MXPA97005371A - Derivatives of triazina and its - Google Patents

Abstract

The present invention relates to novel compounds that are useful as ultraviolet absorbent (UVA) agents, and as fluorescent whitening agents (FWA), and with a method for improving the sun protection factor (SPF) of textile fiber materials, especially cotton, polyamide, and wool, treated with new compunds

Description

DERIVATIVES OF TRIAZINA AND ITS USE DESCRIPTION Background and field of the invention.

The present invention relates to novel compounds that are useful as ultraviolet (UVA) absorbing agents and as fluorescent whitening agents (FWA), and with a method for improving the sun protection factor (SPF) of textile fiber material, especially cotton, polyamide and wool, treated with the new compounds. It is known that ultraviolet 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 erythema and burning of the skin, which can inhibit tanning of the skin. It is known that the radiation of the wavelengths of 320-400 nm (called UV-A radiation) induces tanning of the skin, but it can also cause damage to the skin, especially to sensitive skin that is exposed to sunlight for long periods. Examples of such damages include loss of skin elasticity and the appearance of wrinkles, promotion of the onset of erythema reaction, and the induction of phototoxic or photoallergic reactions. Any effective protection of the skin against the harmful effects of undue exposure to sunlight, clearly needs to induce the means for the absorption of both the UV-A and the UV-B components of sunlight before they reach the surface of the skin. Traditionally, the protection of exposed human skin, against the potential damage of UV components in sunlight, has been effected by direct application to the skin of a preparation containing a UV absorber. In regions of the world, for example, Australia and America, which especially enjoy sunny climates, there has been a great increase in awareness of the potential dangers of undue exposure to sunlight, along with fears of the consequences of the alleged damage to the ozone layer. Some of the most annoying realizations of skin damage caused by excessive exposure and unprotected from sunlight are the development of skin melanomas or carcinomas. One aspect of the desire to increase the level of skin protection against sunlight has been the consideration of additional measures, above and above the direct protection of the skin. For example, consideration has been given to the provision of protection to skin covered with clothing, and therefore, not directly exposed to sunlight. Most natural and synthetic textiles are at least partially permeable to the UV components of sunlight. Consequently, the mere fact of wearing garments does not necessarily provide the skin under the clothing with adequate protection against the damages of UV radiation. While garments containing a deep-colored dye, and / or having a tight texture of fabric, can provide a reasonable level of protection to the skin beneath them, such garments are not practical in warm and sunny climates, from the point of view of personal comfort of the person using them. Therefore, there is a need to provide protection against UV radiation, for the skin that is under the garments, including light summer garments, which are not dyed or which are dyed only in pale shades. According to the nature of the dye, even the skin beneath the garments dyed in some dark shades may also require protection against UV radiation.

