EP0030917B2 - 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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EP0030917B2
EP0030917B2 EP80810378A EP80810378A EP0030917B2 EP 0030917 B2 EP0030917 B2 EP 0030917B2 EP 80810378 A EP80810378 A EP 80810378A EP 80810378 A EP80810378 A EP 80810378A EP 0030917 B2 EP0030917 B2 EP 0030917B2
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formula
compound
fluorescent brightener
weight
carbon atoms
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EP0030917B1 (fr
EP0030917A2 (fr
EP0030917A3 (en
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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, to a process for their preparation and to the intermediates which occur in the process, agents containing such optical brighteners and the use of these optical brighteners or the agents containing them for the optical brightening of organic high-molecular materials .
  • 1,4-bis-styrylbenzene compounds consist of three components, namely about 50% of one asymmetrically substituted and about 25% each 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% by weight, preferably 80-99% by weight, in particular 90-99% by weight, of an asymmetrically substituted 1,4-bis-styrylbenzene compound and 49-1% by weight, preferably 20-1% by weight, in particular 10-1% by weight, of a symmetrically substituted 1,4-bis-styrylbenzene compound is able to achieve significantly higher brightening effects than the known corresponding individual compounds and those above mentioned mixtures.
  • 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% by weight of an asymmetrically substituted compound of the formula wherein R and R1 are the same or different, wherein in the event that R and R1 are the same, R1 must occupy a different position in the phenyl ring to which it is attached than R in its phenyl ring and wherein R and R1 are independently CN or is an optionally substituted carboxylic acid ester group, and 49-1% by weight of a symmetrically substituted compound of the formula in which R has the meaning given above and both R in their phenyl rings are bonded to the same position, with the proviso that both R in the formula (2) have p, p ′ mellowing
  • the bis-styrylbenzene compound (1) must therefore be unsymmetrically substituted in any case.
  • the substituents R and R1 regardless of whether they are the same or different, are 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 with 1 to 6 carbon atoms, alkenyl with 3 to 6 carbon atoms, cycloalkyl with 5 or 6 carbon atoms, Haloalkyl, aralkyl, especially phenylalkyl, especially benzyl, carbalkoxyalkyl, cyanoalkyl, hydroxyalkyl, aminoalkyl, alkylaminoalkyl, dialkylaninoalkyl, 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 means, 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 means chlorine, bromine and fluorine, in particular chlorine or bromine.
  • 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.
  • optical brighteners consisting of 51-99% by weight of the compound of the formula and 49-1% by weight 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% by weight of the asymmetrically substituted compound, e.g. of the formula (1) or (3), and 30-1, in particular 20-1, but especially 10-1% by weight of the symmetrically substituted compound, e.g. of the formula (2) or (4).
  • optical brightener consisting of 90-99% by weight of the compound of formula (3) and 10-1% by weight of the compound of formula (4).
  • 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 consist of two individual components can be produced by a very simple synthesis process.
  • the process according to the invention is characterized in that terephthalaldehyde in the presence of an alkaline condensing agent with a compound of the formula to a mixture of the compounds of the formulas and and this mixture is then reacted further in the presence of an alkaline condensing agent with a compound of the formula to the brightener consisting of the compounds (1) and (2), where R and R1 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 the same or different and independently of one another are a radical of the formula or mean, and wherein the quantitative ratio between terephthalaldehyde and the compound of formula (7) is chosen so that the ratio between symmetrical and asymmetrical component in the end product is in the range given above for the compounds of formulas (1) and (2).
  • the quantitative ratio between terephthalaldehyde and the compound of formula (7) thus depends on which quantitative ratio is desired in the final mixture of asymmetrically and symmetrically substituted bis-styrylbenzenes. Accordingly, the ratio between the monoaldehyde (8) and the compound of formula (9) reacting therewith can be adjusted. In this way, each quantitative ratio defined above for the compounds of the formulas (1) and (2) can be set by the choice of the quantitative ratios in the starting products. The content of monoaldehyde (8) in the reaction mixture can easily be determined analytically will.
