EP0023028B1 - Mixtures of optical brighteners and their use - Google Patents

Mixtures of optical brighteners and their use Download PDF

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EP0023028B1
EP0023028B1 EP80104163A EP80104163A EP0023028B1 EP 0023028 B1 EP0023028 B1 EP 0023028B1 EP 80104163 A EP80104163 A EP 80104163A EP 80104163 A EP80104163 A EP 80104163A EP 0023028 B1 EP0023028 B1 EP 0023028B1
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alkyl
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group
phenyl
alkoxy
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EP0023028A1 (en
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Thomas Dr. Martini
Rüdiger Dr. Erckel
Horst Dr. Frühbeis
Günter Rösch
Heinz Probst
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Hoechst AG
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Hoechst 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

  • optical brighteners Venkataraman, The Chemistry of Synthetic Dyes, Vol. V, Chapter VIII.
  • French Patent No. 1,415,977 it is also known from French Patent No. 1,415,977 to use mixtures of optical brighteners consisting of 1,4-bis (cyano-2-styryl) benzene, 1,4-bis (cyano-4-styryl) benzene and 4- (cyano-2-styryl) -1- (cyano-4-styryl) benzene.
  • a mixture which consists of one of these isomeric bis (cyanostyryl) benzenes, namely 1,4-bis (cyano-2-styryl) benzene and a brightener from the series of naphthalimide derivatives (Chemical Abstracts Vol. 83 , No. 61504 c). It has now been found that the effect of these known mixtures can be exceeded if the mixture known from the French patent mentioned is mixed with other brighteners of the formulas 4 to 8 listed below.
  • alkyl and alkoxy groups and other groups derived therefrom contain 1 to 4 carbon atoms.
  • the term “non-chromophoric substituents” is to be understood as meaning alkyl, alkoxy, aryl, aralkyl, trifluoromethyl, cycloalkyl, halogen, alkylsulfonyl, carboxy, sulfonic acid, cyano, carbonamide, sulfonamide, carboxylic acid alkyl ester, sulfonic acid alkyl ester.
  • component B consisting of one or more compounds of the formulas 2b-6b where R 1 in the 5-position is a hydrogen or chlorine atom, a methyl or phenyl group and R 2 is a hydrogen atom or R 1 and R 2 are both a methyl group in the 5,6- or 5,7-position, n 0 or 1 and B.
  • R 14 is (C 1 -C 6 ) alkyl, (C 1 -C 6 ) chloroalkyl, (C 1 -C 4 ) alkoxy- (C 1 -C 4 ) alkyl, hydroxy (C 1 -C 4 ) alkyl or a group of the formula - (CH 2 CH 2 O) n ⁇ R, n 2 or 3 and R hydrogen or (C 1 -C 4 ) alkyl, R, 5 phenyl, halophenyl, (C 1 -C 4 ) -alkylphenyl or (C 1 -C 4 ) -alkoxiphenyl, R 22 is (C 1 -C 4 ) -alkyl and R 23 is cyano or carbo- (C 1 -C 4 ) -alkoxy, where R 3 is hydrogen or (C 1 -C 6 ) alkyl, (C 1 -C 6 ) chloroalkyl, (C 1 -C 4 ) alk
  • component B consisting of one or more compounds of the following formulas: wherein R 1 and R 2 in the 5,6-position methyl and B carbomethoxy, R hydrogen, R 1 hydrogen or methyl in the 5-position and B carbomethoxy, cyano or a group of the formulas wherein R 14 and R 22 are (C 1 -C 3 ) alkyl and R 15 is phenyl, 4-methylphenyl or 4-methoxyphenyl, or R 1 is hydrogen, methyl or t-butyl in the 5-position, R 2 is hydrogen or methyl in 7-position and B is phenyl, where R 3 is hydrogen or methoxy, or or where R 2 is hydrogen or methyl.
  • component A Mixtures of the following composition are particularly preferred as component A: the proportion of compounds 1 and 3 should be approximately the same.
  • the proportion of the individual compounds 1 to 3 in component A can fluctuate within the limits specified, preference being given to mixtures which contain the compounds 1 and 3 in approximately equal parts. From the limits given above for the weight ratios of compounds 1 to 3, it follows that the proportion of compounds 1 and 3 can be 0% and the proportion of compound 2 can be 100%. In this case there is pure connection 2. It is understood that the composition of component A is chosen within the various limits given above so that the sum of all individual compounds is 100%.
  • the ratio of compounds 10 and 11 determines the composition of the mixture. If the proportion of 10 is higher, the proportion of compound 1 increases at the expense of compound 3, if the proportion of compound 11 is higher, the proportion of compound 3 in mixtures will be higher than 1.
  • one of the symbols X or Q represents an aldehyde group and the other symbol a group of the formulas where R represents an optionally substituted alkyl radical having preferably 1-6 C atoms, an aryl radical preferably phenyl, a cycloalkyl radical or an aralkyl radical, preferably benzyl.
  • the process is preferably carried out in solvents in the presence of a proton acceptor.
  • solvents which may be mentioned are hydrocarbons such as toluene, xylene, alcohols such as methanol, ethanol, isopropanol, butanol, glycols, hexanols, cyclohexanols, and furthermore ethers such as diisopropyl ether, tetrahydrofuran, dioxane and dimethyl sulfoxide.
  • Polar organic solvents such as formamide, dimethylformamide and N-methylpyrrolidone are particularly suitable, with dimethylformamide being particularly emphasized.
  • Suitable proton acceptors are primarily basic compounds, such as alkali or alkaline earth metal hydroxides, alcoholates or amides, strongly basic amines and anion exchange resins in the hydroxyl form.
  • alkali hydrodes in particular potassium hydroxide, is preferred.
  • the reaction temperature depends on the type of components to be reacted, in particular on the type of organic compound containing carbonyl groups and the proton acceptor; it is between - 10 ° C and + 100 ° C, advantageously between 0 ° -50 ° C.
  • a preferred embodiment is to bring the reactants together at lower temperatures and to complete the reaction at a higher temperature.
  • the claimed process can be carried out, for example, by introducing the proton acceptor in the solvent and adding a solution of the reaction components 9-11 in the solvent, but it is also possible to introduce the compounds 9-11 and adding them to the proteone acceptors.
  • a further embodiment consists in presenting the compounds 9-11, in which X or Q represents a group of the formula 12a-d, then first adding the proton acceptor and then the aldehyde component. The reaction generally takes place with intense heat so that cooling may be necessary.
  • the reactor mixture is worked up in a known manner, e.g. by adding methanol or ethanol and separating the precipitated products.
  • the product mixtures obtained in this way can be analyzed and characterized by HPLC (high pressure liquid chromatography).
  • the starting compounds of the formulas 9-11 are known or can be prepared by known processes.
  • R, " and R 2" are hydrogen or alkyl and B "is a group of the formulas ⁇ CN or ⁇ COOalkyl and R, 4 .
  • Alkyl or methoxyethyl means.
  • the following compounds under formula 4 are of particular importance: and
  • the mixing ratio for the individual components is between 0.05 and 0.95 parts by weight for component A and correspondingly 0.95 to 0.05 parts by weight for the other compounds of the formulas 4 to 8.
  • These compounds of the formulas 4 to 8 can be used individually or in any mixture with one another, the mixing ratio of these compounds with one another being completely uncritical and being able to be varied as desired.
  • a mixing ratio of 5 to 50% by weight for component A and 95 to 50% by weight of one or more brighteners of the formulas 4 to 8 (component B) is preferred.
  • the optimal mixing ratio of all compounds depends in individual cases on the structure of the respective compounds and can be easily determined by simple preliminary tests.
  • the individual components are dispersed in a liquid medium e.g. Water brought into the commercial form.
  • the individual components can be dispersed individually and the dispersions can then be added together.
  • the individual components can also be mixed together in bulk and then dispersed together. This dispersion process takes place in the usual way in ball mills, colloid mills, bead mills or dispersion kneaders.
  • the mixtures according to the invention are particularly suitable for lightening textile material made from linear polyesters, polyamides and acetyl cellulose. However, these mixtures can also be used with good results in mixed fabrics which consist of linear polyesters and other synthetic or natural fiber materials, in particular fibers containing hydroxyl groups, in particular cotton.
  • optical brighteners are applied under the conditions customary for the use of optical brighteners, for example using the exhaust process at 90 ° C. to 130 ° C. with or without the addition of accelerators (carriers) or using the thermosol process.
  • the water-insoluble brighteners and the mixtures according to the invention can also be used in organic solvents, e.g. Perchlorethylene, fluorinated hydrocarbons can be used in solution.
  • the textile material can be treated in the exhaust process with the solvent liquor which contains the optical brightener, or one can impregnate, splash, spray the textile material with the brightener-containing solvent liquor and then dry at temperatures of 120-220 ° C, the optical brightener being used is completely fixed in the fiber.
  • the material is squeezed between rollers with a padder so that a moisture absorption of approx. 80% results. This corresponds to an absorption of optical brighteners on the goods of 0.064%.
  • the material which had been blocked in this way was then thermosolated on a stenter for 30 seconds at 170 ° (Table I) or 210 ° (Table 11).
  • the specified degrees of whiteness according to Ganz were obtained. The degrees of whiteness were measured using a DMC-25 reflectance spectrophotometer. (Carl Zeiss company, Oberkochen).

Abstract

Mixtures of optical brighteners consisting of 5 to 95 parts by weight of a mixture consisting of 0 to 80% by weight of the compound of the formula 1 <IMAGE> (1) 20 to 100% by weight of the compound of the formula 2 <IMAGE> (2) and 0 to 80% by weight of the compound of the formula 3 <IMAGE> (3) and 95 to 5% by weight of one or more other optical brighteners.

