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EP0023026B1 - Mixtures of optical brighteners and their use - Google Patents

Mixtures of optical brighteners and their use Download PDF

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Publication number
EP0023026B1
EP0023026B1 EP80104161A EP80104161A EP0023026B1 EP 0023026 B1 EP0023026 B1 EP 0023026B1 EP 80104161 A EP80104161 A EP 80104161A EP 80104161 A EP80104161 A EP 80104161A EP 0023026 B1 EP0023026 B1 EP 0023026B1
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Prior art keywords
alkyl
denotes
group
phenyl
alkoxy
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German (de)
French (fr)
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EP0023026A1 (en
Inventor
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

  • alkyl and alkoxy groups and other groups derived therefrom contain 1 to 4 carbon atoms.
  • non-chromophore 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.
  • Mixtures according to the invention of optical brighteners consisting of a compound of formula 1 are also preferred and 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 O 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 is hydrogen or (C 1 ⁇ C 4 ) -alkyl, R 15 is phenyl, halophenyl, (C 1 ⁇ C 4 ) -alkylphenyl or (C 1 ⁇ C 4 ) -lkoxyphenyl, R 22 is (C 1 -C 4 ) -alkyl and R 23 is cyano or carbo- (C I -C 4 ) -alkoxy, where R 3 is hydrogen or (C 1 ⁇ C 6 ) alkyl, (C 1 ⁇ C 6 ) chloroalkyl, (C 1 ⁇
  • optical brighteners consisting of a compound of the formula 1 a and one or more compounds of the following formulas are also preferred.
  • 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 (C 1 ⁇ C 3 ) alkyl and R 15 is phenyl, 4-methylphenyl, or R 1 is hydrogen, methyl or t-butyl in the 5-position, R 2 is hydrogen or methyl in the 7-position and B is phenyl, where R 3 is hydrogen or methoxy, or or where R 2 is hydrogen or methyl.
  • R 1 " and R 2" are hydrogen or alkyl and B "is a group of the formulas and R 14 " denotes alkyl or methoxyethyl.
  • R 1 " and R 2" are hydrogen or alkyl and B "is a group of the formulas and R 14 " denotes alkyl or methoxyethyl.
  • R 14 denotes alkyl or methoxyethyl.
  • the mixing ratio for the individual components is between 0.05 and 0.95, preferably 0.20-0.80 parts by weight for the compounds of formula 1 and correspondingly 0.95 to 0.05, preferably 0.80-0 , 20 parts by weight for the other compounds of the formulas 2 to 6.
  • These compounds of the formulas 2 to 6 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.
  • the optimal mixing ratio of all compounds of the formulas 1 to 6 depends in individual cases on the structure of the respective compounds and can easily be determined by simple preliminary tests.
  • the individual components are dispersed in a liquid medium, for. B. brought water 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 blended fabrics which consist of linear polyesters and other synthetic or natural fibers, 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 addition of accelerators (carriers) or using the thermosol process.
  • the water-insoluble brightener and the mixtures according to the invention can also be used in organic solvents, for. B. 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 there is a moisture absorption of approx. 80%. 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 ° C. [table (a)] or 210 ° C. [table (b)].
  • the specified degrees of whiteness according to Ganz were obtained. The degrees of whiteness were measured using a DMC-25 spectrophotometer (from Carl Zeiss, Oberkochen).