Said light summer garments usually have a density lower than 200 g / m2, and have a sun protection factor that varies between 1.5 and 20, according to the type of fiber from which the garments are manufactured. The SPF classification of a sunscreen (sunscreen or garment) can be defined as the multiple of the time it takes for a normal person wearing a sunscreen, to suffer from sunburn under normal exposure to the sun. For example, if a normal person would usually suffer from sunburn after 30 minutes under conventional exposure conditions, a sunscreen that has an SPF rating of 5 would extend the protection period from 30 minutes to 2 hours and 30 minutes. For people who live in especially sunny climates, where the average times of sunburn are minimal, for example, only 15 minutes for a normal white-skinned person at the hottest time of day, SPF ratings of at least 20 They are desired for light garments. It is already known, for example from W094 / 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 treated in this way. The increase in SPF value achieved in this way, however, is relatively modest. The use of FWA to effect an increase in the SPF value of textiles has also been proposed. However, most FWAs are only effective in absorbing radiation in the UV-A range. Now we have discovered certain new compounds that can be produced easily, and that unexpectedly, absorb radiation in both UV-A and UV-B ranges, and impart SPF classifications greatly increased, to textile fiber materials treated with the new compounds . Accordingly, the present invention provides, as a first aspect, a compound having the formula: wherein M is hydrogen, an alkali metal atom, ammonium or a cation formed of an amine; Ri is hydrogen or hydroxy; R2 is C1-C4 alkyl or phenyl; Y is -C (= 0) - NR3R4, wherein R3 and R4, independently, are hydrogen or C1-C4 alkyl, -S02-NR3R4 wherein R3 and R4. have their previous meanings, -C (= O) -R2 in which R2 has its previous meaning, or -C (= 0) -OM in which M has its previous meaning; and X is NH or O, or X-R2 denotes a morpholino group; provided that those compounds are excluded in which: a) Y is -C (= 0) -OM in which M has its previous meaning; X is NH; and R2 is phenyl; b) Ri is hydrogen; Y is -C (= 0) -CH3; and X-R2 denotes a morpholino group; or c) Ri is hydrogen; And it is -C (= 0) -OM in which M has its previous meaning; X is NH; and R2 is methyl. When one or more of R2, R3 and R "is CpG alkyl", this group may be branched or unbranched, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec.-butyl, or tere-butyl, especially methyl . In each of the compounds of formula (1) it is preferable that they are used in neutral form, ie that M is another which is not hydrogen, preferably a cation formed of an alkali metal, in particular sodium, or an amine . In the compounds of formula (1), Ri is preferably hydrogen, X-R2 is NH-CH3, and Y is -C (= 0) -NHCH3. The compounds of formula (1) can be produced by reacting, under known reaction conditions, cyanuric chloride, successively, in any desired sequence, with each of an aminostilbenesulfonic acid, an amino compound capable of introducing a group in which Ri and Y have their previous meanings, and a compound capable of introducing a group X-R2, in which X and R2 each have their previous meanings. The initial materials with known compounds that can be obtained easily. The present invention further 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 the textile fiber. textile fiber material, 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 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 less than 200 g / m, and have not been previously dyed in deep ranges. Some of the compounds of formula (1) which are used in the method of the present invention may be only sparingly soluble in water, and may need to be applied in dispersed form. For this purpose, they can be ground with an appropriate dispersant, conveniently using quartz beads and an impeller, at a particle size of 1-2 microns. As dispersing agents for said sparingly soluble compounds of formula (1), there may be mentioned: - acid esters or their salts of alkylene oxide adducts, for example, acid esters or their salts of a polyamide of 4 to 40 moles of ethylene 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 in particular, with 1 mole of compounds that have been produced by adding 1 to 3 moles of styrenes on 1 mole of phenol; polystyrene sulfonates; fatty acid taurides; alkylated diphenyloxide-mono- or di-sulfonates; sulfonates 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 C3-C6 tri- to hexavalent alkanols, the addition products having 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 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 ditolylether sulfonates and formaldehyde; condensation products of naphthalenesulfonic acid and / or naphthol- or naphthylaminesulfonic acids and formaldehyde; condensation products of phenolsulfonic acids and / or sulfonated dihydroxydiphenylsulfone and phenols or cresols with formaldehyde and / or urea; or condensation products of diphenyloxide disulfonic acid derivatives with formaldehyde. According to 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 generally conducted on the temperature scale of from 20 to 140 ° C, for example, near or at the boiling point of the aqueous bath, for example at about 90 ° C. Also, solutions of the compound of formula (1), or their emulsions in organic solvents, can be used in the method of the present invention. For example, the so-called solvent dyeing (thermofix 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, said combined treatment can be advantageously carried out using appropriate stable preparations containing the compound of formula (1) in a concentration so that improvement is achieved. from SPF desired. In certain cases, the compound of formula (1) is made completely effective by a subsequent treatment. This may comprise a chemical treatment such as treatment with an acid, a thermal treatment, or a combined thermal / chemical treatment. It is often advantageous to use the compound of formula (1) in admixture with an auxiliary or filler, such as anhydrous sodium sulfate, sodium sulfate decahydrate, sodium chloride, sodium carbonate, an alkali metal phosphate, such as sodium orthophosphate, sodium 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 (1), 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, coloring dyes, opacifiers, other fluorescent agents, bactericides, non-ionic surfactants, fabric care ingredients, especially fabric softeners, stain-repelling or stain-releasing ingredients, or agents to water test, anti-gelling agents, such as nitrites or nitrates of