and wool, which comprises treating the textile material with the new components.

Description

STYLENE COMPOUNDS AND THEIR USE DESCRIPTION Background and field of the invention.

The present invention relates to novel stilbene compounds which are useful as fluorescent whitening agents (FWAs), which impart high levels of whiteness to the textile fiber materials treated therewith, and which also impart a high sun protection factor (SPF). ) to the textile fiber material treated therewith. The present invention also relates to a method for imparting a high level of whiteness and a high sun protection factor to the textile fiber material, especially cotton, polyamide and wool, which comprises treating the textile material with the new compounds. It is known that the radiation of light of wavelengths of 280-400 nm allows to tan the epidermis. It is also known that rays of wavelengths of 280-320 nm (called UV-B radiation), cause erythemas and skin burns that can inhibit tanning of the skin. Radiation of wavelengths of 320-400 nm (called UV-A radiation) is known to induce tanning of the skin but it can also cause skin lesions, especially on sensitive skin that is exposed to sunlight for long periods of time. periods. Examples of such injuries include loss of skin elasticity and the appearance of wrinkles, promotion of the onset of erythema reactions and the induction of phototoxic or photoallergic reactions. Any effective protection of the skin against the damaging effects of excessive exposure to sunlight needs to include means to absorb the UV-A and UV-B components from sunlight before they reach the surface of the skin.

Traditionally, the protection of human skin exposed to the potential deterioration caused by the UV components of sunlight, has been effected by direct application to the skin of a preparation containing a UV absorber. In areas of the world, for example in Australia and in America, which enjoy especially sunny climates, there is a great state of alert with respect to the potential dangers of excessive exposure to sunlight, due to fears of the consequences of the alleged deterioration of the ozone layer. Some of the most distressing evidence of skin lesions caused by excessive skin and unprotected exposure to sunlight are the development of skin melanomas or carcinomas. One aspect of the desire to increase the level of protection of the skin against sunlight has been the consideration of additional measures, especially for the direct protection of the skin. For example, it has been considered to provide protection for the skin covered with clothes and therefore without being directly exposed to sunlight. Most natural and synthetic materials are at least partially permeable to the UV components of sunlight. Therefore, the simple use of clothing does not necessarily provide the skin under the fabric with adequate protection against deterioration caused by UV radiation. Although clothing that contains a deeply colored dye and / or that has a tightly woven texture can provide a reasonable level of protection for the skin beneath it, such clothing is not practical in hot climates from the point of view. in view of the user's personal comfort. There is a need, therefore, to provide protection against UV radiation for the skin, which is covered by fabric including light summer clothes, which is not dyed or which is dyed only with pale tones. Depending on the nature of the dye, even the skin under clothes dyed in some dark shades may require protection from UV radiation. Said light summer clothing normally has a density of less than 200 g / m and has a sun protection factor between 1.5 and 20, depending on the type of fiber from which the clothing is manufactured.

The nominal value SPF of a sunscreen (sunscreen or clothes) can be defined as the multiple of the time it takes the average person who uses a sunscreen to suffer sunburn under normal exposure to the sun. For example, without an ordinary person would normally suffer sunburn after 30 minutes under conventional exposure conditions, a sunscreen with a SPF rating of 5 would extend the protection period from 30 minutes to 2 hours and 30 minutes. For people who live in places with especially sunny climates, in which the average time for burns is minimal, for example only 15 minutes for a normal person with fair skin in the hottest part of the day, values are desired SPF ratings of at least 20 for light weight clothing. It is already known, for example from WO 94/4515, that the application of specific types of UVA to lightweight textile materials can generally result in an increase in the SPF value of the textile material thus treated. The increase in the SPF value achieved in this way, however, is relatively modest. The use of FWAs has also been proposed in order to effect an increase in the SPF value of the textile materials. Most FWAs, however, are only effective at absorbing radiation in the UV-A range. We have now found some stilbene compounds that can be produced quickly and that, unexpectedly, absorb radiation in both UV-A and UV-B, and impart enormously increased nominal SPF values to the textile fiber materials treated with the new ones. compounds Accordingly, the present invention provides, in its first aspect, a compound having the formula: wherein M is hydrogen, an alkali metal atom, ammonium or a cation formed from an amine; R! it's a group that has the phoenixes: wherein R3 is NR R5 wherein R4 and R5 are independently hydrogen, C1-C20 alkyl, C2-C20 alkyl, which is interrupted by from 1 to 6 oxygen atoms, C1-C20 alkyl, hetero-substituted, aryl, -C? O, or aralkyl C7-C) 3; or NH-CO-Rf, where R 'is C1-C20 alkyl, C1-C20 alkyl which is interrupted by from 1 to 6 oxygen atoms, hetero-substituted C1-C20 alkyl, C5-C12 cycloalkyl, aryl, -C? or, or C7-C13 aralkyl; or the fopula: NH-CO-R, 6 in which Re has the previous meaning; and R2 is NH2, N (CH2CH2OH) 2, N [CH2CH (OH) CH3] 2, NH- C-alkyl, -C2O, NH-aryl C6- - N O-C C20 alkyl, or C6-C 0 O-aryl; with the proviso that the compound of formula (l) in which R] is - NH - (f 7- NH-COCH, and? ^ Is - N Q is excluded.

