EP0030917A2 - Agents de blanchiment optique de la série des bistyrylbenzènes, procédé pour leur préparation et leur utilisation - Google Patents

Agents de blanchiment optique de la série des bistyrylbenzènes, procédé pour leur préparation et leur utilisation Download PDF

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Publication number
EP0030917A2
EP0030917A2 EP80810378A EP80810378A EP0030917A2 EP 0030917 A2 EP0030917 A2 EP 0030917A2 EP 80810378 A EP80810378 A EP 80810378A EP 80810378 A EP80810378 A EP 80810378A EP 0030917 A2 EP0030917 A2 EP 0030917A2
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formula
compound
alkyl
carbon atoms
optical brightener
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EP0030917A3 (en
EP0030917B1 (fr
EP0030917B2 (fr
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Leonardo Dr. Guglielmetti
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Novartis AG
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Ciba Geigy AG
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    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06L—DRY-CLEANING, WASHING OR BLEACHING FIBRES, FILAMENTS, THREADS, YARNS, FABRICS, FEATHERS OR MADE-UP FIBROUS GOODS; BLEACHING LEATHER OR FURS
    • D06L4/00—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs
    • D06L4/60—Optical bleaching or brightening
    • D06L4/65—Optical bleaching or brightening with mixtures of optical brighteners