alkali metals, 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 in the treated fabric. The method of the present invention, in addition to providing protection to the skin, also increases the useful life of an optionally dyed textile article treated in accordance with the present invention. In particular, the breaking strength and / or the light resistance of the treated textile fiber material can be refined. The present invention further provides a textile fabric produced from a fiber treated according to the method of the present invention, as well as also an article of clothing produced from said fabric. Such garment fabrics and garments produced from such fabrics typically have an SPF rating of 20 and above, while untreated cotton, for example, generally has an SPF rating of from 2 to 4. The treatment method 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 material of fiber washed that way. The detergent treatment according to the present invention is preferably effected by washing the textile fiber material at least once with the detergent composition at a temperature ranging from 10 to 100 ° C, especially from 15 to 60 ° C. . The detergent composition preferably used 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 0.1-0.3% of a bleaching catalyst and / or preferably 0.001-0, 05% of a photobleaching agent; v) 0.005 - 2%, preferably 0.01 - 1% of at least one compound of formula (; 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 another aspect of the present invention. The detergent can be formulated as a solid, as an aqueous liquid comprising 5-50, preferably 10-35% water, or as a non-aqueous liquid detergent, containing not more than 5, preferably 0-1 weight% of water, and based on a suspension of a builder in a non-ionic surfactant, as described, for example, in GB-A-2158454. The anionic surfactant component 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 alkyl ethoxy sulfates having 10-20 carbon atoms in the alkyl radical. Preferred sulfonates include alkyl benzene 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 (R1) CH2COOM1, wherein R is alkyl or alkenyl having 9-17 carbon atoms in the alkyl or alkenyl radical, R1 is C1-C4 alkyl, and M1 It's alkaline metal. The nonionic surfactant component can be, for example, a condensate of ethylene oxide with a C9-C15 primary alcohol having 3-8 moles of ethylene 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 these. The preferred silicates are crystalline sodium silicates in layers, of the formula pH20 or Na2Sim02m + ?. pH20 in which m is a number from 1.9 to 4, and p is 0 to 20. The preferred aluminosilicates are the commercially available synthetic materials, designated as Zeolites A, B, X, and HS, or mixtures of these . 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 ethylene diamine tetraacetic acid. Preferred organic phosphonates or aminoalkylene poly (alkylene phosphonates) are alkali metal 1-hydroxy ethane diphosphonates, trimethylene nitrile phosphonates, ethylene diamine tetra methylene phosphonates, and diethylene triamine penta methylene phosphonates. Any peroxide component can be any organic or inorganic peroxide compound, described in the literature or available on the market, that bleach textiles at conventional washing temperatures, for example 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 C atoms, such as diperoxyperazelates, diperoxypersebacates, diperoxyphthalates, and / or diperoxydedecanedioates, especially their corresponding free acids, are of interest. However, it is preferred 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, in particular 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, enzymatic peroxide precursors and / or metal complexes. Preferred metal complexes are iron or manganese complexes, such as iron or manganese phthalocyanines, or the complexes described in EP-A-0509787. Preferred photobleaching agents are phthalocyanines containing water-solubilizing groups, such as sulfo groups. As phthalocyanines soluble in water, it is possible to use metal complexes of phthalocyanines, or phthalocyanines free of metals. The metal complexes of phthalocyanines are preferably those of aluminum, zinc, magnesium, calcium, iron, sodium, or potassium. Particularly preferred photobleaching agents are sulfonated aluminum or zinc phthalocyanines. Mixtures of photobleaching agents, such as mixtures of water soluble aluminum and zinc phthalocyanines, can be used. The detergents used will generally contain one or more auxiliaries, as agents for the suspension of dirt, for example sodium carboxymethylcellulose; salts for adjusting the pH, for example alkali or alkaline earth metal silicates; foaming regulators, for example soap; salts for adjusting spray drying and granulation properties, for example sodium sulfate; perfumes; and also, if appropriate, antistatic agents and softeners; as smectite clays; enzymes, such as amylases and proteases; photobleaching agents; pigments; matting agents; and / or one or more other fluorescent whitening agents, such as those of the types 4,4'-bis- (triazinylamino) -stuebene-2,2'-chsulfonic acid, 4,4, -bis- (triazole-2) acid. il) -stilbene-2,2'-disulfonic acid, 4,4 '- (diffene) -stilbene, 4,4'-diethyryl-biphenyl, 4-phenyl-4'-benzoxazolyl-stilbene, stilbene-naphthriazole, 4-styryl -stilbene, bis- (benzoxazol-2-yl), bis- (benzimidazol-2-yl), coumarin, pyrazoline, naphthalimide, triazinyl-pyrene, 2-styryl-benzoxazole, 2-styryl-naphthoxazole, or benzimidazole-benzofuran. These auxiliary constituents should of course be stable to any whitening system employed. The compounds of the formula (1) have also been found useful for the fluorescent bleaching of textile materials, in which connection polyamides, wool, and cotton should be particularly distinguished, and paper. The compounds of formula (1) are suitable for use in fabric softening or detergent compositions, which do not require the use of a fluorescent whitening agent to maximize the color care performance of the compositions. Certain compounds of formula (1), in particular those containing a group Y having the formula -C (= 0) -R2 in which R2 has its previous meaning, while perfecting the sun protection factor of textiles treated with They are not fluorescent. Said non-fluorescent compounds of formula (1) are especially suitable for use in textile softening or detergent compositions that do not use a fluorescent whitening agent to maximize the color care performance of the compositions. Said textile softening or detergent compositions comprising a non-fluorescent compound of formula (1) form another aspect of the present invention. The following Examples also illustrate the present invention.