The compound of formula (1) in which Ri is -NH-v-NH-COCH and R2 is -N O is described in U.S. Patent No. 2,612,501 in conjunction with its use as a fluorescent whitening agent for textile materials. The C2C2 alkyl groups R4, R5 and Re can be branched or unbranched such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, t-butyl, 2-ethylbutyl, n-pentyl, isopentyl, 1-methylpentyl, 1,3-dimethylbutyl, n-hexyl, 1-methylhexyl, n-heptyl, isoheptyl, 1,3,3-tetramethylbutyl, 1-methylheptyl, 3-methylheptyl, n-octyl, 2- ethylhexyl, 1,1,3-trimethylhexyl, 1,1,3,3-tetramethylpentyl, n-nonyl, n-decyl, n-undecyl, 1-methylundecyl, n-dodecyl, 1, 1,3,3,5, 5-hexamethylhexyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, and n-eicosyl, preferably methyl or ethyl. O-C 1 -C 20 alkyl groups can be branched or unbranched, such as methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy, t-butoxy, 2-ethylbutoxy, n-pentoxy , isopentoxy, 1-methylpentoxy, 1,3-dimethylbutoxy, n-hexoxy, 1-methylhexoxy, n-heptoxy, isoheptoxy, 1, 1,3,3, -tetramethylbutoxy, 1-methylheptoxy, 3-methylheptoxy, n-octoxy, 2-ethylhexoxy, 1,1,3-trimethylhexoxy, 1, 1,3,3-tetramethylpentoxy, n-nonoxy, n-decoxy, n-undecoxy, 1-methylundecoxy, n-dodecoxy, 1, 1,3,3,5,5-hexamethylhexoxy, n-tridecoxy, n-tetradekoxy, n-pentadecoxy, n-hexadecoxy, n-heptadecoxy, n-octadecoxy and n-eicosoxy, preferably groups methoxy, ethoxy or propoxy, especially methoxy groups. When R4, R5 and R are C2-C2o alkyl, which is interrupted by 1 to 6 oxygen atoms, these groups may be branched or unbranched such as 3-oxabutyl, 3-oxapentyl, 3-oxahexyl, 3-oxaoctyl, -oxadecyl, 3-oxadodecyl, 3-oxatetradecyl, 3-oxal? exadecyl, 3-oxaoctadecyl, 3,6-dioxaheptyl, 3,6-dioxaoctyl, 3,6-dioxadecyl, 3,6-dioxadodecyl, 3,6-dioxatetradecyl , 3,6-dioxaheptadecyl, 3,6,9-trioxadecyl, 3,6,9-trioxaundecyl, 3,6,9-trioxadodecyl, 3,6,9-trioxatetradecyl, 3,6,9-trioxahexadecyl or 3,6 , 9-trioxadecaheptyl. When R4, R5 and Re are C? -C20 alkyl, which is substituted with a heterocyclic residue, they can be any of the C20 alkyl groups, listed above in relation to the C? -C20 alkyl groups, R4, R5 and R6? preferably methyl, ethyl or propyl groups, especially a methyl group, substituted with a morpholinyl, piperidyl, 2,2,6,6-tetramethylpiperidyl, piperazinyl or N-methylpiperazinyl residue. The Rf, C5-C] 2 cycloalkyl groups are preferably cyclopentyl, cyclohexyl, cyclooxtyl, cyclodecyl or cyclododecyl groups, especially a cyclohexyl group. When R, R 5 and R are C 6 -C 0 aryl, they may be a naphthyl group or preferably a phenyl group. The C7-C20 aralkyl groups R4, R5 and R can be naphthylalkyl groups but are preferably phenylalkyl groups. Examples of phenylalkyl groups C -C2o R4, R5 and R (, include benzyl, α-methylbenzyl, α, α-dimethylbenzyl, phenylethyl, phenylpropyl, phenyl-butyl, phenylpentyl, phenylhexyl, phenylheptyl, phenyloctyl, phenylnonyl, phenyldecyl, phenyldodecyl and phenyltetradecyl The C6-C10 aryl groups R4, R5 and R6 can be O-aryl groups C6-C? Or, R2, groups NH-aryl C6-C? 0, R2 and aralkyl groups C7-C20, R4, R5 and R? Examples of such substituent groups include hydroxyl, -NH2, -NHRl5 -NR? R2 (in which R] and R2 have their previous meanings), halogen, C? -alkyl, or substituted substituents. C20, C 1 -C 20 alkoxy, C 2 -C 2 alkenyl, C 3 -C 2 akynyl, C 6 -C 2 aryl, sulphonyl, carboxyl, (meth) acryloxy or (meth) acrylamine In each of the compounds of formula ( 1) it is preferred that they be used in a neutral form, ie that M is different from hydrogen, preferably a cation formed from an alkali metal, in particular sodium io, or from an amine. In the compounds of formula (1), preferably Rj is a group of formula: _NH v ~ R3 in which R3 has the previous meaning and is preferably NH-COR6, where Re, has its previous meaning and is preferably CpC-t alkyl, especially methyl; and preferably R2 is NH or - NO • V __ / The compounds of formula (1) can be produced by reaction, under known reaction conditions, of cyanuric chloride, successively, in any desired sequence, with each of an aminostilbenesulfonic acid, an amino compound capable of introducing a group R \ and a compound capable of introducing a group R2, where Ri and R2 each have their previous meaning. The starting materials are known compounds that are easily obtainable. The present invention also provides, as a second aspect, a method of fluorescent whitening and for improving the SPF of a textile fiber material, it comprises treating the textile fiber material with 0.05 to 3.0% by weight, based on the Weight of the textile fiber material, of one or more compounds having the formula: wherein M is hydrogen, an alkali metal atom, ammonium or a cation formed from an amine; Ri is a group that has the formula: wherein R3 is NR4R5 where R4 and R5 are, independently, hydrogen, C20 alkyl, C2-C20 alkyl, which is comprised of from 1 to 6 oxygen atoms, hetero-substituted C1-C20 alkyl, C6-C aryl? 0, or C7-C aralkyl] 3; or NH-CO-R6 where R < , is C1-C20 alkyl, C2-C2o alkyl, which is interrupted by from 1 to 6 oxygen atoms, hetero-substituted C20 alkyl, C5-C20 cycloalkyl, C6C00 aryl or C7-C3 aralkyl; or the formula: wherein R <; has the previous meaning; and R 2 is NH 2, N (CH 2 CH 2 OH) 2, N [CH 2 CH (OH) CH 3] 2, NH-C C 20 alkyl, NH-C 6 -C aryl, O-C 1 -C 2 alkyl, or C 6 -C 10 O-aryl. The textile fibers treated according to the method of the present invention can be natural fibers or synthetic fibers or mixtures thereof. Examples of natural fibers include vegetable fibers such as cotton, viscose, linen, rayon or linen yarn, preferably cotton and animal fibers such as wool, mohair, cashmere, angora and silk, preferably wool. Synthetic fibers include polyester, polyamide and polyacrylonitrile fibers. The preferred textile fibers are cotton, polyamide and wool fibers. Preferably, the textile fibers treated according to the method of the present invention have a density of less than 200 g / m and have not been previously dyed in dark shades. Some of the compounds of formula (1A) used in the method of the present invention can be only sparingly soluble in water and it may be necessary to apply them in dispersed form. To that end, they can be crushed with an appropriate dispersant, conveniently using quartz beads and an impeller, until they are converted to a size of 1-2 microns. As dispersing agents for said sparingly water-soluble compounds of formula (1A), mention may be made of: Acid esters or their salts of alkylene oxide adducts, for example acid esters or their salts of a polyadduct of 4 to 40 moles of ethylene oxide with 1 mole of a phenol, or phosphoric acid esters of the adduct of 6 to 30 moles of ethylene oxide with 1 mole of 4-nonylphenol, 1 mole of dinonylphenol or, especially with 1 mole of compounds that have been produced by the addition of 1 to 3 moles of styrenes on 1 mole of phenol; polystyrene sulfonates; taurides of fatty acid; mono or di-sulfonates of alkylated diphenyl oxide; sulphonates of polycarboxylic acid esters; addition products of 1 to 60, preferably 2 to 30 moles of ethylene oxide and / or propylene oxide on fatty amines, fatty amides, fatty acids or fatty alcohols, each having 8 to 22 carbon atoms, or on C3 alkanols -C6 tri- to hexavalent, the addition products having been converted to an acid ester with an organic dicarboxylic acid or with an inorganic polybasic acid; ligninsulphonates, and in particular, condensation products of fodder, for example condensation products of lignin sulphonates and / or phenol and fnalnaldehyde; condensation products of formaldehyde with aromatic sulfonic acids, for example condensation products of ditolyl ether sulfonates and formaldehyde; condensation products of naphthalenesulfonic acid and / or naphthol or naphthylamin sulfonic acids and formaldehyde; condensation products of phenol sulfonic acids and / or sulfonated dihydroxydiphenylsulfone and phenols or cresols with formaldehyde and / or urea; or condensation products of diphenyl oxide-disulfonic acid derivatives with fopnaldehyde. Depending on the type of compound of formula (1A) used, it may be beneficial to carry out the treatment in a neutral, alkaline or acid bath. The method is usually carried out in a temperature range of from 20 to 140 ° C, for example at or near the boiling point of the aqueous bath, for example up to about 90 ° C. Solutions of the formula (1A) or its emulsions in organic solvents can also be used in the method of the present invention. For example, the so-called solvent dyeing (application of thermofixation with pad) or by methods of dyeing by extraction in dyeing machines. If the method of the present invention is combined with a textile treatment or finishing method, said combined treatment can be advantageously carried out using appropriate stable preparations containing the compound of the formula (1A) in such a concentration that the improvement is obtained of SPF desired. In certain cases, the compound of formula (1A) becomes fully effective by post-tracing. This may comprise a chemical treatment such as acid treatment, a technical treatment or a combined thermal / chemical treatment. It is often advantageous to use the compound of formula (1A) in admixture with an auxiliary or extender such as anhydrous sodium sulfate, sodium sulfate decahydrate, sodium chloride, sodium carbonate, an alkali metal phosphate such as sodium orthophosphate. or potassium, sodium or potassium pyrophosphate or sodium or potassium tripolyphosphate, or an alkali metal silicate such as sodium silicate. In addition to the compounds of formula (1A), a minor proportion of one or more adjuvants may also be employed in the method of the present invention. Examples of adjuvants include emulsifiers, perfumes, dye dyes, opacifiers, other fluorescent whitening agents, bactericides, nonionic surfactants, fabric care ingredients, especially fabric softeners, stain repellents or soil release ingredients, or waterproofing agents, agents anti-gelling agents such as nitrites or nitrates of alkali metals, especially sodium nitrate, and co-deposition inhibitors such as sodium silicate. The amount of each of these optional adjuvants should not exceed 1%, and preferably fluctuate from 0.01 to 1% by weight of treated fiber. The method of the present invention, in addition to providing fluorescent whitening of a treated textile article according to the present invention and sunscreen protection for the skin covered with the textile article treated in this way, can also increase the useful life of the textile article Well treated. In particular, they can improve the resistance to detachment and / or lightfastness of the textile fiber material. The present invention also provides a textile fabric produced from a fiber treated according to the method of the present invention as well as a garment article made from said fabric. Said fabrics and textile articles for garments produced from said fabrics typically have a nominal value of SPF of 20 and above, while the cotton not subjected to treatment, for example, has in general a nominal value of SPF of from 2. a 4. The treatment method according to the present invention can also be carried out by washing the textile fiber material with a detergent containing at least one (1A), which imparts an excellent level of fluorescent whiteness and a factor of extraordinary solar protection to the fiber material thus washed. The detergent treatment according to the present invention is preferably carried out by washing the textile fiber material at least once with the detergent composition at a temperature comprised between 10 to 100 ° C, especially 15 to 60 ° C. The detergent composition used preferably comprises: i) 5-90%, preferably 5-70% of an anionic surfactant and / or a non-ionic surfactant; ii) 5 - 70%, preferably 5 - 40% of a detergency builder; iii) 0-30%, preferably 1-12% of a peroxide; iv) 0-10%, preferably 1-6% of a peroxide activator and / or 0-1%, preferably 0.1-3% of a bleaching catalyst; v) 0.005-2%, preferably 0.01-1% of at least one compound of formula (1A); and vi) 0.005-10%, preferably 0.1-1.5% of one or more auxiliaries, each by weight, based on the total weight of the detergent.

