MXPA98010407A - Asymmetric estilb compounds - Google Patents

Abstract

The present invention provides, as a first aspect, an asymmetric compound having the formula (1), wherein M is hydrogen, an alkali metal atom, ammonium or a cation formed from an amine, Xa and Xb are the same or different and each is NH2; NH (C1-C4 alkyl); NH (C2-C4 alkoxyalkyl); N (C1-C4 alkoxy) 2; N (CH2CH2OH) 2; a NH-Z-NR1R2 group in wherein Z is optionally substituted C2-C14-arylene alkylene, and R1 and R2 are the same or different and each is C1-C12-R1 alkyl and R2, together with the nitrogen atom to which they are attached, form a morpholino ring , piperidino or piperazino, a residual amino acid, C1-C4 alkoxy, C2-C4 alkoxy substituted with hydroxy and Ya and Yb are the same or different and each is a substituted amino group that has UVA and UVB absorption properties, preferably a group having the formula (2), wherein R3 is CN; SO2R5 wherein R5 is, C1-C12 alkyl, C1-C12 alkoxy, NH2, NH (alkyl), C1-C4), N (C1-C4 alkyl) 2, N (CH2CH2OH) 2, C1-C4 alkoxy or C2-C4 alkoxy substituted with hydroxy; COR5 in which R5 has its previous meaning; COOM in which M has its previous meaning or NHCOR5 in which R5 has its previous meaning and R4 has the same meaning as R3óes H, OH, C1-C4 alkyl or C1-C4 alkoxy, and one of Xa and Xb may be identical to one of Ya and Yb, as long as one Xa and Xb is different from the other and / or one Ya and Yb is different from the other. The present invention also relates to a method for improving the sun protection factor (SPF) of textile fiber materials, especially cotton, polyamide and wool, which comprises treating them with novel compounds

Description

ASYMETRICAL COMPOUNDS OF ESTHYLENE The present invention relates to novel compounds, in particular asymmetric UV-absorbing stilbene compounds which are useful as sunscreen agents; and with a method for improving the sun protection factor (SPF) of textile fiber materials, especially cotton, polyamide and wool, which comprises treating them with novel compounds. It is known that light radiation of wavelengths of 280-400 nm allows the tanning of the epidermis. It is also known that rays of wavelengths of 280-320 nm (called UV-B radiation), cause erythemas and skin burns which can inhibit tanning. It is known that radiation of wavelengths of 320-400 nm (called UV-A radiation) induces tanning of the skin but can also cause damage to the skin, especially sensitive skin exposed to sunlight for periods of time prolonged Examples of such damage include loss of skin elasticity and the appearance of wrinkles, promotion of the appearance of the erythemal reaction and the induction of phototoxic or photoallergenic reactions. Any effective protection of the skin from the damaging effects of undue exposure to sunlight clearly needs to include means to absorb both UV-A and UV-B components from sunlight before they reach the surface of the skin. Traditionally, the protection of human skin 'exposed to potential damage by UV components in sunlight has been effected by applying directly to the skin a preparation containing a UV absorber. In areas of the world, for example Australia and America, which enjoy particularly sunny climates, there has been a great increase in awareness of the potential dangers of undue exposure to sunlight, mixed with fears of the consequences of the alleged damage to the ozone layer. Some of the most distressing modalities of skin damage caused by excessive exposure, without protection, to sunlight are the development of melanomas or carcinomas in the skin. One aspect of the desire to increase the level of protection of the skin against sunlight has been the consideration of additional measures, especially the direct protection of the skin. For example, consideration has been given to the provision of skin protection covered by clothing and thus not exposed directly to sunlight. Most natural and synthetic textiles are at least partially permeable to the UV components of sunlight. Consequently, the simple use of clothes does not necessarily provide the skin under the clothes with adequate protection against damage by UV radiation. Although clothing that contains a deeply colored dye and / or has a tight fabric texture may provide a reasonable level of protection to the skin beneath it, such clothing is not practical in hot sunny climates, from the point of view of comfort. user's personal- There is a need, therefore, to provide protection against UV radiation for the skin beneath the clothing including lightweight summer clothing, which is not dyed or dyed only in pale tones. Depending on the nature of the dye, even the skin under the clothes dyed in some dark tones may also require protection from UV radiation. Such lightweight summer clothes usually have a density of less than 200 g / m2 and have a sun protection factor that ranges from 1.5 to 20, depending on the type of fiber from which the clothes are manufactured. The nominal SPF of a sunscreen (sunscreen or clothes) can be defined as the multiple of the time it takes for an average person who uses the sunscreen to suffer sunburn under average sun exposure. For example, if an average person would normally suffer sunburn after 30 minutes under standard exposure conditions, a sunscreen with a nominal SPF of 5 would extend the protection period from 30 minutes to 2 hours and 30 minutes. For people who live in particularly sunny climates, where the average times of sunburn are minimal, for example only 15 minutes for an average white-skinned person at the hottest time of the day, nominal SPFs of minus 20 for lightweight clothing. It is already known, for example from WO 94/4515, that the application of specific types of UVA to lightweight textile materials in general can effect an increase in the SPF value of the textile thus treated. The increase in the value of the SPF achieved in this way, however, is relatively modest. The use of fluorescent whitening agents (FWA) has also been proposed to effect an increase in the SPF value of textiles. Most FWAs, however, are only effective in absorbing radiation in the UV-A range. Certain symmetric FWAs have been described in EP-A-728,749 which absorb radiation in both UV-A and UV-B ranges, and impart SPF values greatly increased to textile fiber materials treated with them. In Chem. Abstracts, 1962, 12913a (Japan 14,728), certain asymmetric FWAs are described, but those known compounds do not have UV-B absorption properties, so they are not capable of imparting useful SPF values to the treated textile materials with them. Now, certain asymmetric UV absorbing stilbene compounds have been found, which, in relation to the known symmetric stilbene compounds which absorb known UV, are easy to formulate and impart excellent levels of whiteness and SPF values to textile materials treated with they. Accordingly, the present invention provides, as a first aspect, an asymmetric compound having the formula: wherein M is hydrogen, an alkali metal atom, ammonium or a cation formed from an amine; Xa and Xb are the same or different and each is NH2; NH (CX-C4 alkyl); N (C? -C4 alkyl) 2; NH (C2-C4 alkoxyalkyl)} N (CH2CH20H) 2; an NH-Z-NR? R2 group in which Z is C2-C14 alkylene or optionally substituted arylene, and R_ and R2 are the same or different and each is C1-C12 alkyl or Ri and R2, together with the nitrogen atom to which they are each bound, form a ring • of morpholino, piperidino or piperazino; a residual amino acid; C 4 -C 4 alkoxy; C2-C4 alkoxy substituted with hydroxy; •Do not; Y Ya and Yb are the same or different and each is a substituted amino group that has UVA and UVB absorption properties, preferably a group having the formula: NH ~ C2 R4 < 2 > in which R3 is CN; SO2R5 in which R5 is, C1-C12 alkyl, C? -C? 2 alkoxy, NH2, NH (Cx-C4 alkyl), N (d-C4 alkyl) 2, N (CH2CH2OH) 2, alkoxy of C1-C.1 or C2-C4 alkoxy substituted with hydroxy; COR5 in which Rj, has its previous meaning; COOM in which M has its previous meaning or NHCOR5 in which 5 has its previous meaning and R4 has the same meaning as R3. or is H, OH, C? -C4 alkyl or C-d alkoxy; and one of Xa and Xb can be identical to one of Ya and Yb, as long as one Xa and Xb is different from the other and / or one of Ya and Yb is different from the other.

