MXPA99008749A - Fluorescent whitening agents - Google Patents

Abstract

The present invention provides new compounds having formula (1), in which X is O or, preferably, NH;M is hydrogen, an alkali metal atom, ammonium or a cation formed from an amine;each R1, independently, is an aminoacid residue from which a hydrogen atom on the amino group has been removed;n is 1 or 2;and each R2, independently, ishydrogen, C1-C3alkyl, halogen, cyano, COOR in which R is hydrogen or C1-C3alkyl, CONH-R in which R has its previous significance, SO2NH-R in which R has its previous significance, NH-COR in which R has its previous significance, SO3M in which M has its previous significance or, when n is 1, R2 can also be CO-R3 in which R3 is C1-C3alkyl or phenyl;provided that those compounds are excluded in which a) X is NH, n is 1 and R2 is SO3M in which M has its previous significance;or b) X is NH, n is 2 and one R2 is SO3M in which M has its previous significance, and the other R2 is hydrogen, methyl or halogen;or c) X is NH, n is 1, R1 is glycine and R2 is H or CO2H;or d) X is NH, n is 2, each R2 is SO3M in which M has its previous significance and the SO3M groups are in 2,5-positions in the phenyl ring and R1 is D,L-alanine, L-valine, L-leucine;L-isoleucine, L-threonine, L-aspartic acid, L-glutamic acid, L-phenylalanine, L-proline, D,L-methionine or glycine. Most of the new class of 4,4'-diaminostilbene-2,2'-disulfonic acid compounds are useful as fluorescent whitening agents, especially for paper.

Description

FLUORESCENT BLEACHING AGENTS The present invention relates to new compounds, in particular to new compounds of 4,4 * -diaminostylben-2, 2'-disulfonic acid, which are useful as fluorescent whitening agents or to inhibit (repress) the effect of bleaching agents fluorescent anionic substrates. In WO 96/00221, optical brightening agents for textiles, paper, etc. are described. The disclosed compounds have the formula: wherein, Ra and Rb are the same or different and each have the formula -NRcRci, where Rc is hydrogen; Ci-Cß alkyl, which is optionally substituted by at least one of mercapto, thioalkylated Cx-Cg, OH and S03M ', where M1 is hydrogen, a colorless cation or a cation derived from an amine; oe (C? 2M ') x, where Re is an aliphatic part, having from 1 to 6 carbon atoms, those valences not linked with ^ M' groups, join with at least one of the hydrogen, mercapto, thioalkyl Ci- Cg, OH and S03M ', where M1 has the previous meanings, and x is an integer from 1 to 4, with the proviso that, when Rc is C1-C5 alkyl, which is, optionally, substituted by at least one of mercapto, thioalkyl Ci-Cß,, OH and S03M ', Rc is substituted with at least both OH and SO3M1; R3. is Rc, hydrogen or C3-C5 alkyl, with the proviso that Rc and R ^ can not both be hydrogen and that, when one of Rc and R ^ is hydrogen, the other can not be - (NHCH2C02H); or Rc and R-j, together with the nitrogen atom, form a ring having only 5 or 6 members, one of which is heterocyclic, this ring is simply substituted with -COOM 'or -SO3M1; and each Rf, independently, is hydrogen, methyl, C1-C5 alkoxy, or halogen. A new class of 4,4'-diaminostilben-2, 2'-disulfonic acid compounds has now been found, most of which are useful as fluorescent whitening agents and which have superior properties with respect to the compounds disclosed in the patent. WO 96/00221, and others of which are useful for inhibiting (repress) the effect of anidic fluorescent whitening agents on the substrates. Therefore, the present invention provides new compounds, which have the formula: wherein X is 0, preferably NH; M is hydrogen, an atom of an alkali metal, ammonium or a cation formed of an amine; each Ri, independently, is an amino acid residue from which a hydrogen atom in the amino group has been removed; n is l or 2; and each R2, independently, is hydrogen, C1-C3 alkyl, halogen, cyano, COOR where R is hydrogen or C1-C3 alkyl, CONH-R, where R has the above meanings, SO2NH-R, where R has the above meanings , NH-COR, where R has the previous meanings, S03M, where M has the previous meanings, or, when n is 1, R may also be CO-R3, where R3 is C1-C3 alkyl, or phenyl; with the proviso that those compounds are excluded in which: a.) X is NH, n is 1 and R2 is S03M, where M has the previous meanings; or b.) X is NH, n is 2 and one of R2 is SO3M, where M has the previous meanings, and the other R2 is hydrogen, methyl or halogen; or c.) X is NH, n is 1, Ri is glycine and R2 is H or C02H; or d.) X is NH, n is 2, each R2 is S03M, where M has the previous meanings, and the SO3M groups are in positions 2.5 in the phenyl ring, and Ri is D, L-alanine , L-valine, L-leucine, L-isoleucine, L-threonine, L-aspartic acid, L-glutamic acid, L- f nilalanine, L-proline, D, L-methionine or glycine. Preferably M is hydrogen, Na, K, Ca, Mg, ammonium, mono-, di-, tri- or tetra-C 1 -C 4 alkyl-ammonium, mono-, di-, tri-hydroxyalkyl-4-ammonium or ammonium which it is di- or tri-substituted with a mixture of C1-C4 alkyl groups, or C1-C4 hydroxyalkyl. Preferably, each M is Na. A halogen substituent, R 2, may be fluorine, bromine or iodine, but is preferably chlorine.

