EP0035694A1 - Mixtures of optical brighteners - Google Patents

Abstract

Mixtures of optical brighteners consisting of (a) 1 to 99 weight % of one or several compounds of the formula 1 <IMAGE> (1) (b) 99 to 1 weight % of one or several compounds of the formula 2 <IMAGE> (2) wherein n is 0 or 1, X is oxygen or sulfur, B is a group of the formulae <IMAGE> +TR <IMAGE> and the other substituents are defined a specified in the description.

Description

It is known that mixtures of optical brighteners can give a higher degree of whiteness than the respective individual components used in the same amount. Such synergism was observed in mixtures, their individual components very significantly differ in shade, such as at a viol _ß-tt stichi- gene and a greenish-Dlau single component. It has now been found that such a synergism, which manifests itself in an increase in the degree of whiteness, also occurs with those brighteners which differ only slightly in their nuance.

• a) 1 bis 99 Gew.% einer oder mehrerer Verbindungen der Formel 1,
  
  worin R₁, R gleich oder verschieden sein können und Wasserstoff oder Alkyl bedeuten, und
• b) 99 bis 1 Gew.% einer oder mehrerer Verbindungen der Formel 2
  
  wobei
  • n O oder 1,
  • X ein Sauerstoff- oder Schwefelatom,
  • R₃ und R₄ 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 bedeuten, wobei zwei benachbarte Reste R₃ und R₄ zusammen auch für einen Benzoring, eine niedere Alkylen- oder eine 1,3-Dioxapropylengruppe stehen können,
  • B Cyano, eine Gruppe der Formel -COOR₅ oder CONR₅R₅, wobei R₅ Wasserstoff, C₁-C₁₈Alkyl, Cycloalkyl, Aryl, Alkylaryl, Halogenaryl, Aralkyl, Alkoxyalkyl, Halogenalkyl, Hydroxyalkyl, Alkylaminoalkyl, Carboxyalkyl oder Carboalkoxyalkyl bedeutet oder zwei Alkyl- bzw. Alkylenreste unter der Bedeutung von R₅ zusammen mit dem Stickstoffatom auch einen Morpholin-, Piperidin- oder Piperazinring bilden können, bedeutet, oder B
• B eine Gruppe der Formeln
  
  oder
  
  bedeutet
  wobei R₆ eine geradkettige oder verzweigte Alkygruppe 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 R₆ eine Gruppe der Formel -(CH₂CH₂0)_n-R mit n 1, 2 oder 3 und R=H, Alkyl, eine Dialkylaminoalkoxyalkyl oder Alkylthioalkoxyalkylgruppe, wobei die Dialkylgruppen im Dialkylaminoalkoxyalkyl zusammen einen Piperidin-, Pyrrolidin-, Hexamethylenimen-, Morpholin- oder Piperazinring bilden können, oder R₆ einen Rest der Formel
  
  bedeutet, worin R₉ und R₁₀ 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 R₉ und R₁₀ zusammen auch für eine Alkylengruppe, einen ankondensierten Benzoring oder eine 1,3-Dioxapropylengruppe stehen können, R₇ 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 R₈ eine Cyangruppe oder eine Gruppe der Formeln
  
  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 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
  
  bedeutet, worin X ein Sauerstoff- oder Schwefelatom, R₁₁ einen Phenylring, der durch ein oder zwei Chloratome, ein oder zwei Alkyl- oder Alkoxyalkylgruppen, eine Phenyl-, Cyano-, Carboxy-, Carbalkoxy-, Carbonsäureamid-, Sulfonsäure-, Sulfonsäureamid- oder Sulfonsäurealkylestergruppe substituiert sein kann, bedeutet.

The invention relates to mixtures of optical brighteners consisting of

• a) 1 to 99% by weight of one or more compounds of the formula 1,
  
  wherein R ₁ , R may be the same or different and denote hydrogen or alkyl, and
• b) 99 to 1% by weight of one or more compounds of the formula 2
  
  in which
  • n O or 1,
  • X is an oxygen or sulfur atom,
  • R ₃ and R _{4 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, where two adjacent radicals R ₃ and R ₄ together also represent a benzo ring, a lower one Can be alkylene or a 1,3-dioxapropylene group,
  • B cyano, a group of the formula -COOR ₅ or CONR ₅ R ₅ , where R _{5 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 with the meaning of R ₅ together with the nitrogen atom can also form a morpholine, piperidine or piperazine ring, or B
• B is a group of formulas
  