Example 1 (A) 27.7 g of cyanuric chloride are incorporated in 154 g of acetone and 205 g of ice, cooled to -5 ° C, and treated, dropwise, with a solution of 27 g of the acid disodium salt 4,4, -diaminostilbene-2,2'-disulfonic acid in 190 ml of water. The pH of the reaction mixture is maintained at 5.5-6.0 by the addition of an aqueous soda solution. The reaction mixture is then treated with a suspension of 22.5 g of 4-aminobenzoylmethylamide in 112 g of acetone. The pH of the reaction mixture is maintained at 8.0 by the addition of an aqueous sodium hydroxide solution. The resulting suspension is stirred for 27 hours whereupon the temperature rises to 25 ° C. The precipitate that forms is separated by filtration, washed and dried under vacuum. In this way, 71.7 g of the yellowish compound of formula (101) are obtained. Elemental analysis of the compound having the formula (101) and having the empirical formula C36H2gCl2Ni2? 8S2.8.76H20 gives:% Req. C, 39.17; H, 4.19; N 15.34; S, 5.85; Cl 6.17; H20 14.41. Found: C 37.7; H 4.1; N 14.6; S, 5.6; Cl 5.8; H20 14.41.

Example 1 (B) 37.5 g of the compound (101) obtained in Example 1 (A) are dispersed in 500 ml of water and treated with 29 g of a 40% aqueous methylamine solution. The mixture obtained in this way is slowly heated to 90 ° C, and is stirred at this temperature for 4 hours. The reaction mixture is then treated with 55 g of sodium chloride, cooled to 20 ° C, filtered and washed. 34.1 g of a yellowish compound of formula (102) are obtained. The elemental analysis of the compound having the formula (102) and having the empirical formula C38H36Ni4Na2? 8S2.8.87H20 gives:% Req. C, 42.00; H 4.98; N, 18.04; S, 5.90; O 24.84; H20 14.70. Found: C 40.9; H 4.9; N 17.5; S, 5.6; O 27.6; H20 14.7.

Example 2 Compound (102) is produced using the procedure described in Example 1 (A) and (B), except that intermediate (101) is not isolated. Using this modified process, 69.5 g of the yellow compound (102) are obtained.