Description

Es ist bereits eine sehr große Anzahl von Einzelverbindungen bekannt, die als optische Aufheller verwendet werden können (Venkataraman, The Chemistry of Synthetic Dyes, Bd. V, Kapitel VIII). Darüberhinaus ist es auch aus der französischen Patentschrift 1 415977 bekannt, Mischungen von optischen Aufhellern einzusetzen, bestehend aus 1,4-Bis(cyano-2-styryl)-benzol, 1,4-Bis-(cyano-4-styryl)-benzol und 4-(Cyano-2-styryl)-1-(cyano-4-styryl)-benzol. Auch ist eine Mischung bekannt, die aus einem dieser isomeren Bis(Cyanostyryl)-benzole, nämlich 1,4-Bis(cyano-2-styryl)-benzol und einem Aufheller aus der Reihe der Naphthalimid-Derivate besteht (Chemical Abstracts Bd. 83, Nr. 61504 c). Es wurde nun gefunden, daß man die Wirkung dieser bekannten Mischungen noch übertreffen kann, wenn man die aus der genannten französischen Patentschrift bekannte Mischung mit weiteren Aufhellern der weiter unten aufgeführten Formeln 4 bis 8 abmischt.A very large number of individual compounds are already known which can be used as optical brighteners (Venkataraman, The Chemistry of Synthetic Dyes, Vol. V, Chapter VIII). In addition, it is also known from French Patent No. 1,415,977 to use mixtures of optical brighteners consisting of 1,4-bis (cyano-2-styryl) benzene, 1,4-bis (cyano-4-styryl) benzene and 4- (cyano-2-styryl) -1- (cyano-4-styryl) benzene. A mixture is also known which consists of one of these isomeric bis (cyanostyryl) benzenes, namely 1,4-bis (cyano-2-styryl) benzene and a brightener from the series of naphthalimide derivatives (Chemical Abstracts Vol. 83 , No. 61504 c). It has now been found that the effect of these known mixtures can be exceeded if the mixture known from the French patent mentioned is mixed with other brighteners of the formulas 4 to 8 listed below.

Gegenstand der vorliegenden Erfindung sind Mischungen von optischen Aufhellern bestehend aus