  or
  
  means
  wherein R _{6 is} a straight-chain or branched alkyl group having 1 to 18 carbon atoms, preferably 1 to 6 carbon atoms, which is substituted by hydroxyl groups, halogen atoms, alkoxy, dialkylamino, alkylmercapto, chloroaryloxy, aryloxy, arylmercapto or aryl radicals can be, in the case of the dialkylaminoalkyl groups, the two alkyl groups together can also form a morpholine, piperidine or piperazine ring, or R _{6 is} a group of the formula - (CH ₂ CH ₂ 0) _n -R with n 1, 2 or 3 and R = H, alkyl, a dialkylaminoalkoxyalkyl or alkylthioalkoxyalkyl group, where the dialkyl groups in the dialkylaminoalkoxyalkyl together can form a piperidine, pyrrolidine, hexamethyleneimene, morpholine or piperazine ring, or R _{6 is} a radical of the formula
  
  means, wherein R ₉ and R _{10 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 ₉ and R ₁₀ together can also represent an alkylene group, a fused-on benzo ring or a 1,3-dioxapropylene group, R _{7 represents} a hydrogen atom, a triphenylmethyl group or a lower alkyl radical which may be replaced by a lower carbalkoxy, carbonamido or mono- or dialkylcarbonamido, carboxy or benzoyl group and R _{8 is} a cyano group or a group of the formulas
  
  means, wherein R ', R ", R"' represent a hydrogen atom, a lower alkyl radical or a phenyl radical, and wherein the lower alkyl radicals are substituted by hydroxyl, lower alkoxy, lower dialkylamino or lower halogen atoms, lower alkyl or lower alkoxy groups can be, and in which R ", R"'can also together form a saturated divalent radical, Y = 0, S or NR with R = H or (C ₁ to C ₄ ) alkyl, or B is a group of the formula
  
  means wherein X is an oxygen or sulfur atom, R _{11 is} a phenyl ring which is substituted by one or two chlorine atoms, one or two alkyl or alkoxyalkyl groups, a phenyl, cyano, carboxy, carbalkoxy, carboxamide, sulfonic acid, sulfonic acid or Alkyl sulfonate group may be substituted.

wobei R'₁ und R" die oben angegebene Bedeutung haben. Von den Verbindungen der Formel 2 sind die Verbindungen der Formel 2a bevorzugt

wobei R₃ und R₄ zusammen einen ankondensierten Phenylring oder in 5- und 7-Stellung Wasserstoff oder Chlor, Alkyl, Phenyl, X Sauerstoff oder Schwefel und B' eine Gruppe der Formeln

bedeutet, wobei R'₆ Alkyl, Chloralkyl, Alkoxyalkyl, Hydroxyalkyl oder eine Gruppe der Formel -(CH₂CH₂0)_n-^R bedeutet, wobei n 1, 2 oder 3 und R Wasserstoff oder Alkyl ist, R'₁₁ 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, R'₈ Cyano oder Carboalkoxy und R'₇ Alkyl bedeutet.Of the compounds of formula 1, the compounds of formula 1a are preferred

where R ' ₁ and R "have the meaning given above. Of the compounds of the formula 2, the compounds of the formula 2a are preferred

where R ₃ and R ₄ together form a fused phenyl ring or in the 5- and 7-position hydrogen or chlorine, alkyl, phenyl, X oxygen or sulfur and B 'a group of the formulas

means, wherein R ' _{6 is} alkyl, chloroalkyl, alkoxyalkyl, hydroxyalkyl or a group of the formula - (CH ₂ CH ₂ 0) _n - ^R , where n is 1, 2 or 3 and R is hydrogen or alkyl, R' _{11 is} phenyl , which can be substituted by one or two chlorine atoms, one or two alkyl, alkoxyalkyl groups, a phenyl, cyano, carboxylic acid, carboalkoxy, carboxamide, sulfonic acid, sulfonic acid amide or sulfonic acid alkyl ester group, R ' ₈ cyano or Carboalkoxy and R ' ₇ means alkyl.

wobei R"₃ und R"₄ Wasserstoff oder Alkyl, n 1 oder O und B" eine Gruppe der Formeln

-CN oder -COOAlkyl und R₆ Alkyl oder Methoxyäthyl bedeutet. Von besonderer Wichtigkeit sind die folgenden Verbindungen unter der Formel 2:

und

Of the compounds under formula 2, the compounds of the formula are very particularly preferred

where R " ₃ and R" _{4 are} hydrogen or alkyl, n 1 or O and B "is a group of the formulas

-CN or -COOalkyl and R _{6 is} alkyl or methoxyethyl. The following compounds under formula 2 are of particular importance:

and

Unless otherwise defined, alkyl and alkoxy groups and other groups derived therefrom contain 1 to 4 carbon atoms.