Example 3 12.6 g of cyanuric chloride are dissolved in 80 ml of acetone and poured onto 75 g of crushed ice. While the mixture obtained in this way is vigorously stirred and cooled with ice, an aqueous solution of 15.6 g of the disodium salt of 4,4'-diaminostilbene-2,2 'is added to the mixture by dripping. -disulfonic. The addition is conducted for 40 - 50 minutes, and the temperature is not allowed to exceed +5 ° C. The reaction mixture has a pH of 1. The pH of the reaction mixture is adjusted to 6-7, and the mixture is stirred for 1 hour at 0 ° C. Then 14.53 g of the sodium salt of 4-aminosalicylic acid are added to the reaction mixture, followed by the dropwise addition of 34.4 ml of 1M sodium carbonate solution, whereby the pH of the mixture rise to 10-11. The reaction mixture is heated to 40-50 ° C, and after 30 minutes, a clear solution having a pH of 7-8 is obtained, 6 ml of morpholine are added, by dripping, to the reaction mixture. The reaction mixture is distilled, and after the removal of 100 ml of acetone, a clear solution remains. The solid compound (103) is precipitated by the addition of 150 ml of aqueous sodium acetate, separated by suction and washed again with sodium acetate solution. The wet residue is then boiled with 1 liter of alcohol to liberate it from sodium acetate. After drying, 28.6 g of the compound (103) (74% theory) are obtained. The elemental analysis of the compound having the formula (103) and having the empirical formula C42H36Ni2? I4S2Na4.10.5 H20 gives:% Req. C 39.49; H 4.49; N 13.15; S 5.01; H20 15,09. Found: C 39.46; H 4.53; N, 13.26; S, 4.89; H20 14.78.

Example 4 Using the procedure described in Example 3, but replacing the morpholine reagent used therein, by the equivalent amount of methylamine, the compound (104) is obtained in a 98% theory yield. Elemental analysis of the compound having the formula (104) and having the empirical formula C36H28N? 2Oi2S2Na .12H20 gives:% Req. C 36.25; H 4.34; N, 14.09; S, 5.37; H20 18.1. Found: C 36.16; H 4.41; N, 13.85; S, 5.30; H20 18.5.

Example 5 (A) Using the procedure described in Example 1 (A), but replacing the 4-aminobenzoylmethylamide reagent used therein, by the equivalent amount of aniline, compound (105) is obtained.

Example 5 (B1 0.0115 mol of the compound (105) are heated at 130 ° C in 50 ml of ethylene glycol monomethylether together with 0.026 mol of sulfanilamide. At the beginning, a clear solution is obtained, and then the compound (106) is precipitated as yellow flakes. After filtration by suction and washing with water, 0.009 mol (79.5% theory) of the compound (106) is obtained as a yellow powder. Elemental analysis of the compound having the formula (106) and having the empirical formula C44H38Ni4S4 ?? or 3 H20 gives:% Req. C 47.0; H 4.05; N 17,0; S, 11.54; H20 4.83. Found: C 47.9; H 4.09; N 17.4; S, 11.0; H204.83. The corresponding sodium salt of the compound (106) is obtained by treating the compound (106) with sodium methylate in methanol.

Example 6 Using the procedure described in Example 3, but replacing the 4-aminosalicylic acid reagent used therein, by sulfanilamide, compound (107) is obtained. The reaction product is isolated by precipitation with sodium chloride. After washing with ice water and drying, 36.28 g (95.5% theory) of the compound (107) are obtained. Elemental analysis of the compound having the formula (107) and having the empirical formula C4oH42Ni4S2 2Na2.8 H20 gives:% Req. C, 39.02; H 4.76; N, 15.93; S, 10.42; H20 12.69. Found: C 39.1; H 4.7; N 15.8; S 10.1; H20 12.69.

Example 7 1.2 g of 4-aminoacetophenone are dissolved in 30 ml of methyl cellosolve. To this solution are then added 3.3 g of the compound (91% purity) having the formula: The reaction mixture is stirred at 130 ° C in an oil bath, and it is kept at this temperature for 4 hours. After a short time, the free acid version of the salt compound (108) is separated by crystallization. After suction filtration, the filter block, dissolved in methanol, is converted to the disodium salt of formula (108) using sodium methylate. After filtration with suction, washing with water and drying, 4.0 g (91% theory) of the disodium salt of formula (108) are obtained. The elemental analysis of the compound having the formula (108) and having the empirical formula C48H38Ni2Na208S2.11, 0H20 gives:% Req. C 47.29; H 4.96; N, 13.78; S, 5.26; H20 16.24. Found: C 47.05; H 4.96; N, 13.87; S, 5.28; H20 15.99.