  • A) 0,05 bis 0,95 Gew.-Teilen eines Gemisches bestehend aus 0 bis 80 Gew.-% der Verbindung der Formel 1
    Figure imgb0001
    20 bis 100 Gew.-% der Verbindung der Formel 2
    Figure imgb0002
    und 0 bis 80 Gew.-% der Verbindung der Formel 3
    Figure imgb0003
    sowie
  • B) 0,95 bis 0,05 Gew.-Teilen einer oder mehrerer Verbindungen der Formeln 4, 5, 6, 7 oder 8
    Figure imgb0004
    Figure imgb0005
    Figure imgb0006
    Figure imgb0007
    und
    Figure imgb0008
    wobei
    • n 0 oder 1,
    • X ein Sauerstoff- oder Schwefelatom,
    • R1 und R2 gleiche oder verschiedene Reste aus der Gruppe Wasserstoff-, Fluor- oder Chloratome, Phenyl, Trifluormethyl, C1-C9 Alkyl, Alkoxy, Dialkylamino, Acylamino, Cyano, Carboxy, Carboalkoxy, Carbonsäureamid, Sulfonsäure, Sulfonsäureamid oder Sulfonsäurealkylester, bedeutet, wobei zwei benachbarte Reste R1 und R2 zusammen auch für einen Benzoring, eine niedere Alkylen- oder eine 1,3-Dioxapropylengruppe stehen können, Cyano, eine Gruppe der Formel ―COOR11 oder CONR11R11 wobei R11 Wasserstoff, C1-C18 Alkyl, Cycloalkyl, Aryl, Alkylaryl, Halogenaryl, Aralkyl, Alkoxyalkyl, Halogenalkyl, Hydroxyalkyl, Alkylaminoalkyl, Carboxyalkyl oder Carboalkoxyalkyl bedeutet oder zwei Alkyl- bzw. Alkylenreste unter der Bedeutung von R11 zusammen mit dem Stickstoffatom auch einen Morpholin-, Piperidin- oder Piperazinring bilden können, bedeutet, oder B eine Gruppe der Formel
      Figure imgb0009
      bedeutet, worin R12 und R13 gleiche oder verschiedene Reste aus der Gruppe Wasserstoff, Fluor- oder Chloratome, Phenyl, Alkyl, Alkoxy, Acylamino, Cyano, Carboxy, Carboalkoxy, Carbonsäureamid, Sulfonsäure, Sulfonsäureamid oder Sulfonsäurealkylester, bedeuten, wobei zwei benachbarte Reste R12 und R13 zusammen auch für eine Alkylengruppe, einen ankondensierten Benzoring oder eine 1,3-Dioxapropylengruppe stehen können, oder B eine Gruppe der Formeln
      Figure imgb0010
      oder
      Figure imgb0011
      bedeutet, wobei R14 eine geradkettige oder verzweigte Alkylgruppe mit 1-18 C-Atomen, vorzugsweise 1-6 C-Atomen, die durch Hydroxylgruppen, Halogenatome, Alkoxy-, Dialkylamino-, Alkylmercapto-, Chloraryloxy-, Aryloxy-, Arylmercapto- oderArylreste substituiert sein kann, wobei im Falle der Dialkylaminoalkylgruppen die beiden Alkylgruppen zusammen auch einen Morpholin-, Piperidin- oder Piperazinring bilden können, oder R14 eine Gruppe der Formel ―(CH2CH2O)n―R mit n 1, 2 oder 3 und R = H, Alkyl, Dialkylaminoalkoxyalkyl oder Alkylthioalkoxyalkyl, wobei die Dialkylgruppen im Dialkylaminoalkoxyalkyl zusammen einen Piperidin-, Pyrrolidin-, Hexamethylenimen-, Morpholin- oder Piperazinring bilden können, oder R14 einen Rest der Formel
      Figure imgb0012
      bedeutet,
    • R22 ein Wasserstoffatom, eine Triphenylmethylgruppe oder einen niederen Alkylrest bedeutet, der gegebenenfalls durch eine niedere Carbalkoxy-, Carbonamido-, Mono- oder Dialkylcarbonamido-, Carboxy- oder Benzoylgruppe substituiert ist und R23 eine Cyangruppe oder eine Gruppe der Formeln
      Figure imgb0013
      bedeutet, wobei R', R", R"' ein Wasserstoffatom, einen niederen Alkylrest oder einen Phenylrest bedeuten, und wobei die niederen Alkylreste durch Hydroxy-, niedere Alkoxy-, niedere Dialkylamino- oder niedere Trialkylammoniumgruppen und die Phenylgruppe durch Halogenatome, niedere Alkyl- oder niedere Alkoxygruppen substituiert sein können, und in der R", R"' auch zusammen einen gesättigten zweiwertigen Rest bilden können, Y, 0, S oder N-R mit R = H oder (C, bis C4)-Alkyl bedeuten, oder B eine Gruppe der Formel
      Figure imgb0014
      bedeutet, worin R15 einen Phenylring, der durch ein oder zwei Chloratome, ein oder zwei Alkyl- oder Alkoxyalkylgruppen, eine Phenyl-, Cyano-, Carboxy-, Carboalkoxy-, Carbonsäureamid-, Sulfonsäure-, Sulfonsäureamid- oder Sulfonsäurealkylestergruppe substituiert sein kann,
      bedeutet,
    • R3 und R4 gleich oder verschieden sein können und Wasserstoff, Alkyl, Cycloalkyl, Alkoxy, Hydroxyalkoxyethyl, Halogenalkyl, Aralkyl, Aryl oder N,N-di-alkylamin bedeuten oder R3 und R4 bilden zusammen einen fünfgliedrigen Heterocyclus mit 1 bis 3 Heteroatomen, vorzugsweise N-Atomen,
    • R5 geradkettige oder verzweigtes Alkyl, Alkoxyalkyl, Dialkylaminoalkyl oder einen Rest der Formel
      Figure imgb0015
      bedeutet, worin R16 Wasserstoff, C2-C8-Alkanoyl, Benzoyl oder ein Rest der Formel
      Figure imgb0016
      und R17 Wasserstoff, Alkyl oder Phenyl, R18 Alkyl, Phenyl, Halogenphenyl oder Tolyl und R,9 C1-C8-Alkyl, Alkoxyalkyl, Cyclohexyl, Benzyl, Phenyläthyl oder gegebenenfalls durch nichtchromophore Substituenten substituiertes Phenyl ist, oder R5 einen Rest der Formel
      Figure imgb0017
      bedeutet, worin R20 C1-C10-Alkyl, C2-C6-Alkenyl, C2-C6-Alkinyl, C1-C8-Alkoxy, C1-C8-Alkyl- oder Dialkylamino, Phenoxymethyl, Phenyl, Tolyl, Benzyl oder Phenyläthyl und R21 C3-Clo-Alkyl ist, das durch Phenyl, Hydroxyphenyl, Methoxy oder Dimethoxy substituiert sein kann, R6 einen gegebenenfalls durch nichtchromophore Substituenten substituierten Arylrest, einen 1,2,4-Triazol-1-yl-phenyl-, 1,2,3-Triazol-4-yl-phenyl-, 1,2,3-Triazol-3-yl-phenyl- oder 1,2,3-Triazol-2-yl-phenylrest bedeutet, die gegebenenfalls durch 1 oder 2 C1-C3-Alkyl- oder Oxalkylgruppen, durch Oxaryl, Oxalkenyl oder Oxalkanoyl substituiert sein können, oder R6 einen heterocyclischen Ring mit 1-3 Heteroatomen, vorzugsweise N oder 0 bedeutet, der durch Alkyl, Alkoxy, Halogen, Aryl oder Halogenaryl substituiert sein kann, oder R6 einen 1-Oxa-2,4-diazol-5-yl-Rest bedeutet, der durch Benzyl, Alkoxyphenyl, Styryl, Halogen, Alkoxy oder eine weitere heterocyclische Gruppe substituiert sein kann oder R6 einen Benzimidazol-1-yl, Benzimidazol-2-yl-, Benzthiazol-1-yl- oder Benzthiazol-2-yl-Rest bedeutet, die durch nichtchromophore Substituenten substituiert sein können,
    • R7 Wasserstoff, Alkyl, Alkoxy, Aryl, oder einen über ein Stickstoffatom gebundenen fünfgliedrigen Heterocyclus mit 1-3 N oder O Heteroatomen bedeutet, der durch Alkyl, Aryl, Hydroxy, Oxalkyl, Oxalkenyl, Oxaryl, Oxarylalkyl, Oxalkoxycarbonyl, Oxcarbamoyl, Oxepoxyalkyl, Styryl oder Halogenstyryl, einen anellierten Phenyl-, Naphthyl- oder Phenanthrylring, oder eine anellierte Gruppe der Formeln
      Figure imgb0018
      substituiert sein kann, wobei die aromatischen Ringe in den anellierten Gruppen noch durch Alkyl oder Alkoxy substituiert sein können und X Sauerstoff, NH oder N-Alkyl ist,
    • R8 ein polycyclischer, aromatischer Rest mit mindestens drei kondensierten Ringen, die.gegebenenfalls nichtchromophore Substituenten tragen,
    • Rg eine Aminogruppe, die durch ein oder zwei Alkyl-, Hydroxyalkyl-, Acyl- oder Phenylgruppen substituiert ist, wobei die Phenylgruppe eine oder mehrere nichtchromophore Reste enthalten kann und zwei Alkylgruppen zusammen mit dem Stickstoffatom der Aminogruppe einen Pyrrolidin- oder Piperidinring oder unter Einschluß eines weiteren Stickstoff- oder Sauerstoffatoms einen Piperazin- oder Morpholinring bilden können ; eine Alkoxy-, Hydroxyalkoxy-, Acyloxy-, Alkylthio- oder Carbalkylmercaptogruppe darstellt,
    • R10 unabhängig von R8 die gleiche Bedeutung wie Rg hat und zusätzlich ein Chloratom bedeuten kann,
      und
    • V eine Gruppe der Formeln
      Figure imgb0019
      bedeutet.
The present invention relates to mixtures of optical brighteners consisting of
  • A) 0.05 to 0.95 parts by weight of a mixture consisting of 0 to 80% by weight of the compound of formula 1
    Figure imgb0001
     20 to 100% by weight of the compound of the formula 2
    Figure imgb0002
     and 0 to 80% by weight of the compound of formula 3
    Figure imgb0003
     such as
  • B) 0.95 to 0.05 part by weight of one or more compounds of the formulas 4, 5, 6, 7 or 8
    Figure imgb0004
    Figure imgb0005
    Figure imgb0006
    Figure imgb0007
     and
    Figure imgb0008
     in which
    • n 0 or 1,
    • X is an oxygen or sulfur atom,
    • R 1 and R 2 are identical or different radicals from the group consisting of hydrogen, fluorine or chlorine atoms, phenyl, trifluoromethyl, C 1 -C 9 alkyl, alkoxy, dialkylamino, acylamino, cyano, carboxy, carboalkoxy, carboxylic acid amide, sulfonic acid, sulfonic acid amide or sulfonic acid alkyl ester , means, where two adjacent radicals R 1 and R 2 together can also represent a benzo ring, a lower alkylene or a 1,3-dioxapropylene group, cyano, a group of the formula ―COOR 11 or CONR 11 R 11 where R 11 is hydrogen C 1 -C 18 alkyl, cycloalkyl, aryl, alkylaryl, haloaryl, aralkyl, alkoxyalkyl, haloalkyl, hydroxyalkyl, alkylaminoalkyl, carboxyalkyl or carboalkoxyalkyl or two alkyl or alkylene radicals under the meaning of R 11 together with the nitrogen atom also mean a morpholine -, Piperidine or piperazine ring means, or B is a group of the formula
      Figure imgb0009
       means, wherein R 12 and R 13 are identical or different radicals from the group hydrogen, fluorine or chlorine atoms, phenyl, alkyl, alkoxy, acylamino, cyano, carboxy, carboalkoxy, carboxamide, sulfonic acid, sulfonic acid amide or sulfonic acid alkyl ester, with two adjacent radicals R 12 and R 13 together can also represent an alkylene group, a fused-on benzo ring or a 1,3-dioxapropylene group, or B a group of the formulas
      Figure imgb0010
       or
      Figure imgb0011
       means, wherein R 14 is a straight-chain or branched alkyl group having 1-18 carbon atoms, preferably 1-6 carbon atoms, which are substituted by hydroxyl groups, halogen atoms, alkoxy, dialkylamino, alkylmercapto, chloroaryl oxy, aryloxy, arylmercapto or aryl radicals can be substituted, where in the case of dialkylaminoalkyl groups the two alkyl groups together can also form a morpholine, piperidine or piperazine ring, or R 14 is a group of the formula - (CH 2 CH 2 O) n ―R with n 1, 2 or 3 and R = H, alkyl, dialkylaminoalkoxyalkyl or alkylthioalkoxyalkyl, where the dialkyl groups in the dialkylaminoalkoxyalkyl together can form a piperidine, pyrrolidine, hexamethyleneimine, morpholine or piperazine ring, or R 14 a radical of the formula
      Figure imgb0012
       means
    • R 22 represents a hydrogen atom, a triphenylmethyl group or a lower alkyl radical which is optionally substituted by a lower carbalkoxy, carbonamido, mono- or dialkylcarbonamido, carboxy or benzoyl group and R 23 represents a cyano group or a group of the formulas
      Figure imgb0013
       means, wherein R ', R ", R"' represent a hydrogen atom, a lower alkyl radical or a phenyl radical, and wherein the lower alkyl radicals by hydroxyl, lower alkoxy, lower dialkylamino or lower trialkylammonium groups and the phenyl group by halogen atoms, lower alkyl - Or lower alkoxy groups can be substituted, and in which R ", R"'can also together form a saturated divalent radical, mean Y, 0, S or NR with R = H or (C, to C 4 ) alkyl, or B is a group of the formula
      Figure imgb0014
       means in which R 15 is a phenyl ring which may be substituted by one or two chlorine atoms, one or two alkyl or alkoxyalkyl groups, a phenyl, cyano, carboxy, carboalkoxy, carboxamide, sulfonic acid, sulfonic acid amide or sulfonic acid alkyl ester group,
      means
    • R 3 and R 4 can be the same or different and represent hydrogen, alkyl, cycloalkyl, alkoxy, hydroxyalkoxyethyl, haloalkyl, aralkyl, aryl or N, N-di-alkylamine or R 3 and R 4 together form a five-membered heterocycle with 1 to 3 Heteroatoms, preferably N atoms,
    • R 5 straight-chain or branched alkyl, alkoxyalkyl, dialkylaminoalkyl or a radical of the formula
      Figure imgb0015
       means wherein R 16 is hydrogen, C 2 -C 8 alkanoyl, benzoyl or a radical of the formula
      Figure imgb0016
       and R 17 is hydrogen, alkyl or phenyl, R 18 alkyl, phenyl, halophenyl or tolyl and R, 9 C 1 -C 8 alkyl, alkoxyalkyl, cyclohexyl, benzyl, phenylethyl or phenyl optionally substituted by non-chromophoric substituents, or R 5 is one Rest of the formula
      Figure imgb0017
       where R 20 is C 1 -C 10 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C 1 -C 8 alkoxy, C 1 -C 8 alkyl- or dialkylamino, phenoxymethyl, phenyl, tolyl, benzyl or phenylethyl and R 21 is C 3 -C lo alkyl, which may be substituted by phenyl, hydroxyphenyl, methoxy or dimethoxy, R 6 is an unsubstituted or substituted by non-chromophoric substituents, aryl group, a 1,2,4-triazole -1-yl-phenyl-, 1,2,3-triazol-4-yl-phenyl-, 1,2,3-triazol-3-yl-phenyl- or 1,2,3-triazol-2-yl- phenyl radical, which may optionally be substituted by 1 or 2 C 1 -C 3 -alkyl or oxalkyl groups, by oxaryl, oxalkenyl or oxalkanoyl, or R 6 is a heterocyclic ring having 1-3 heteroatoms, preferably N or 0, by Alkyl, alkoxy, halogen, aryl or haloaryl may be substituted, or R 6 represents a 1-oxa-2,4-diazol-5-yl radical which is substituted by benzyl, alkoxyphenyl, styryl, halogen, alkoxy or another heterocyclic group can be substituted or he R 6 represents a benzimidazol-1-yl, benzimidazol-2-yl, benzthiazol-1-yl or benzthiazol-2-yl radical, which may be substituted by non-chromophoric substituents,
    • R 7 denotes hydrogen, alkyl, alkoxy, aryl, or a five-membered heterocycle with 1-3 N or O heteroatoms which is bonded via a nitrogen atom and which is characterized by alkyl, aryl, hydroxy, oxalkyl, oxalkenyl, oxaryl, oxarylalkyl, oxalkoxycarbonyl, oxcarbamoyl, oxepoxyalkyl, Styryl or halostyryl, a fused phenyl, naphthyl or phenanthryl ring, or a fused group of the formulas
      Figure imgb0018
       can be substituted, where the aromatic rings in the fused groups can also be substituted by alkyl or alkoxy and X is oxygen, NH or N-alkyl,
    • R 8 is a polycyclic, aromatic radical with at least three condensed rings which may carry non-chromophoric substituents,
    • Rg is an amino group which is substituted by one or two alkyl, hydroxyalkyl, acyl or phenyl groups, where the phenyl group can contain one or more non-chromophoric radicals and two alkyl groups together with the nitrogen atom of the amino group form a pyrrolidine or piperidine ring or including one further nitrogen or oxygen atom can form a piperazine or morpholine ring; represents an alkoxy, hydroxyalkoxy, acyloxy, alkylthio or carbalkyl mercapto group,
    • R 10 has the same meaning as Rg independently of R 8 and can additionally represent a chlorine atom,
      and
    • V is a group of formulas
      Figure imgb0019
       means.