Definitions

  • the present invention relates to optical brighteners consisting of two bis-styrylbenzene compounds, a process for their preparation and new intermediates which occur, agents containing such optical brighteners and the use of these optical brighteners or the agents containing them for optically brightening organic high-molecular materials .
  • 1,4-bis-styrylbenzene compounds consist of three components, namely about 50% of an asymmetrically substituted and about 25% of two different symmetrically substituted bis-styrylbenzene compounds. Such mixtures arise purely statistically when reacting one mole of terephthalaldehyde with a mixture of one mole each of two optionally substituted benzylphosphonates.
  • Mixtures of two or more symmetrically substituted bis-styrylbenzenes are also known, which can be obtained by simply mixing pure symmetrical compounds.
  • these known three-component mixtures mentioned can contain at most about 50% of the respective asymmetrically substituted bis-styrylbenzene compound.
  • an optical brightener consisting of 51-99%, preferably 80-99%, in particular 90-99%, of an asymmetrically substituted 1,4-bis-styrylbenzene compound and 49-1%, preferably 20-1 %, in particular 10-1% of a symmetrically substituted 1,4-bis-styrylbenzene compound is able to achieve significantly higher brightening effects than the known corresponding individual compounds and the mixtures mentioned above.
  • this composite brightener can be produced very well by the new method according to the invention.
  • the optical brightener according to the invention consists of 51-99% of an asymmetrically substituted compound of the formula wherein R and R 1 are the same or different, wherein in the event that R and R1 are the same, R 1 must occupy a different position in the phenyl ring to which it is attached than R in its phenyl ring and wherein R and R 1 are independent from each other CN or a carboxylic acid ester group mean:, and 49-1% of a symmetrically substituted compound of the formula where R has the above meaning and both R are attached to the same position in their phenyl rings.
  • the bis-styrylbenzene compound (1) must therefore be unsymmetrically substituted in any case.
  • the substituents R and R 1 regardless of whether they are the same or different, are preferably attached to different positions of the respective phenyl ring.
  • the compound (2) is symmetrical both with regard to the substituent R and with regard to its position.
  • Preferred carboxylic ester groups are those of the formula -COOY, in which Y is alkyl having 1 to 6 carbon atoms, alkenyl having 3 to 6 carbon atoms, cycloalkyl having 5 or 6 carbon atoms, haloalkyl, aralkyl, especially phenylalkyl, especially benzyl, carbalkoxyalkyl, cyanoalkyl, hydroxyalkyl , Aminoalkyl, alkylaminoalkyl, dialkylaminoalkyl, it being possible for all of the composite alkyl groups mentioned above to have 1 to 6 carbon atoms in each alkyl part; Propargyl, tetrahydrofurfuryl or a group of the formula (CH 2 - H XO) n -alkyl, where in the latter group X is hydrogen or methyl and n is a number between 1 and 4 and the alkyl group has 1 to 6 carbon atoms.
  • Halogen is chlorine,
  • Y particularly preferably represents alkyl having 1 to 6, in particular 1 to 4, carbon atoms, alkenyl with 3 to 6 carbon atoms and benzyl, especially alkyl with 1 to 4 carbon atoms. All alkyl groups belonging to compound groups (which form the substituent Y) preferably have 1 to 4 carbon atoms.
  • Optical brighteners according to the invention in which the individual components R and R 1 are identical and each denote CN, have particularly good properties.
  • the two optical brighteners consisting of 51-99% of the compound of the formula and 49-1% of the compound of the formula and from 51-99 7 of the compound of the formula and 49-1% of the compound of the formula
  • optical brighteners according to the invention have particularly valuable properties if they consist of 70-99, in particular 80-99, but above all 90-99% of the asymmetrically substituted compound, for example of the formula (1) or (3), and 30-1, in particular 20-1, but especially 10-1 7 of the symmetrically substituted compound, for example the formula ( 2), (4) or (6).
  • optical brightener consisting of 90-99% of the compound of formula (3) and 10-1 Z of the compound of formula (4) and that consisting of 90-99 Z of the compound of formula (3) and 10 -1% of the compound of formula (6).
  • optical brighteners according to the invention are produced by a new process which is also the subject of the invention.
  • optical brighteners according to the invention can be produced from two individual components by a very simple synthesis process.
  • the process according to the invention is characterized in that terephthalaldehyde with a compound of the formula to a mixture of the compounds of the formulas and and this mixture is then reacted further with a compound of the formula to the brightener consisting of the compounds (1) and (2), where R and R 1 have the meanings given in formulas (1) and (2) and must meet the conditions specified there with regard to their positions in the phenyl rings and where X and Y are identical or different and independently of one another are hydrogen or a radical of the formula -COOZ, in which Z is alkyl, mean.
  • the quantitative ratio between terephthalaldehyde and the compound of formula (7) depends on which quantitative ratio is desired in the final mixture of asymmetrically and symmetrically substituted bis-styrylbenzenes. Accordingly, the quantitative ratio between the monoaldehyde (8) and the compound of formula (9) reacting therewith can be adjusted. In this way, each quantitative ratio defined in claim 1 can be easily adjusted by the selection of the quantitative ratios in the starting products. The content of monoaldehyde (8) in the reaction mixture can easily be determined analytically.
  • alkyl preferably denotes an unsubstituted alkyl group having 1 to 6 carbon atoms or the benzyl group and aryl, preferably phenyl, optionally substituted with chlorine, methyl or methoxy.
  • a preferred implementation in the process according to the invention is characterized in that terephthalaldehyde with a compound of the formula to a mixture of the compounds of the formula and of the formula (4) or to a mixture of the compounds of the formula (17) and formula (6) reacted and the mixture obtained in each case subsequently with a compound of the formula to the optical brighteners according to the invention consisting of the compounds of the formulas (3) and (4) or (3) and (6),
  • the reaction of terephthalaldehyde with a compound of the formula (7), in which X denotes one of the groups (10) - (13) or with a compound of the formula (14) or (15) (first stage) is preferably carried out in the presence of an alkaline Condensing agent that serves as a proton acceptor performed.
  • alkaline Condensing agent that serves as a proton acceptor performed.