Preferably, M is hydrogen, sodium, potassium, calcium, magnesium, ammonium, mono-, di-, tri- or tetra-alkylammonium of C? -C, mono-, di-, tri-, or tetra C1-C4 hydroxyalkylammonium, or ammonium which is di or trisubstituted with a mixture of C?-C4 alkyl groups and C?-C hydroxyalkyl. Preferably, each M is sodium. When one or more of Xa, Xb and R5 are NH (C? -C4 alkyl), examples of such groups are NH-ethyl, NH-n-propyl, NH-isopropyl, NH-n-butyl and, in particular, the NH-methyl groups. When one or more of Xa and Xb are NH (C -.- C) alkoxyalkyl, examples of such groups are ethoxyethyl, methoxypropyl and, in particular, ethoxyethyl. When one or more of Xa, Xb and R5 are (Ci-C4 alkyl) 2, examples of such groups are N (ethyl) 2, N (n-propyl) 2, N (isopropyl) 2, N (n-) butyl) 2 and, in particular, N (methyl) groups 2. When one or both of Xa and Xb is an NH-Z-NR [beta] R2 group, the C2-C [beta] Z alkylene groups include, for example, ethylene groups , 1,3-prolylene, 1,4-butylene, 1,5-pentylene, 1,6-hexylene, 1,8-octylene, 1,10-decylene, 1,12-dodecylene and 1,4-tetradecylene. Preferred uncles are the alkylene groups of C2-Cs Z, more preferably the group 1, 3-propylene% The arylene Z optionally substituted includes naphthylene and, preferably, the phenylene group. The optionally substituted arylene Z may be substituted, for example with one or more C? -C4 alkyl groups. The C1-C12 alkyl groups Ri and 2 can be, for example, methyl, ethyl, "n-propyl, isopropyl, n-butyl, n-pentyl, n-hexyl, n-octyl, n-decyl and n- groups. Dodecyl, preferably methyl or ethyl groups A residual amino acid Xa and / or Xb may be, for example, one having the formula -NH-CH (C02H) -R6 in which R6 is hydrogen or a group having the formula -CHRRs wherein R7 and Rs are independently hydrogen or C ?C alkyl optionally substituted by one or two substituents selected from hydroxy, thio, methylthio, amino, carboxy, sulfo, phenyl, 4-hydroxyphenyl, 3,5-diiodo 4-hydroxyphenyl, β-indolyl, β-imidazolyl and NH = C (NH2) NH- The specific examples of amino acids of which such preferred residual amino acids Xa and / or Xb are derived and include glycine, alanine, sarcosine, serine, cysteine, phenylalanine, tyrosine (4-hydroxyphenylalanine), diiodotyrosine, tryptophan (β-indolilalanine), histidine (β-imidazolylalanine), a-aminobut acid uric, methionine, valine (a-aminoisovaleric acid), norvaline, leucine (ot-aminoisocaproic acid), isoleucine (a-amino-β-methylvaleric acid), norleucine (a-amino-n-caproic acid), arginine, ornithine (a, d-diaminovaleric acid), lysine (a-acid, e-diaminocaproic acid), aspartic acid (aminosuccinic acid), glutamic acid (a-aminoglutaric acid), threonine, hydroxyglutamic acid and taurine, as well as mixtures optical isomers thereof. Of those amino acids from which such preferred residual amino acids Xa and / or Xb are derived, sarcosine, taurine, glutamic acid and aspartic acid are particularly preferred. A further preferred example of an amino acid from which a residual amino acid Xa and / or Xb can be derived is iminodiacetic acid. Other less preferred examples of amino acids from which residual amino acids Xa and / or Xb can be derived include cystine, lanthionine, proline and hydroxyproline. An alkoxy residue of C 1 -C 4 Xa and / or Xb, R 4 or R 5 can be, for example, a residue of ethoxy, n-propoxy, isopropoxy, n-butoxy or, especially a methoxy residue. A C2-C alkoxy group substituted with hydroxy Xa and / or Xb or R5 can be, for example, the 2-hydroxy-ethoxy, 3-hydroxypropoxy or 4-hydroxybutoxy group. A C 1 -C 4 alkyl group R can be, for example, ethyl, n-propyl, isopropyl, n-butyl or, especially, a methyl group. Preferred asymmetric compounds of formula (1) are those in which Xa and Xb are the same and Ya and Yb are different; and those in which Ya and Yb are the same and Xa and Xb are different. In the groups Ya and Yb of formula (2), preferably the substituents R3 and R4 are, in the 2- and 4- positions relative to the NH substituent. Preferably, in the groups Ya and Yb of formula (2), R3 is CN; SO2R5 in which R5 is Ci-C12 alkyl, C1-C12 alkoxy, NH2, NH (C1-C4 alkyl), N (C2-C4 alkyl) 2, N (CH2CH20H) 2, C alco alkoxy C4 or C2-C4 alkoxy substituted with hydroxy; COR5 in which R5 has its previous meaning; COOM in which M has its previous meaning or NHCOR5 in which R5 has its previous meaning and R4 is hydrogen. The asymmetric compounds of formula (1) can be produced by reacting, under known reaction conditions, cyanuric chloride, successively, in any desired sequence, with each of an aminostilben-sulfonic acid, an amino compound capable of introducing a group Xa and Xb in which Xa and Xb have their previous meanings, and a compound capable of introducing a group Ya and Yb in which Ya and Yb have their previous meaning, provided that one of Xa and Xb is different from the other and / or one of Ya and Yb be different from the other. Alternatively, the asymmetric compounds of formula (1) can be obtained as a mixture with the analogous symmetrical compounds by reacting, in a vessel, cyanuric chloride, an aminostilbenesulphonic acid and the respective stoichiometric amounts of an amino compound capable of introducing a group Xa and Xb, in which Xa and Xb have their previous meaning, and a compound capable of introducing a compound Ya and Yb, in which Ya and Yb have their previous meaning. The starting materials are known compounds which are readily available. Particularly