Soweit nicht anders definiert, enthalten Alkyl- und Alkoxygruppen sowie andere, davon abgeleitete Gruppen 1 bis 4 C-Atome. Unter dem Begriff « nichtchromophore Substituenten" sind zu verstehen Alkyl, Alkoxy, Aryl, Aralkyl, Trifluormethyl, Cycloalkyl, Halogen, Alkylsulfonyl, Carboxy, Sulfonsäure, Cyan, Carbonamid, Sulfonamid, Carbonsäurealkylester, Sulfonsäurealkylester.Unless otherwise defined, alkyl and alkoxy groups and other groups derived therefrom contain 1 to 4 carbon atoms. The term “non-chromophoric substituents” is to be understood as meaning alkyl, alkoxy, aryl, aralkyl, trifluoromethyl, cycloalkyl, halogen, alkylsulfonyl, carboxy, sulfonic acid, cyano, carbonamide, sulfonamide, carboxylic acid alkyl ester, sulfonic acid alkyl ester.

Diese Aufheller der Formeln 4 bis 8 sind dem Fachmann hinreichend bekannt, etwa aus « The Chemistry of Synthetic Dyes », Bd. V, Kapitel VIII von Venkataraman.These brighteners of the formulas 4 to 8 are sufficiently known to the person skilled in the art, for example from “The Chemistry of Synthetic Dyes”, vol. V, chapter VIII of Venkataraman.

Bevorzugt sind erfindungsgemäße Mischungen von optischen Aufhellern, wobei die Komponente B besteht aus einer oder mehreren Verbindungen der Formeln 2b-6b

Figure imgb0020
wobei R1 in 5-Stellung ein Wasserstoff- oder Chloratom, eine Methyl- oder Phenylgruppe und R2 ein Wasserstoffatom oder R1 und R2 beide eine Methylgruppe in 5,6- oder 5,7- Stellung, n 0 oder 1 und B eine Cyano- oder Carbo-(C1-C4)-alkoxygruppe oder eine Gruppe der Formeln
Figure imgb0021
oder
Figure imgb0022
bedeutet, wobei R14 (C1-C6)-Alkyl, (C1-C6)-Chloralkyl, (C1-C4)-Alkoxy-(C1-C4)-alkyl, Hydroxi-(C1-C4)-alkyl oder eine Gruppe der Formel ―(CH2CH2O)n―R, n 2 oder 3 und R Wasserstoff oder (C1-C4)-Alkyl, R,5 Phenyl, Halogenphenyl, (C1-C4)-Alkylphenyl oder (C1-C4)-Alkoxiphenyl, R22 (C1-C4)-Alkyl und R23 Cyano oder Carbo-(C1-C4)-alkoxy bedeutet,
Figure imgb0023
wobei R3 Wasserstoff oder (C1-C4)-Alkoxy, R4(C1-C4)-Alkoxy und R5(C1-C6,)-Alkyl oder (C1-C4)-Alkoxi-(C1-C4)-alkyl bedeutet,
Figure imgb0024
wobei R6 Phenyl oder die Gruppe der Formeln
Figure imgb0025
und R7 eine Gruppe der Formel
Figure imgb0026
bedeutet, worin R1 Wasserstoff oder (C1-C4)-Alkyl und R2 Phenyl oder (C1-C4)-Alkoxi oder R1 und R2 zusammen einen Benzo- oder (1,2-d) Naphthoring darstellen,
Figure imgb0027
wobei R8 die Pyrenylgruppe und R9 und R10 (C1-C4)-Alkoxy bedeutet,
Figure imgb0028
wobei R1 und R2 die gleiche Bedeutung haben wie bei Formel 2b und V eine Gruppe der Formeln
Figure imgb0029
und ―CH = CH-, bedeutet.Mixtures of optical brighteners according to the invention are preferred, component B consisting of one or more compounds of the formulas 2b-6b
Figure imgb0020
 where R 1 in the 5-position is a hydrogen or chlorine atom, a methyl or phenyl group and R 2 is a hydrogen atom or R 1 and R 2 are both a methyl group in the 5,6- or 5,7-position, n 0 or 1 and B. a cyano or carbo (C 1 -C 4 ) alkoxy group or a group of the formulas
Figure imgb0021
 or
Figure imgb0022
 means, wherein R 14 is (C 1 -C 6 ) alkyl, (C 1 -C 6 ) chloroalkyl, (C 1 -C 4 ) alkoxy- (C 1 -C 4 ) alkyl, hydroxy (C 1 -C 4 ) alkyl or a group of the formula - (CH 2 CH 2 O) n ―R, n 2 or 3 and R hydrogen or (C 1 -C 4 ) alkyl, R, 5 phenyl, halophenyl, (C 1 -C 4 ) -alkylphenyl or (C 1 -C 4 ) -alkoxiphenyl, R 22 is (C 1 -C 4 ) -alkyl and R 23 is cyano or carbo- (C 1 -C 4 ) -alkoxy,
Figure imgb0023
 where R 3 is hydrogen or (C 1 -C 4 ) alkoxy, R 4 (C 1 -C 4 ) alkoxy and R 5 (C 1 -C 6 ) alkyl or (C 1 -C 4 ) alkoxy Is (C 1 -C 4 ) alkyl,
Figure imgb0024
 where R 6 is phenyl or the group of the formulas
Figure imgb0025
 and R 7 is a group of the formula
Figure imgb0026
 means, wherein R 1 is hydrogen or (C 1 -C 4 ) alkyl and R 2 is phenyl or (C 1 -C 4 ) alkoxy or R 1 and R 2 together represent a benzo or (1,2-d) naphthoring ,
Figure imgb0027
 where R 8 is the pyrenyl group and R 9 and R 10 are (C 1 -C 4 ) alkoxy,
Figure imgb0028
 where R 1 and R 2 have the same meaning as in formula 2b and V is a group of the formulas
Figure imgb0029
 and ―CH = CH-, means.

Bevorzugt sind weiterhin erfindungsgemäße Mischungen von optischen Aufhellern, wobei die Komponente B aus einer oder mehreren Verbindungen der folgenden Formeln besteht :

Figure imgb0030
wobei R1 und R2 in 5,6-Stellung Methyl und B Carbomethoxy, R Wasserstoff, R1 Wasserstoff oder Methyl in 5-Stellung und B Carbomethoxy, Cyano oder eine Gruppe der Formeln
Figure imgb0031
worin R14 und R22 (C1-C3)-Alkyl und R15 Phenyl, 4-Methylphenyl oder 4-Methoxyphenyl ist, oder R1 Wasserstoff, Methyl oder t-Butyl in 5-Stellung, R2 Wasserstoff oder Methyl in 7-Stellung und B Phenyl ist,
Figure imgb0032
wobei R3 Wasserstoff oder Methoxy ist,
Figure imgb0033
Figure imgb0034
oder
Figure imgb0035
Figure imgb0036
Figure imgb0037
Figure imgb0038
oder
Figure imgb0039
wobei R2 Wasserstoff oder Methyl ist.Mixtures of optical brighteners according to the invention are further preferred, component B consisting of one or more compounds of the following formulas:
Figure imgb0030
 wherein R 1 and R 2 in the 5,6-position methyl and B carbomethoxy, R hydrogen, R 1 hydrogen or methyl in the 5-position and B carbomethoxy, cyano or a group of the formulas
Figure imgb0031
 wherein R 14 and R 22 are (C 1 -C 3 ) alkyl and R 15 is phenyl, 4-methylphenyl or 4-methoxyphenyl, or R 1 is hydrogen, methyl or t-butyl in the 5-position, R 2 is hydrogen or methyl in 7-position and B is phenyl,
Figure imgb0032
 where R 3 is hydrogen or methoxy,
Figure imgb0033
Figure imgb0034
 or
Figure imgb0035
Figure imgb0036
Figure imgb0037
Figure imgb0038
 or
Figure imgb0039
 where R 2 is hydrogen or methyl.

Als Komponente A der Verbindungen der Formeln 1-3 sind Mischungen der folgenden Zusammensetzung bevorzugt :

Figure imgb0040
Mixtures of the following composition are preferred as component A of the compounds of the formulas 1-3:
Figure imgb0040

Besonders bevorzugt sind als Komponente A Mischungen der folgenden Zusammensetzung :

Figure imgb0041
wobei der Anteil der Verbindungen 1 und 3 in etwa gleich sein soll.Mixtures of the following composition are particularly preferred as component A:
Figure imgb0041
 the proportion of compounds 1 and 3 should be approximately the same.