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Detergent Compositions (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Abstract

Mixtures of optical brighteners consisting of 5 to 95% by weight of a compound of the formula <IMAGE> in which A denotes a o- or p-cyanophenyl group, and 95 to 5% by weight of one or more further 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). Darüber hinaus ist aus der französischen Patentschrift 1 415 977 der Einsatz von 1,4-Bis-(cyano-4-styryl)-benzol und 1,4-Bis-(cyano-2-styryl)-benzol als optische Aufheller bekannt. Aus Chemical Abstracts Bd. 83, Nr. 8, S. 165, Nr. 61504 c (1975) ist ferner die Verwendung eines Gemisches der letztgenannten Verbindung mit einem Naphthalimid-Derivat zum optischen Aufhellen bekannt. Es wurde nun gefunden, daß man die Wirkung dieser Einzelkomponenten noch deutlich steigern kann, wenn man das 1,4-Bis-(cyano-4-styryl)-benzol mit weiteren Aufhellern der im folgenden aufgeführten Formeln 2 bis 6 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, the use of 1,4-bis (cyano-4-styryl) benzene and 1,4-bis (cyano-2-styryl) benzene as optical brighteners is known from French patent specification 1,415,977. Chemical Abstracts Vol. 83, No. 8, p. 165, No. 61504 c (1975) also discloses the use of a mixture of the latter compound with a naphthalimide derivative for optical brightening. It has now been found that the effect of these individual components can be significantly increased if the 1,4-bis (cyano-4-styryl) benzene is mixed with further brighteners of the formulas 2 to 6 listed below.

Gegenstand der vorliegenden Erfindung sind Mischungen von an sich bekannten optischen Aufhellern mit verbesserten Eigenschaften bestehend aus 0,05-0,95 Gew.-Teilen einer Verbindung der Formel 1