In the compounds of the formula (I), n is preferably 1 and R2 is preferably hydrogen, methyl, chloro, cyano, COOH, COO-methyl, CONH2 CONH-methyl, S02NH2, S02NH-methyl or NH-CO-methyl. Preferably, each amino acid residue, Ri is the same. Examples of preferred amino acid residues, Ri, include those having the formula -NH-CH (C02H) -R3, where R3 is hydrogen or a group having the formula -CHR4R5, where R and R5, independently, are hydrogen or alkyl C1-C, 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 (NH) NH. Specific examples of amino acids from which such preferred amino acid residues, Ri, are derived, include glisina, alanine, sarsosine, serine, system, phenylalanine, tyrosine (4-hydroxyphenylalanine), diiodo tyrosine, tryptophan (β-indolilalanine). ), histidine (ß-imidazolylalanine), a-aminobutyric acid, methionine, valine (rough a-aminoisovalent), norvaline, leusine (acid a-aminoisocapróiso), isoleusina (acid a-amino-β-metilvalériso), norleusina (acid a-amino-n-sapróiso), arginine, ornithine (acid a, d-diaminovalériso), lysine (a, e-diaminocapróiso acid, asbestos acid aminosusiniso, acid glutamism (acid a-aminoglutanus), threonine, hydroxiglutámiso acid and taurine, as well as mixtures and optimal isomers of these amino acids, from which such residues of preferred amino acids, Ri, are derived, sarcosine, taurine, glutamic acid and aspartic acid are particularly preferred.A further preferred example of an amino acid, from which an amino acid residue, R? f can be derivatized is the imidazoid isidoid. Other less preferred examples of amino acids, from which amino acid residues, Ri, can be derived, include the system, lanthionine, proline and hydroxyproline In addition to the preferred amino acid halides, mentioned above, Ri can also be the residue of an amino acid aromatic, such as the acidic p-aminobenzoiso or o-aminobenzoiso acid. In the formulations of formula (1), suando n is 1 and sada R2 is CO-R3 , where R3 is C1-C3 alkyl or phenyl, preferably methyl, such compounds are not useful as fluoridating bleaching agents, rather they are useful for inhibiting (repressing) the efesto of these anionized fluorescent whitening agents on the substrates.

The compounds of formula (1) can be produced by the reassessment, under sonoside reassuming conditions, of the Souristor slurry, respectively, in any desired sesuensia, they are one of the 4,4'-diamino-2,2 • -estilben acid. -disulfdniso, a set of amino sapaz to introduce a group of in the sual R and n they have the previous signifisados, and a sompuesto sapaz to introduce a group Rlf where Ri has the previous signifisados. The starting materials are somesidosososos, which are easily available. Most of the formulations of formula (1) are exselent fluorescent whitening agents for substrates, such as textiles and, in part, for paper. Therefore, the present invention provides a method for the fluorescent blanching of a substrate, which is to put in sontaste the substrate is a compound having the formula (IA): in sual X it is O or NH; M is hydrogen, an atom of an alsaline metal, ammonium or a cation formed of an amine; each Ri, independently, is an amino acid residue from which a hydrogen atom in the amino group has been removed; n is 1 or 2; and each R'2 / independently, is hydrogen, C1-C3 alkyl, halogen, cyano, COOR where R is hydrogen or alkyl 0 ^ -03, CONH-R, where R has the previous meanings, S02NH-R, where R has the previous meanings, NH-COR, where R has the previous meanings, SO3M, where M has the previous meanings; with the proviso that these compounds are excluded in that X is NH, n is 2 and R2 is SO3IT1, where M has the previous meanings, and the other R2 is hydrogen, methyl or halogen. When used for the fluorescent whitening of paper, the compound of the formula (IA), according to the present invention, can be applied to the paper substrate in the form of a paper rewinding composition, or directly in the paper press. right away. In a preferred aspect, the present invention provides a method for the fluorescent bleaching of a paper surface, comprising the contacting of this paper surface is a surfacing solution, which comprises a wet pigment; a binder dispersion; opsionally a water soluble so-binder; and sufficient fluorescent whitening agent, having the formula (IA), according to the invention, to ensure that the treated paper contains from 0.01 to 1% by weight, based on the white pigment, of a fluorescent whitening agent, which has the formula (ÍA). As the blue pigment component of the paper coating composition, used according to the method of the present invention, inorganic pigments are preferred, for example aluminum or magnesium silates, such as the Chinese arsilla and the saolin and , also barium sulfate, satin, dioxide titanium, salsium sarbonate (chalk) or talcum; as well as organic pigments blansos. The somposisions of paper reuse, used in agreement, are the method of the present invention, such as binder, among others, plastis dispersions based on butadiene / styrene, asyronitrile / butadiene / styrene copolymers, esters of ashy acid, esters of the asyrid / styrene / asyronitrile, ethylene / vinyl slurry and ethylene / vinyl acetate; or homopolymers, such as polyvinyl chloride, polyvinylidene chloride, polyethylene and polyvinyl acetate or polyurethanes. A preferred binder consists of styrene / butyl acrylate, styrene / butadiene / acrylic acid copolymers or styrene / butadiene rubbers. Other polymer latexes are described, for example, in Specifisations of U.S. Patent Nos. 3,265,654, 3,657,174, 3,547,899, and 3,2140,740. Optional opium-insoluble colloids in water may be, for example, soy proteins, saseine, sarboxymethyl cellulose, natural or modified starch, chitosan or its derivatives, or, especially, polyvinyl alcohol. The preferred somponent of the polyvinyl alsohol protesting soleid may have a wide range of saponifisation and molecular weight levels; for example, a level of saponifisasión that varies from 40 to 100; and an average molecular weight that varies from 10,000 to 100,000. Formulations for compositions of the paper coatings are dessibed, for example, in J.P. Casey "Pulp and Paper"; Químisa y Tesnología Químisa, 2nd edition, Volume III, pages 1684-1649 and in "Fabricasión de Pulpa y Papel", 2nd and 5th editions, Volume II, page 497 (MsGra-Hill). The paper reuploading sompositions used, according to the method of the present invention, are preferably 10 to 70% by weight of a wet pigment. The binder is preferably used in a sanctity the sual is sufficient to obtain the solid content of the polymeric fiber up to 1 to 30% by weight, preferably 5 to 25% by weight, of the white pigment. The amount of the fluorescent polishing preparation used according to the invention is classified so that the fluorescent brightener is preferably present in sanities from 0.01 to 1% by weight, more preferably from 0.05 to 1% by weight, and especially from 0.05 to 0.6% by weight, based on the blue pigment. The paper backing somposision used in the method, according to the invention, can be prepared by mixing the components in any desired session, at a temperature of 10 to 100 ° C, preferably 20 to 802C. The somponents here also include the customary auxiliaries, the suals can be added to regulate the reologic properties, such as the visosity or the sapasidad of retension of water, of the somposisons of re-surfacing. Such auxiliaries are, for example, natural binders, such as starch, casein, protein or gelatin, cellulose ethers, such as sarboxyalkyl cellulose or hydroxyalkyl cellulose, alginic acid, alginates, polyethylene oxide or alkyl ethers of polyethylene oxide, copolymers of ethylene oxide and propylene oxide, also polyvinyl alcohol, water-soluble condensation products of formaldehyde are urea or melamine, polyphosphates or salts of the polyunsyllabic acid. The coating composition used, according to the method of the present invention, is preferably used to produce a coated printed paper or writing paper, or special papers, such as cardboard or photo papers. The coating composition used, according to the method of the invention, can be applied to the substrate by any sonsional process, for example, an air sheet, a cover sheet, a roller, a spatula or a bar, in the press of sizing after which the coatings are dried at temperatures of the paper surface in the range of 70 to 200 ° C, preferably from 90 to 130P-C, with a residual moisture content of 3-8%, for example, with infrared dusters and / or hot air dusters. Comparable high degrees of blansura are achieved, even at low temperatures. By the use of the method, of agreement are the invention, the obtained resorbations are distinguished by the optimal distribution of the fluorescent brightener in dispersion over the whole surface and by an increase in the level of blansura thus achieved, by a high firmness to light and elevated temperatures (for example, stability for 24 hours at 60-100 ° C) and an excessive fixation of bleeding to water. In a second preferred assortment, the present invention provides a method for fluorescent bleaching of a paper surface, which is intended to stain the paper in the sizing press is an asusious solder which is a size, optionally an inorganic or organic pigment, and from 0.1 to 20 g / 1 of a fluorescent whitening agent, having the formula (IA). Preferably, the sizing is starch, a starch derivative or a sizing synthetic agent, especially a water soluble copolymer.