Der Anteil der einzelnen Verbindungen 1 bis 3 in der Komponente A kann innerhalb der angebenen Grenzen schwanken, wobei solche Mischungen bevorzugt sind, die die Verbindungen 1 und 3 in etwa gleichen Teilen enthalten. Aus den oben angegebenen Grenzen für die Gewichtsverhältnisse der Verbindungen 1 bis 3 ergibt sich, daß der Anteil der Verbindungen 1 und 3 0 % und der Anteil der Verbindung 2 100 % betragen kann. In diesem Fall liegt die reine Verbindung 2 vor. Es versteht sich, daß die Zusammensetzung der Komponente A innerhalb der verschiedenen, oben angegebenen Grenzen so gewählt wird, daß die Summe aller Einzelverbindungen 100 % ausmacht.The proportion of the individual compounds 1 to 3 in component A can fluctuate within the limits specified, preference being given to mixtures which contain the compounds 1 and 3 in approximately equal parts. From the limits given above for the weight ratios of compounds 1 to 3, it follows that the proportion of compounds 1 and 3 can be 0% and the proportion of compound 2 can be 100%. In this case there is pure connection 2. It is understood that the composition of component A is chosen within the various limits given above so that the sum of all individual compounds is 100%.

Das als Komponente A bezeichnete Gemisch wird hergestellt, indem man 1 Mol-Äquivalent einer Verbindung der Formel

Figure imgb0042
mit insgesamt 2 Mol-Äquivalent eines Gemisches aus den Verbindungen
Figure imgb0043
und
Figure imgb0044
umsetzt.The mixture referred to as component A is made by mixing 1 mole equivalent of one Compound of formula
Figure imgb0042
 with a total of 2 mole equivalent of a mixture of the compounds
Figure imgb0043
 and
Figure imgb0044
 implements.

Das Verhältnis der Verbindungen 10 und 11 bestimmt die Zusammensetzung des Gemisches. Liegt der Anteil an 10 höher, wächst der Anteil der Verbindung 1 auf Kosten der Verbindung 3, liegt der Anteil an Verbindung 11 höher wird der Anteil der Verbindung 3 in Gemische höher als 1 sein.The ratio of compounds 10 and 11 determines the composition of the mixture. If the proportion of 10 is higher, the proportion of compound 1 increases at the expense of compound 3, if the proportion of compound 11 is higher, the proportion of compound 3 in mixtures will be higher than 1.

Vorteilhaft ist es, die Umsetzung von 9 mit je einem Mol-Äquivalent der Verbindungen 10 und 11, durchzuführen, wobei ein Überschuß von 10 und 11 bis zu 10 % möglich, aber nicht von Vorteil ist. In den Formeln 9-10 bedeutet eines der Symbole X oder Q eine Aldehydgruppe und das andere Symbol eine Gruppe der Formeln

Figure imgb0045
Figure imgb0046
Figure imgb0047
Figure imgb0048
wobei R einen gegebenenfalls substituierten Alkylrest mit vorzugsweise 1-6 C-Atomen, eine Arylrest vorzugsweise Phenyl, eine Cycloalkylrest oder einen Aralkylrest, vorzugsweise Benzyl darstellt..It is advantageous to carry out the reaction of 9 with one molar equivalent each of the compounds 10 and 11, an excess of 10 and 11 up to 10% being possible but not advantageous. In formulas 9-10, one of the symbols X or Q represents an aldehyde group and the other symbol a group of the formulas
Figure imgb0045
Figure imgb0046
Figure imgb0047
Figure imgb0048
 where R represents an optionally substituted alkyl radical having preferably 1-6 C atoms, an aryl radical preferably phenyl, a cycloalkyl radical or an aralkyl radical, preferably benzyl.

Eine bevorzugte Verfahrensvariante besteht darin, daß man eine Verbindung der Formel 9, wobei X für eine Aldehydgruppe steht, mit Verbindungen der Formel 10 und 11, wobei Q für eine Gruppe der Formel 12a mit R = C1-4 Alkyl steht, umsetzt.A preferred process variant consists in reacting a compound of formula 9, where X is an aldehyde group, with compounds of formulas 10 and 11, where Q is a group of formula 12a with R = C1-4 alkyl.

Man führt das Verfahren vorzugsweise in Lösungsmitteln durch in Gegenwart eines Protonenacceptors. Als Lösungsmittel seien bespielsweise genannt Kohlenwasserstoffe wie Toluol, Xylol, Alkohole wie Methanol, Äthanol, Isopropanol, Butanol, Glykole, Hexanole, Cyclohexanole, ferner Äther wie Diisopropyläther, Tetrahydrofuran, Dioxan und Dimethyisulfoxyd genannt. Besonders geeignet sind polare organische Lösungsmittel wie Formamid, Dimethylformamid und N-Methylpyrrolidon, wobei Dimethylformamid besonders hervorzuheben ist.The process is preferably carried out in solvents in the presence of a proton acceptor. Examples of solvents which may be mentioned are hydrocarbons such as toluene, xylene, alcohols such as methanol, ethanol, isopropanol, butanol, glycols, hexanols, cyclohexanols, and furthermore ethers such as diisopropyl ether, tetrahydrofuran, dioxane and dimethyl sulfoxide. Polar organic solvents such as formamide, dimethylformamide and N-methylpyrrolidone are particularly suitable, with dimethylformamide being particularly emphasized.

Als Protonenacceptoren eignen sich vornehmlich basische Verbindungen, wie Alkali- oder Erdalkalihydroxyde, -alkoholate oder -amide, stark basische Amine und Anionenaustauscherharze in der Hydroxylform. Bevorzugt ist der Einsatz von Alkalihydröxyden, im besonderen Kaliumhydroxyd.Suitable proton acceptors are primarily basic compounds, such as alkali or alkaline earth metal hydroxides, alcoholates or amides, strongly basic amines and anion exchange resins in the hydroxyl form. The use of alkali hydrodes, in particular potassium hydroxide, is preferred.

Die Umsetzungstemperatur hängt von der Art der umzusetzenden Komponenten, insbesondere von der Art der Carbonylgruppen enthaltenden organischen Verbindung und dem Protonenacceptor ab ; sie liegt zwischen - 10 °C und + 100 °C, vorteilhaft zwischen 0°-50°C. Eine bevorzugte Ausführungsform besteht darin, die Reaktionspartner bei tieferen Temperaturen zusammenzugeben und die Reaktion bei höherer Temperatur zu Ende zu führen.The reaction temperature depends on the type of components to be reacted, in particular on the type of organic compound containing carbonyl groups and the proton acceptor; it is between - 10 ° C and + 100 ° C, advantageously between 0 ° -50 ° C. A preferred embodiment is to bring the reactants together at lower temperatures and to complete the reaction at a higher temperature.

Das beanspruchte Verfahren läßt sich beispielsweise so durchführen, daß man den Protonenacceptor im Lösungsmittel vorlegt und eine Lösung der Reaktionskomponenten 9-11 im Lösungsmittel zutropft, es ist aber ebenfalls möglich, die Verbindungen 9-11 vorzulegen und den Proteonacceptoren zuzugeben. Eine weitere Ausführungsform besteht darin, die Verbindungen 9-11, worin X oder Q für eine Gruppe der Formel 12a-d steht, vorzulegen, anschließend zuerst den Protonenacceptor und dann die Aldehydkomponente zuzugeben. Die Umsetzung läuft im allgemeinen unter starker Wärmeentwicklung ab, so daß man gegebenenfalls kühlen muß. Die Aufarbeitung des Reaktorgemisches erfolgt in bekannter Weise z.B. durch Zusatz von Methanol oder Äthanol und Abtrennen der ausgefallenen Produkte. Die so erhaltenen Produktgemische lassen sich durch HPLC (High pressure liquid chromatography) analysieren und charakterisieren.The claimed process can be carried out, for example, by introducing the proton acceptor in the solvent and adding a solution of the reaction components 9-11 in the solvent, but it is also possible to introduce the compounds 9-11 and adding them to the proteone acceptors. A further embodiment consists in presenting the compounds 9-11, in which X or Q represents a group of the formula 12a-d, then first adding the proton acceptor and then the aldehyde component. The reaction generally takes place with intense heat so that cooling may be necessary. The reactor mixture is worked up in a known manner, e.g. by adding methanol or ethanol and separating the precipitated products. The product mixtures obtained in this way can be analyzed and characterized by HPLC (high pressure liquid chromatography).

Die Ausgangsverbindungen der Formeln 9-11 sind bekannt bzw. können nach bekannten Verfahren hergestellt werden.The starting compounds of the formulas 9-11 are known or can be prepared by known processes.