Figure imgb0001
und 0,95 bis 0,05 Gew.-Teilen einer oder mehrerer Verbindungen der Formeln 2, 3, 4, 5 und 6
Figure imgb0002
Figure imgb0003
Figure imgb0004
Figure imgb0005
und
Figure imgb0006
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―C9Alkyl, 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,
  • B Cyano, eine Gruppe der Formel ―COOR11 oder CONR11 R11 wobei R11 Wasserstoff, C1―C18Alkyl, Cycloalkyl, Aryl, Alkylaryl, Halogenaryl, Aralkyl, Alkoxyalkyl, Hglogenalkyl, 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 imgb0007
    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 imgb0008
    oder
    Figure imgb0009
    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- oder Arylreste 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 imgb0010
    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 imgb0011
    bedeutet, worin 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 (C1 bis C4)-Alkyl bedeuten,
    oder B eine Gruppe der Formel
    Figure imgb0012
    bedeutet, worin R15 einen Phenylring, der durch ein oder zwei Chloratome, ein oder zwei Alkyl-oder Alkoxyalkylgruppen, eine Phenyl-, Cyano-, Carboxy-, Carboalkoxy-, Carbonsäureamid-, Sul- . fonsäure-, 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 imgb0013
    bedeutet, worin R16 Wasserstoff, C2-C8-Alkanoyl, Benzoyl oder ein Rest der Formel
    R18NHCO- oder R19OCO-
    und R17 Wasserstoff, Alkyl oder Phenyl, R18 Alkyl, Phenyl, Halogenphenyl oder Tolyl und R19 C1-C8-Aklyl, Alkoxyalkyl, Cyclohexyl, Benzyl, Phenyläthyl oder gegebenenfalls durch nichtchromophore Substituenten substituiertes Phenyl ist,
    oder R5 einen Rest der Formel
    Figure imgb0014
    bedeutet, worin R20 C1-C10-Alkyl, C1-C6-Alkenyl, C2-C6-Alkinyl, C1-C8-Alkoxy, C1-C8-Alkyl-oder Dialkylamino, Phenoxymethyl, Phenyl, Tolyl, Benzyl oder Phenyläthyl und R21 C3-C10-Alkyl ist, das durch Phenyl, Hydroxyphenyl, Methoxy oder Dimethoxy substituiert sein kann,
  • R6 einen gegebenenfalls durch nicht-chromophore Substituenten substituierten Arylrest, einen 1,2,4-Triazo)-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 O 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 nicht-chromophore 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 imgb0015
    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 R9 hat und zusätzlich ein Chloratom bedeuten kann, und
  • V eine Gruppe der Formeln
    Figure imgb0016
    bedeutet.
The present invention relates to mixtures of optical brighteners known per se with improved properties consisting of 0.05-0.95 parts by weight of a compound of the formula 1
Figure imgb0001
 and 0.95 to 0.05 part by weight of one or more compounds of the formulas 2, 3, 4, 5 and 6
Figure imgb0002
Figure imgb0003
Figure imgb0004
Figure imgb0005
 and
Figure imgb0006
 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, carboxamide, 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,
  • B 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, hglogenalkyl, hydroxyalkyl, alkylaminoalkyl, carboxyalkyl or carboalkoxyalkyl or two alkyl or alkylene radicals with the meaning of R 11 together with the nitrogen atom can also form a morpholine, piperidine or piperazine ring, or B is a group of the formula
    Figure imgb0007
     means in which 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 is a group of formulas
    Figure imgb0008
     or
    Figure imgb0009
     means, wherein R 14 is a straight-chain or branched alkyl group with 1-18 C atoms, preferably 1-6 C atoms, which are substituted by hydroxyl groups, halogen atoms, alkoxy, dialkylamino, alkylmercapto, chloroaryloxy, 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 imgb0010
     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 imgb0011
     means in which R ', R ", R ‴ represent a hydrogen atom, a lower alkyl radical or a phenyl radical, and wherein the lower alkyl radicals are represented 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 1 to C 4 ) alkyl,
    or B is a group of the formula
    Figure imgb0012
     means, wherein R 15 is a phenyl ring which is substituted by one or two chlorine atoms, one or two alkyl or alkoxyalkyl groups, a phenyl, cyano, carboxy, carboalkoxy, carboxamide, sul. fonic acid, sulfonic acid amide or sulfonic acid alkyl ester group may be substituted,
  • 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 imgb0013
     means wherein R 16 is hydrogen, C 2 -C 8 alkanoyl, benzoyl or a radical of the formula
    R 18 NHCO- or R 19 OCO-
    and R 17 is hydrogen, alkyl or phenyl, R 18 is alkyl, phenyl, halophenyl or tolyl and R 19 is C 1 -C 8 -alkyl, alkoxyalkyl, cyclohexyl, benzyl, phenylethyl or phenyl optionally substituted by non-chromophoric substituents,
    or R 5 is a radical of the formula
    Figure imgb0014
     where R 20 is C 1 -C 10 alkyl, C 1 -C 6 alkenyl, C 2 -C 6 alkynyl, C 1 -C 8 alkoxy, C 1 -C 8 alkyl or dialkylamino, phenoxymethyl, Is phenyl, tolyl, benzyl or phenylethyl and R 21 is C 3 -C 10 alkyl, which can be substituted by phenyl, hydroxyphenyl, methoxy or dimethoxy,
  • R 6 is an aryl radical which is optionally substituted by non-chromophoric substituents, a 1,2,4-triazo) -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 with 1-3 heteroatoms, preferably N or O, which can be substituted by alkyl, alkoxy, halogen, aryl or haloaryl, or R 6 is a 1-oxa-2,4-diazol-5-yl -Rest means which can be substituted by benzyl, alkoxyphenyl, styryl, halogen, alkoxy or another heterocyclic group or R 6 is a benzimidazol-1-yl, benzimidazol-2-yl, benzothiazol-1-yl or benzothiazole 2-yl radical, which can 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 bonded via a nitrogen atom, which is represented 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 imgb0015
     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 carbalkylmercapto group,
  • R 10 independently of R 8 has the same meaning as R 9 and can additionally represent a chlorine atom, and
  • V is a group of formulas
    Figure imgb0016
     means.

Bevorzugt sind Verbindungen der Formel worin A für eine p-Cyanophenylgruppe steht.Compounds of the formula in which A represents a p-cyanophenyl group are preferred.

Soweit nicht anders definiert, enthalten Alkyl- und Alkoxygruppen sowie andere, davon abgeleitete Gruppen 1 bis 4 C-Atome. Unter dem Begriff >nichtchromophpre 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-chromophore 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.