  • 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 of the invention is characterized in that terephthalaldehyde with a compound of the formula to a mixture of the compounds of the formula and the formula (4) and then the mixture obtained with the compound of the formula to the optical brighteners according to the invention consisting of the compounds of the formulas (3) and (4).
  • the reaction of terephthalaldehyde with a compound of the formula (7) or with a compound of the formula (14) (first stage) is carried out in the presence of an alkaline condensing agent which serves as a proton acceptor.
  • alkaline condensing agent which serves as a proton acceptor.
  • condensation agents are inorganic or organic bases, for example hydroxides, hydrides, alkoxides and amides of alkali or alkaline earth metals, monomeric or polymeric strongly basic amines and resin exchangers 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) is also carried out in the presence of an alkaline conden
  • the process according to the invention is expediently carried out in a solvent which is inert under the reaction conditions.
  • Apolar and dipolar aprotic and protic solvents such as e.g. 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) and (16) are sparingly soluble, e.g. in methanol, ethanol, hexane or toluene.
  • the resulting aldehydes precipitate out during the reaction together with the symmetrical compounds of the formulas (2) and (4) and can be isolated by filtration or preferably 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), as mixtures together with the symmetrical compounds of the formulas (2) or (4), 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 compounds of the formulas (7) and (9) used as starting products are known or can be prepared analogously to known processes (see, for example, DE-A-1 921 466, GB-A-920 988 and 929 436) or according to Example 14 below ( Production of the starting product).
  • the invention further relates to a process for the preparation of the stilbenaldehydes of the formula which occur as intermediates in a mixture with stilbene compounds of the formula wherein R 2 ' cyano or a carboxylic acid ester group, in particular one of the formula _COOY, wherein Y is alkyl, haloalkyl, aralkyl, carbalkoxyalkyl, cyanoalkyl, hydroxyalkyl, aminoalkyl, alkylaminoalkyl, dialkylaminoalkyl, all of the aforementioned alkyl groups and alkyl parts in composite groups each having 1 to 6 Have carbon atoms; Alkenyl with 3 to 6 carbon atoms, cycloalkyl with 5 to 6 carbon atoms, propargyl, tetrahydrofurfuryl or a group of the formula represents in which X is hydrogen or methyl and n is an integer between 1 and 4 and the alkyl group has 1 to 6 carbon atoms, which
  • the reaction is carried out in the presence of an alkaline condensing agent in a solvent in which the stilbene aldehydes are sparingly soluble.
  • alkaline condensing agent in a solvent in which the stilbene aldehydes are sparingly soluble.
  • condensing agents and solvents are given above in the description of the first stage of the process for the preparation of the brightener mixtures.
  • Preferred temperature ranges and preferred compounds of formula (24) correspond to those described for the first step mentioned.
  • the aldehydes are expediently purified 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.
  • the inventive method leads to the stilbenaldehydes mentioned in a very simple manner, while according to DE-A-2 647179 (see above), stilbenaldehydes can only be obtained via a complicated, multi-stage synthesis.
  • optical brighteners according to the invention are used for optically brightening a wide variety of synthetic, semi-synthetic or natural organic materials.
  • Semi-synthetic organic materials e.g. Cellulose esters of various degrees of esterification (so-called 21 ⁇ 2-acetate, triacetate) or cellulose ether, regenerated cellulose (viscose, copper ammonia cellulose) or their after-treatment products, casein plastics.
  • Natural organic materials of animal or vegetable origin for example based on cellulose or proteins such as cotton, wool, linen, silk, natural lacquer resins, starch, casein.
  • 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, that is, for example, predominantly three-dimensionally extended bodies such as plates, profiles, injection moldings, various types of workpieces, chips, granules or foams, furthermore as predominantly two-dimensional bodies such as films, foils, lacquers, coatings, impregnations and coatings or as predominantly one-dimensional bodies such as threads, fibers, flakes, Wires.
  • the said materials can also be in unshaped states in the most varied of homogeneous or inhomogeneous forms of distribution, such as, for example, powders, solutions, emulsions, dispersions, latices, pastes or waxes.