Said detergent compositions are also new and, as such, form a further aspect of the present invention. The detergent can be formulated in the form of a solid, in the form of an aqueous liquid comprising 5-50, preferably 10-35% water or in the form of a non-aqueous liquid detergent, containing not more than 5, preferably 0-1. % by weight of water, and based on a detergent builder suspension in a nonionic surfactant, such as has been described, for example, in British Patent GB-A-2158454. The anionic surfactant component can be, for example , a surfactant, a sulfate, sulfonate or carboxylate, or a mixture thereof. Preferred sulfates are alkyl sulfates having 12-22 carbon atoms in the alkyl radical, optionally in combination with alkyl ethoxy sulfates having from 10-20 carbon atoms in the alkyl radical. Preferred sulfonates include alkylbenzene sulfonates having 9-15 carbon atoms in the alkyl radical. In each case, the cation is preferably an alkali metal, especially sodium. Preferred carboxylates are alkali metal sarcosinates of formula R-CO (R 1) CH 2 COOM 1 in which R is alkyl or alkenyl having 9-17 carbon atoms in the alkyl or alkenyl radical, R 1 is C 4 alkyl and M 1 is a metal alkaline. The nonionic surfactant component can be, for example, a condensate of ethylene oxide with a primary C -C 15 alcohol having 3-8 moles of clylene oxide per mole. The builder component may be an alkali metal phosphate, especially a tripolyphosphate; a carbonate or bicarbonate, especially the sodium salts thereof; a silicate or disilicate; 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 crystalline sodium silicates in layers having the formula NaHSimO2mu pH2? or Na2SimO2ni41.pH2O in which m is a number from 1.9 to 4 and p is 0 to 20. The preferred aluminosilicates are the commercially available synthetics designated as Zeolites A, B, X, and HS, or mixtures thereof. same. Zeolite A is preferred. Preferred polycarboxylates include hydroxypolycarboxylates, in particular citrates, polyacrylates and their copolymers with maleic anhydride. Preferred polycarboxylic acids include nitrilotriacetic acid, and ethylenediaminetetraacetic acid. Preferred organic phosphonates or poly (alkylene phosphonate) aminoalkylenes are 1-hydroxy ethane diphosphonates of alkali metals, nitrilotrimethylene phosphonates, ethylene diamine tetramethylene phosphonates and diethylenetriamine pentamethylene phosphonates. The peroxide component can be an organic or inorganic peroxide compound, described in the literature or commercially available, which whitens textile articles at conventional washing temperatures, for example at temperatures in the range of from 5 ° C to 90 ° C. In particular, the organic peroxides are, for example, monoperoxides or polyperoxides having alkyl chains of at least 3, preferably 6 to 20 carbon atoms; in particular diperoxydicarboxylates having 6 to 12 carbon atoms, such as diperoxyperactates, diperoxypersebacates, diperoxyphthalates and / or diperoxy dodecanedioates, especially their free acid co-ingredients, which are of interest. It is preferred, however, to employ highly active inorganic peroxides such as persulfate, perborate and / or percarbonate. Of course, it is also possible to use mixtures of organic and / or inorganic peroxides. The peroxides, especially the inorganic peroxides, are preferably activated by the inclusion of an activator such as tetraacetyl ethylenediamine or nonoyloxybenzene sulfonate. Bleaching catalysts that can be added include, for example, peroxide enzymatic precursors and / or metal complexes. Preferred metal complexes are complexes of manganese or polyp such as manganese phthalocyanines or the complexes described in European patent EP-A-0509787. The detergents used will usually contain one or more auxiliaries such as agents for suspending dirt, for example sodium carboxymethylcellulose.; salts for adjusting the pH, for example alkali or alkaline metal silicates; foam regulators, for example soap, salts for adjusting the spray-drying and granulation properties, for example sodium sulfate; or perfumes; and also, if appropriate, antistatic and softening agents; such as smectite clays; enzymes, such as amylases and proteases; photobleaching agents; pigments; and / or tonalizing agents. These constituents should be naturally stable for any bleaching system employed. The following Examples further illustrate the present invention. The compound of formula (101) of Example 1 has been described in US Pat. No. 2,612,501.