Von den Verbindungen unter den Formeln 2 bis 6 sind in den erfindungsgemäßen Gemischen die Verbindungen der folgenden Formeln bevorzugt:

  • Formel 2:
    Figure imgb0017
    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 imgb0018
    Figure imgb0019
    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 3:
    Figure imgb0020
    wobei R3' Wasserstoff oder Alkoxy, R4' Alkoxy und R5, Alkyl, Alkoxyalkyl oder Dialkylaminoalkyl bedeutet.
  • Formel 4:
    Figure imgb0021
    wobei R6' Phenyl oder die Gruppe der Formel
    Figure imgb0022
    und R7' die Gruppen der Formeln
    Figure imgb0023
    bedeutet.
  • Formel 5:
    Figure imgb0024
  • Formel 6:
    Figure imgb0025
    wobei R1' und R2' Wasserstoff oder Alkyl und V' eine Gruppe der Formeln
    Figure imgb0026
    und X 0 oder S bedeutet.
Of the compounds of the formulas 2 to 6, the compounds of the following formulas are preferred in the mixtures according to the invention:
  • Formula 2:
    Figure imgb0017
     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 imgb0018
    Figure imgb0019
     means, wherein R 14 'is 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, R 15' is phenyl which can be substituted by one or two chlorine atoms, one or two alkyl, alkoxyalkyl groups, a phenyl, cyano, carboxylic acid, carboalkoxy, carboxylic acid amide, sulfonic acid, sulfonic acid amide or sulfonic acid alkyl ester group, R 23 cyano or carboalkoxy and R 22 Alkyl means.
  • Formula 3:
    Figure imgb0020
     wherein R 3 'is hydrogen or alkoxy, R 4' alkoxy and R 5 , alkyl, alkoxyalkyl or dialkylaminoalkyl.
  • Formula 4:
    Figure imgb0021
     where R 6 'is phenyl or the group of the formula
    Figure imgb0022
     and R 7 ' the groups of the formulas
    Figure imgb0023
     means.
  • Formula 5:
    Figure imgb0024
  • Formula 6:
    Figure imgb0025
     where R 1 ' and R 2' are hydrogen or alkyl and V 'is a group of the formulas
    Figure imgb0026
     and X represents 0 or S.

Bevorzugt sind auch erfindungsgemäße Mischungen von optischen Aufhellern bestehend aus einer Verbindung der Formel 1