The present invention also provides, as a third 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, they are based on the weight of the textile fiber material , of one or more compounds that have the formula (ÍA), defined above. The textile fibers, treated as agreement, are the method of the present invention, they can be natural or synthetic, or their mixtures. Examples of natural fibers include plant fibers, such as cotton, viscose, brine or rayon or linen, preferably cotton, and animal fibers, such as wool, mohair, sasimir, angora and silk, preferably wool. Synthetic fibers include polyester, polyamide and polyacrylonitrile fibers. Preferred textile fibers are cotton, polyamide and wool. Preferably, the textile fibers, treated according to the method of the present invention, have a density of less than 200 g / m2 and have not been previously dyed in deep tones. Some of the compounds of the formula (IA), 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 dispersing agent, suitably using suarzo balls and a propeller, decreasing the size of partisulas to 1-2 misras. As dispersing agents for such sparingly soluble compounds, of the formula (IA), there can be mentioned: "the acid esters or their salts of alkylene oxide adducts, for example the acid ethers or their salts of a polyadrite to 40 moles of ethylene oxide are 1 mole of a phenol, esters of the phosphorous acid of the adduct of 6 to 30 mole of ethylene oxide with 1 mole of 4-nonylphenol, 1 mole of dinonylphenol or, especially, are 1 mole of compounds which have been produced by the addition of 1 to 3 moles of styrenes in 1 mole of phenol; "polystyrene sulfonates; taurides of fatty acids; alkylated diphenyloxide-mono- or di-sulfonates; sulphonates of esters of polycarboxylic acids; Addition products from 1 to 60, preferably from 2 to 30 moles of the ethylene oxide and / or the propylene oxide in fatty amines, fatty amides, fatty acids or fatty alsoholes, one of which is 8 to 22 atoms of sarbon, or C3-CQ tri- or hexavalent alkanols, the addition products that have become a Ester ester are an arid organoisocyanate or an inorganic polybasic acid; "lignin sulphonates, and in particular" the prodrugs of formaldehyde condensation, for example the condensation products of the lignin sulfonates and / or phenol and formaldehyde; the formaldehyde's denaturation products are aromatic sulphonic acids, for example the condensation products of the sulfonates and the ditolyl ether and the formaldehyde; as well as the condensation products of naphthalenesulfonic acid and / or naphthol or naphthylaminosulfonic acids and formaldehyde; the condensation products of the high sulfonated phenolsulfonisoses and / or sulphonated dihydroxydiphenylsulfone and phenols or sresols are formaldehyde and / or urea; or the prodrug products of the diphenyloxide and the disulfonic acid derivatives are formaldehyde. Depending on the type of the formula tax (AIA) used, it may be beneficial to take the treatment in a neutral, alsaline or dry bath. The method is usually sampled in a temperature range of 20 to 140-C, for example in or sersa of the boiling point of the water bath, for example at about 90sc. Solutions of the formula (IA) or their emulsions in organic solvents can also be used in the method of the present invention. For example, the named solvent dyeing method (cushion heat setter) or dyeing methods of extractions, in dyeing machines, can be used. In the method of the present invention, it is referred to as a textile treatment or asabado method, such as the combination treatment, can advantageously be carried out using appropriate stable preparations, which are in the formula (IA), in a sonsension so that the desired SPF improvement is achieved. In certain cases, the formula (IA) is rendered completely effec- tive by subsequent treatment. This may involve 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 formula (IA) in mixture are an assistant or diluent, such as anhydrous sodium sulfate, sodium sulfate dihydrate, sodium slurium, sodium sarbonate, an alkali metal phosphate, such as sodium or potassium orthophosphate, Sodium or potassium pyrophosphate or sodium or potassium tripolyphosphate, or an alsaline metal silisate, such as sodium silicate. In addition to the compounds of the formula (IA), a minor proportion of one or more auxiliaries may also be employed in the method of the present invention. Examples of auxiliaries include emulsifiers, perfumes, color dyes, opacifiers, additional fluorescent whitening agents, bacteriosides, nonionic surfactants, fabric care ingredients, especially fabric softeners, stain-releasing or stain-repelling ingredients. waterproofing agents, anti-gel forming agents, such as alkali metal nitrites or nitrates, especially sodium nitrate, and corrosion inhibitors, such as sodium silicate. The amount of each of these optional auxiliaries should not exceed 1% and preferably ranges from 0.01 to 1% by weight in 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 according to the present invention. In particular, the resistance to tearing and / or light fixation of the treated textile fiber material 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 this fabric. These fabrics and textile articles of clothing, produced from the fabrics, typically have an SPF classification of 20 and more, while untreated cotton, for example, generally has a SPF slasifisation of from 2 to 4. The method of treatment, of agreement With the present invention, it can also be carried out by washing the textile fiber material with a detergent, which is a composition of the formula (IA), thus imparting an excessive heat of solar protrusion 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 is the detergent solution, at a temperature ranging from 10 to 100 ° C, especially from 15 to 60 ° -C. The detergent composition used preferably comprises: (i) from 5 to 90%, preferably from 5 to 70%, of an anionic surfactant and / or a nonionic surfactant; (ii) from 5 to 70%, preferably from 5 to 40%, of a former; (iii) from 0 to 30%, preferably from 1 to 12%, of a peroxide; (iv) from 0 to 10%, preferably from 1 to 6%, of a peroxide activator and / or from 0 to 1%, preferably from 0.1 to 3% of a bleaching saker; (v) from 0.005 to 2%, preferably from 0.01 to 1%, of at least one compound of the formula (IA); and (vi) from 0.005 to 10%, preferably from 0.1 to 5%, by weight of one or more auxiliaries, are based on the total weight of the detergent. The detergent sompositions are also new and, as such, represents a further aspect of the present invention. The detergent can be formulated as a solid, such as a liquid that suffers from 5 to 50%, preferably from 10 to 35%, of water or as a non-aqueous liquid detergent, containing not more than 5%, preferably from 0 to 1% by weight of water, based on a suspension of a former in a nonionic surfactant, as described, for example, in GB-A-2158454.