  • condensation agents are inorganic or organic bases, e.g. Hydroxides, hydrides, alkoxides and amides of the alkali or alkaline earth metals, monomeric or polymeric strongly basic amines and resin exchangers of the OH series in question. Sodium and potassium hydroxide and sodium methylate are of particular practical importance. A mixture of different bases can also be used.
  • the amount of condensing agent to be used is within wide limits. The equivalent amount is advantageously used, but an excess can also be used.
  • the second stage reaction of the mixture of monoaldehyde and symmetrical bis-styrylbenzene compound
  • the process according to the invention is expediently carried out in a solvent which is inert under the reaction conditions.
  • solvents are apolar and dipolar aprotic and protic solvents such as hexane, octane, cyclohexane, toluene, xylene, chlorobenzene, etc; Formamide, dimethylformamide, N-methylpyrrolidone, acetonitrile, dimethyl sulfoxide, etc .; methanol, ethanol, isopropanol, hexanol etc. into consideration.
  • the process of the invention can also be carried out in water or in water-containing mixtures in the presence or absence of phase transfer catalysts.
  • the first stage is preferably carried out in a solvent in which the resulting monoaldehydes of the formulas (8) or (16) and (17) are sparingly soluble, e.g. in methanol, ethanol, hexane or toluene.
  • the aldehydes formed precipitate during the reaction together with the symmetrical compounds of the formulas (2) or (4) and (6) and can be isolated by filtration or, preferably, can be reacted further without isolation. If the mixtures obtained are isolated, they are preferably used further without purification.
  • reaction of the monoaldehydes of the formulas (8) or (16) and (17), as mixtures together with the symmetrical compounds of the formulas (2) or (4) and (6), with a compound of the formula (9) or (15) or (14) (second stage) is preferably carried out in a solvent in which the monoaldehydes are partially or completely soluble.
  • Aprotic dipolar solvents such as e.g. Dimethyl- and diethylformamide and dimethyl sulfoxide in question.
  • the reaction temperature varies within wide limits depending on the solvent selected and can easily be determined by preliminary tests.
  • the first stage is expediently carried out at temperatures between 0 ° C. and 50 ° C., preferably between 20 ° C. and 30 ° C. Temperatures between 20 ° C. and 100 ° C., preferably between 30 ° C. and 50 ° C., are particularly suitable for the second stage.
  • the invention further relates to the new compounds of the formulas (17) and (302) which occur as intermediates, namely 4'-cyanostilben-4-aldehyde and 3'-cyanostilben-4-aldehyde, and the ester aldehydes of the formula in which R 2 is a carboxylic acid ester group, in particular one of the formula -COOY, in which Y is alkyl, haloalkyl, aralkyl, carbalkoxyalkyl, cyanoalkyl, hydroxyalkyl, aminoalkyl, alkylaminoalkyl, dialkylaminoalkyl, all of the abovementioned alkyl groups and alkyl parts in compound groups each having 1 to 6 carbon atoms ; Alkenyl with 3 to 6 carbon atoms, cycloalkyl with 5 to 6 carbon atoms, propargyl, tetrahydrofurfuryl or a group of the formula (CH 2 - H represents XO
  • This process is characterized in that terephthalaldehyde with a compound of the formula where X 'is a radical of the formula means, and the corresponding aldehyde is separated from the mixture obtained by repeated recrystallization, if necessary, or by chromatography.
  • the process conditions for the reaction of terephthalaldehyde with the compounds of the formulas (18), (19) and (24) correspond to those specified for the first stage of the process according to the invention for the preparation of the brightener mixtures.
  • the final purification of the aldehydes is conveniently carried out by chromatography, e.g. Column chromatography or preferably by recrystallization, if necessary by multiple recrystallization, optionally with the addition of activated carbon or bleaching earth. Dioxane is preferred as the solvent for the recrystallization.
  • R 2 is a group of the formula -COOY 1 , in which Y 1 is alkyl having 1 to 4 carbon atoms.
  • optical brighteners according to the invention are used for optically brightening a wide variety of synthetic, semi-synthetic or natural organic materials.
  • the organic materials to be optically brightened can belong to the most varied of processing states (raw materials, semi-finished or finished products).
  • they can be in the form of a wide variety of shaped structures, i.e.
  • shaped structures i.e.
  • two-dimensionally designed bodies such as films, foils, lacquers, coatings, impregnations and coatings or as predominantly one-dimensionally designed bodies such as threads, fibers , Flakes, wires.
  • said materials can also be in unshaped states in a wide variety of homogeneous or inhomogeneous forms of distribution, such as e.g. as powders, solutions, emulsions, dispersions, latices, pastes or waxes.
  • Fiber materials can be, for example, as endless threads (drawn or undrawn), staple fibers, flakes, strand goods, Textile threads, yarns, threads, non-woven fabrics, felts, wadding, flocking structures or as textile fabrics or textile composites, knitted fabrics and as papers, cardboards or paper pulps.
  • the brighteners to be used according to the invention are of particular importance for the treatment of textile organic materials, in particular textile fabrics. If fibers which can be in the form of staple fibers or continuous threads, in the form of strands, fabrics, knitted fabrics, nonwovens, flocked substrates or composites, are to be optically brightened according to the invention, this is advantageously done in an aqueous medium, in which the compounds in question are in finely divided form (suspensions, so-called microdispersions, optionally solutions) are present. If necessary, dispersants, stabilizers, wetting agents and other auxiliaries can be added during the treatment.
  • optical brighteners according to the present invention can also be added or incorporated into the materials before or during their deformation.
  • they can be added to the molding compound or injection molding compound during the production of films, foils (e.g. rolling in polyvinyl chloride in the heat) or moldings.
  • Such agents which contain the optical brighteners according to the invention, are also the subject of the invention.
  • the usual formulation additives are e.g. various auxiliaries and coupling agents, e.g. anhydrous sodium sulfate, sodium sulfate decahydrate, sodium chloride, sodium carbonate, alkali metal phosphates such as sodium or potassium orthophosphate, sodium or potassium pyrophosphate and sodium or potassium tripolyphosphates or alkali metal silicates.
  • aqueous formulations also fall under the agents according to the invention, e.g. also the application solutions with which textile fibers are brightened optically and which contain the usual additives.