preferred asymmetric compounds of formula (1) are those obtained in the form of a mixture with the analogous symmetrical compounds by reacting, in a vessel, the respective stoichiometric amounts of cyanuric chloride, each of an aminostilbenesulfonic acid, an amino compound able to introduce a group Xa and Xb, in which Xa and Xb have their previous meaning, and a compound capable of introducing a group Ya and Yb, in which Ya and Yb have their previous meaning. For example, if Ya and Yb are the same and Xa and Xb are different, in this same way, a mixture of the following compounds is obtained: The present invention also provides, as a second aspect, a method * for improving the SPF of a textile fiber material, which comprises treating the textile fiber material with 0.05 to 3.0% by weight, based on the weight of fiber material textiles, of one or more compounds having the formula (1). The textile fibers treated according to the method of the present invention may be natural or synthetic fibers or mixtures thereof. Examples of natural fibers include plant fibers such as cotton, viscose, linen, rayon or linen, 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 according to the method of the present invention have a density of less than 200 g / m2 and have not been previously dyed in dark shades. Some of the compounds of formula (1) used in the method of the present invention may be only poorly soluble in water and may need to be applied in dispersed form. For this purpose, they can be mixed with an appropriate dispersant, conveniently using quartz beads and an impeller, below a particle size of 1-2 microns. As dispersing agents of such sparingly soluble compounds of formula (1), there may be mentioned: acid esters or their alkylene oxide adducts salts, for example, acid esters or their salts of a polyamide from 4 to 40 moles of ethylene oxide with 1 mole of a phenol, or esters of phosphoric acid 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 which have been produced by the addition of 1 to 3 moles of styrene in 1 mole of phenol; - polystyrene sulfonates; taurides of fatty acid; mono-diphenyloxide or alkylated di-sulfonates; sulphonates of polycarboxylic acid esters; addition products of 1 to 60, preferably 2 to 30 moles of ethylene oxide and / or propylene oxide of fatty amines, fatty amides, fatty acids or fatty alcohols, each having from 8 to 22 carbon atoms, or tri-hexavalent C3-C6 alkanols, the addition products have been converted to an acid ester with an organic dicarboxylic acid or with an inorganic polybasic acid; - lignin sulfonates; and, in particular condensation products of the formaldehyde, for example, condensation products of lignin sulfonates and / or phenol and formaldehyde; 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 phenylsulfonic acids and / or sulfonated dihydroxydiphenylsulfone and phenols or cresols with formaldehyde and / or urea; or condensation products of diphenyloxide disulfonic acid derivatives with formaldehyde. Depending on the type of compound of formula (1) used, it may be beneficial to carry out the treatment in a neutral, alkaline or acid bath. The method is usually conducted in the temperature range of 20 to 140 ° C, for example at or near the boiling point of the aqueous bath, for example at about 90 ° C. The solutions of the compound of formula (1), or their emulsions in organic solvents can also be used in the method of the present invention. For example, the so-called dyeing with solvents (heat-set pad application) or exhaustive dyeing methods can be used in dyeing machines. If the method of the present invention is combined with a textile treatment or finishing method, such combined treatment can be advantageously carried out using appropriate stable preparations containing the compounds of formula (1) in such a concentration that the improvement is achieved. of the desired SPF. In certain cases, the compound of formula (1) becomes completely effective by a subsequent treatment. This may comprise a chemical treatment such as a treatment with an acid, a heat treatment or a combined thermal / chemical treatment. It is often advantageous to use the compound of formula (1) in admixture with an adjuvant or expander such as anhydrous sodium sulfate, sodium sulfate decahydrate, sodium chloride, sodium carbonate, sodium carbonate, metal phosphate. alkali metal such as sodium or potassium orthophosphate, 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 (1), an minor portion of one or more adjuvants in the method of the present invention Examples of adjuvants include emulsifiers, perfumes, dyes, opacifiers, additional fluorescent whitening agents, bactericides, non-ionic surfactants, fabric care ingredients, especially fabric softeners, ingredients removes stains or repellents from stains or water-tight agents, anti-gelling agents such as alkali nitrides or nitrates alinos, especially sodium nitrate and corrosion inhibitors such as sodium silicate. The amount of each of these optional adjuvants should not exceed 1%, and preferably ranges from 0.01 to 1% by weight on the treated fiber. The method of the present invention, in addition to providing protection to the skin, also increases the useful life of a textile article treated in accordance with the present invention. In particular, the tear resistance and / or photoresist of the treated textile fiber materials can be improved.