Examples 8 to 12 A conventional washing powder (ECE) is made from the following components in the indicated proportions (weight%): 8.0% Sodium alkylbenzene sulfonate (Cpfs) 2.9% Alcohol glycol ether -tetradecane-ethylene tallow (14 moles EO) 3.5% Sodium soap 43.8% Sodium tripolyphosphate 7.5% Sodium silicate 1.9% Magnesium silicate 1.2% Carboxymethyl cellulose, 2% EDTA 21 , 2% Sodium Sulfate 00.19% compound (102) and 100% Water.

A wash liquor is prepared by dissolving 0.8 g of the top wash powder in 200 ml of tap water. 10 g of bleached cotton cloth is added to the bath and washed at 40 ° C for 15 minutes, then rinsed, spin dried, and ironed at 160 ° C. This washing procedure is repeated up to ten times. After the ten washes, the whiteness and the Sun Protection Factor of the washed samples are measured. Whiteness (W) is determined using a DC1 / SF 500 spectrophotometer according to the Ganz method. The Ganz method is described in detail in the Ciba-Geigy Review, 1973/1, and also in the article "Whiteness Measurement," ISCC Conference on Fluorescence and Fluorescent Material Colorimetry, Williamsburg, February 1972, published in the Jornal de Color y Appearance, 1, No. 5 (1972). The whiteness is equal to 60 when washed without the compound (102), and is 222 when washed with 0.19% of the compound (102), on the weight of the detergent. The Sun Protection Factor (SPF) is determined by measuring the UV light transmitted through the fabric sample, using a double grid spectrophotometer equipped with an Ulbritch vessel. The calculation of the SPF is carried out as described by B. L. Diffey and J. Robson in "J. Soc. Cosm. Chem." 40 (1989), pages 130-131. Five measurements are made at different points in each fabric sample. The average of these 5 measurements is calculated and provides the following results: The SPF is 3 for the initial bleached cotton fabric; The SPF is 4 after 10 washes in the absence of the compound (102); and The SPF is 24 after 10 washes with 0.19% of the compound (102), on the weight of the detergent. When the above procedure is repeated, but replacing the compound (102) with Compound (103), (104), (106), or (107), the results obtained in the following Table 1 are obtained.

Table 1 Example 13 A series of samples of cotton poplin fabric is screened using a range of reactive dyes, using the exhaustion method and the dyeing conditions recommended in the technical bulletin issued for each of the separate reactive dyes. Each of the fabric samples is then washed under the following conditions: A conventional washing powder (ECE) is made from the following components in the indicated proportions (weight%): 8.0% alkylbenzene sulfonate (?, 5) Sodium 2.9% Tallow alcohol-tetradecane-ethylene glycol ether (14 moles EO) 3.5% Sodium soap 43.8% Sodium tripolyphosphate 7.5% Sodium silicate 1.9% Silicate of magnesium 1.2% Carboxymethyl cellulose 0.2% EDTA 21.2% Sodium sulfate 0 or 0.3% compound (102) and Water at 100%.

Using a liquor ratio of 20: 1, washing is carried out with this washing composition for 15 minutes at 40 ° C. The washed fabric samples are then rinsed with cold tap water for 30 seconds at 40 ° C, rotated and dried in the dark. Each sample of washed cloth is then divided into two parts, a part O that is stored without exposure to light, and a part E that is exposed to light in an Atlas Weather-O-Meter instrument, under the following conditions: lamp: 5.0 kW dry light bulb: 29.5 ° C wet light bulb: 20.6 ° C wet light bulb depression: 9.4 ° C (corresponding to 40% relative humidity) ambient air: 31.4 ° C lamp distance to gender: such that the irradiation on the surface of the fabric is 0.36 W / m2 time: 45 hours Light firmness evaluation: The Lo, ao and bo colorimetric values of the cloth samples O not exposed, and the values Le, a «, and be of the E fabric samples exposed are measured using a Spectraflash SF 500 spectrophotometer. It has a UV cut filter up to 460 nm. The color difference? E is calculated between the sample of fabric exposed to light, and the corresponding sample of non-exposed fabric of the same dye, according to the formula: ? E = [(Lß - L0) z + (aß - aor + (be - b0r 2] -? L / 2 The difference d (? E) between the values? E, with and without the evaluation compound (102), is a measure of the influence of the evaluation compound on the light resistance of the given dyeing. The results obtained are shown in the following Table 2.