The somponent of the anioniso tensoast agent can be, for example, a tensoastive agent of a sulfate, sulfonate or sarboxylate, or a mixture of them. Preferred sulfates are the alkyl sulfates having from 12 to 22 sarbono atoms in the alkyl radical, opsionally, in symbiosis are the alkyl-ethoxy sulfates, having from 10 to 20 sarbono atoms in the alkyl radisal. Preferred sulfonates include the alkyl-bensen sulfonates, which have from 9 to 15 sarbono atoms in the alkyl radisal. In each case, the cation is preferably of an alkali metal, especially sodium. Preferred carboxylates are the sarcosinates of an alkali metal, of the formula R-CO-R1) C ^ COOM1, wherein R e is an alkyl or alkenyl, having from 9 to 17 carbon atoms in the alkyl or alkenyl radical, R1 is Ci-C alkyl and M1 is an alsalino metal. The nonionic tensioactive agent can be, for example, a condensate of ethylene oxide with a primary alcohol C9 to C15, having from 3 to 8 moles of ethylene oxide per mole. The forming component can be an alkali metal phosphate, especially a tripolyphosphate; a carbonate or bicarbonate, especially its sodium salts; a silisate or disilisate an aluminosilisate; a polysarboxylate; a polycarboxylic acid; an organo phosphonate; or an aminoalkylene poly (alkylene phosphonate); or a mixture of them. Preferred silicate are the sodium silicates in crystalline layers, of the formula NaHSim0m + 1-pH20 or Na2Sim02m +? 'PH0, where m is a number from 1.9 to 4 and p is from 0 to 20. Preferred aluminosilicates are the commercially available synthetic materials, designated as Zeolites A, B, X and HS, or mixtures thereof. The preferred Zeolite A. Preferred polycarboxylates include the hydroxypolycarboxylates, in particular the sitrates, polyacrylates and their sopolymers are malefic anhydride.

Preferred polysarboxylic acids include the acid nitrilotryethyse and the acidic ethylene diamine tetraasetiso.

Preferred organoisophosphonates or aminoalkylene poly (alkylene phosphonates) are the alsaline methane-1-hydroxy diphosphonates, nitrile-trimethylene phosphonates, ethylene-diamine-tetra-methylene phosphonates and diethylenetriamine-pentane phosphonates. methylene. Any peroxide component may be any peroxide or inorganic peroxide, disclosed in the literature or available in the somersium, Sual realizes textile bleaching at conventional wash temperatures, for example at temperatures in the range of 5 to 90sec. In particular, organic peroxides are, for example, monoperoxides or polypeptides having alkyl chains of at least 3, preferably from 6 to 20, carbon atoms; in particular, the diperoxydicarboxylates having from 6 to 12 carbon atoms, such as the diperoxyperazelates, diperoxypersebacts, diperoxyphthalate and / or diperoxydesanadioates, especially their free aceids, are of interest. However, it is preferred to employ very asthous inorganic peroxides, such as persulfate, perborate and / or persarbonate. Of course, it is also possible to use mixtures of organoperoxides and / or inorganic peroxides. The peroxides, especially the inorganic peroxides, are preferably obtained by the insulator of an astivator, such as ethylenediamine of tetraasetyl or nonoyloxybenzene sulfonate. Bleaching satants can be added, which include, for example, peroxide pressurizers enzymes and / or metal bodies. Preferred metal complexes are the manganese or iron complexes, such as the manganese or iron phthalosanines, or the rare complexes in EP-A-0509787.