The present invention also provides a textile fabric produced from a fiber treated according to the method of the present invention as well as an article of clothing produced from such a fabric. Such textile fabrics and articles of clothing produced from such fibers typically have an SPF value of 20 and above while untreated cotton, for example, generally has an SPF value of from 2 to 4. The method of treatment according to the present invention can also be conducted by washing the textile fiber material with a detergent containing at least one compound of formula (1), thereby imparting an excellent sun protection factor 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 ranging from 10 to 100 ° C, specifically from 15 to 60 ° C. The detergent composition used preferably comprises: i) 5-90%, preferably 5-70% of an anionic surfactant and / or a nonionic surfactant; ii) 5-70%, preferably 5-40% of an additive; iii) 0-30%, preferably 1-12% of a peroxide; iv) 0-10%, preferably 1-6% of a peroxide activator and / or 0-1%, preferably 0.1-0.3% of a bleaching catalyst; v) 0.005-2%, preferably 0.01-1% of at least one compound of formula (1), and vi) 0.005-10%, preferably 0.1-5% of one or more auxiliaries, each by weight , based on the total weight of the detergent. The detergent compositions are also novel and, as such, form a further aspect of the present invention. The detergent can be formulated as a solid, an aqueous liquid comprising 5-50, preferably 10-35% water or as a non-aqueous liquid detergent, containing no more than 5, preferably 0-1% in size. water weight, and based on a suspension of an additive in a non-ionic surfactant, as described, for example, in GB-A-2158454. The anionic surfactant component can 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 alkyl ethoxy sulfates having 10-20 carbon atoms in the alkyl radical. Preferred sulfonates include benzene alkyl 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-COÍR ^ CH? COOM1 in which R is alkyl or alkenyl having 9-17 carbon atoms in the alkyl or alkenyl radical, R 1 is C 1 -C alkyl and M 1 It is an alkaline metal. The nonionic surfactant component can be, for example, a condensate of ethylene oxide with a primary C9-C15 alcohol having 3-8 moles of ethylene oxide per mole. The additive component can 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 psychocarboxylic acid; an organic phosphonate; or an aminoalkylene poly (alkylene phosphonate); or a mixture of those. The preferred silicates are crystalline, layered sodium silicates of the formula NaHSim02m +? PH20 or Na2Sim02m +? PH20, which is a number from 1.9 to 4 and p is from 0 to 20. The preferred aluminosilicates are the commercially available synthetic materials. designated as zeolites A, B, X and HS, or mixtures thereof. Zeolite A is preferred. Preferred polycarboxylates include the hydroxypropylcarboxylates, in particular citrates, polyacrylates and their copolymers with maleic anhydride. Preferred polycarboxylic acids include nitrilotriacetic acid and ethylene diamine tetraacetic acid. Preferred organic phosphonates or aminoalkylene poly (alkylene phosphonates) are the alkali metal ethane 1-hydroxy diphosphonates, trimethylene nitrile phosphonates, ethylene diamine tetrahydrofuran methylene phosphonates and diethylene triamine penta methylene phosphonates. Any peroxide component can be any organic or inorganic peroxide compound, described in the literature or commercially available, which whiten textiles at conventional washing temperatures, for example temperatures in the range of 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 from 6 to 12 C atoms, such as the diperoxyperacetates, diperoxypersebacates, diperoxyphthalates and / or diperoxydecandioates, especially their corresponding free acids, 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. Bleach catalysts that can be added include, for example, enzymatic peroxide precursors and / or metal complexes. Preferred metal complexes are manganese or iron complexes such as manganese or iron phthalocyanines or the complexes described in EP-A-0509787. The detergents used will usually contain one or more auxiliaries such as soil suspending agents, for example sodium carboxymethyl cellulose; salts for adjusting the pH, for example alkali metal or alkaline earth silicates; foam regulators, for example soap; salts for adjusting spray drying and granulating properties, for example sodium sulfate; perfumes; and also, if appropriate, antistatic and softening agents; such as smectite clays; enzymes, such as amylases and proteases; photobleaching agents; pigments; and / or matting agents. These constituents must, of course, be stable in any whitening system employed. It has also been found that the compounds of formula (1) are useful for the fluorescent bleaching of textile materials, in which the connecting polyamides, wool and cotton should be particularly unique, and of paper. The asymmetric compounds of formula (1) offer several advantages over their symmetric analogs: since more substituents are present in the molecule, the properties that can be applied of the corresponding symmetric analogs can be combined, or even ived; the asymmetric compounds of formula (1) dissolve in water more rapidly and to a greater degree than the corresponding symmetric analogs; and, since the color tone and affinity depend on the type of substituent, the fact that the asymmetric compounds of formula (1) contain three different substituents gives more room to modify each of those important properties. The following Examples further illustrate the present invention.