Figure imgb0027
und einer oder mehreren Verbindungen der Formeln 2b―6b
Figure imgb0028
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 O oder 1 und B eine Cyano- oder Carbo-(C1-C4)-alkoxygruppe oder eine Gruppe der Formeln
Figure imgb0029
oder
Figure imgb0030
bedeutet, wobei R14 (C1―C6)-Alkyl, (C1―C6)-Chloralkyl, (C1―C4)-Alkoxy-(C1―C4)-alkyl, Hydroxy-(C1―C4)-alkyl oder eine Gruppe der Formel ―(CH2CH2O)n―R, n 2 oder 3 und R Wasserstoff oder (C1―C4)-Alkyl, R15 Phenyl, Halogenphenyl, (C1―C4)-Alkylphenyl oder (C1―C4)-Mlkoxyphenyl, R22 (C1-C4)-Alkyl und R23 Cyano oder Carbo-(CI-C4)-alkoxy bedeutet,
Figure imgb0031
wobei R3 Wasserstoff oder (C1―C4)-Alkoxy, R4 (C1―C4)-Alkoxy und R6 (C1―C6)-Alkyl oder (C1―C4)-Alkoxy-(C1―C4)-alkyl bedeutet,
Figure imgb0032
wobei R6 Phenyl oder die Gruppe der Formeln
Figure imgb0033
und R7 eine Gruppe der Formel
Figure imgb0034
bedeutet, worin R1 Wasserstoff oder (C1―C4)-Alkyl und R2 Phenyl oder (C1―C4)-Alkoxy oder R1 und R2 zusammen einen Benzo- oder (1,2-d) Naphthoring darstellen,
Figure imgb0035
wobei R8 die Pyrenylgruppe und R9 und R10 (C1―C4)-Alkoxy bedeutet,
Figure imgb0036
wobei R1 und R2 die gleiche Bedeutung haben wie bei Formel 2b und V eine Gruppe der Formeln
Figure imgb0037
und
Figure imgb0038
bedeutet.Mixtures according to the invention of optical brighteners consisting of a compound of formula 1 are also preferred
Figure imgb0027
 and one or more compounds of the formulas 2b ― 6b
Figure imgb0028
 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 O or 1 and B. a cyano or carbo (C 1 -C 4 ) alkoxy group or a group of the formulas
Figure imgb0029
 or
Figure imgb0030
 means, where 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 is hydrogen or (C 1 ―C 4 ) -alkyl, R 15 is phenyl, halophenyl, (C 1 ―C 4 ) -alkylphenyl or (C 1 ―C 4 ) -lkoxyphenyl, R 22 is (C 1 -C 4 ) -alkyl and R 23 is cyano or carbo- (C I -C 4 ) -alkoxy,
Figure imgb0031
 where R 3 is hydrogen or (C 1 ―C 4 ) alkoxy, R 4 (C 1 ―C 4 ) alkoxy and R 6 (C 1 ―C 6 ) alkyl or (C 1 ―C 4 ) alkoxy- ( C 1 ―C 4 ) alkyl means
Figure imgb0032
 where R 6 is phenyl or the group of the formulas
Figure imgb0033
 and R 7 is a group of the formula
Figure imgb0034
 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 imgb0035
 where R 8 is the pyrenyl group and R 9 and R 10 are (C 1 ―C 4 ) alkoxy,
Figure imgb0036
 where R 1 and R 2 have the same meaning as in formula 2b and V is a group of the formulas
Figure imgb0037
 and
Figure imgb0038
 means.

Bevorzugt sind auch Mischungen von optischen Aufhellern bestehend aus einer Verbindung der Formel 1 a und einer oder mehreren Verbindungen der folgenden Formeln.

Figure imgb0039
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 imgb0040
worin R14 und R22 (C1―C3)-Alkyl und R15 Phenyl, 4-Methylphenyl ist, oder R1 Wasserstoff, Methyl oder t-Butyl in 5-Stellung, R2 Wasserstoff oder Methyl in 7-Stellung und B Phenyl ist,
Figure imgb0041
wobei R3 Wasserstoff oder Methoxy ist,
Figure imgb0042
Figure imgb0043
oder
Figure imgb0044
Figure imgb0045
Figure imgb0046
Figure imgb0047
oder
Figure imgb0048
wobei R2 Wasserstoff oder Methyl ist.Mixtures of optical brighteners consisting of a compound of the formula 1 a and one or more compounds of the following formulas are also preferred.
Figure imgb0039
 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 imgb0040
 wherein R 14 and R 22 (C 1 ―C 3 ) alkyl and R 15 is phenyl, 4-methylphenyl, or R 1 is hydrogen, methyl or t-butyl in the 5-position, R 2 is hydrogen or methyl in the 7-position and B is phenyl,
Figure imgb0041
 where R 3 is hydrogen or methoxy,
Figure imgb0042
Figure imgb0043
 or
Figure imgb0044
Figure imgb0045
Figure imgb0046
Figure imgb0047
 or
Figure imgb0048
 where R 2 is hydrogen or methyl.