Von den Verbindungen unter den Formeln 4 bis 8 sind in den erfindungsgemäßen Gemischen die Verbindungen der folgenden Formeln bevorzugt :

  • Formel 4 :
    Figure imgb0049
    wobei R1, und R2, in 5- und 7-Stellung Wasserstoff oder Chlor, Alkyl, Phenyl oder zusammen einen ankondensierten Phenylring, X Sauerstoff oder Schwefel, n = 1 und B eine Gruppe der Formeln
    Figure imgb0050
    Figure imgb0051
    bedeutet, wobei R14. Alkyl, Chloralkyl, Alkoxyalkyl, Hydroxyalkyl oder eine Gruppe der Formel ―(CH2CH2O)n―R bedeutet, wobei n 2 oder 3 und R Wasserstoff oder Alkyl ist, R15 Phenyl bedeutet, das durch ein oder zwei Chloratome, ein oder zwei Alkyl-, Alkoxyalkylgruppen, eine Phenyl-, Cyano-, Carbonsäure-, Carboalkoxy-, Carbonsäureamid-, Sulfonsäure-, Sulfonsäureamid-, oder Sulfonsäurealkylestergruppe substituiert sein kann, R23 Cyano oder Carboalkoxy und R22 Alkyl bedeutet.
  • Formel 5 :
    Figure imgb0052
    wobei R3 Wasserstoff oder Alkoxy, R4, Alkoxy und R5. Alkyl, Alkoxyalkyl oder Dialkylaminoalkyl bedeutet.
  • Formel 6 :
    Figure imgb0053
    wobei R6, Phenyl oder die Gruppe der Formel
    Figure imgb0054
    und R7, die Gruppen der Formeln
    Figure imgb0055
    bedeutet
  • Formel 7 :
    Figure imgb0056
  • Formel 8 :
    Figure imgb0057
    wobei R1, und R2, Wasserstoff oder Alkyl und V' eine Gruppe der Formeln
    Figure imgb0058
    oder ―GH = CH- und X O oder S bedeutet.
Of the compounds of the formulas 4 to 8, the compounds of the following formulas are preferred in the mixtures according to the invention:
  • Formula 4:
    Figure imgb0049
     where R 1 , and R 2 , in the 5- and 7-positions are hydrogen or chlorine, alkyl, phenyl or together a fused phenyl ring, X is oxygen or sulfur, n = 1 and B is a group of the formulas
    Figure imgb0050
    Figure imgb0051
     means, where R 14 . Alkyl, chloroalkyl, alkoxyalkyl, hydroxyalkyl or a group of the formula - (CH 2 CH 2 O) n ―R, where n is 2 or 3 and R is hydrogen or alkyl, R15 is phenyl which is substituted by one or two chlorine atoms, one or two alkyl, alkoxyalkyl groups, one phenyl, cyano, carboxylic acid, carboalkoxy, carboxamide, sulfonic acid, sulfonic acid amide or sulfonic acid alkyl ester group may be substituted, R 23 is cyano or carboalkoxy and R 22 is alkyl.
  • Formula 5:
    Figure imgb0052
     where R 3 is hydrogen or alkoxy, R 4 , alkoxy and R 5 . Means alkyl, alkoxyalkyl or dialkylaminoalkyl.
  • Formula 6:
    Figure imgb0053
     where R 6 , phenyl or the group of the formula
    Figure imgb0054
     and R 7 , the groups of the formulas
    Figure imgb0055
     means
  • Formula 7:
    Figure imgb0056
  • Formula 8:
    Figure imgb0057
     where R 1 , and R 2 , hydrogen or alkyl and V 'is a group of the formulas
    Figure imgb0058
     or ―GH = CH- and XO or S means.

Ganz besonders bevorzugt sind von den Verbindungen unter der Formel 4 die Verbindungen der Formel

Figure imgb0059
wobei R," und R2" Wasserstoff oder Alkyl und B" eine Gruppe der Formeln
Figure imgb0060
―CN oder ―COOAlkyl
und R,4. Alkyl oder Methoxyäthyl bedeutet. Von besonderer Wichtigkeit sind die folgenden Verbindungen unter der Formel 4 :
Figure imgb0061
und
Figure imgb0062
 Of the compounds under the formula 4, the compounds of the formula are very particularly preferred
Figure imgb0059
 where R, " and R 2" are hydrogen or alkyl and B "is a group of the formulas
Figure imgb0060
 ―CN or ―COOalkyl
and R, 4 . Alkyl or methoxyethyl means. The following compounds under formula 4 are of particular importance:
Figure imgb0061
 and
Figure imgb0062

Das Mischungsverhältnis für die einzelnen Komponenten liegt zwischen 0,05 und 0,95 Gew.-Teilen für die Komponente A und entsprechend 0,95 bis 0,05 Gew.-Teilen für die übrigen Verbindungen der Formeln 4 bis 8. Diese Verbindungen der Formeln 4 bis 8 können einzeln aber auch in beliebiger Mischung untereinander eingesetzt werden, wobei das Mischungsverhältnis dieser Verbindungen untereinander gänzlich unkritisch ist und beliebig variiert werden kann.The mixing ratio for the individual components is between 0.05 and 0.95 parts by weight for component A and correspondingly 0.95 to 0.05 parts by weight for the other compounds of the formulas 4 to 8. These compounds of the formulas 4 to 8 can be used individually or in any mixture with one another, the mixing ratio of these compounds with one another being completely uncritical and being able to be varied as desired.

Bevorzugt ist ein Mischungsverhältnis von 5 bis 50 Gew.-% für die Komponente A und 95 bis 50 Gew.-% eines oder mehrerer Aufhellern der Formeln 4 bis 8 (Komponente B).A mixing ratio of 5 to 50% by weight for component A and 95 to 50% by weight of one or more brighteners of the formulas 4 to 8 (component B) is preferred.

Das optimale Mischungsverhältnis aller Verbindungen hängt im Einzelfall von der Struktur der jeweiligen Verbindungen ab und läßt sich durch einfache Vorversuche unschwer ermitteln.The optimal mixing ratio of all compounds depends in individual cases on the structure of the respective compounds and can be easily determined by simple preliminary tests.

Wie bei optischen Aufhellern üblich, werden die einzelnen Komponenten durch Dispergierung in einem flüssigen Medium z.B. Wasser in die Handelsform gebracht. Man kann dabei die einzelnen Komponenten jede für sich dispergieren und dann die Dispersionen zusammen geben. Man kann aber auch die Einzelkomponenten in Substanz miteinander mischen und dann gemeinsam dispergieren. Dieser Dispergiervorgang geschieht in üblicher Weise in Kugelmühlen, Kolloidmühlen, Perlmühlen oder Dispersionsknetern. Die erfindungsgemäßen Mischungen eignen sich besonders zum Aufhellen von Textilmaterial aus linearen Polyestern, Polyamiden und Acetylcellulose. Man kann diese Mischungen aber auch mit gutem Ergebnis bei Mischgeweben verwenden, die aus linearen Polyestern und anderen synthetischen oder natürlichen Faserstoffen namentlich hydroxylgruppenhaltigen Fasern, insbesondere Baumwolle bestehen. Die Applikation dieser Mischungen geschieht dabei unter den für die Anwendung von optischen Aufhellern üblichen Bedingungen so beispielsweise nach dem Ausziehverfahren bei 90 °C bis 130 °C mit oder ohne Zusatz von Beschleunigern (Carriern) oder nach dem Thermosolverfahren. Die in Wasser unlöslichen Aufheller und die erfindungsgemäßen Mischungen können auch in organischen Lösemitteln z.B. Perchloräthylen, fluorierten Kohlenwasserstoffen gelöst zum Einsatz kommen. Dabei kann das Textilmaterial im Ausziehverfahren mit der Lösemittelflotte, welche den optischen Aufheller gelöst enthält, behandelt werden, oder man imprägniert, pflatscht, sprüht das Textilgut mit der aufhellerhaltigen Lösemittelflotte und trocknet anschließend bei Temperaturen von 120-220 °C, wobei der optische Aufheller dabei restlos in der Faser fixiert wird. Man erhält dabei eine hervorragend aufgehellte Ware mit ausgezeichneter Lichtbeständigkeit, sowie Beständigkeit gegenüber Oxidations-und Reduktionsmitteln. Diese erfindungsgemäßen Mischungen weisen im Vergleich zu den Mischungen des japanischen Patents Sho 50 (1975)-25 877 höhere Weißgrade auf ; sie ergeben ferner auch bereits bei niedrigen Thermosoliertemperaturen von z.B. 150 °C hervorragende Weißgrade.As usual with optical brighteners, the individual components are dispersed in a liquid medium e.g. Water brought into the commercial form. The individual components can be dispersed individually and the dispersions can then be added together. However, the individual components can also be mixed together in bulk and then dispersed together. This dispersion process takes place in the usual way in ball mills, colloid mills, bead mills or dispersion kneaders. The mixtures according to the invention are particularly suitable for lightening textile material made from linear polyesters, polyamides and acetyl cellulose. However, these mixtures can also be used with good results in mixed fabrics which consist of linear polyesters and other synthetic or natural fiber materials, in particular fibers containing hydroxyl groups, in particular cotton. These mixtures are applied under the conditions customary for the use of optical brighteners, for example using the exhaust process at 90 ° C. to 130 ° C. with or without the addition of accelerators (carriers) or using the thermosol process. The water-insoluble brighteners and the mixtures according to the invention can also be used in organic solvents, e.g. Perchlorethylene, fluorinated hydrocarbons can be used in solution. The textile material can be treated in the exhaust process with the solvent liquor which contains the optical brightener, or one can impregnate, splash, spray the textile material with the brightener-containing solvent liquor and then dry at temperatures of 120-220 ° C, the optical brightener being used is completely fixed in the fiber. This gives an excellently lightened product with excellent lightfastness and resistance to oxidizing and reducing agents. These mixtures according to the invention have higher degrees of whiteness than the mixtures of the Japanese patent Sho 50 (1975) -25,877; they also result in low thermal insulation temperatures of e.g. 150 ° C excellent whiteness.