Example 1 A) 8 g (200 mmol) of 4-amino-4'-nitro-2,2'-stilbene-disulfonic acid were dissolved in 90 ml of water and 20 ml of aqueous sodium hydroxide solution. 1M at 0 ° C to form solution A. B) 3.7 g (20 mmol) of cyanuric chloride were dissolved in 20 ml of acetone and poured into 20 ml of ice water. To this mixture was then added, at 0 ° C for 15 minutes, solution A. The pH of the mixture thus obtained was then adjusted to 7 by the addition of 10 ml of 1M aqueous sodium hydroxide solution. C) 2.88 g (21 mmol) of 4-aminobenzoic acid were dissolved in 10 ml of water and 10.5 ml of 1M aqueous sodium hydroxide solution. This solution was then added to the mixture obtained in step B) at 55 ° C while maintaining the pH value of the reaction at 8-9 by the addition of 10 ml of 1M aqueous sodium hydroxide solution. 2 hours later, 4-aminobenzoic acid had reacted completely.

D) The reaction mixture from step C) was treated with 1.97 g (25 mmol) of 40% methylamine solution in water and the mixture thus obtained was boiled and, after the addition of 10 ml of 1 M aqueous sodium hydroxide solution. , the reaction mixture was heated further at 55 ° C for 2 hours. The intermediate product thus obtained was isolated by precipitation with isopropanol to give a brick-colored powder having the formula: To reduce the nitro group in the compound of formula (101A) to the corresponding amino group, 23 g (20 mmol maximum) of wet compound of formula (101A) were reacted with 9 g (150 mmol) of acetic acid and 21 g ( 376 mmol) of iron. The amino compound thus obtained was then reacted sequentially with additional cyanuric chloride as described in step B); with 4-aininobenzamide as described in step C), but replacing the 4-aminobenzoic acid used therein with 4-aminobenzamide; and with methylamine, as described in step D). The product thus obtained was isolated by saline displacement and washing with little water. In this way, the compound of formula (101) was obtained. Elemental analysis of the compound having the formula (101) and having the empirical formula C36H3oNi3? 9S2Na3.7H20 gives:% Theory C 41.26; H 4.23; N 17.38; S 6.11; H20 12.% Found C 41.34; H 4.32; N 17.18; S 5.91; H20 11.1 Example 2 19.3 g (100 i-imol) of cyanuric chloride was dissolved in a mixture of acetone-water and this solution was reacted with 18.42 g (50 mmol) of 2,2-diaminostilben-4,4'-disulfonic acid to pH 5-5.5. 9.7 g (56 mmol) of sulfanilamide and 7.84 g (56 mmol) of 4-a-inomethylbenzamide were added and the reaction temperature was raised to 55 ° C. The pH of the mixture was then adjusted to 8 by the addition of 1M aqueous sodium hydroxide solution and the mixture was stirred for 3 hours at this temperature and pH. Examination of the reaction product by CLAP showed that it consists of 3 products. The reaction product was treated with 15 g (220 ir-raol) of 40% aqueous methylamine solution, then 50 ml of 1M aqueous sodium hydroxide solution was added and the mixture was heated under reflux conditions for 3 hours until the reaction was completed. The reaction mixture thus obtained was concentrated to 100 ml, and added, with stirring, to a solution of hydrochloric acid-acetone. An acid-free mixture was obtained, which was filtered with suction and washed with acetone. The filter cake was dispersed in ethanol-water and the pH adjusted to 8.5. The mixture was then evaporated to dryness. After drying, 53 g (88% of theoretical) of the mixed product (102) was obtained which, according to the analysis by CLAP, has the following composition: The proportions of the respective% of A: B: C, according to the CLAP are 50:25:25. Logically, the elementary analysis corresponds to formula A). Elemental analysis of the mixture (102) of the compound having the respective formulas A), B) or C) and having the empirical formula C36H34 14O9S5Na2.lNaCl.HH2O gives:% Theory C 36.14; H 4.64; N 16.2; S 7.97; Cl 2.93% Found C 35.93; H 4.77; N 16.12; S 7.99; Cl 2.90.

Example 3 The procedure described in Example 2 was repeated except that the sulfonamide used therein was replaced by the equivalent amount of aniline. A mixed product (103) was obtained which, according to the analysis by CLAP, has the following composition: The proportions of the respective% of A: B: C, according to the CLAP are 50:25:25. Logically, the elementary analysis corresponds to formula A). Elemental analysis of the mixture (103) of the compound having the respective formulas A), B) or C) and having the empirical formula C36H33 i3? 7S2Na2.10H2O gives:% Theory C 41.62; H 5.10; N 17.49; S 5.88. % Found C 41.62; H 5.14; N, 17.52; S 6.17.

Example 4 According to the method described in Example 1, 3.8 g of cyanuric chloride in a mixture of acetone / water were reacted with 8 g of 4-amino-4 '-nitrostilbene-2,2'-disulfonic acid followed by 12 g of sodium chloride solution. 40% aqueous methylamine. The reduction of the resulting nitro compound with 21g of iron powder and 9g of glacial acetic acid in 150ml of water yields 8.2g of the intermediate amine of formula The successive reaction of this compound with cyanuric chloride, aniline and methylamine in acetone / water according to the procedure described in Example ID produces the compound (104) having the following elemental analysis: C36H33Ni3? 7S2Na2. 10H2O gives:% Theoretical C 41. 62; H 5.10; N 17.49; S 5.88. % Found C 41. 62; H 5.14; N, 17.52; S 6.17.