  • agents according to the invention are those which, in addition to a greenish one on the substrate to be treated optical brighteners according to the invention which produce a bluish shade (for example mixtures of the compounds (1) and (2), (3) and (4) or (3) and (6)) additionally contain an optical brightener which is based on the material to be treated Produces a reddish shade.
  • Such combinations have the advantage that a particularly beautiful neutral white tone of high brilliance can be achieved on textile fibers, especially on polyester fibers.
  • Means which have an optical brightener consisting of the compounds (3) and (4) or (3) and (6) or other mixtures of a symmetrical and asymmetrical component from which the brighteners according to the invention consist and additionally an optical brightener are therefore very advantageous from the class of naphthalimides, bis-benzoxazolyl-ethylenes, bis-benzoxazolyl-thiophenes, stilbenylbenzoxazoles, naphthotriazol-2-yl-stilbenes (known from German Offenlegungsschriften 25 39 537 and 25 39 461) or coumarins, for example the 3-phenyl-7-pyrazolylcoumarins, the 3-pyrazolyl-7-v-triazolylcoumarins or the 3-v-triazolylcoumarins (known from the Swiss patents 566,359 and 592,189), in particular those which contain 5-90 as a brightening active substance %, in particular 30-70% of an optical brightener according to the invention which produces a greenish to
  • agents according to the invention as brighteners which produce a reddish shade are those from the class of the naphthotriazolyl-stilbene and the triazolylcoumarins.
  • Substrates made of polyester are particularly preferably brightened with the optical brighteners according to the invention, in particular textile materials made of polyester.
  • the combined treatment can advantageously be carried out with the aid of corresponding stable preparations which contain the optically brightening compounds in such a concentration that the desired lightening effect is achieved.
  • the brighteners are brought to full effect by post-treatment.
  • This can be, for example, a chemical (eg acid treatment), a thermal or a combined chemical / thermal treatment.
  • the optical brightening of a number of fiber substrates, for example polyester fibers, with the brighteners according to the invention is expediently carried out in such a way that these fibers are mixed with the aqueous dispersions (if appropriate also solutions) of the brighteners at temperatures below 75 ° C., for example at Room temperature, impregnated and subjected to a dry heat treatment at temperatures above 100 ° C, where it is generally recommended that the fiber material before moderately elevated temperature, eg to dry at least 60 ° C to about 130 ° C.
  • the heat treatment in the dry state is then advantageously carried out at temperatures between 120 and 225 ° C., for example by heating in a drying chamber, by ironing in the specified temperature interval or by treatment with dry, superheated steam.
  • the drying and dry heat treatment can also be carried out immediately one after the other or combined in a single operation.
  • the amount of the optical brightener to be used according to the invention can vary within wide limits. Even with very small quantities, in certain cases e.g. of 0.001 percent by weight, a clear and durable effect can be achieved. However, amounts of up to about 0.8 percent by weight and optionally up to about 2 percent by weight can also be used. For most practical purposes, amounts between 0.01 and 0.5 percent by weight are preferred.
  • Example 1 53.6 g of terephthalaldehyde are suspended in 300 ml of absolute ethanol and 144 g of a 30% methanolic sodium methylate solution are added at 20 to 25.degree. C. with stirring and nitrogen within 15 minutes. An almost clear solution is formed which, at 20 to 25 ° C. with stirring and nitrogen, with 102 g of the phosphonate of the formula within 20 minutes is added, the reaction product immediately precipitating crystalline.
  • the resulting thick crystalline slurry is then stirred for six hours at 20 to 25 ° C under nitrogen, then suction filtered, washed with about 50 ml of absolute ethanol and dried under vacuum at 50 ° C to constant weight.
  • 60.06 g (about 64.4% of theory) of a light yellow crystalline powder of melting point 144 to 149 ° C. are obtained, which by gas chromatographic analysis is a mixture consisting of 87.8% of the compound of the formula and 11.3% of the compound of the formula can be identified.
  • the phosphonate of the formula (14) used as starting material is prepared in analogy to Example 1 of German Offenlegungsschrift 1 921 466 and purified by distillation (K p 0.35 : 136-138 ° C).
  • reaction product is filtered off with suction, washed with about 100 ml of dimethylformamide / water (1: 1) and then with about 100 ml of methanol and dried under vacuum at 100 ° C. to constant weight. 28.9 g (about 86.9% of theory) of a light yellow crystalline powder of melting point 188 to 233 ° C. are obtained, which, according to gas chromatographic analysis, is a mixture consisting of 91.2% of the compound of the formula and 7.7 of the compound of formula (4).
  • the phosphonate of the formula (15) used as starting material is prepared in accordance with Example 1 of German Offenlegungsschrift 1 921 466.
  • Example 2 67 g of terephthalaldehyde are suspended in 300 ml of absolute methanol and 180 g of a 30% strength methanolic sodium methylate solution are added at 20 to 25 ° C. with stirring and nitrogen within 15 minutes. An almost clear solution is formed, to which a solution of 126.6 g of the phosphonate of the formula (15) in 100 ml of absolute methanol is added at 20 to 25 ° C. with stirring and nitrogen within 20 minutes, the reaction product immediately precipitating out in crystalline form . The resulting crystalline reaction mixture is further treated as described in Example 1. 106.1 g (about 91.0% of theory) of a light yellow crystalline powder of melting point 198 to 205 ° C. are obtained, which can be analyzed analytically as a mixture consisting of 92.3% of the compound of the formula and 7.1% of the compound of the formula turns out.
  • Example 3 26.8 g of terephthalaldehyde are suspended in 100 ml of absolute methanol and 72 g of a 30% methanolic sodium methylate solution are added at 20 to 25 ° C. with stirring and nitrogen within 15 minutes. An almost clear solution is formed which, at 20 to 25 ° C. with stirring and nitrogen, within 20 minutes with a solution of 50.6 g of the phosphonate of the formula in 60 ml of absolute methanol, the reaction product slowly precipitating out in crystalline form.
  • the resulting crystalline reaction mixture is then stirred for 24 hours at 20 to 25 ° C under nitrogen, cooled to 0 ° C, then suction filtered, with about 50 ml of absolute Washed ethanol and dried under vacuum at 50 ° C to constant weight.
  • the phosphonate of the formula (301) used as starting material is prepared according to Example 2 of GB-PS 920,988.