  • Fiber materials can be, for example, as endless threads (drawn or undrawn), staple fibers, flakes, extrudates, textile threads, yarns, threads, non-woven fabrics, felts, wadding, flocking structures or as textile fabrics or textile composites, knitted fabrics, as well as papers, cardboards or paper stocks are available.
  • 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 filaments, 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 to or incorporated into the materials before or during their deformation.
  • they can be added to the molding compound or injection molding compound in 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 auxiliary and coupling agents, such as 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.
  • auxiliary and coupling agents such as 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 come 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 an optical brightener according to the invention which produces a greenish to bluish shade on the substrate to be treated (for example mixtures of the compounds (1) and (2), (3) and (4) contain an optical brightener, which produces a reddish shade on the substrate to be treated.
  • Such combinations have the advantage that a particularly beautiful neutral white shade of high brilliance can be achieved on textile fibers, especially on polyester fibers.
  • agents according to the invention as brighteners which produce a reddish shade are those from the class of the naphthotriazolyl-stilbene and the triazolylcoumarins.
  • Examples of brighteners which produce a reddish shade and which can be used in agents according to the invention include:
  • 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 in many cases advantageously be carried out with the aid of appropriate 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 (optionally also solutions) of the brightening agents 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 be dried beforehand at a moderately elevated temperature, for example 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 also by treating with dry, superheated steam.
  • the drying and dry heat treatment can also be carried out in quick succession 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.
  • 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 pale 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 the starting material is prepared analogously to Example 1 of DE-A-1 921 466 and purified by distillation (bp 0.35 : 136-138 ° C.).
  • reaction product is filtered off, 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 according to Example 1 of DE-A-1 921 466.
  • 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, washed with about 50 ml of absolute ethanol and dried under vacuum at 50 ° C to constant weight.
  • 32.0 g (about 68.7% of theory) of a light yellow crystalline powder of melting point 117 to 192 ° C. are obtained, which can be analyzed analytically as a mixture consisting of 81.5% of the compound of the formula and 17.2% of the compound of the formula turns out.
  • the phosphonate of the formula (301) used as starting material is prepared according to Example 2 of GB-A-920 988.
  • reaction product is filtered off with suction, washed with about 100 ml of dimethylformamide / water (1: 1) and then 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 (303).
  • the phosphonate of the formula (801) used as the starting material is prepared analogously to Example 2 of GB-A-929 436 and purified by distillation (bp 0.25 : 181-185 ° C.).
  • 1 g of the brightener consisting of 91.2% of the compound of formula (3) and 7.7% of the compound of formula (4) is dispersed in 1000 ml of water. 7.5 ml of this dispersion are added to 100 ml of water containing 0.1 g of a fatty alcohol polyglycol ether. To this heated to 60 ° C Brightener dispersion is given a 15 g polyester fabric. 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 fabric 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.
  • Polyester fabric is padded at room temperature with an aqueous dispersion which contains 0.5 g of a brightener consisting of 91.2% of the compound of the formula (3) and 7.7% of the compound of the formula (4) and 1 g of an addition product per liter contains about 8 moles of ethylene oxide to 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 lightening effect and good lightfastness.
  • 1 g of the brightener consisting of 91.2% of the compound of formula (3) and 7.7% of the compound of formula (4) is dispersed in 1000 ml of water. 3 ml of this dispersion are added to 100 ml of water 40 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 fabric is then rinsed in running cold water for 2 minutes and then dried at 60 ° C for 20 minutes.
  • the fabric thus obtained has a strong lightening effect with good light fastness.