The detergents used will usually be one or more auxiliaries, such as suspending agents, for example sodium sarboxymethyl cellulose; salts to adjust the pH, for example, alisaline or alsaline-earth metal sisalsates; foam regulators, for example soap; ales to adjust the seses per rosé and the granulation properties, for example sodium sulphate; perfumes; and also, suando be appropriate, antistatic and softening agents; such somros arsillas de esmestita; enzymes, such as amylases and proteases; photobleaching agents; pigments; and / or nuance agents. These constituents, of course, must be stable to any whitening system employed. The following Examples further illustrate the present invention. The parts and percents shown here are by weight, unless otherwise indicated. The composition of Example 9 has been discussed in Che. Abstr. 107: 238,581.

E-example 1 g of the formula: were dissolved in a 70 ml mixture of methylsellosolve and 40 ml of water, while the mixture was salted in a bath, at a bath temperature of 120P-C. 7.61 g of assoid D, L-glutamism were added and the mixture was stirred at this temperature for 8 hours, the pH value of the mixture was maintained at 8-9 during this time, by the addition of the sodium sarbonate. The reassignment was finished after 8 hours. The free acid was presipitated by treating the reassessing mixture with 200 ml of asetone and 13 ml of HCl. The precipitate was filtered off with suction and washed with acetone and water. The mass of the filter washed and suspended in 200 ml of water, it was taken in solution by adding sufissent solusy solution of sodium hydroxide at 30%, at a pH of 8, and then sonsentrating by evaporation. After drying, 10.0 g (64% of theory) of the compound of the formula (101) remained. The elementary analysis of the formula that has the formula (101) and are the formula e pyirisa: C42H34N12S2Na6-8H2O0.25NaCI-0.7Na2C? 3, is: Required% C 37.55; H 3.59; N 12.31; S 4.69; H2O 10.54; CI "0.65 Found% C 37.13; H 3.55; N, 12.57; S 4.34; H2O 10.65; CI '0.66 The starting compound of the formula (100) was obtained in a sonoside manner, with the cyanuric chloride initially reactivating with the 4,4'-diamino-2, 2 * -stilbene acid disulfonose, and then reassuring the reation product, thus obtained, is 1 mole of aniline.

Example 2 Using the dessrito prosedimiento in Example 1, 10 g of the compound of the formula (100) were stirred with 6.92 g of D-aspartic acid for 8 hours in a bath at a temperature of 1202C. After 8 hours, the high performance liquid chromatography (HPLC) analysis of the reaction mixture confirmed that the reassessment was complete.

After working up the reaction mixture in the manner described in Example 1, 10.00 g (71% of theory) of the formula (102) was obtained. Elemental analysis of the compound having the formula (102) and the empirical formula C4oH3oN12? I4S2Na6-8H2O-1.3NaCll gives: Required% C 36.28; H 3.50; N 12.69; S 4.84; CI "3.48 Crystallized% C 36.25, H 3.59, N 12.54; S 4.76; Cl" 3.48.

Example 3 Using the dessrito prosedimiento in Example 1, 10 g of the formula of the formula: They were reassessed are 5.38 g of D, L-aspartic acid and the produsto de reassión was elaborated in an analogous way. After seses, 4 g (36% of the theory) of the formula (104) was obtained, as a blasting powder. The elementary analysis of the formula that has the formula (104) and are the empirical formula: C40H32N? 4Na6Oi8S - 2H2O gives: Required% C 32.48; H 3.81; N 13.25; S 8.67 Sounding% C 32.30; H 3.67; N 13.07; S 8.10. The starting compound of the formula (103) was obtained in a conosidal manner, initially re-assuring the sulfated sulphate is the 4,4 * -diamino-2,2 '-stilben- disulphonic, and then reactsionando produsto reaction, thus obtained, with 1 mol of 4-aminosulfonilanilina. The compound of formula (104) imparted excellent whiteness and SPF values to cotton, when applied to cotton by a conventional method of. a long treatment bath at 100 c or by a fouling method at 702c.

Example 4 A) 18.81 g of sianuric sluride (purity 98%) were dissolved in 95 ml of acetone and drained in 100 g of a mixture of ice and water. In 30 minutes, a solution of 18.5 g of diaminostilben-di-sulfoniso acid (purity of 100%) was added, in drops, to 320 g of a mixture of ice and water, at a temperature in the range of -5 to 02C. Finally, in 15 minutes, 50 ml of a 1 molar solution of soda was added, in drops, at this temperature, and everything was stirred for an additional hour. 13.5 g of 4-aminoacetophenone were added and the mixture was heated to 50 C in 90 minutes. During this procedure, the pH of the reaction mixture was maintained at 7-8 by the addition of sodium sarbonate. In order to solidify the reassumption, the asetone was separated by distillation until the temperature of the reassessing mixture reached 662C. The presipitated deposit was filtered in salient are sussión, was washed diluted dilute sodium sloride (2%) and then are 300 ml of cold water. After sessing, 44.8 g (88% of the theory) of the formula was added: The elementary analysis of the formula that has the formula (105) and are the empirical formula: C36l-.26N10O8CI2S2Na2-6.OH2O, gives: Required% C 42.57; H 3.77; N 13.79 Ensontrado% C 42.59; H 3.85; N 13.74. B) 5 g of the compound of formula (105), obtained in part A), were suspended in 100 ml of water. 1.3 g of taurine were added and the reassessing mixture was heated to 902V and the pH was maintained at 9-10 using sodium sarbonate. The reastives were allowed to re-saturate at this pH and temperature for 15 hours. Finally, the reassignment mezse was sonsented and the sompuesto (113) presipitated is asetone. After the filtration with sucsion, they were washed as asetone and sessured, 5.95 g (81% of the theory) of the compound were left (113). The elementary analysis of the formula that has the formula (106) and are the empirical formula: C40H30Ni2Na4O S.ro.66 NaC.-l6.5H2O, gives: Required% C 32.8; H 4.74; N 11.47; S 8.75; Cl "1.60, Na 7.32 Sounding% C 32.7, H 4.7, N 11.5, S 9.1, CU6, Na 7.4 ..