  • reaction product is filtered off with about 100 ml Dimethylformamide / water (1: 1) and then washed with about 80 ml of ethanol and dried under vacuum at 100 ° C to constant weight. 28.55 g (about 85.9% of theory) of a light yellow crystalline powder with a melting point of 199 to 217 ° C. are obtained, which can be analyzed as a mixture consisting of 88.3% of the compound of the formula and 10.9% of the compound of formula 1303).
  • Example 4 23.3 g of the mixture of compounds (17) and (6) obtained according to Example 2 and 25.3 g of the phosphonate of the formula (301) are reacted as described in Example 3. 29.4 g (about 88.5% of theory) of a light yellow crystalline powder with a melting point of 204 to 220 ° C. are obtained, which can be analyzed as a mixture consisting of 95.7% of the compound of the formula (304) and 3 , 8% of the compound of formula (6) proves.
  • Example 5 23.3 g of the mixture of compounds (302) and (303) obtained according to Example 3 and 25.3 g of the phosphonate of the formula (14) are reacted in 100 ml of dimethylformamide as described in Example 3. 23.5 g (about 70% of theory) of a pale yellow crystalline powder with a melting point of 174 to 183 ° C. are obtained, which can be analyzed analytically as a mixture consisting of 85.1% of the compound of the formula and 13.8% of the compound of formula (303).
  • Example 6 23.3 g of the mixture obtained according to Example 1. Compounds (16) and (4) and 25.3 g of the phosphonate of the formula (301) are reacted in 100 ml of dimethylformamide as described in Example 3. 24.5 g (about 73.5% of theory) of one are obtained pale yellow crystalline powder with a melting point of 176 to 188 ° C, which analytically turns out to be a mixture consisting of 91.6% of the compound of formula (501) and 7.1% of the compound of formula (4).
  • Example 7 7 g of the mixture of compounds (16) and (4) obtained according to Example 1 and 7.8 g of the phosphonate of the formula are reacted in 80 ml of dimethylformamide as described in Example 3. 9.5 g (about 87% of theory) of a yellow crystalline product having a melting point of 187 to 205 ° C. are obtained, which can be analyzed analytically as a mixture consisting of 93.3 7 of the compound of the formula and 5.6% of the compound of formula (4).
  • the phosphonate of the formula (701) used as starting material is prepared according to Example 2 of GB-PS 929,436.
  • Example 8 9.3 g of the mixture of compounds (16) and (4) obtained according to Example 1 and 12 g of the phosphonate of the formula are suspended in 120 ml of dimethylformamide and 22 ml of an ethanolic 2M sodium ethylate solution are added at 30 ° C. with stirring and nitrogen within 15 minutes. The reaction mixture is worked up as described in Example 3. 13 g (about 86 of theory) of a yellow crystalline product with a Melting point of 178 to 181 ° C., which can be analyzed analytically as a mixture consisting of 95.3% of the compound of the formula and 3.9% of the compound of formula (4).
  • the phosphonate of the formula (801) used as starting material is prepared analogously to Example 2 of GB-PS 929,436 and purified by distillation (K p0.25 : 181-185 ° C).
  • Example 9 40 g of terephthalaldehyde are suspended in 100 ml of absolute ethanol and 300 ml of an ethanolic 2M sodium ethylate solution are added at 20 to 25 ° C. with stirring and nitrogen within 15 minutes. An almost clear solution is formed, to which 90 g of the phosphonate of the formula (801) are added at 20 to 25 ° C. with stirring and nitrogen within 20 minutes, the reaction product immediately precipitating in crystalline form. The resulting thick crystalline slurry is then stirred for 16 hours at room temperature under nitrogen, then suction filtered, washed with about 50 ml of absolute ethanol and dried under vacuum at 50 ° C to constant weight.
  • Example 10 8 g of the mixture of compounds (302) and (303) obtained according to Example 3 and 9 g of the phosphonate of the formula (701) are reacted in 80 ml of dimethylformamide as described in Example 3. 10 g (about 78% of theory) of a pale yellow crystalline powder with a melting point of 228 to 236 ° C. are obtained, which can be analyzed analytically as a mixture consisting of 93.4% of the compound of the formula and 5.5% of the compound of formula (303).
  • Example 11 9.3 g of the mixture of the compounds (302) and (303) obtained according to Example 3 and 12 g of the phosphonate of the formula (801) are suspended in 120 ml of dimethylformamide and at 30 ° C. with stirring and nitrogen within 15 minutes treated with 22 ml of an ethanolic 2 M sodium ethylate solution.
  • the reaction mixture is worked up as described in Example 3. This gives 12.5 g (about 82% of theory) of a yellow crystalline product with a melting point of 194 to 197 ° C., which can be analyzed analytically as a mixture consisting of 92.6% of the compound of the formula and 6.5% of the compound of formula (303).
  • Example 12 11.7 g of the mixture of compounds (17) and (6) obtained according to Example 2 and 13 g of the phosphonate of the formula (701) are reacted in 100 ml of dimethylformamide as described in Example 3. 16 g (about 87% of theory) of a yellow crystalline powder with a melting point of 219 to 225 ° C. are obtained analytically as a mixture consisting of 97.2% of the compound of the formula and 2.6% of the compound of formula (6).
  • Example 13 9.3 g of the mixture of compounds (17) and (6) and 12 g of the phosphonate of the formula (801) obtained according to Example 2 are suspended in 120 ml of dimethylformamide and at 30 ° C. with stirring and nitrogen within 15 minutes treated with 22 ml of an ethanolic 2 M sodium ethylate solution. The reaction mixture is worked up as described in Example 3. 13.5 g (about 89% of theory) of a yellow crystalline powder having a melting point of 219 to 221 ° C. are obtained, which can be analyzed as a mixture consisting of 95.5% of the compound of the formula and 3.4% of the compound of formula (6).
  • Example 14 18.6 g of the mixture of compounds (17) and (6) obtained according to Example 2 and 24 g of the phosphonate of the formula are suspended in 60 ml of dimethylformamide and 35 ml of an ethanolic 2.5 M sodium ethylate solution are added at 30 ° C. with stirring and nitrogen within 15 minutes. The reaction mixture is worked up as described in Example 3. 11.5 g (about 38% of theory) of a yellow crystalline powder of melting point 143 to 169 ° C. are obtained, which can be analyzed analytically as a mixture consisting of 90.6% of the compound of the formula and 8.3% of the compound of formula (6).
  • the phosphonate of formula (1401) used as the starting material is prepared as follows:
  • the 2-bromomethyl-benzoic acid ethyl ester of formula (1403) is according to J. Chem. Soc. 121, 2202-2215 (1922).