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Claims (21)

1. Agent de blanchiment optique constitué par un mélange de deux composés de la série des bis-styrylbenzènes, caractérisé par le fait qu'il comprend 51-99% en poids d'un composé dissymétriquement substitué de formule
Figure imgb0075
 dans laquelle R et R₁ sont identiques ou différents et, pour le cas où R et R₁ sont identiques, R₁ doit posséder une autre position dans le noyau phényle auquel il est lié que celle de R dans son noyau phényle respectif et dans laquelle R et R₁ désignent indépendamment l'un de l'autre un groupe CN ou un groupe ester d'acide carboxylique, et 49-1% en poids d'un composé symétriquement substitué de formule
Figure imgb0076
 dans laquelle R est défini comme spécifié ci-dessus et les deux substituants R sont liés sur leurs noyaux phényle dans la même position, avec la condition que les deux substituants R, dans la formule (2), ne se trouvent pas en positions p-p′.
2. Agent de blanchiment optique selon la revendication 1, caractérisé par le fait que, dans le composé dissymétriquement substitué de formule (1), R₁ possède, dans le noyau phényle auquel il est lié, une autre position que R dans son noyau phényle respectif.
3. Agent de blanchiment optique selon la revendication 1 ou 2, caractérisé par le fait que dans les deux composants individuels, R et R₁ désignent indépendamment l'un de l'autre un groupe CN ou un groupe de formule _COOY, dans laquelle Y représente un groupe alkyle, halogéno-alkyle, aralkyle, carbalcoxyalkyle, cyanoalkyle, hydroxyalkyle, aminoalkyle, alkylaminoalkyle, dialkylalminoalkyle, tous les groupes alkyle précités et tous les fragments alkyle des groupes composés précités présentant chacun un à six atomes de carbone; alcényle ayant trois à six atomes de carbone, cycloalkyle ayant cinq à six atomes de carbone, propargyle, tétrahydrofurfuryle ou un groupe de formule (CH₂-XCH-O)n-alkyle, dans laquelle X est un atome d'hydrogène ou un groupe méthyle et n est un nombre entier compris entre 1 et 4 et le groupe alkyle présente un à six atomes de carbone.
4. Agent de blanchiment optique selon la revendication 3, caractérisé par le fait que R et R₁ sont chacun indépendamment l'un de l'autre un radical _CN ou _COOY′, dans lequel Y′ est un groupe alkyle ayant un à quatre atomes de carbone, R et R₁ désignant toutefois de préférence chacun un radical _CN.
5. Agent de blanchiment optique selon la revendication 4, composé de 51-99% en poids du composé de formule
Figure imgb0077
 et 49-1% en poids du composé de formule
Figure imgb0078
6. Agent de blanchiment optique selon l'une quelconque des revendications 1 à 5, composé de 70-99% en poids, de préférence 80-99% en poids, en particulier 90-99% en poids du composé dissymétriquement substitué, en particulier de formule (1) ou (3), et 30-1% en poids, de préférence 20-1% en poids, en particulier 10-1% en poids du composé symétriquement substitué, en particulier de formule (2) ou (4).
7. Procédé de préparation d'un agent de blanchiment optique défini dans la revendication 1 ou 2, caractérisé par le fait que l'on fait réagir le téréphtaldéhyde, en présence d'un agent de condensation alcalin, avec un composé de formule
Figure imgb0079
 pour obtenir un mélangé des composés de formules
Figure imgb0080
 et on fait ensuite réagir le mélange, en présence d'un agent de condensation alcalin, avec un composé de formule
Figure imgb0081
 pour obtenir l'agent de blanchiment optique défini dans la revendication 1 ou 2, R et R₁ étant définis comme spécifié dans la revendication 1 ou 2 et devant satisfaire les conditions indiquées dans celles-ci en ce qui concerne leur positions sur les noyaux phényle, X et Y étant identiques ou différents et désignant indépendamment l'un de l'autre un reste de formule
Figure imgb0082
 et le rapport pondéral entre le téréphtaldéhyde et le composé de formule (7) étant choisi de façon que la proportion entre les composants symétrique et dissymétrique dans le produit final se situe dans l'intervalle indiqué dans la revendication 1.
8. Procédé selon la revendication 7, caractérisé par le fait que l'on effectue la réaction du téréphtaldéhyde avec un composé de formule
Figure imgb0083
 dans un solvant ou un mélange de solvants dans lequel le monoaldéhyde formé est peu soluble et se cristallise.
9. Procédé selon la revendication 7 ou 8, caractérisé par le fait que l'on effectue la réaction du téréphtaldéhyde avec un composé de formule
Figure imgb0084
 en présence d'un alcoolate de métal alcalin et à des températures comprises entre 0°C et 50°C, de préférence entre 20°C et 30°C.