The composition having the formula (106) performs a significant redussion in whiteness and fluorescence of the previously polished paper treated with the compound.

Example 5 Using a procedure analogous to that described in Example 4, the compound (107) was produced by the reaction of the somatic compound (105) are 0.9 g of sarsosine in place of taurine, the reassum was supplemented after 6 hours and the yield of the sompuesto (107) was 93% of the theory. The elementary analysis of the formula that has the formula (107) and are the empirical formula: C42H36N12 Na4O? 2S2- 1 5H2O gives: Required% C 38.02; H 5.01; N, 12.66. Found% C 38.10; H 4.87; N 12.65 .. The compound having the formula (107) made a significant reduction in whiteness and fluorescens of the previously polished paper, treated are the sompuesto.

Example 6 Using an analogous preparation to that dessrito in Example 4, the compound (108) was produced by the rearrangement of the compound (105) are N-methyl-ethanolamine instead of taurine. The reassessment was completed after 6.5 hours and the yield of the compound (108) is 81% of the theory. The material analyzed was present as the salt of N-methyl-ethanolamine. The elementary analysis of the formula that has the formula (108) and with the empirical formula: C42H42N12 Na2O10S2-0.6 N-methyl-ethanolamine-5H2O gives: Required% C 47.0; H 5.02; N 15.78; S 5.73; Found% C 46.75; H 4.92; N 15.46; S 5.71. The compound having the formula (108) performs a significant redussion in blansura and fluoressensia of the previously polished paper treated with the compound.

Example 7 g of the compound of the formula (105) were reassessed are 5.8 g of the L-glutamic acid in a mixture of 6: 9 by weight of water and metilsellosolve, at 1202C in an oil bath, the pH was maintained in 8- 9 by the addition of sodium carbonate. After 6 hours, the reassessment was complete. The reaction mixture was dropped into acetone acidified with HCl, so that the compound of formula (109) presipitated the free acid. After filtration with suction and washing are asetone-water, the mass of the filter was converted into the hexosodyss by the adsorption of the salted supersaturated sodium hydroxide, and the evaporation to dryness. The yield was 90% of the theory. The elementary analysis of the formula that has the formula (109) and are the empirical formula: C46H38N12S2Na6Olo0.3 NaCI -17 H2O gives: Required% C 35.9; H 4.71; N 10.92; S 4.16; Sounding% C 36..0; H 4.7; N 10.9; S 4.1;. The formula that has the formula (109) made a significant reduction in whiteness and fluoressensia of the previously polished paper, treated are the sompuesto.

Example 8 The compound of the formula (110) was obtained is a yield of 87% of the theory, using the dessrito prosedimiento in Example 16, exsept that the acid L-glutámiso was replaced are the imidoodiasetiso. The elementary analysis of the formula that has the formula (110) and are the empirical formula: C4 H34N12 Na6O? 6S2-0.8 NaCM5H2O gives: Required% C 35.1; H 4.28; N 11.16; S 4.26 .. Reinforced% C 35.0; H 4.3; N 11.2; S 4.4 ...

The compound having the formula (110) made a significant reduction in blastura and fluoressensia of the previously polished paper, treated are the sompuesto.

Example 9 3. 88 g of the cyanuric chloride were dissolved in 50 ml of acetone and the solution was added to 20 g of ice. Then, in this mixture, in 2 hours at 0 C, a solution of 5.32 g of anilin-2,5-disulfonic acid, dissolved in 30 ml of ice-water, was added to the mixture, the pH was maintained at 6 by the addition of carbonate. sodium. To the reaction mixture, thus obtained, were added, in drops, to 30sc, in 1 hour, 3.7 g of the disodium salt of the acid 4, 4 • -dismino-2, 2'-estilben- disulfonose, dissolved in 50 ml of water, the pH was maintained at 6.5 by the addition of sodium sarbonate. After the admission of 5.29 g of the acid L-glutámiso, the H was adjusted to 8.5 and the asetone was separated by distillation from the reassessing mixture in 5 hours at a bath temperature of 952C. The free acid, which corresponds to the sodium salt of the formula (111), was presipred in asetone, using HCl and the free acid, thus obtained, was separated by filtration and sussión. The filter residue was then dissolved in 100 ml of water and the solution adjusted to a pH of 8.5. After evaporation and drying, 17.5 g (67% of theory) of the compound of the formula (111) remained. The elementary analysis of the formula of the formula (111) and with the empirical formula: C42H3oN12Na10O26S6-14.5 NaCI-18H2O gives: Required% C 18.6 H 2.45; N 6.2; S 7.09; Cl 18.9; H20 11.9.

Found% C 18.6; H 2.50; N 6.2; S 7.0; Cl 19.0; H2o n.6 ...

Example 10 In a manner analogous to the dessrite in Example 9, but replacing the acidic L-glutamis used there for the equivalent sanctity of the acid D, L-aspartite, the compound of formula (112) was obtained in a yield of 70%. The elementary analysis of the formula that has the formula (112) and are the empirical formula: C40H26N12 Na? O? 2? Sß-1.18 NaCI-18H2O gives: Required% C 25.2; H, 3.27; N, 8.81; S 10.08 .. Sounding% C 25.2; H 3.3; N 8.8; S 9.9 ...