Example 5 The procedure described in Example 2 was repeated except that the 4-aminobenzamide used therein was replaced by the equivalent amount of 4-aminoacetophenone, the sulfanilamide by 4-aminobenzamide and the methylamine by 2-methoxyethylamine. The mixed product (105) was obtained which, according to the analysis by CLAP, has the following composition: B) The proportions of the respective% of A: B: C, according to CLAP are 25:25:50. Logically, the elementary analysis corresponds to formula A). Elemental analysis of the mixture (105) of the compound having the respective formulas A), B) or C) and having the empirical formula C4? H? N? 3Na2O? OS2, 0.4NaCl and 9.15H20 gives:% Theoretical C 41.95; H 5.09; N 15.51; S 5.46, Cl 1.21; Water 14.03% Found C 42.0; H 5.1; N 15.6; S 5.5, Cl 1.1; Water 14.05 Following the procedure described in the Example 1, but substituting 4-aminobenzoic acid, methylamine and 4-aminobenzamide by equimolar amounts of the appropriate amines, the compounds of formula (3) of the following Table 1 can also be obtained.

Table 1 By repeating the procedure of Example 2, using the corresponding amines, mixtures of the above compounds (106) - (112) together with the corresponding symmetrical derivatives can be obtained.

Example 6 A standard washing powder (ECE) was made from the following components in the indicated proportions (% by weight): 8. 0% (Cu.5) sodium l-benzene sulfonate 2.9% Alcoho-tetradecan-ethylene glycol bait ether (14 moles of EO) 3.5% Sodium soap 43.8% Sodium tripolyphosphate 7.5% Sodium silicate 1.9% Magnesium silicate 1.2% Carboxymethyl cellulose 0.2% EDTA 21.2% Sodium Sulfate 0 or 0.2% Compound (103) and Water for 100%. g of bleached cotton cloth were washed in a wash liquor containing 4 g / l of the previous wash powder and water (liquor ratio 1:20) at 40 ° C in a Linitest apparatus for 15 minutes and then rinsed, they were dried by centrifugation and ironed at 160 ° C. This washing procedure was repeated three times and 10 times respectively.

After the third and tenth washings, the whiteness of the washed samples was measured with a DCI / SF 500 spectrophotometer according to the Ganz method. The G-anz method is. described in details in Ciba-Geigy Review 1973/1, and also in the article "Measurement of Whiteness", 1SCC Conference on Fluorescence and Fluorescence Materials Colorimetry, Williamsburg, February 1972, published in the Journal of Color and Appearance, 1, No. 5 (1972). The Sun Protection Factor (SPF) was also determined by measuring the UV light transmitted through the patch, using a double-grid spectrophotometer equipped with an Ulbricht cell. The calculation of the SPF was conducted according to that described by B. L. Diffey and J. Robson in J. Soc. Cosm. Chem. 40 (1989), pp. 130-131. The results obtained are shown in the following Table 2: Table 2 Compared to the control experiment, the SRF values obtained according to the invention are 6-7 times larger.

Example 7 An aqueous bleach liquor having a liquor ratio of 1:40 (deionized water) having a content of 0.025, 0.05, 0.1 or 0.2% by weight of a fluorescent bleaching agent was formulated; 5 ml / 1 of a 10% Ultravon EL solution; 20 ml / 1 of a 3% NaOH solution; 5 ml / 1 of a 10% Tinoclarit GS solution; and 3 ml / 1 of a 35% hydrogen peroxide solution. A sample of bleached cotton was immersed in the bleach liquor and the liquor was heated at 85 ° C for 30 minutes, kept at this temperature for 60 minutes and then cooled from 85 ° C to 40 ° C for 20 minutes. The degree of exhaustion of the test fluorescent whitening agent on the cotton substrate was then determined by measuring the Ganz whiteness of each treated cotton sample. The results are shown in the following Table 3. fabla á

Claims (46)