Example 1 A solution of 17.3 g of 4,4'-diaminostilbene-2,2'-disulfonic acid (85%) in 150 ml of water and 60 g of ice was added, in the course of 1 hour, to a solution of 12.66 g of cyanuric chloride in 80 ml of acetone and 75 g of ice. During the addition, the temperature was maintained at 0 ° C. In a period of 10 minutes, 34.4 ml of a 1 molar solution of soda were added. , whereby the pH is increased from 1 to 7. The solution is treated with 10.5 g of 4-aminoacetanilide and with 34.4 ml more than 1 molar soda solution and heated to 50 ° C, using a external heating bath. After the addition of 12.6 g of morpholine, the bath temperature is raised to 95 ° C and acetone is distilled off until the internal temperature of the reaction mixture is 90 ° C. After cooling the reaction mixture to 20 ° C, it is adjusted to pH 7.5 using 2N hydrochloric acid and treated with 3 liters of acetone. The reaction mixture is then filtered to obtain 26.4 g of a light yellow compound of formula (101) having an? Niax of 283 nm and 355 nm. The elemental analysis of the compound having the formula (101) and the empirical formula C H44N? 4O? 0Na2S2.8H2O gives: % Req .: C 44.66; H 5.11; N 16.57; S, 5.41; H2O 12, 17.% Found: C 44.96; H 5.15; N, 16.83; S 5.03; H2O 1.81.