Ganz besonders bevorzugt sind von den Verbindungen unter der Formel 2 die Verbindungen der Formel

Figure imgb0049
wobei R1" und R2" Wasserstoff oder Alkyl und B" eine Gruppe der Formeln
Figure imgb0050
Figure imgb0051
und R14" Alkyl oder Methoxyäthyl bedeutet. Von besonderer Wichtigkeit sind die folgenden Verbindungen unter der Formel 2:
Figure imgb0052
und
Figure imgb0053
 Of the compounds under formula 2, the compounds of the formula are very particularly preferred
Figure imgb0049
 where R 1 " and R 2" are hydrogen or alkyl and B "is a group of the formulas
Figure imgb0050
Figure imgb0051
 and R 14 " denotes alkyl or methoxyethyl. Of particular importance are the following compounds under formula 2:
Figure imgb0052
 and
Figure imgb0053

Das Mischungsverhältnis für die einzelnen Komponenten liegt zwischen 0,05 und 0,95, vorzugsweise 0,20-0,80 Gew.-Teilen für die Verbindungen der Formel 1 und entsprechend 0,95 bis 0,05, vorzugsweise 0,80-0,20 Gew.-Teilen für die übrigen Verbindungen der Formeln 2 bis 6. Diese Verbindungen der Formeln 2 bis 6 können einzeln aber auch in beliebiger Mischung untereinander eingesetzt werden, wobei das Mischungsverhältnis dieser Verbindungen untereinander gänzlich unkritisch ist und beliebig variiert werden kann. Gleiches gilt für die beiden unter Formel 1 fallenden Aufheller die sowohl einzeln als auch im Gemisch unter allen denkbaren Mischungsverhältnissen eingesetzt werden können.The mixing ratio for the individual components is between 0.05 and 0.95, preferably 0.20-0.80 parts by weight for the compounds of formula 1 and correspondingly 0.95 to 0.05, preferably 0.80-0 , 20 parts by weight for the other compounds of the formulas 2 to 6. These compounds of the formulas 2 to 6 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. The same applies to the two brighteners falling under Formula 1, which can be used both individually and in a mixture under all conceivable mixing ratios.

Das optimale Mischungsverhältnis allerVerbindungen der Formeln 1 bis 6 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 of the formulas 1 to 6 depends in individual cases on the structure of the respective compounds and can easily be 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 und ergeben bereits bei niedrigen Temperaturen, z. B. 150°C, hervorragende Weißgrade.As is usual with optical brighteners, the individual components are dispersed in a liquid medium, for. B. brought water 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 blended fabrics which consist of linear polyesters and other synthetic or natural fibers, 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 addition of accelerators (carriers) or using the thermosol process. The water-insoluble brightener and the mixtures according to the invention can also be used in organic solvents, for. B. 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 result is an excellently lightened product with excellent lightfastness and resistance to oxidizing and reducing agents. These mixtures according to the invention have a higher degree of whiteness than the mixtures of the Japanese patent Sho 50 (1975) -25,877 and result even at low temperatures, e.g. B. 150 ° C, excellent degrees of 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 1 und 3 mit einer Einsatzmenge von 0,08 Gew.-% oder ein Gemisch aus 0,064 Gew.-%, 0,04 Gew.-% und 0,016 Gew.-%des Aufhellers der Formel I mit 0,016, 0,04 bzw. 0,064 Gew.-% der Aufheller der Formel 3 enthalten.
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 1 and 3 with an amount of 0.08% by weight or a mixture of 0.064% by weight, 0.04% by weight and 0.016% by weight of the brightener of the formula I with 0.016, 0.04 and 0.064% by weight of the brightener of the formula 3, respectively.

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°C [Tabelle (a)] bzw. 210°C [Tabelle (b)] thermosoliert. Dabei wurden die jeweils angegebenen Weißgrade nach Ganz erhalten. Die Weißgrade wurden mit einem Spektralphotometer Typ DMC-25 gemessen (Firma Carl Zeiss, Oberkochen).