1. g-EIVINDICATIONS 1. An asymmetric compound, characterized because it has the formula: wherein M is hydrogen, an alkali metal atom, ammonium or a cation formed from an amine; Xa and Xb are the same or different and each is NH2; NH (C-C4 alkyl); N (C? -C4 alkyl) 2; NH (C2-C4 alkoxyalkyl); N (CH2CH20H) 2; an NH-Z-NR? R2 group in which Z is C2-C14 alkylene or optically substituted arylene, and Ri and R2 are the same or different and each is C? -C? 2 alkyl or Ri and R2, together with the nitrogen atom to which each is attached, form a morpholino, piperidino or piperazino ring; a residual amino acid; C1-C4 akoxy,: C2-C4 alkoxy substituted with hydroxy; NH, -_ < < Q 'N >;;;? Ya and Yb are the same or different and each is a substituted amino group which has UVA and UVB absorption properties, and in which one of Xa and Xb can be identical to one of Ya and Yb, provided that one of Xa and Xb is different from the other and / or one of Ya and? b is different from the other, so Ya and Yb are each a group that has the formula: in which R3 is CN; SO 2 R 5 wherein R 5 is, C 1 -C 12 alkyl, C 1 -C 12 alkoxy, NH 2, NH (C 1 -C 4 alkyl), N (C 1 -C 4 alkyl) 2, N (CH 2 CH 20 H) 2, alkoxy of C? -C4 or C2-C4 alkoxy substituted with hydroxy; COR5 in which 5 has its previous meaning; COOM in which M has its previous meaning or NHCOR5 in which R5 has its previous meaning and R4 has the same meaning as R3 or is H, OH, C? -C4 alkyl or C? -C4 alkoxy.
2. 2. The compound according to claim 1, characterized in that M is hydrogen, sodium, potassium, calcium, magnesium, ammonium, mono-, di-, tri- or tetra-alkylammonium of C? -C4, mono-, di-, tri-, or tetrahydroxyalkyl ammonium of C? -C4, or ammonium which is di or trisubstituted with a mixture of C1-C4 alkyl groups and C? -C4 hydroxyalkyl.
3. 3. The compound according to claim 2, characterized in that each M is sodium.
4. 4. The compound according to any of the preceding claims, characterized in that one or more of Xa, Xb and R5 are NH (C? -C4 alkyl), NH (C2-C4 alkoxyalkyl), or one or more of Xa , Xb and R5 are N (C1-C4 alkyl) groups. The compound according to claim 4, characterized in that one or more of Xa, Xb and R5 are NH-methyl groups or N (methyl) groups 2. 6. The compound according to any of claims 1 to 3, characterized in that one or both of Xa and Xb is a group NH-Z-NH? R2, in which the alkylene group of .C2-C? 4Z is the 1,3-propylene group. The compound according to any of claims 1 to 3, characterized in that a residual amino acid Xa and / or Xb can be, for example, one having the formula -NH-CH (C02H) -R6 in which R5 is hydrogen or a group having the formula -CHR7Rβ in which R7 and Rs are independently hydrogen or C?-C4 alkyl optionally substituted by one or two substituents selected from hydroxy, thio, methylthio, amino, carboxy, sulfo, phenyl, -hydroxyphenyl, 3,5-diiodo-4-hydroxyphenyl, β-indolyl, β-imidazolyl and NH = C (NH 2) NH-. 8. The compound according to claim 7, characterized in that the preferred residual amino acids Xa and / or Xb are derived from glycine, alanine, sarcosine, serine, cysteine, phenylalanine, tyrosine (4-hydroxyphenylalanine), diiodotyrosine, tryptophan (β-indolilalanine). ), histidine (ß-imidazolylalanine), α-aminobutyric acid, methionine, valine (a-aminoisovaleric acid), norvaline, leucine (a-aminoisocaproic acid), isoleucine (beta-amino-β-methylvaleric acid), norleucine (amine-n-caproic acid), arginine, ornithine (a, d-diaminovaleric acid) , lysine (a-acid, e-diaminocaproic acid), aspartic acid (aminosuccinic acid), glutamic acid (α-aminoglutamic acid), threonine, hydroxyglutamic acid and taurine, as well as mixtures and optical isomers thereof. 9. The compound according to claim 8, characterized in that the amino acid from which the residual amino acids Xa and / or Xb are derived is sarcosine, taurine, glutamic acid or aspartic acid. 10. The compound according to any of the preceding claims, characterized in that Xa and / or Xb, R or R5 is a methoxy residue. 11. The compound according to any of claims 1 to 9, characterized in that Xa and / or Xb or R5 is a 2-hydroxy-ethoxy group. 12. The compound according to any of claims 1 to 9, characterized in that R 4 is a methyl group. The compound according to any of the preceding claims, characterized in that the asymmetric compound of formula (1) is one in which Xa and Xb are the same and Ya and Yb are different; or one in which Ya and Yb are the same and Xa and Xb are different. 14. The compound according to any of the preceding claims, characterized in that, in the groups Ya and Yb of formula (2) the substituents R3 and R4 are in positions 2 and 4 in relation to the NH substituent. 15. The compound according to any of the preceding claims, characterized in that, in the groups Ya and Yb of formula (2), R3 is CN; SO2R5 in which R5 is C1-C12 alkyl, C1-C12 alkoxy, NH2, NH (C? -C4 alkyl), N (C? -C4 alkyl) 2, N (CH2CH20H) 2, C1 alkoxy -C4 or C2-C alkoxy substituted with hydroxy; COR5 in which R5 has its previous meaning; COOM in which M has its previous meaning or NHC0R5 in which R5 has its previous meaning and in which R is hydrogen. 16. The compound of formula (1) according to any of the preceding claims, characterized in that it is obtained in the form of a mixture with analogous symmetrical compounds by reacting, in a vessel, the respective stoichiometric amounts of cyanuric chloride, an aminostilbenesulfonic acid , an amino compound capable of introducing a group Xa and Xb, in which Xa and Xb are as defined in claim 1, and a compound capable of introducing a group Ya and Yb, in which Ya and Yb are as defined in claim 1. A method for increasing the SPF value of a textile fiber material, characterized in that 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 (1) according to claim 1. 18. The method according to claim 17, characterized in that the textile fibers are treated The fibers are cotton, viscose, linen, rayon, linen, wool, ohair, cashmere, angora, silk, polyester, polyamide or polyacrylonitrile. The method according to claim 17, characterized in that the textile fibers are cotton, polyamide or wool fibers. 20. The method according to any of claims 17 to 19, characterized in that the textile fibers have a density of less than 200 g / m2 and have not been previously dyed in dark shades. 21. The method according to any of claims 17 to 20, characterized in that the compound of formula (1) is only slightly soluble in water and is applied in dispersed form. 22. The method according to any of claims 17 to 21, characterized in that, in addition to the compound of formula (1), a smaller proportion of one or more adjuvants is also used. 23. The method according to claim 22, characterized in that the adjuvants are emulsifiers, perfumes, bleaching agents, enzymes, coloring dyes, opacifiers, optical brighteners, bactericides, non-ionic surfactants, fabric care ingredients, anti-gelling agents or corrosion inhibitors. 