Example 2 A) 12.65 g. of cyanuric chloride in 80 ml of acetone and 75 g of ice water were then treated, dropwise, with a solution of 15 g of 4,4'-diaminostilbene-2,2'-disulfonic acid (81.6%) in 200 ml of ice water. During the addition, the temperature was maintained at 0 ° C. After stirring the reaction mixture for 30 minutes, 10 g of 30% ammonia solution was added and the resulting mixture was treated with 68.8 ml of a 1 molar solution of soda for 20 minutes. The reaction mixture was stirred for 5 hours at 50 ° C. After cooling to 20 ° C, the reaction mixture was filtered off, washed with water and dried to give 21.4 g of a light yellow product of formula (102) having a max of 352 nm . The elemental analysis of the compound having the formula (102) and the empirical formula C2oH? 4NiüCl2S2Na2? 6 10.5H20 gives: % Req .: C 27.53; H, 4.20; N, 16.05; S 7.35; Cl 8.13; H2O 23.06. % Found: C 27.58; H 4.31; N 16.53; S 7.26; Cl 8.31; H20 23.06 B) 10 g of the compound (102) obtained in Part A) were added, dropwise at 100 ° C, for 30 minutes, to a solution of 5 g of p-aminoacetanilide in 150 ml of methyl cellosolve and the reaction mixture was added. then heated to 130 ° C, after which the compound of formula (103) was precipitated as the free acid. The reaction was then cooled, filtered and washed with hydrochloric acid and then with water. The wet filter cake was then adjusted to pH 11 using 2N NaOH and then filtered with suction. After drying, 9.8 g of a light beige compound of fopula (103) having a?, Nax of 283 nm, and 352 nm was obtained. Elemental analyzes of the compound having the formula (103) and having the empirical formula C36H32N14S2O8Na 7.4H20 gives: % Req .: C 41.89; H 4.57; N, 19.00; S 6.21; H2O 12.92% Found: C 42.22; H 4.48; N 19.19; S, 6.20; H2O 12.92.