Die folgenden Tabellen-Beispiele illustrieren die Erfindung. Das angewandte Applikationsverfahren soll hier beispielgebend geschildert werden :

  • Gewebeabschnitte aus Polyester-Stapelfasern werden gewaschen, getrocknet und auf einen Foulard mit wäßrigen Dispersionen imprägniert, die entweder den reinen optischen Aufheller der Formeln 4 bis 8 (Komponente B) mit einer Einsatzmenge von 0,08 Gew.-% oder ein Gemisch aus 0,064 Gew.-%, 0,04 Gew.-% bzw. 0,016 Gew.% der Komponente A mit 0,016, 0,04 bzw. 0,064 Gew.-% der Aufheller der Komponente B enthalten. Als Komponente A wurde in allen Beispielen ein Gemisch aus 1,5 Gew.-Teilen 1,4-Bis-(4'-cyano-styryl)-benzol, 1,5 Gew.-Teilen 1,4-Bis-(2'-cyano-styryl)-benzol und 7-Gew.-Teilen 1-(2-Cyano-sturyl)-4-(4'-cyano-styryl)-benzol eingesetzt.
The following table examples illustrate the invention. The application method used is described here as an example:
  • Fabric sections made of polyester staple fibers are washed, dried and impregnated onto a foulard with aqueous dispersions which either contain the pure optical brightener of the formulas 4 to 8 (component B) with an amount of 0.08% by weight or a mixture of 0.064% by weight %, 0.04% by weight or 0.016% by weight of component A with 0.016, 0.04 or 0.064% by weight of the brightener of component B. In all examples, component A was a mixture of 1.5 parts by weight of 1,4-bis (4'-cyano-styryl) benzene, 1.5 parts by weight of 1,4-bis- (2 ' -cyano-styryl) -benzene and 7 parts by weight of 1- (2-cyano-sturyl) -4- (4'-cyano-styryl) -benzene.

Das Material wird mit einem Foulard zwischen Rollen so abgequetscht, daß sich eine Feuchtigkeitsaufnahme von ca. 80 % ergibt. Das entspricht einer Aufnahme an optischen Aufhellern auf die Ware von 0,064 %. Das so geklotzte Material wurde anschließend auf einem Spannrahmen 30 Sek. bei 170° (Tabelle I) bzw. 210° (Tabelle 11) thermosoliert. Dabei wurden die jeweils angegebenen Weißgrade nach Ganz erhalten. Die Weißgrade wurden mit einem Remissionsspektralphotometer Typ DMC-25 gemessen. (Firma Carl Zeiss, Oberkochen).The material is squeezed between rollers with a padder so that a moisture absorption of approx. 80% results. This corresponds to an absorption of optical brighteners on the goods of 0.064%. The material which had been blocked in this way was then thermosolated on a stenter for 30 seconds at 170 ° (Table I) or 210 ° (Table 11). The specified degrees of whiteness according to Ganz were obtained. The degrees of whiteness were measured using a DMC-25 reflectance spectrophotometer. (Carl Zeiss company, Oberkochen).

(Siehe die Tabellen, Seiten 14, 15, 16, 17, 18, 19)(See the tables, pages 14, 15, 16, 17, 18, 19)

Figure imgb0063
Figure imgb0063
Figure imgb0064
Figure imgb0064
Figure imgb0065
Figure imgb0065
Figure imgb0066
Figure imgb0066
Figure imgb0067
Figure imgb0067
Figure imgb0068
Figure imgb0068

Claims (8)

1. Mixtures of optical brighteners consisting of
A) 0.05 to 0.95 part by weight of a mixture consisting of 0 to 80 % by weight of the compound of the formula I
Figure imgb0118
20 g to 100 % by weight of the compound of the formula 2
Figure imgb0119
and 0 to 80 % by weight of the compound of the formula 3
Figure imgb0120
and
B) 0.95 to 0.05 part by weight of one or more compounds of the formulae 4, 5, 6, 7 or 8
Figure imgb0121
Figure imgb0122
Figure imgb0123
Figure imgb0124
and
Figure imgb0125
in which
n denotes 0 or 1,
X denotes an oxygen or sulfur atom,
R1 and R2 denote identical or different radicals from the group comprising hydrogen, fluorine or chlorine atoms, phenyl, trifluoromethyl, C1-C9 alkyl, alkoxy, dialkylamino, acylamino, cyano, carboxyl, carbalkoxy, carboxamide, sulfonic acid, sulfonamide or sulfonic acid alkyl ester, it being possible for two adjacent radicals R1 and R2 together also to represent a benzo ring, a lower alkylene group or a 1,3-dioxapropylene group,
B denotes cyano or a group of the formula ―COOR11 or CONR11R11, in which R11 denotes hydrogen, C1-C18 alkyl, cycloalkyl, aryl, alkylaryl, halogenoaryl, aralkyl, alkoxyalkyl, halogenoalkyl, hydroxyalkyl, alkylaminoalkyl, carboxyalkyl or carboalkoxyalkyl, or two alkyl or alkylene radicals with the meaning of R11 can also form, together with the nitrogen atom, a morpholine, piperidine or piperazine ring, or B denotes a group of the formula
Figure imgb0126
in which R12 and R13 denote identical or different radicals from the group comprising hydrogen, fluorine or chlorine atoms, phenyl, alkyl, alkoxy, acylamino, cyano, carboxyl, carbalkoxy, carboxamide, sulfonic acid, sulfonamide or sulfonic acid alkyl ester and two adjacent radicals R12 and R13 together can also represent an alkylene group, a fused benzo ring or a 1,3-dioxapropylene group, or B denotes a group of the formulae
Figure imgb0127
or
Figure imgb0128
in which R14 denotes a straight-chain or branched alkyl group having 1-18 C atoms and preferably 1-6 C atoms, which can be substituted by hydroxyl groups, halogen atoms or alkoxy, dialkylamino, alkylmercapto, chloroaryloxy, aryloxy, arylmercapto or aryl radicals, it being possible, in the case of the dialkylaminoalkyl groups, for the two alkyl groups together also to form a morpholine, piperidine or piperazine ring, or R14 denotes a group of the formula ―(CH2CH2O)n―R in which n is 1, 2 or 3 and R is H, alkyl, dialkylaminoalkoxyalkyl or alkylthioalkoxyalkyl, it being possible for the dialkyl groups in dialkylaminoalkoxyalkyl together to form a piperidine, pyrrolidine, hexamethyleneimine, morpholine or piperazine ring, or R14 denotes a radical of the formula
Figure imgb0129
R22 denotes a hydrogen atom, a triphenylmethyl group or a lower alkyl radical, which is optionally substituted by a lower carbalkoxy, carboxamide, mono- or di-alkylcarboxamido, carboxyl or benzoyl group, and R23 denotes a cyano group or a group of the formulae
Figure imgb0130
in which R', R" and R"' denote a hydrogen atom, a lower alkyl radical or a phenyl radical, and it being possible for the lower alkyl radicals to be substituted by hydroxyl, lower alkoxy, lower dialkylamino or lower trialkylammonium groups and for the phenyl group to be substituted by halogen atoms or lower alkyl or lower alkoxy groups, and in which R" and R"' together can also form a saturated, divalent radical, and Y denotes O, S or N-R, in which R is H or (C1 to C4)-alkyl, or B denotes a group of the formula
Figure imgb0131
in which R15 denotes a phenyl ring which can be substituted by one or two chlorine atoms, one or two alkyl or alkoxyalkyl groups or one phenyl, cyano, carboxyl, carbalkoxy, carboxamide, sulfonic acid, sulfonamide or sulfonic acid alkyl ester group,
R3 and R4 can be identical or different and denote hydrogen, alkyl, cycloalkyl, alkoxy, hydroxyalkoxyethyl, halogenoalkyl, aralkyl, aryl or N,N-di-alkylamine, or R3 and R4 together form a five-membered heterocyclic radical having 1 to 3 heteroatoms, preferably N atoms,
R5 denotes straight-chain or branched alkyl, alkoxyalkyl, dialkylaminoalkyl or a radical of the formula
Figure imgb0132
in which R16 is hydrogen, C2-C8-alkanoyl, benzoyl or a radical of the formula
Figure imgb0133
and R17 is hydrogen, alkyl or phenyl, R18 is alkyl, phenyl, halogenophenyl or tolyl and R19 is C1-C8-alkyl, alkoxyalkyl, cyclohexyl, benzyl, phenylethyl or phenyl which is optionally substituted by non-chromophoric substituents, or R5 denotes a radical of the formula
Figure imgb0134
in which R20 is C1-C10-alkyl, C2-C6-alkenyl, C2-C6-alkinyl, C1-C8-alkoxy, C1-C8-afkylamino or dialkylamino, phenoxymethyl, phenyl, tolyl, benzyl or phenylethyl and R21 is C3-C10-alkyl, which can be substituted by phenyl, hydroxyphenyl, methoxy or dimethoxy,
Re denotes an aryl radical, which is optionally substituted by non-chromophoric substituents, or denotes a 1,2,4-triazol-1-yl-phenyl, 1,2,3-triazol-4-yl-phenyl, 1,2,3-triazol-3-yl-phenyl or 1,2,3-triazol-2-yl- phenyl radical, which optionally can be substituted by 1 or 2 C1-C3-alkyl or oxalkyl groups or by oxaryl, oxalkenyl or oxalkanoyl, or R6 denotes a heterocyclic ring having 1-3 heteroatoms, preferably N or O, which can ben substituted by alkyl, alkoxy, halogen, aryl or halogenoaryl, or Re denotes a 1-oxa-2,4-diazol-5-yl radical, which can be substituted by benzyl, alkoxyphenyl, styryl, halogen, alkoxy or a further heterocyclic group, or R6 denotes a benzimidazol-1-yl, benzimidazol-2-yl, benzthiazo(-1-y( or benzthiazol-2-yl radical, which can be substituted by non-chromophoric substituents,
R7 denotes hydrogen, alkyl, alkoxy, aryl or a five-membered heterocyclic radical which has 1-3 N or 0 hetero-atoms and is bonded via a nitrogen atom and can be substituted by alkyl, aryl, hydroxyl, oxalkyl, oxalkenyl, oxaryl, oxarylalkyl, oxalkoxycarbonyl, oxcarbamoyl, oxepoxyalkyl, styryl or halogenstyryl, a fused phenyl, naphthyl or phenanthryl ring or a fused group of the formulae
Figure imgb0135
and the aromatic rings in the fused groups can also be substituted by alkyl or alkoxy and X is oxygen, NH or N-alkyl,
R8 represents a polycyclic, aromatic radical having at least three fused rings, which optionally carry non-chromophoric substituents,
R9 represents an amino group, which is substituted by one or two alkyl, hydroxyalkyl, acyl or phenyl groups, it being possible for the phenyl group to contain one or more non-chromophoric radicals and for two alkyl groups, together with the nitrogen atom of the amino group, to form a pyrrolidine or piperidine ring or, with the inclusion of a further nitrogen or oxygen atom, a piperazine or morpholine ring, or Rg represents an alkoxy, hydroxyalkoxy, acyloxy, alkylthio or carbalkylmercapto group,
R10 independently of R8 has the same meaning as Rg and in addition can denote a chlorine atom and
V denotes a group of the formulae
Figure imgb0136
2. Mixtures of optical brighteners according to Claim 1, in which component A) consists of 5 to 35 % by weight of compound (1), 30 to 90 % by weight of compound (2) and 5 to 35 % by weight of compound (3).
3. Mixtures of optical brighteners according to Claim 1, in which component A) consists of 15 to 28 % by weight of compound (1), 15 to 28 % by weight of compound (2) and 44 to 70 % by weight of compound (3).
4. Mixtures of optical brighteners according to Claim 1, in which component B) consists of one or more compounds of the formulae 4a to 8a
Figure imgb0137
in which R1, and R2, in the 5-position and 7-position denote hydrogen or chlorine, alkyl or phenyl or together denote a fused phenyl ring, X denotes oxygen or sulfur, n denotes 1 and B denotes a group of the formulae
Figure imgb0138
Figure imgb0139
in which R14, denotes alkyl, chloroalkyl, alkoxyalkyl, hydroxyalky or a group of the formula ―(CH2CH2O)n―R, in which n is 2 or 3 and R is hydrogen or alkyl, R15 denotes phenyl, which can be substituted by one or two chlorine atoms, one or two alkyl or alkoxyalkyl groups or one phenyl, cyano, carboxylic acid, carbalkoxy, carboxamide, sulfonic acid, sulfonamide or sulfonic acid alkyl ester group, R23 denotes cyano or carbalkoxy and R22 denotes alkyl,
Figure imgb0140
in which R3, denotes hydrogen or alkoxy, R4, denotes alkoxy and R5, denotes alkyl, alkoxyalkyl or dialkylaminoalkyl,
Figure imgb0141
in which R6, denotes phenyl or the group of the formula
Figure imgb0142
and R7, denotes the groups of the formulae
Figure imgb0143
Figure imgb0144
Figure imgb0145
in which R1, and Rz denote hydrogen or alkyl and V' denotes a group of the formulae
Figure imgb0146
or -CH=CH- and X denotes O or S.
5. Mixtures of optical brighteners according to Claim 2, in which component B consists of one or more compounds of the formulae 2b-6b
Figure imgb0147
in which R1 in the 5-position denotes a hydrogen or chlorine atom or a methyl group in the 5,6- or 5,7- position, n denotes 0 or 1 and B denotes a cyano or carbo-(C1-C4)-alkoxy group or a group of the formulae
Figure imgb0148
or
Figure imgb0149
in which R14 denotes (C1-Cs)-chloroalkyl, (C1-C4)-alkoxy-(C1-C4)-alkyl, hydroxy-(C1-C4)-alkyl or a group of the formula ―(CH2CH2O)n―R, n denotes 2 or 3 and R denotes hydrogen or(Ci-C4)-alkyl, R15 denotes phenyl, halogenophenyl, (C1-C4)-alkylphenyl or (C1-C4)-alkoxyphenyl, R22 denotes (C1-C4)-alkyl and R23 denotes cyano or carbo-(C1-C4)-alkoxy,
Figure imgb0150
in which R3 denotes hydrogen or (C1-C4)-alkoxy, R4 denotes (Ci-C4)-alkoxy and R5 denotes (Ci-C6)-alkyl or (C1-C4)-alkoxy-(C1-C4 )-alkyl,
Figure imgb0151
in which R6 denotes phenyl or the group of the formulae
Figure imgb0152
and R7 denotes a group of the formula
Figure imgb0153
in which R1 represents hydrogen or (C1-C4)-alkyl and R2 represents phenyl or (C1-C4)-alkoxy, or R1 and R2 together represent a benzo or (1,2-d)-naphtho ring,
Figure imgb0154
in which R8 denotes a pyrenyl group and R9 and R10 denote (C1-C4)-alkoxy, and
Figure imgb0155
in which R1 and R2 have the same meaning as in formula 2b and V denotes a group of the formulae
Figure imgb0156
or -CH = CH-.
6. Mixtures of optical brighteners according to Claim 1, in which component B consists of one or more compounds of the following formulae
Figure imgb0157
in which R1 and R2 in the 5,6-position are methyl and B is carbomethoxy, R1, is hydrogen, R2 is hydrogen or methyl in the 5-position and B is carbomethoxy, cyano or a group of the formulae
Figure imgb0158
in which R14 and R22 are (C1-C3)-alkyl and R15 is phenyl, 4-methylphenyl or 4-methoxyphenyl, or R, is hydrogen, methyl or t-butyl in the 5-position, R2 is hydrogen or methyl in the 7-position and B is phenyl,
Figure imgb0159
in which R3 is hydrogen or methoxy
Figure imgb0160
Figure imgb0161
Figure imgb0162
in which R2 is hydrogen or methyl.
7. Mixtures of optical brighteners according to Claim 1, consisting of 5 to 50 % by weight of component A and 95 to 50 % by weight of component B.
8. Use of the brightener mixtures according to Claim 1 to 7 for brightening polyester fibers.
EP80104163A 1979-07-21 1980-07-16 Mixtures of optical brighteners and their use Expired EP0023028B1 (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3313332A1 (en) * 1983-04-13 1984-10-18 Hoechst Ag, 6230 Frankfurt Mixtures of optical brighteners for brightening polyvinyl chloride