These results show that the compound (102) perfects the light resistance of the dyed evaluation articles. The improvement is visually clear. Its importance depends on the tincture.

Claims (41)

1. CLAIMS 1. A compound that has the formula: wherein M is hydrogen, an alkali metal atom, ammonium or a cation formed of an amine; Ri is hydrogen or hydroxy; R2 is C1-C4 alkyl or phenyl; Y is wherein R 3 and R 4, independently, are hydrogen or C 1 -C 4 alkyl, -SO 2 -NR 3 R 4 wherein R 3 and R 4. have their previous meanings, -C (= 0) -R2 in which R2 has its previous meaning, or -C (= 0) -OM in which M has its previous meaning; and X is NH or O, or X-R2 denotes a morpholino group; provided that those compounds are excluded in which: a) Y is -C (= 0) -OM in which M has its previous meaning; X is NH; and R2 is phenyl; b) Ri is hydrogen; Y is -C (= 0) -CH3; and X-R2 denotes a morpholino group; or c) Ri is hydrogen; And it is -C (= 0) -OM in which M has its previous meaning; X is NH; and R2 is methyl.
2. 2. A compound according to claim 1, wherein Ri is hydrogen.
3. 3. A compound according to claim 1 or 2, wherein X is NH.
4. 4. A compound according to any of the preceding claims, wherein R2 is methyl.
5. 5. A compound according to any of the preceding claims, wherein Y is wherein R3 and R4, independently, are hydrogen or C1-C4 alkyl.
6. 6. A compound according to claim 5, wherein Y is -C (= 0) -NHCH3.
7. 7. A compound according to any of the preceding claims, wherein M is a cation formed of an alkali metal.
8. 8. A compound according to claim 7, wherein M is sodium.
9. 9. A process for the production of a compound of formula (1), which comprises reacting cyanuric chloride, successively, in any desired sequence, with each of an aminostilbenesulfonic acid, an amino compound capable of introducing a group wherein R and Y are each as defined in claim 1, and a compound capable of introducing a group X-R2, wherein X and R2 are each as defined in claim 1.
10. 10. A method for increasing the SPF classification 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 the textile fiber material, of one or more compounds that have the formula (1) as defined in claim 1.
11. 11. A method according to claim 10, wherein the treated textile fibers are fibers of cotton, viscose, linen, rayon, linen yarn, wool, mohair. , cashmere, angora, silk, polyester, polyamide, or polyacrylonitrile.
12. 12. A method according to claim 11, wherein the treated textile fibers are cotton, polyamide, or wool fibers.
13. 13. A method according to any of claims 10 to 12, wherein the treated textile fibers have a density less than 200 g / m2, and have not been previously dyed in deep ranges.
14. 14. A method according to any of claims 10 to 13, wherein the compound of formula (1) is only sparingly soluble in water, and applied in dispersed form.
15. 15. A method according to any of claims 10 to 14, wherein, in addition to the compound of formula (1), a minor proportion of one or more adjuvants is also employed.
16. 16. A method according to claim 15, wherein the adjuvants are emulsifiers, perfumes, bleaching agents, enzymes, coloring dyes, opacifiers, optical bleaching agents, bactericides, non-ionic surfactants, ingredients for the care of the genders, agents anti-gelling, or corrosion inhibitors.
17. 17. A method according to claim 16, wherein the amount of each of the adjuvants does not exceed 1% by weight on the treated fiber.
18. 18. A method for increasing the SPF classification of a textile fiber material, according to claim 10, which comprises washing the textile fiber material with a detergent containing at least one compound of formula (1), imparting that form an excellent factor of solar protection to the fiber material washed in that way.
19. 19. A method according to claim 18, which comprises washing the textile fiber material at least once with the detergent composition at a temperature ranging from 10 to 100 ° C.
20. 20. A method according to claim 19, comprising washing the textile fiber material at least once with the detergent composition at a temperature ranging from 15 to 60 ° C.