Example 3 g. of the compound that has the formula: they were suspended in 10 ml of a 0.1 molar sodium hydroxide solution, treated with 3.3 g of a 40% solution of methylamine in water and the reaction mixture is then heated to 90 ° C. The compound of the formula (105) is obtained according to the procedure described in Example 1 except that the final reaction step thereof, ie the reaction with morpholine, was omitted. The reaction mixture was stirred at this temperature for 2 hours until the reaction was complete, as indicated by HPLC. The free acid was first precipitated in 200 ml of acetone containing 25 ml of 2N HCl. After filtration with suction and washing with 100 ml of acetone, the filter residue was suspended in methanol and converted to the disodium salt using 2N NaOH. After concentration by evaporation and air drying, 8.88 g (73% in theory) of the compound (104) remained. The elemental analysis of the compound having the formula (104) and the empirical formula C38H34N14? 8S2Na2.9H2? .0.4 NaCL gives:% Req .: C 41.00; H 4.89; N, 17.62; S, 5.76; Na 4.96; Cl 1.27; H20 14.56% Found: C 40.82; H 4.92; N, 17.51; S, 5.76; Na 4.83; Cl 1.34; H2O 14.33 The procedure described in one or more of Examples 1 to 3 can be used to prepare the following compounds of formula (1): Compounds having the formula: wherein the substituents R2, R3 and M are as defined in the following Table: - l í Compounds that have the formula: wherein the substituents R2, R3 and M are as defined in the following table: Example 4 g of cotton cloth samples were treated in an aqueous solution of 200 ml with O, or with 0.2% by weight of the test compound (103) (based on the weight of the cotton) and 1 g. of crystalline sodium sulfate, heated at 20-60 ° C for 10 minutes, kept at 60 ° C for 20 minutes and cooled from 60 ° C to 40 ° C in 10 minutes. The samples were then rinsed in cold running water, dried and ironed. The whiteness of the treated samples was measured with a DC1 / SF 500 spectrophotometer according to the Ganz method. The Ganz method is described in detail in the Ciba-Geigy Magazine, 1973/1, and also in the article "Whiteness Measurement," ISCC "Conference on Fluorescence and the Colorimetry of Fluorescent Materials, Williamsburg, February 1972, published in "Journal of Color and Appearance", 1 No. 5 (1972) The Sun Protection Factor (SPF) is determined by measuring the UV light transmitted through the sample, using a double-grid spectrophotometer fitted with an Ulbricht bowl The calculation of SPF was carried out as described by BL Diffey and J. Robson in J. Soc. Cosm. Chem. 40. (1989), pages 130-131. The results (an average of 5 measurements at different points). in each sample) are shown in the following Table 1: Table 1 Compared with the control experiment, the SPF value obtained according to the invention is 7-8 times higher and the Ganz Whiteness also increased in substantial fopna. Similar results were obtained when the compound of formula (103) was replaced by compound (101) or (104).

Example 5 A conventional washing powder (ECE) was prepared from the following components in the indicated proportions (% by weight): 8.0% (Cu s) sodium alkylbenzene sulfonate 2.9% Tallow alcohol - tetradecane - ethylene glycol ether (14 moles OE) 3.5% Sodium soap 43.8% Sodium tripolyphosphate 7.5% Sodium silicate 1.9% Magnesium silicate 1.2% Carboxymethylcellulose 0.2% EDTA 21.2% Sodium sulphate 0 or 0.2 % Compound (103 and Water up to 100%.

A wash liquor was prepared by dissolving 0.8 g of the preceding wash powder in 200 ml of tap water. 10 g were added. of cotton cloth bleached to said bath and washed at 40 ° C, for 15 minutes and then rinsed, dried by centrifugation and ironed at 160 ° C. This washing procedure was repeated three and ten times. After the third and tenth wash, the whiteness of the washed samples was measured with a DC1 / SF 500 spectrophotometer according to the Ganz method and the SPF value was determined as described by B. L. Diffey and J. Robson. The results obtained are indicated in the following Table 2: Table 2 The results of Table 2 demonstrate that washing with a detergent containing a compound of formula (103) increases the SPF value substantially and improves Ganz Whiteness (GW) with successive washes. Similar results are obtained when the compound of formula (103) is replaced by compound (101) or (104).