10. Procédé selon la revendication 7 ou 8, caractérisé par le fait que l'on fait réagir ultérieurement sans isolement le mélange contenant le monoaldéhyde, obtenu dans le premier stade.
11. Procédé selon la revendication 7, caractérisé par le fait que l'on effectue la réaction du mélange, obtenu dans le premier stade, avec un composé de formule
Figure imgb0085
 en présence d'un alcoolate de métal alcalin et à des températures comprises entre 20°C et 100°C, de préférence entre 30°C et 50°C.
12. Produit pour le blanchiment optique de matières organiques à poids moléculaire élevé, caractérisé par le fait qu'il contient un agent de blanchiment optique selon l'une des revendications 1 à 6.
13. Produit selon la revendication 12, caractérisé par le fait qu'il contient en outre des additifs de formulation courants.
14. Produit selon la revendication 12, caractérisé par le fait qu'en plus d'un agent de blanchiment optique défini dans les revendications 1 à 6, et produisant sur le substrat traité une nuance verdâtre à bleuâtre, il contient également un agent de blanchiment optique qui produit sur le substrat traité une nuance rougeâtre.
15. Produit selon la revendication 14, caractérisé par le fait qu'il contient, comme agent de blanchiment optique supplémentaire, un agent de la classe des naphtalimides, bis-benzoxazolyléthylènes, bis-benzoxazolyl-thiophènes, stilbénylbenzoxazoles, naphtotriazol-stilbènes ou triazolylcoumarines.
16. Produit selon la revendication 14, caractérisé par le fait qu'il contient, comme substance active de blanchiment, 5-90% en poids, en particulier 30-70% en poids, d'un agent de blanchiment défini dans les revendications 1-6 et produisant sur le substrat traité une nuance verdâtre à bleuâtre, et 95-10% en poids, en particulier 70-30% en poids, d'un agent de blanchiment optique qui produit sur le substrat traité une nuance rougeâtre.
17. Produit selon la revendication 16, caractérisé par le fait qu'il contient un agent de blanchiment optique constitué par les composés (3) et (4) selon la revendication 5, et en outre, un agent de blanchiment optique de la classe des naphtotriazolyl-stilbènes ou des triazolylcoumarines.
18. Procédé de blanchiment optique de substrats organiques naturels, semi-synthétiques ou synthétiques à poids moléculaires élevés, par exemple en polyester, en particulier de fibres textiles, par exemple des fibres de polyesters, caractérisé par le fait que l'on incorpore au substrats ou que l'on applique sur les substrats, de préférence des fibres textiles, un agent de blanchiment optique défini dans les revendications 1-6 ou un produit selon l'une quelconque des revendications 12, 17.
19. Application des agents de blanchiment définis dans les revendications 1 à 6, au blanchiment optique de matières organiques naturelles, semi-synthétiques ou synthétiques, de poids moléculaires élevés, en particulier en polyesters, surtout en fibres de polyesters.
20. Procédé de préparation d'aldéhydes stilbéniques de formule
Figure imgb0086
 en mélange avec des bis-styrylbenzènes de formule
Figure imgb0087
 dans lesquelles R₂ désigne un groupe cyano ou un groupe ester d'acide carboxylique, en particulier un groupe de formule _COOY, dans lequel Y représente un groupe alkyle, halogénoalkyle, arylalkyle, carbalcoyxalkyle, cyanoalkyle, hydroxyalkyle, aminoalkyle, alkylaminoalkyle, dialkylamino-alkyle, tous les groupes alkyle précités et tous les fragments alkyle des groupes composés précités présentant chacun un à six atomes de carbone; alcényle ayant trois à six atomes de carbone, alcényle ayant trois à six atomes de carbone, cycloalkle ayant cinq à six atomes de carbone, propargyle, tétrahydrofurfuryle ou un groupe de formule
Figure imgb0088
 dans laquelle X est un atome d'hydrogène ou un groupe méthyle et n est un nombre entie compris entre 1 et 4 et le groupe alkyle présente un à six atomes de carbone, caractérisé par le fait que l'on fait réagir le téréphtaldéhyde avec un composé de formule.
Figure imgb0089
 dans un solvant dans lequel l'aldéhyde stilbénique est peu soluble et en présence d'un agent de condensation alcalin, X′ désignant un reste de formule
Figure imgb0090
 avec la condition que les deux groupes R₂ ne se trouvent pas en position p-p′.
21. Procédé selon la revendication 20, caractérisé par le fait que pour l'isolement de l'aldéhyde stilbénique, on sépare celui-ci du mélange obtenu par recristallisation, reprise éventuellement plusieurs ou par chromatographie.
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
CH11040/79 1979-12-13
CH11040/79A CH650792A5 (en) 1979-12-13 1979-12-13 Optical brighteners from bisstyrylbenzene compounds and preparation thereof
CH3058/80 1980-04-21
CH305880 1980-04-21