  • Example 15 19.6 g of the mixture of compounds (901) and (902) obtained according to Example 9 and 21 g of the phosphonate of the formula (1401) are suspended in 60 ml of dimethylformamide and at 30 ° C. with stirring and nitrogen within 15 minutes mixed with 31 ml of an ethanolic 2.5M sodium ethylate solution. The reaction mixture is worked up as described in Example 3.
  • Example 16 19.6 g of the mixture of compounds (901) and (902) obtained according to Example 9 and 21 g of the phosphonate of the formula are suspended in 50 ml of dimethylformamide and mixed with 31 ml of an ethanolic 2.5 M sodium ethylate solution at 30 ° C. with stirring and nitrogen within 15 minutes. The reaction mixture is worked up as described in Example 3. 23 g (about 74% of theory) of a pale yellow crystalline powder of melting point 183 to 250 ° C. are obtained, which can be analyzed analytically as a mixture consisting of 94.7% of the compound of the formula and 5.4% of the compound of formula (902).
  • the phosphonate of the formula (1601) used as starting material is prepared in analogy to Example 2 of GB-PS 929,436 and purified by distillation (K p0.3 : 183-185 ° C).
  • Example 17 From brighteners consisting of 91, 2% of the compound of formula (3) and 7.7% of the compound of formula (4) 1 g in 1000 ml of water dispersed. 7.5 ml of this dispersion are added to 100 ml of water containing 0.1 g of a fatty alcohol polyglycol ether. A 15 g polyester fabric is added to this brightener dispersion heated to 60 ° C. The temperature is raised to 120 ° C. in the course of 15 to 20 minutes and left at this temperature for 30 minutes. Then it is cooled to 60 ° C. within 10 to 15 minutes. The tissue is then rinsed in running cold water for 2 minutes and then dried at 60 ° C. for 20 minutes.
  • the fabric treated in this way has a strong lightening effect and good lightfastness.
  • Example 18 Polyester fabric is padded at room temperature with an aqueous dispersion which contains 0.5 g of a brightener in a liter consisting of 91.2% of the compound of the formula (3) and 7.7% of the compound of the formula (4) and 1 g contains an adduct of about 8 moles of ethylene oxide with 1 mole of p-tert-octylphenol.
  • the fluid intake is 60 to 70%.
  • the fabric is dried at 100 ° C and then heated to 180 ° C for 15 seconds.
  • the fabric treated in this way has a strong fogging effect with good lightfastness.
  • the brightener used is a two-component brightener consisting of 95.7% of the compound of the formula (304) and 3.8% of the compound of the formula (6); 85.1% of the compound of formula (501) and 13.8% of the compound of formula (303); 91.6% of the compound of formula (501) and 7.1% of the compound of formula (4); 93.3% of the compound of formula (702) and 5.6% of the compound of formula (4); 95.3% of the compound of formula (802) and 3.9% of the compound of formula (4); 93.4 2 of the compound of formula (1001) and 5.5% of the compound of formula (303); 92.6% of the compound of formula (1101) and 6.5% of the compound of formula (303); 97.2 Z of the compound of formula (1201) and 2.6% of the compound of formula (6); 95.5% of the compound of formula (1301) and 3.4% of the compound of formula (6); 90.6% of the compound of formula (1402) and 8.3% of the compound
  • Example 19 From the brightener consisting of 91.2% of the compound of formula (3) and 7.7% of the compound of formula (4), 1 g is dispersed in 1000 ml of water. 3 ml of this dispersion are added to 100 ml of water containing 0.06 g of an alkyl polyglycol ether. A 3 g heavy polyamide fabric (polyamide 6 or 66) is added to this brightener dispersion heated to 60 ° C. The temperature is raised to 95 to 97 ° C. within 10 to 15 minutes and left at this temperature for 30 minutes. The tissue is then rinsed in running cold water for 2 minutes and then dried at 60 ° C. for 20 minutes.
  • polyamide 6 or 66 polyamide 6 or 66
  • the fabric thus obtained has a strong lightening effect with good light fastness.
  • Example 20 A bath is produced which contains 0.0125, 0.025 or 0.05% by weight, based on the polyester material to be lightened, of a brightener mixture consisting of a brightener composed of 95.7% of the compound of the formula per liter of soft water (3) and 3.2% of the compound of formula (6) and a brightener of the formula in a mixing ratio of 1: 2 or 2: 1, and 1 g of a fatty alcohol polyglycol ether.
  • a brightener mixture consisting of a brightener composed of 95.7% of the compound of the formula per liter of soft water (3) and 3.2% of the compound of formula (6) and a brightener of the formula in a mixing ratio of 1: 2 or 2: 1, and 1 g of a fatty alcohol polyglycol ether.
  • a polyester fabric ("Terylene type 540") in a liquor ratio of 1:20 is introduced into the bath, which is located in a conventional HT dyeing machine.
  • the mixture is heated to 110, 120 and 130 ° C. over a period of 30 minutes and the bath is kept at the respective temperature for 30 minutes.
  • the mixture is then cooled to 40 ° C. within 15 minutes.
  • the treated tissue is rinsed in flowing, softened water for 30 seconds and then dried.
  • the treated fabric pieces show strong, brilliant lightening effects with a pleasing nuance.
  • the greenish-bluish one obtained from the compounds (3) and (6) when lightened with the brightener Nuance is clearly shifted into the reddish area.
  • Example 21 Polyester fabric ("Terylene type 540") is padded at room temperature with an aqueous dispersion which contains 0.125, 0.25, 0.5 or 1 g of a brightener mixture per liter, consisting of a brightener made from 95.7% of the compound of the formula (3) and 3.2% of the compound of the formula (6) and a brightener of the formula (2001) in a mixing ratio of 1: 2 or 2: 1, and 1 ml of an alkylphenol polyglycol ether.
  • the fleet intake is 80%.
  • the fabric is dried at 80 ° C for 10 minutes and then heat-set at 180 °, 200 or 220 ° C for 30 seconds.
  • the treated fabric pieces show strong, brilliant lightening effects with a pleasing nuance.
  • the greenish-bluish shade obtained from the compounds (3) and (6) when lightening with the brightener is clearly shifted into the reddish area.
  • Example 22 If Example 20 or 21 is repeated, but instead of the brightener of the formula (2001), the same amount of one of the brighteners of the formulas is used or a, similarly good effects are obtained on the treated tissue pieces as described in Examples 20 and 21.
  • the brightener from the compounds (3) and (6) can also be replaced by any other two-component brightener obtainable according to Examples 1, 3-8 and 10-16.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Detergent Compositions (AREA)
  • Coloring (AREA)
EP80810378A 1979-12-13 1980-12-08 Agents de blanchiment optique de la série des bistyrylbenzènes, procédé pour leur préparation et leur utilisation Expired - Lifetime EP0030917B2 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
CH11040/79A CH650792A5 (en) 1979-12-13 1979-12-13 Optical brighteners from bisstyrylbenzene compounds and preparation thereof
CH11040/79 1979-12-13
CH305880 1980-04-21
CH3058/80 1980-04-21