Claims (43)

1. A compound that has the formula: wherein M is hydrogen, an alkali metal atom, ammonium or a cation formed from an amine; Ri is a group that has the formulas: wherein R3 is NR4R5 wherein R_j and R5 are independently hydrogen, C) -C or alkyl, C2-C20 alkyl which is interrupted by from 1 to 6 oxygen atoms, hetero-substituted C1-C20 alkyl, C6 aryl C10, or C7-C3 aralkyl; or NH-CO-R6 wherein R is C1-C20 alkyl, C2-C2o alkyl which is interrupted by from 1 to 6 oxygen atoms, C-C20 hetero-substituted alkyl, C5 cycloalkyl, C2 aryl , or C7-C? 3 aralkyl; or the formula: in which R ^ has the previous meaning; and R2 is NH2, N (CH2CH2OH) 2, N [CH2CH (OH) CH3] 2, NH-C-alkyl, -C2, NH-aryl Cfl- - DO NOT O-C 1 -C 20 alkyl, or C 6 -C 0 O-aryl; with the proviso that the compound of formula (I) in which R i is - NH- fi V-NH-COCR, and R? is _N or is excluded.

2. A compound according to claim 1 wherein a C20 alkyl group Ri, R5 or Re is methyl or ethyl.

3. A compound according to claim 1 or 2 in which an O-alkyl group C? -C20 R2 is methoxy, ethoxy or propoxy.

4. A compound according to claim 1 wherein a C5-C12 cycloalkyl group R ^ is cyclohexyl.

5. A compound according to claim 1 wherein an aryl group Cfi-Cio R, R5 or Re is phenyl.

6. A compound according to any of the preceding claims, wherein the compound is in neutral form.

7. A compound according to claim 6 wherein M is a cation formed from an alkali metal.

8. A compound according to claim 7 wherein the alkali metal is sodium.

9. A compound according to any of the preceding claims, wherein Ri is a group having the formula: wherein R3 is as defined in claim 1.

10. A compound according to claim 9 wherein R3 is NH-CO-Rf, wherein R6 is as defined in claim

1 1. A compound according to claim 10 wherein R6 is CrC4 alkyl.

12. A compound according to claim 1 wherein R < -, it's methyl.

13. A compound according to any of the preceding claims wherein R2 is NH2 or

14. A process for the production of a compound of formula (1) comprising reacting cyanuric chloride, successively, in any desired sequence, with each of an amino stilbenesulfonic acid, an amino compound capable of introducing a group R1 and a compound which is capable of introducing a group R2, in which Ri and R2 are each as defined in claim 1.

15. A method for increasing the nominal value SPF of a textile fiber material, which comprises treating the material of textile fiber with 0.05 to 3.0% by weight, based on the weight of the textile fiber material, of one or more compounds having the formula: wherein M is hydrogen, an alkali metal atom, ammonium or a cation formed from an amine; Ri is a group that has the formula: wherein R3 is NR4R5 wherein R4 and R5 are, independently, hydrogen, C20 alkyl, C2-C2alkyl which is interrupted by from 1 to 6 oxygen atoms, hetero-substituted C2C2o alkyl, C6-C aryl? 0, or C7-C aralkyl] 3; or NH-CO-Rf, where R6 is C] -C20 alkyl, C2-C20 alkyl which is inteputed by from 1 to 6 oxygen atoms, hetero-substituted C2O2 alkyl, C5-C2 cycloalkyl, C6-C aryl 0, or C7-C aralkyl?; or the formula: in which Re has the previous meaning; and R 2 is NH 2, N (CH 2 CH 2 OH) 2, N [CH 2 CH (OH) CH 3] 2, NH-C C 20 alkyl, NH-C 6 -C aryl, - DO NOT O-alkyl -C20, or O-aryl C6-C? 0.

16. A method according to claim 15, wherein the textile fiber material is cotton, viscose, linen, rayon or linen yarn, wool, mohair, cashmere, angora and silk, polyester, polyamide or polyacrylonitrile.

17. A method according to claim 16, in which the textile fiber material is cotton, polyamide or wool.

18. A method according to any of claims 15 to 17 in which the textile fiber material has a density of less than 200 g / m and has not been previously dyed in dark shades.

19. A method according to any of claims 15 to 18 in which the compound of formula (1A) is only sparingly soluble in water and is applied in dispersed form.

20. A method according to any of claims 15 to 19 wherein, in addition to the compound of formula (1A), a minor proportion of one or more adjuvants is also used.