Example 11 In a manner analogous to the dessrite in Example 9, but replacing the L-glutamic acid used there by the equivalent amount of the iminodiased acid, the compound of the formula (113) was obtained, yielding 60%. The elementary analysis of the formula that has the formula (113) and are the empirical formula: C4oH2oN12 Na10O26S6-1.41 NaCl; 24 H2O gives: Required% C 23.7; H 3.7; N 8.2; S 9.1. Found% C 23.70; H 3.68; N 8.29; S 9.48.

Examples 12 to 16 A coating somposision was obtained, having the following formulation: 40 parts of China clay 60 parts of calcium carbonate 9 parts of a styrene / butyl rubber latex 0.2 parts of polyvinyl toohol and 0.25 parts of a poly (acrylic acid) The pH value of the coating somposission was adjusted to 9.5 by the addition of the necessary amount of NaOH. To separate portions of the re-cover somposission. 0.2% or 0.4% (based on the total weight of China clay and calcium carbonate) of the fluorescent whitening agent (substansia astiva) under the test was added. The content of the sesa substance in the coating solution was adjusted to 60% by weight and everything was stirred for 10 minutes. A base paper, the sual is free of wood and the fluorescent whitening agent, then it is resubri- cated is the rewind somposisance, using a laboratory sheet re-cover, at a re-weighing weight of 11 g / m2. After biasing using IR radiation and outgoing air, the blansura (Blansura CIÉ, as measured by SCAN-P 66:93) and the brightness (ISO Brilliance, measured by ISO 2470) of sada sample of re-coated paper is determined using a spectrophotometer. The fluorescence of each coated paper sample was determined from the difference between the brightness and brightness values measured with and without UV in the light source. Fluorescent bleaching test compounds have the formula: The results obtained, using arrays having several R substituents are indicated in the following Table 1.

Table 1 The composition used in Example 13 is the composition of Example 2; the composition used in the Example 14 is the composition of Example 3; the package used in the Example 15 is the compound of Example 10; and the composition used in Example 16 is the composition of Example 11.

The results of Table 1 show that the samples of re-coated paper, produced by agreement, are the present invention, have good properties of blansura, brilliance and fluoressensia.

Example 17 Using the procedure outlined in Example 3, but using 5 g of the starting compound of the formula (103) and reassuring this are 1.8 g of a 40% solssion of sarsosine, 1.9 g of the formula (114) was obtained . The elemental analysis of the compound that has the formula (114) and with the molecular formula: Required% C 33.8; H 4.18; N 14.52; S 9.49. Sounding% C 33.8; N 4.13; N 14.33; S 9.1.

Examples 18 and 19 A standard washing powder (ECE) was made of the following components, in the indexed pro-actions (% by weight): 8.0% alkylbensose sulfonate (Cu.5) sodium 2.9% tetradesan-ethylene-glisol- tallow ether tallow (14 moles of EO) 3.5% sodium soap 43.8% sodium tripolyphosphate 7.5% sodium silisate 1.9% magnesium silicate 1.2% carboxymethylcellulose 0.2% EDTA 21.2% sulphate sodium 0 or 0.2% of the compound (102) and water up to 100%. A wash liquor was prepared by dissolving 0.8 g of the previous wash powder in 200 ml of tap water, 5 g of cotton reinforcement was added to the bath and washed at 40 C in 15 minutes and then rinsed, dried by rotation and ironed at 1602C. The washing procedure was repeated three or ten times. After the third and thirteen washes, the blansura of the washed samples was measured as a DCI / SF spectrophotometer, according to the Ganz method.

This method of Ganz is discussed in detail in the Ciba-Geigy Review, 1973/1, and also in the article "Measurement of Whiteness", ISCC Conferense on Fluoressense and the Colorimetry of Fluoressent Materials, Williamsburg, February 1972, published in the journal JOurnal of Color and Appearanc, 1, No. 5 (1972). The sun protection factor (SPF) was determined by measuring the UV light transmitted through a sample, using a double grid spectrometer, equipped with an Ulbricht bowl. The SPF cell was sonduced as described by B.L. Diffey and J.Robson in J.Soc.Cosm. Chem. 40. (1989), pages 130-31. The results obtained are indicated in the following Table 2:

Claims (15)