Publications (4)

Publication Number Publication Date
EP0030917A2 true EP0030917A2 (fr) 1981-06-24
EP0030917A3 EP0030917A3 (en) 1982-02-17
EP0030917B1 EP0030917B1 (fr) 1985-01-23
EP0030917B2 EP0030917B2 (fr) 1991-03-20

Family

ID=25692061

Family Applications (1)

Application Number Title Priority Date Filing Date
EP80810378A Expired - Lifetime EP0030917B2 (fr) 1979-12-13 1980-12-08 Agents de blanchiment optique de la série des bistyrylbenzènes, procédé pour leur préparation et leur utilisation

Country Status (7)

Country Link
US (3) US4785128A (fr)
EP (1) EP0030917B2 (fr)
JP (1) JPH01152161A (fr)
BR (1) BR8008161A (fr)
CA (1) CA1175608A (fr)
DE (1) DE3070041D1 (fr)
ES (2) ES8205746A1 (fr)

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0064303A1 (fr) * 1980-01-12 1982-11-10 BASF Aktiengesellschaft Mélanges de biscyanostyrylbenzènes
EP0252009A1 (fr) * 1986-07-01 1988-01-07 Ciba-Geigy Ag Composés distyryl-1,4 benzéniques et leurs mélanges avec d'autres composés distyryl-1,4 benzéniques
DE3802204A1 (de) * 1987-01-29 1988-08-11 Ciba Geigy Ag Mischungen von optischen aufhellern
US4778622A (en) * 1986-03-21 1988-10-18 Ciba-Geigy Corporation Mixtures of fluorescent whitening agents
WO1995008017A1 (fr) * 1993-09-13 1995-03-23 Basf Aktiengesellschaft Melanges de blanchiment optique a base de composes bistyryle
EP0680947A2 (fr) * 1994-05-02 1995-11-08 Basf Aktiengesellschaft Procédé pour la préparation d'azurants optiques à base de stilbènes
FR2732015A1 (fr) * 1995-03-24 1996-09-27 Basf Ag Melanges d'agents de blanchiment optique a base de composes bisstyryliques
CH688877GA3 (de) * 1992-06-17 1998-05-15 Hoechst Ag Mischungen aus 1,4-Bis-(cyanostyryl)-benzolen.
CN1064037C (zh) * 1994-02-18 2001-04-04 电化学工业有限公司（国际） 茋基物质及其制备方法
WO2004053221A1 (fr) * 2002-12-10 2004-06-24 Ciba Specialty Chemicals Holding Inc. Melanges d'agents de blanchiment fluorescents

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DE3911221A1 (de) * 1989-04-07 1990-10-11 Bayer Ag Verfahren zur herstellung von bifunktionellen, mindestens eine z-konfigurierte stilbengruppierung enthaltenden stilbenverbindungen, neue bifunktionelle, mindestens eine z-konfigurierte stilbengruppierung enthaltende stilbenverbindungen sowie die verwendung der stilbenverbindungen zur herstellung von polymeren
ATE321066T1 (de) * 1998-05-06 2006-04-15 Genentech Inc Anti-her2 antikörperzusammensetzung
DE10237186A1 (de) * 2002-08-14 2004-03-18 Clariant Gmbh Verfahren zum Aufhellen synthetischer Fasern und Kunstoffe mit granulierten optischen Aufhellern
JP4439327B2 (ja) * 2004-04-30 2010-03-24 富士フイルム株式会社 平版印刷版用原版
ATE493688T1 (de) * 2007-05-25 2011-01-15 Agfa Graphics Nv Flachdruckplattenvorläufer

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CH416078A (de) * 1959-06-24 1966-06-30 Basf Ag Makromolekularen organischen Stoff und optischen Aufheller enthaltende Mischung
CH465548A (de) * 1963-10-31 1968-08-15 Basf Ag Verfahren zum optischen Aufhellen von Textilmaterialien aus synthetischen Polyestern und Polyamiden
US3959340A (en) * 1969-06-05 1976-05-25 Ciba-Geigy Ag Cyano-distyrylbenzenes