Figure imgb0054
The material is squeezed between rollers with a padder so that there is a moisture absorption of approx. 80%. 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 ° C. [table (a)] or 210 ° C. [table (b)]. The specified degrees of whiteness according to Ganz were obtained. The degrees of whiteness were measured using a DMC-25 spectrophotometer (from Carl Zeiss, Oberkochen).
Figure imgb0054

Claims (6)

1. Mixtures of optical brighteners known as such consisting of 0.05-0.95 parts by weight of a compound of the formula 1
Figure imgb0105
and 0.95 to 0.05 parts by weight of one or more compounds of the formulae 2, 3, 4, 5 or 6
Figure imgb0106
Figure imgb0107
Figure imgb0108
Figure imgb0109
and
Figure imgb0110
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―C9alkyl, 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, a group of the formula ―COOR11 or CONR11 R11 in which R11 denotes hydrogen, C1―C18alkyl, 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 imgb0111
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, it being possible for two adjacent radicals R12 and R13 together also to represent an alkylene group, a fused benzo ring or a 1,3-dioxapropylene group, or B denotes a group of the formulae
Figure imgb0112
or
Figure imgb0113
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 dialkylamino alkyl 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 alkylthio- alkoxyalkyl, 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 imgb0114
R22 denotes a hydrogen atom, a triphenylmethyl group or a lower alkyl radical, which is optionally substituted by a lower carbalkoxy, carboxamido, mono- or di-alkylcarboxamido, carboxyl or benzoyl group, and R23 denotes a cyano group or a group of the formulae
Figure imgb0115
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, Y denotes 0, S or N-R, in which R is H or (C1 to C4)-alkyl, or B denotes a group of the formula
Figure imgb0116
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 rester group,
R3 and R4 can be identical or different and denote hydrogen, alkyl, cycloalkyl, alkoxy, hydroxyalkoxy- ethyl, halogenoalkyl, aralkyl, aryl or N,N-di-alkylamine, or R3 and R4 together form a five-membered heterocyclic radical having 1 to 3 hetero-atoms, preferably N atoms,
R5 denotes straight-chain or branched alkyl, alkoxyalkyl, dialkylaminoalkyl or a radical of the formula
Figure imgb0117
in which R16 is hydrogen, C2―C8-alkanoyl, benzoyl or a radical of the formula R18NHCO- or R19OCO- 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 imgb0118
in which R20 is C1―C10-alkyl, C2―C6-alkenyl. C2―C6-alkinyl. C1―C8-alkoxy. C1―C8-alkylamino or dialkylamino, phenoxymethyl, phenyl, tolyl, benzyl or phanylethyl and R21 is C3―C10-alkyl, which can be substituted by phenyl, hydroxyphenyl, methoxy or dimethoxy,
R6 denotes an aryl radical, which is optionally substituted by nonchromophoric 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 can optionally 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 hetero-atoms, preferably N or O, which can be substituted by alkyl, alkoxy, halogen, aryl or halogenoaryl, or R6 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, benz- imidazol-2-yl, benzthiazol-1-yl 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 O 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 halogenostyryl, a fused phenyl, naphthyl or phenanthryl ring or a fused group of the formulae
Figure imgb0119
and the aromatic rings in the fused groups can also be substitute 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 morpholino ring, or R9 represents an alkoxy, hydroxyalkoxy, acyloxy, alkylthio or carbalkyl- mercapto group,
R10 independently of R8 has the same meaning as R9 and in addition can denote a chlorine atom and
V denotes a group of the formulae
Figure imgb0120