21. 21. A method according to any of claims 18 to 20, wherein the detergent composition used comprises: i) 5-90% of an anionic surfactant and / or a non-ionic surfactant; ii) 5 - 70% of a detergency filter; iii) O - 30% of a peroxide; iv) 0-10% of a peroxide activator and / or 0-1% of a bleach catalyst; v) 0.005 - 2% of at least one compound of formula (1); and vi) 0.005-10% of one or more auxiliaries, each by weight, based on the total weight of the detergent.
22. 22. A method according to claim 21, 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; iii) 1 - 12% of a peroxide; iv) 1-6% of a peroxide activator and / or 0.1-0.3% of a bleach 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.
23. 23. A method according to claim 21 or 22, wherein the detergent is formulated as a solid, as an aqueous liquid comprising 5-50% water, or as a non-aqueous liquid detergent, containing no more than 5 weight% of water, and based on a suspension of a surface active agent and a detergency builder in a nonionic surfactant.
24. 24. A method according to any of claims 21 to 23, wherein the anionic surfactant component is a sulfate, sulfonate, or carboxylate surfactant, or a mixture thereof.
25. 25. A method according to any of claims 21 to 24, wherein the nonionic surfactant component is a condensate of ethylene oxide with a C9-C15 primary alcohol having 3-8 moles of ethylene oxide per mole.
26. 26. A method according to any of claims 21 to 25, 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 these.
27. 27. A method according to any of claims 21 to 26, wherein any peroxide component is any organic or inorganic peroxide compound that bleaching textiles at convenient wash temperatures.
28. 28. A method according to claim 27, wherein the peroxide component is a persulfate, perborate, and / or percarbonate.
29. 29. A method according to any of claims 21 to 28, wherein the bleach catalyst is an enzyme peroxide precursor and / or a metal complex.
30. 30. A method according to any of claims 21 to 29, wherein the detergent contains one or more auxiliaries selected from suspending agents; salts to adjust the pH; foaming regulators; salts for adjusting spray drying and granulation properties; perfumes; and antistatic and softening agents; enzymes; photobleaching agents; pigments; and nuancing agents.
31. 31. A method according to any of claims 10 to 30, whereby the resistance to breakage and / or light resistance of the treated textile fiber material are also perfected.
32. 32. A garment produced from a fiber treated according to a method as set forth in any of claims 10 to 31.
33. 33. A garment article produced from a garment according to claim 32.
34. 34. A detergent composition comprising: 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) O-10% of a peroxide activator and / or 0-1% of a bleaching catalyst, and / or 0.001-0.05% of a photo-bleaching agent; v) 0.005 - 2% of at least one compound of formula (1) as defined in claim 23; and vi) 0.005-10% of one or more auxiliaries, each by weight, based on the total weight of the detergent.
35. 35. A detergent composition comprising: i) 5-70% of an anionic surfactant and / or a non-ionic surfactant; ii) 5 - 40% of a detergency builder; iii) 1 - 12% of a peroxide; iv) 1-6% of a peroxide activator and / or 0.1-0.3% of a bleach 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.
36. 36. A process for fluorescent bleaching of textile or paper materials, comprising contacting the textile or paper with at least one compound of formula (1), as defined in claim 1.
37. 37. A process of according to claim 36, wherein the textile materials are polyamides, wool, or cotton.
38. 38. A method for the protection of human skin, comprising covering the skin with a garment article produced from a textile fabric according to claim 32.
39. 39. Composition for color care and softener or detergent textile comprising a compound of formula (1).
40. 40. Color care and softener composition or textile detergent comprising a non-fluorescent compound of formula (1).
41. 41. A composition according to claim 40, wherein the non-fluorescent compound of formula (1) contains a group Y having the formula -C (= 0) -R2, wherein R2 is as defined in claim 1 .