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CH388929A (de) * 1959-05-15 1965-03-15 Basf Ag Verfahren zur Herstellung von Verbindungen der 1,4-Divinylbenzol-Reihe
DE1419003A1 (de) * 1959-05-15 1968-12-12 Basf Ag Optisch aufhellende Mischungen
DE1108219B (de) * 1959-05-15 1961-06-08 Basf Ag Verfahren zur Herstellung von Verbindungen der 1, 4-Divinyl-benzol-reihe
NL254044A (fr) * 1959-07-21
DE1129947B (de) * 1959-07-29 1962-05-24 Basf Ag Verfahren zur Herstellung von 1, 4-Bis-(p-carboxystyryl)-benzolen
DE1112072B (de) * 1959-08-12 1961-08-03 Basf Ag Verfahren zur Herstellung von Verbindungen der 1, 4-Bis-(styryl)-benzolreihe
US3076762A (en) * 1960-06-20 1963-02-05 Halliburton Co Acidizing of wells
DE2000027A1 (de) * 1970-01-02 1971-07-08 Basf Ag Optische Aufheller
US4216105A (en) * 1972-07-26 1980-08-05 Hickson & Welch Limited Compositions for the optical whitening of organic materials and use thereof
US4093645A (en) * 1972-07-26 1978-06-06 Hickson & Welch Limited Styryl-tetrahydronaphthyl derivatives
DE2363416A1 (de) * 1973-12-20 1975-07-03 Hoechst Ag Neue bis-naphthyl-aethylene, verfahren zu deren herstellung und ihre verwendung als optische aufhellungsmittel
CH624108A5 (fr) * 1975-10-28 1981-07-15 Sandoz Ag
DE2807497A1 (de) * 1978-02-22 1979-08-23 Bayer Ag Distyryl-verbindungen
DE2929599A1 (de) * 1979-07-21 1981-02-05 Hoechst Ag Mischungen von optischen aufhellern, deren herstellung und verwendung
DE2929687A1 (de) * 1979-07-21 1981-02-12 Hoechst Ag Mischungen von optischen aufhellern
DE2929591A1 (de) * 1979-07-21 1981-02-05 Hoechst Ag Mischungen von optischen aufhellern
DE3001065A1 (de) * 1980-01-12 1981-07-16 Basf Ag, 6700 Ludwigshafen Verfahren zur herstellung von optischen aufhellern

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Publication number Priority date Publication date Assignee Title
CH416078A (de) * 1959-06-24 1966-06-30 Basf Ag Makromolekularen organischen Stoff und optischen Aufheller enthaltende Mischung
CH465548A (de) * 1963-10-31 1968-08-15 Basf Ag Verfahren zum optischen Aufhellen von Textilmaterialien aus synthetischen Polyestern und Polyamiden
US3959340A (en) * 1969-06-05 1976-05-25 Ciba-Geigy Ag Cyano-distyrylbenzenes

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0032254B1 (fr) * 1980-01-12 1984-05-16 BASF Aktiengesellschaft Procédé de préparation des bis-styrylbenzenes
US4464284A (en) * 1980-01-12 1984-08-07 Basf Aktiengesellschaft Mixtures of optical brighteners
EP0064303A1 (fr) * 1980-01-12 1982-11-10 BASF Aktiengesellschaft Mélanges de biscyanostyrylbenzènes
US4778622A (en) * 1986-03-21 1988-10-18 Ciba-Geigy Corporation Mixtures of fluorescent whitening agents
EP0252009A1 (fr) * 1986-07-01 1988-01-07 Ciba-Geigy Ag Composés distyryl-1,4 benzéniques et leurs mélanges avec d'autres composés distyryl-1,4 benzéniques
DE3802204A1 (de) * 1987-01-29 1988-08-11 Ciba Geigy Ag Mischungen von optischen aufhellern
CH688877GA3 (de) * 1992-06-17 1998-05-15 Hoechst Ag Mischungen aus 1,4-Bis-(cyanostyryl)-benzolen.
WO1995008017A1 (fr) * 1993-09-13 1995-03-23 Basf Aktiengesellschaft Melanges de blanchiment optique a base de composes bistyryle
CN1064037C (zh) * 1994-02-18 2001-04-04 电化学工业有限公司（国际） 茋基物质及其制备方法
EP0680947A3 (fr) * 1994-05-02 1995-11-29 Basf Ag
EP0680947A2 (fr) * 1994-05-02 1995-11-08 Basf Aktiengesellschaft Procédé pour la préparation d'azurants optiques à base de stilbènes
FR2732015A1 (fr) * 1995-03-24 1996-09-27 Basf Ag Melanges d'agents de blanchiment optique a base de composes bisstyryliques
WO2004053221A1 (fr) * 2002-12-10 2004-06-24 Ciba Specialty Chemicals Holding Inc. Melanges d'agents de blanchiment fluorescents
US7497971B2 (en) 2002-12-10 2009-03-03 Ciba Specialty Chemicals Corporation Mixtures of fluorescent whitening agents

Also Published As

Publication number Publication date
JPH01152161A (ja) 1989-06-14
US5001253A (en) 1991-03-19
BR8008161A (pt) 1981-06-30
ES497647A0 (es) 1982-07-01
EP0030917A3 (en) 1982-02-17
US4785128A (en) 1988-11-15
EP0030917B1 (fr) 1985-01-23
EP0030917B2 (fr) 1991-03-20
US4778623A (en) 1988-10-18
CA1175608A (fr) 1984-10-09
ES501488A0 (es) 1982-08-16
ES8206433A1 (es) 1982-08-16
DE3070041D1 (en) 1985-03-07
ES8205746A1 (es) 1982-07-01

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