Families Citing this family (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0030917B2 (en) * 1979-12-13 1991-03-20 Ciba-Geigy Ag Optical brighteners from bistyryl benzene, process for their preparation and their use
CH650792A5 (en) * 1979-12-13 1985-08-15 Ciba Geigy Ag Optical brighteners from bisstyrylbenzene compounds and preparation thereof
DE3001065A1 (en) * 1980-01-12 1981-07-16 Basf Ag, 6700 Ludwigshafen METHOD FOR PRODUCING OPTICAL BRIGHTENERS
DE3027479A1 (en) * 1980-07-19 1982-03-04 Hoechst Ag, 6000 Frankfurt MIXTURES OF OPTICAL BRIGHTENERS AND THEIR USE
DE3104992A1 (en) * 1981-02-12 1982-08-26 Hoechst Ag, 6000 Frankfurt "MIXTURES OF OPTICAL BRIGHTENERS"
DE3339383A1 (en) * 1983-10-29 1985-05-09 Bayer Ag, 5090 Leverkusen DISTYRYLIC COMPOUNDS
JPS60217999A (en) * 1984-03-31 1985-10-31 株式会社新潟鐵工所 Fluid cargo gear
US4778622A (en) * 1986-03-21 1988-10-18 Ciba-Geigy Corporation Mixtures of fluorescent whitening agents
EP0252009B1 (en) * 1986-07-01 1990-08-01 Ciba-Geigy Ag 1,4-distyryl benzene compounds and their mixtures with other 1,4-distyryl benzene compounds
CH671956A5 (en) * 1987-01-29 1989-10-13 Ciba Geigy Ag
US4830763A (en) * 1987-02-26 1989-05-16 Ciba-Geigy Corporation Process for increasing the degree of whiteness of polyester-containing textile material
ES2053806T3 (en) * 1987-11-27 1994-08-01 Ciba Geigy Ag STABLE WHITENING DISPERSION AND PROCEDURE FOR ITS PREPARATION.
DE3878550D1 (en) * 1987-11-27 1993-03-25 Ciba Geigy Ag LIGHTER DISPERSION.
US6492032B1 (en) 2000-10-12 2002-12-10 Eastman Chemical Company Multi-component optically brightened polyolefin blend
DE10219993A1 (en) * 2002-05-03 2003-11-20 Basf Ag Process for lightening textile materials
CN100338296C (en) * 2002-12-10 2007-09-19 西巴特殊化学品控股有限公司 Mixtures of fluorescent whitening agents

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1469821B2 (en) * 1959-06-24 1972-03-23 Badische Anilin & Soda Fabrik AG, 6700 Ludwigshafen Optical brighteners for macromolecular organic substances
CH533670A (en) * 1968-12-05 1973-02-15 Ciba Geigy Ag Inorganic white pigments containing optical brighteners
DE2037854C2 (en) * 1970-07-30 1983-07-07 Bayer Ag, 5090 Leverkusen 3- (4-Chloro-1-pyrazolyl) -7-v-triazol-2-yl-coumarin compounds and their use for optical brightening
JPS51100522A (en) * 1975-03-01 1976-09-04 Kubota Ltd SAGYOKI RATSUKABOSHISOCHI
JPS544973A (en) * 1977-06-13 1979-01-16 Daiken Trade & Industry Waterproof treatment for board

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
"The Chemistry of Synthetic Dyes", Band V, Kapital VIII, Venkataraman *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3313332A1 (en) * 1983-04-13 1984-10-18 Hoechst Ag, 6230 Frankfurt Mixtures of optical brighteners for brightening polyvinyl chloride

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