21. A method according to claim 20 wherein the adjuvant is one or more of an emulsifier, perfume, coloring dyes, opacifiers, additional fluorescent whitening agents, bactericidal, non-ionic surfactant, fabric care ingredients, anhydrous agents, -gclificanles and inhibitors of coposition.

22. A method according to claim 20 or 21, wherein the amount of each of these adjuvants is between 0.01 to 1% by weight based on the treated fiber material.

23. A method for increasing the SPF nominal value of a textile fiber material according to claim 15 comprising washing the textile fiber material with a detergent containing at least one (1A) formula of pomade imparting in this way an excellent sun protection factor to the fiber material washed in this way.

24. A method according to claim 23 comprising washing the textile fiber material at least once with the detergent composition at a temperature comprised between 10 to 100 ° C.

A method according to claim 24 comprising washing the textile fiber material at least once with the detergent composition at a temperature that is comprised between 15 to 60 ° C.

A method according to any of claims 23 to 25 in which the detergent composition used comprises : i) 5-90% of an anionic surfactant and / or a non-ionic surfactant; ii) 5-70% of a detergency builder; iii) 0-30% of a peroxide; iv) 0-10% of a peroxide activator and / or 0-1% of a bleaching catalyst; v) 0.005-2% of at least one compound of formula (I?); and vi) 0.005-10% of one or more auxiliaries, each by weight, based on the total weight of the detergent.

27. A method according to claim 26, wherein the detergent composition used comprises: i) 5-70% of an anionic surfactant and / or a nonionic surfactant; ii) 5-40% of a detergency builder; ii) 1-12% of a peroxide; iv) 1-6% of a peroxide activator and / or 0.1-3% of a bleaching catalyst; v) 0.01-1% of at least one compound of formula (I A); and vi) 0, 1-5% of one or more auxiliaries, each by weight, based on the total weight of the detergent.

28. A method according to claim 26 or 27 in which the detergent is formulated in the form of a solid, in the form of an aqueous liquid comprising 5-50% water or in the form of a non-aqueous liquid detergent, which they contain no more than 5% by weight of water and are based on a suspension of a surface activating agent and a builder in a nonionic surfactant.

29. A method according to any of claims 26 to 28 in which the anionic surfactant component is a sulfate, sulfonate or carboxylate, or a mixture thereof.

30. A method according to any of claims 26 to 29 in which the nonionic surfactant component is a condensate of ethylcne oxide with a primary alcohol C9-C] 5 having 3-8 moles of ethylene oxide per mole .

31. A method according to any of claims 26 to 30 wherein the builder component is an alkali metal phosphate; a carbonate or bicarbonate; a silicate or disilicate; an aluminosilicate; a polycarboxylate; a polycarboxylic acid; an organic phosphonate; an aminoalkylene poly (alkylene phosphonate); or a mixture of them.

32. A method according to any of claims 26 to 31 wherein the peroxide component is any organic or inorganic peroxide compound that bleaches textile products at conventional wash temperatures.

33. A method according to claim 32 in which the peroxide component is a persulfate, a perborate and / or a percarbonate.

34. A method according to any of claims 26 to 33 in which the bleaching catalyst is a precursor of enzymatic peroxide and / or a metal complex.

35. A method according to any of claims 26 to 34 in which the detergent contains one or more auxiliaries selected from suspending agents; salts to adjust the pH; foam regulators, salts for adjusting spray drying and granulation properties; perfumes; and antistatic agents and softeners; enzymes; otoblanking agents; pigments; and tonalizing agents.

36. A method according to any of claims 15 to 35 by which the tear strength and / or light fastness of the treated textile fiber material is also improved.

37. A textile fabric produced from a fiber treated according to a method claimed in any of claims 15 to 36.

38. A garment article produced from a textile fabric according to claim 37.

39 A detergent composition comprising: i) 5-90% of an anionic surfactant and / or a nonionic surfactant; ii) 5-70% of a detergency builder; iii) 0-30% of a peroxide; iv) 0-10% of a peroxide activator and / or 0-1% of a bleaching catalyst; v) 0.005-2% of at least one compound of formula (1A) as defined in claim 15; and vi) 0.005-10% of one or more auxiliaries, each by weight, based on the total weight of the detergent.

40. A detergent composition according to claim 39, comprising: i) 5-70% of an anionic surfactant and / or a nonionic surfactant; ii) 5-40% of a detergency builder; iii) 1-12% of a peroxide; iv) 1-6% of a peroxide activator and / or 0.1-3% of a bleaching catalyst; v) 0.01-1% of at least one compound of formula (1A); and vi) 0.1-5% of one or more auxiliaries, each by weight, based on the total weight of the detergent.

41. A process for fluorescent whitening of textile or paper materials comprising contacting textiles or paper with at least one compound of formula (1A), as defined in claim 15.

42. A The method according to claim 41, wherein the textile materials are polyamides, wool or cotton.

43. A method for the protection of human skin comprising covering the skin with a cloth article according to claim 38.