2. Mixtures of optical brighteners as claimed in claim 1, consisting of a compound of the formula
Figure imgb0121
and one or more compounds of the formulae 2a-6a
Figure imgb0122
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 imgb0123
Figure imgb0124
in which R14, denotes alkyl, chloroalkyl, alkoxyalkyl, hydroxyalkyl 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, carboalkoxy, carboxamide, sulfonic acid, sulfonamide or sulfonic acid alkyl ester group, R23 denotes cyano or carboalkoxy and R22 denotes alkyl,
Figure imgb0125
in which R3, denotes hydrogen or alkoxy, R4, denotes alkoxy and R5, denotes alkyl, alkoxyalkyl or dialkylaminoalkyl,
Figure imgb0126
in which R6. denotes phenyl or the group of the formula
Figure imgb0127
and R7, denotes the groups of the formulae
Figure imgb0128
Figure imgb0129
and
Figure imgb0130
in which R1, and R2, denote hydrogen or alkyl and V' denotes a group of the formulae
Figure imgb0131
and X denotes 0 or S.
3. Mixtures of optical brighteners as claimed in claim 1, consisting of a compound of the formula 1 a
Figure imgb0132
and one or more compounds of the formulae 2b-6b
Figure imgb0133
in which R1 in the 5-position denotes a hydrogen or chlorine atom or a methyl or phenyl group and R2 denotes a hydrogen atom, or R1 and R2 both denote 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 imgb0134
or
Figure imgb0135
in which R14 denotes (C1―C6)-alkyl, (C1―C6)-chloroalkyl, (C1―C4)-alkoxy-(C1―C4)-alkyl, hydroxy-(C1―C4)-alkyl or a group of the formula ―(CH2CN2O)n―R, n denotes 2 or 3 and R denotes hydrogen or (C1―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 imgb0136
in which R3 denotes hydrogen or (C1―C4)-alkoxy, R4 denotes (C1―C4)-alkoxy and R5 denotes (C1―C6)-alkyl or (C1―C4)-alkoxy-(C1―C4)-alkyl,
Figure imgb0137
in which R6 denotes phenyl or the group of the formulae
Figure imgb0138
and R7 denotes a group of the formula
Figure imgb0139
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 imgb0140
in which R8 denotes the pyrenyl group and R9 and R10 denote (C1―C4)-alkoxy, and
Figure imgb0141
in which R1 and R2 have the same meaning as in formula 2b and V denotes a group of the formulae
Figure imgb0142
or
Figure imgb0143
4. Mixtures of optical brighteners as claimed in claim 1, consisting of a compound of the formula 1 and one or more compounds of the following formulae
Figure imgb0144
in which R1 and R2 in the 5,6-position are methyl and B is carbomethoxy, or R1 is hydrogen, R2 is hydrogen or methyl in the 5-position and B is carbomethoxy, cyano or a group of the formulae
Figure imgb0145
in which R14 and R22 are (C1―C3)-alkyl and R15 is phenyl, 4-methylphenyl or 4-methoxyphenyl, or R1 is hydrogen, methyl or t-butyl in the 5-position, R2 is hydrogen or methyl in the 7-position and B is phenyl,
Figure imgb0146
in which R3 is hydrogen or methoxy,
Figure imgb0147
Figure imgb0148
or
Figure imgb0149
Figure imgb0150
and
Figure imgb0151
Figure imgb0152
or
Figure imgb0153
in which R2 is hydrogen or methyl.
5. Mixtures of optical brighteners as claimed in claims 1 to 4, consisting of 20 to 80% by weight of a compound of the formula 1 and 80 to 209%by weight of one or more compounds of the formulae 2 to 6.
6. Use of the brightener mixtures as claimed in claim 1 to 5 for brightening polyester fibers.
EP80104161A 1979-07-21 1980-07-16 Mixtures of optical brighteners and their use Expired EP0023026B1 (en)

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DE3066691D1 (en) 1984-03-29
PH16626A (en) 1983-12-05
CA1153160A (en) 1983-09-06
AU6063880A (en) 1981-01-22
EP0023026A1 (en) 1981-01-28
DE2929591A1 (en) 1981-02-05
ATE6375T1 (en) 1984-03-15
ZA804367B (en) 1981-07-29
JPH0116868B2 (en) 1989-03-28
ES493375A0 (en) 1981-05-16
ES8105054A1 (en) 1981-05-16
US4336155A (en) 1982-06-22
AU533250B2 (en) 1983-11-10
JPS5618656A (en) 1981-02-21
BR8004499A (en) 1981-01-27

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