24. The method according to claim 23, characterized in that the amount of each of the adjuvants does not exceed 1% by weight on the treated fiber. 25. The method for increasing the SPF value of a textile fiber material according to claim 17, characterized in that it comprises washing the textile fiber material with a detergent containing at least one compound of formula (1), thereby imparting both an excellent sun protection factor to the fiber material thus washed. 26. The method according to claim 25, characterized in that it comprises washing the textile fiber material at least once with the detergent composition at a temperature ranging from 10 to 100 ° C. 27. The method according to claim 26, characterized in that it comprises washing the textile fiber material at least once with the detergent composition at a temperature ranging from 15 to 60 ° C. The method according to any of claims 25 to 27, characterized in that the detergent composition used comprises: i) 5-90%, of an anionic surfactant and / or a nonionic surfactant; ii) 5-70%, of an additive; 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 (1), and vi) 0.005-10%, of one or more auxiliaries, each in weight, based on the total weight of the detergent. 29. The method according to claim 28, characterized in that the detergent composition used comprises; i) 5-70%, of an anionic surfactant and / or a non-ionic surfactant; ii) 5-40%, of an additive; iii) 1-12%, of a peroxide; iv) 1-6%, of a peroxide activator and / or 0.1-0.3%, of a bleaching catalyst; v) 0.01-1%, of at least one compound of formula (1), and vi) 0.1-5%, of one or more auxiliaries, each by weight, based on the total weight of the detergent. 30. The method according to any of claims 25 to 29, characterized in that the detergent is formulated as a solid, as an aqueous liquid comprising 5-50% in water or as a non-aqueous liquid detergent, containing no more than 5% by weight of water, based on a suspension of a surfactant and an additive in a nonionic surfactant. ' 31. The method according to claim 28 or 29, characterized in that the anionic surfactant component is a sulphate, sulfonate or carboxylate surfactant, or a mixture thereof. 32. The method according to claim 28 or 29, characterized in that the nonionic surfactant component is a condensate of ethylene oxide with a primary C8-C15 alcohol having 3-8 moles of ethylene oxide per mole. 33. The method of compliance with the claim 28 or 29, characterized in that the additive 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 these. 34. The method according to claim 28 or 29, characterized in that any peroxide component is any organic or inorganic peroxide compound that whitens textiles at conventional washing temperatures. 35. The method according to claim 34, characterized in that the peroxide component is a persulfate, perborate and / or percarbonate. 36. The method of compliance with the claim 28 or 29, characterized in that the bleaching catalyst is an enzyme peroxide precursor and / or a metal complex. 37. The method according to any of claims 25 to 36, characterized in that the detergent contains one or more auxiliaries selected from suspending agents; salts to adjust the pH; foam regulators; salts to adjust spray drying and granulating properties; perfumes; and antistatic agents and softeners; enzymes; photobleaching agents; pigments; and matifying agents. 38. The method according to any of claims 17 to 37, characterized in that resistance to tearing and / or photoresist of the treated textile fiber material is also provided. 39. A textile fabric produced from a fiber treated according to a method according to any of claims 17 to 38. 40. An article of clothing produced from a textile fabric according to claim 39. 41. A detergent composition, characterized in that it comprises: i) 5-90%, of an anionic surfactant and / or a nonionic surfactant; ii) 5-70%, of an additive; iii) 0-30%, of a peroxide; iv) 0-10%, of a peroxide activator and / or 0-1%, of a bleaching catalyst; and / or 0.001-0.05% of a photobleaching agent; v) 0.005-2%, of at least one compound of formula (1), according to claim 1; and vi) 0.005-10%, of one or more auxiliaries, each in weight, based on the total weight of the detergent. 42. The detergent composition according to claim 41, characterized in that it comprises: i) 5-70%, of an anionic surfactant and / or a nonionic surfactant; ii) 5-40%, of an additive; iii) 1-12%, of a peroxide; iv) 1-6%, of a peroxide activator and / or 0.1-0.3%, of a bleaching catalyst; v) 0.01-1%, of at least one compound of formula (1), and vi) 0.1-5%, of one or more auxiliaries, each by weight, based on the total weight of the detergent. 43. A process for fluorescent bleaching of textiles or paper, characterized in that it comprises contacting the textile or paper materials with at least one compound of formula (1), according to claim 1. 44. The process according to Claim 43, characterized in that the textile materials are polyamides, wool or cotton. 45. A method for the protection of human skin, characterized in that it comprises covering the skin with an article of clothing produced from a textile fabric of according to claim 39. 46. A detergent or fabric softener composition for preserving the color of textiles, characterized in that it comprises a compound of formula (1). SUMMARY OF THE INVENTION The present invention provides, as a first aspect, an asymmetric compound having the formula: wherein M is hydrogen, an alkali metal atom, ammonium or a cation formed from an amine; Xa and Xb are the same or different and each is NH2; NH (C? -C4 alkyl); NH (C2-C4 alkoxyalkyl); N (C? -C4 alkyl) 2; N (CH2CH20H) 2; an NH-Z-NR1R2 group in which Z is alkylene of C2-C? or optionally substituted arylene, and Ri and R2 are the same or different and each is C1-C12 alkyl or Ri and R2, together with the nitrogen atom to which they are each attached, form a morpholino, piperidino or piperazino ring; a residual amino acid; C 4 -C 4 alkoxy; C2-C4 alkoxy substituted with hydroxy; Ya and Yb are the same or different and each is a substituted amino group that has UVA and ÜVB absorption properties, preferably a group having the formula: in which R3 is CN; S02R5 wherein R5 is, C? -C? 2 alkyl, C? -C? 2 alkoxy, NH2, NH (C1-C4 alkyl), N (Ci-C4 alkyl) 2, N (CH2CH20H) 2, C1-C4 alkoxy or C2-C4 alkoxy substituted with hydroxy; C0R5 in which R5 has its previous meaning; COOM in which M has its previous meaning or NHCOR5 in which R5 has its previous meaning and R4 has the same meaning as R3 or is H, OH, C1-C4 alkoyl or C? -C4 alkoxy; and one of Xa and Xb can be identical to one of Ya and Yb, as long as one Xa and Xb is different from the other and / or one gives Ya and Yb is different from the other. The present invention also relates to a method for improving the solar protection factor (SPF) of textile fiber materials, especially cotton, polyamide and wool, which comprises treating them with novel compounds.