Publications (4)

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

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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

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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)

Families Citing this family (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3001065A1 (de) * 1980-01-12 1981-07-16 Basf Ag, 6700 Ludwigshafen Verfahren zur herstellung von optischen aufhellern
US4778622A (en) * 1986-03-21 1988-10-18 Ciba-Geigy Corporation Mixtures of fluorescent whitening agents
EP0252009B1 (fr) * 1986-07-01 1990-08-01 Ciba-Geigy Ag Composés distyryl-1,4 benzéniques et leurs mélanges avec d'autres composés distyryl-1,4 benzéniques
CH671956A5 (fr) * 1987-01-29 1989-10-13 Ciba Geigy Ag
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
DE4219772A1 (de) * 1992-06-17 1993-12-23 Hoechst Ag Mischungen aus 1,4-Bis-(cyanostyryl)-benzolen
DE4330968A1 (de) * 1993-09-13 1995-03-16 Basf Ag Aufhellermischungen auf Basis von Bisstyrylverbindungen
KR0165729B1 (ko) * 1994-02-18 1999-03-20 로베르트 뢰머 스틸벤 기재물질, 그 제조방법 및 그 사용
DE4415351A1 (de) * 1994-05-02 1995-11-09 Basf Ag Verfahren zur Herstellung von optischen Aufhellern auf Stilbenbasis
DE19609956A1 (de) * 1995-03-24 1996-09-26 Basf Ag Mischungen von optischen Aufhellern auf Basis von Bisstyrylverbindungen
US6489447B1 (en) * 1998-05-06 2002-12-03 Genentech, Inc. Protein purification
DE10237186A1 (de) * 2002-08-14 2004-03-18 Clariant Gmbh Verfahren zum Aufhellen synthetischer Fasern und Kunstoffe mit granulierten optischen Aufhellern
CN100338296C (zh) * 2002-12-10 2007-09-19 西巴特殊化学品控股有限公司 荧光增白剂的混合物
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

Family Cites Families (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1108219B (de) * 1959-05-15 1961-06-08 Basf Ag Verfahren zur Herstellung von Verbindungen der 1, 4-Divinyl-benzol-reihe
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
DE1469821B2 (de) * 1959-06-24 1972-03-23 Badische Anilin & Soda Fabrik AG, 6700 Ludwigshafen Optische Aufheller für makromolekulare organische Stoffe
BE593216A (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
DE1444003A1 (fr) * 1963-10-31 1970-03-12
US3959340A (en) * 1969-06-05 1976-05-25 Ciba-Geigy Ag Cyano-distyrylbenzenes
DE2000027A1 (de) * 1970-01-02 1971-07-08 Basf Ag Optische Aufheller
US4093645A (en) * 1972-07-26 1978-06-06 Hickson & Welch Limited Styryl-tetrahydronaphthyl derivatives
US4216105A (en) * 1972-07-26 1980-08-05 Hickson & Welch Limited Compositions for the optical whitening of organic materials and use thereof
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
DE2929687A1 (de) * 1979-07-21 1981-02-12 Hoechst Ag Mischungen von optischen aufhellern
DE2929599A1 (de) * 1979-07-21 1981-02-05 Hoechst Ag Mischungen von optischen aufhellern, deren herstellung und verwendung
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

Also Published As

Publication number Publication date
JPH01152161A (ja) 1989-06-14
US4785128A (en) 1988-11-15
EP0030917B1 (fr) 1985-01-23
US5001253A (en) 1991-03-19
US4778623A (en) 1988-10-18
ES497647A0 (es) 1982-07-01
ES501488A0 (es) 1982-08-16
ES8206433A1 (es) 1982-08-16
DE3070041D1 (en) 1985-03-07
ES8205746A1 (es) 1982-07-01
CA1175608A (fr) 1984-10-09
BR8008161A (pt) 1981-06-30
EP0030917A2 (fr) 1981-06-24
EP0030917A3 (en) 1982-02-17

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