1. CLAIMS 1. A compound that has the formula: in sual X it is O or NH; M is hydrogen, an atom of an alsaline metal, ammonium or a satin formed of an amine; each Rl independently, is a residue of an amino acid from the sual a hydrogen atom in the amino group has been removed; n is 1 or 2; and R2, independently, is hydrogen, C1-C3 alkyl, halogen, cyano, COOR where R is hydrogen or C2-C3 alkyl, CONH-R, where R has the above meanings, S0NH-R, where R has the meanings previous, NH-COR, where R has the previous meanings, SO3M, where M has the meanings previous, or, where n is 1, R may also be CO-R3, where R3 is C1-C3 alkyl, or phenyl; are the sondisión that exsluyen those sompuestos in the suales: a.) X is NH, n is 1 and R2 is S03M, where M has the previous signifisados; or b.) X is NH, n is 2 and one of R2 is SO3M, where M has the previous signifisados, and the other R2 is hydrogen, methyl or halogen; or s.) X is NH, n is 1, Rx is glisina and R is H or C02H; X is NH, n is 2, sada R is SO3M, where M has the previous signifisados, and groups of SO3M are in positions 2.5 in the phenyl ring, and Ri is D, L-alanine, L-valine , L-leusine, L-isoleusin, L-threonine, acid L- aspartite, L-glutamic acid, L-phenylalanine, L-proline, D, L-methionine or glycine.
2. 2. A compound, according to claim 1, wherein one of the amino acid residues, Ri, is the same and one has the formula -NH-CH (C0 J) -R3, where R3 is hydrogen or a group that has the formula -CHR4R5, where P4 and R5, independently, are hydrogen or C1-C4 alkyl, optionally substituted by one or two substituents, seleaded with hydroxy, thio, methylthio, amino, sarboxi, sulfo, phenyl, 4-hydroxyphenyl, 3,5-diiodo-4-hydroxyphenyl, β-indolyl, β-imidzolyl and NH = C (NH 2) NH-.
3. 3. A method for the fluorescent blanching of a substrate, which consists in putting the substrate into sontaste, is a composition having the formula ** (IA): wherein X is O or NH; M is hydrogen, an atom of an alkali metal, ammonium or a satin formed of an amine; sada R-L, independently, is an amino acid residue from the sual a hydrogen atom in the amino group has been removed; n is 1 or 2; and Sada R * 2, independently, is hydrogen, C1-C3 alkyl, halogen, cyano, COOR where R is hydrogen or C1-C3 alkyl, CONH-R, where R has the previous signifisados, S02NH-R, where R has the previous signifisados, NH-COR, where R has the previous signifisados, SO3M, where M has the previous signifisados; they are the condition that excludes those compounds in which X is NH, n is 2 and one R2 is SO3M, where M has the previous meanings, and the other R is hydrogen, methyl or halogen.
4. 4. A method, according to claim 3, for the fluorescent blanching of a paper surface, the suturing of the sontaste of this paper surface is a rewinding somposission that includes a blue pigment; a binder dispersion; opsionally, a water-soluble co-binder; and sufficient fluorescent whitening agent, having the formula (IA), to ensure that the treated paper is from 0.01 to 1% by weight, based on the white pigment, of a fluorescent whitening agent of the formula (IA).
5. 5. A method, according to claim 3, for fluorescent whitening of a paper surface, which involves the sontasting of the paper in a sizing press, is an asusious solder which is a sizing, opsionally an inorganic or organoisolated pigment, and 0.1 to 20 g / 1 of a fluorescent whitening agent having the formula (IA).
6. 6. A method according to claim 3, for fluorescent whitening of paper, comprising adding the fluorescent whitening agent, having the formula (A) to an aqueous paper pulp at the wet end.
7. 7. A method for increasing the classification of the solar protrusion fastor (SPF) of a textile fiber material, which consists of treating the textile fiber material with 0.05 to 3.0% by weight, based on the weight of the textile fiber material, one or more packages that have the formula (IA), as defined in claim 3.
8. 8. One method of agreement is the claim 7, in the sual, in addition to the formula of the formula (IA), you can also use a minor proporosión one or more auxiliaries.
9. 9. One method, according to claim 8, in which the auxiliaries are emulsifiers, perfumes, bleaching agents, enzymes, solder dyes, dressings agents, optical bleaching agents, bactericides, nonionic surfactants, ingredients for the Sweating of fabrics, agents are gel formations, or sorrosion inhibitors.
10. 10. A method for increasing the slasifisation of the solar protection factor (SPF) of a textile fiber material, according to claim 7, is that the textile fiber material is a detergent, which is at least one compound of the formula (ÍA), so sual imparts a fast expletive of solar protessión to the fiber material so washed.
11. 11. One method, of agreement are the vindication 10, in the sual the used detergent composition comprises: (i) from 5 to 90% of an anionic surfactant and / or a nonionic surfactant; (ii) from 5 to 70% of a trainer; (iii) from 0 to 30% of a peroxide; (iv) from 0 to 10% of a peroxide scavenger and / or from 0 to 1% of a bleaching catalyst; (v) from 0.005 to 2% of at least one compound of the formula (IA); and (vi) from 0.005 to 10% of one or more auxiliaries, based on the total weight of the detergent.
12. 12. A textile fabric, produced from a treated fiber of agreement, is the method as claimed in any of claims 7 to 11.
13. 13. A somposision of detergent, sual somprende: (i) from 5 to 90% of an anioniso tensoast agent and / or a nonionic surfactant; (ii) from 5 to 70% of a trainer; (iii) from 0 to 30% of a peroxide; (iv) from 0 to 10% of a peroxide activator and / or from 0 to 1% of a bleaching catalyst; (v) from 0.005 to 2% of at least one compound of the formula (IA); and (vi) from 0.005 to 10% of one or more auxiliaries, based on the total weight of the detergent.
14. 14. A process for the fluorescent bleaching of textile or paper materials, the sual is to put into sontaste the textile materials or the paper are at least one composition of the formula (1), as defined in claim 7.
15. 15. A composition of textile detergent or softener, which cares for color, which comprises a non-fluorescent compound of the formula (IA). SUMMARY OF THE INVENTION The present invention provides new proposals, which have the formula: in sual X is O or, preferably, NH; M is hydrogen, an atom of an alsaline metal, ammonium or a cation formed of an amine; each Ri, independently, is a residue of an amino acid from which a hydrogen atom in the amino group has been removed; n is 1 or 2; and each R2, independently, is hydrogen, C1-C3 alkyl, halogen, sian, COOR where R is hydrogen or alkyl ^ -03, CONH-R, where R has the previous meanings, S0NH-R, where R has the previous signifisados , NH-COR, where R has the previous signifiers, SO3M, where M has the signifisados previous, or, when n is 1, R2 may also be CO-R3, where R3 is C1-C3 alkyl, or phenyl; with the proviso that those compounds are excluded in which: a.) X is NH, n is 1 and R2 is SO3M, where M has the previous meanings; or b.) X is NH, n is 2 and one of R2 is SO3M, where M has the previous meanings, and the other R2 is hydrogen, methyl or halogen; or s.) X is NH, n is 1, Rj is glycine and R2 is H or C? H; X is NH, n is 2, sada R2 is SO3M, where M has the previous signifisados, and groups of SO3M are in positions 2.5 in the phenyl ring, and R ^ is D, L-alanine, L- valine, L-leusine, L-isoleusin, L-threonine, acid L- aspartite, acid L-glutamism, L-phenylalanine, L-proline, D, L-methionine or glisina.