The compounds of formula 1 are known from DT-PS 1 594 834 and the compounds of formula 2 from DT-OS 2 709 924 as well as from the published Japanese patent applications Sho 51/40090 and Sho 70/4568.

The mixing ratio for the individual components is between 1 and 99% by weight for the compound of the formula 1 and correspondingly 99 to 1% by weight for the rest of the compound of the formula 2. These compounds of the formulas 1 and 2 can also be used individually any mixture can be used with each other, the mixing ratio of these compounds with one another is completely uncritical and can be varied as desired. A mixing ratio of 50 to 99% by weight for the compound of the formula 1 and 50 to 1% by weight of the compound of the formula 2 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.

As is usual with optical brighteners, the individual components are brought into the commercial form by dispersion in a liquid medium, for example water. 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. You can also mix these with good Use the result for blended fabrics that consist of linear polyesters and other synthetic or natural fibers, especially fibers containing hydroxyl groups, especially cotton. The application of these mixtures is done here in the normal manner for the application of optical brighteners conditions such as by the exhaust method at 90 ⁰ C to 130 ° C with or without the addition of accelerators (carriers), or by the thermosol process. The water-insoluble brighteners and the mixtures according to the invention can also be used in solution in organic solvents, for example perchlorethylene, fluorinated hydrocarbons. The textile material can be treated in the exhaust process with the solvent liquor, which contains the optical brightener dissolved, or one can impregnate, splash, spray the textile material with the brightener-containing solvent liquor and then dry at temperatures of 120-220 C, whereby the optical brightener remains completely is fixed in the fiber. This gives an excellently brightened product with excellent lightfastness and resistance to oxidizing and reducing agents, the degree of whiteness of the mixture being significantly higher than the degree of whiteness which can be achieved with the same amount of only one compound of formula 1 or 2.

The following examples illustrate the invention.

example 1

Fabric sections made of polyester staple fibers are washed, dried and impregnated onto a padder with aqueous dispersions which either contain only a brightener of the formula 1 or 2 for comparison or a mixture of both brighteners in a weight ratio of 8 to 2, based on the active substance. The brighteners of formula 1 are taken from a commercially available dispersion (20% setting). The brighteners of formula 2 are used in a 10% dispersion in polyvinyl alcohol.

The total amount of brightener is 1.66 g / l. The material is squeezed between rollers with a padder so that a moisture absorption of approx. 80% results. The material thus sealed is then dried at 110 ° C and thermosolated on a tenter at the temperatures given in the table. The specified degrees of whiteness according to Ganz were obtained. The degrees of whiteness were measured with a reflectance spectrophotometer type DMC-25 (Carl Zeiss, Oberkochen). The shade was determined according to the formula N = - 1132.0X + 725, OY + 115.46 by Ganz.

example 1

Example 2

und 20 Gew.-Teilen an Komponente 3 bzw. jeweils 100 mg der reinen Komponenten 3 und 4 werden in einer Mischung aus 5 ml Dimethylformamid und 5 ml eines 85 proz. Nonylphenol-oxethylats mit 22 - 26 Ethylenoxideinheiten klar gelöst und unter Rühren in 90 g Eiswasser gleichmäßig zugegeben. Mit dieser Dispersion wird dann wie bei Beispiel 1 weitergearbeitet.100 mg of a mixture consisting of 80 parts by weight of component 4

and 20 parts by weight of component 3 and 100 mg each of the pure components 3 and 4 are in a mixture of 5 ml of dimethylformamide and 5 ml of an 85 percent. Nonylphenol oxyethylate with 22 - 26 ethylene oxide units clearly dissolved and evenly added with stirring in 90 g of ice water. This dispersion is then used as in Example 1.

After thermosoling on PES staple fiber fabric at 190 ° and 30 seconds, the following degrees of whiteness are obtained:

Example 3

• a) 2 g/l des Aufhellers der Formel
• 
  b) 2 g/l des Aufhellers der Formel
  
• c) 2 g/l eines Gemischs aus 80 Gew.% des Aufhellers unter a) und 20 Gew.% des Aufhellers unter b).

The procedure is as given in Example 1 at a thermal insulation temperature of 200 ° C. It was used

• a) 2 g / l of the brightener of the formula
• 
  b) 2 g / l of the brightener of the formula
  
• c) 2 g / l of a mixture of 80% by weight of the brightener under a) and 20% by weight of the brightener under b).

The following degrees of whiteness were achieved:

Claims (5)

1) Mixtures of optical brighteners, characterized in that they consist of a) 1 to 99% by weight of one or more compounds of the formula 1

wherein R ₁ and R _{2 may be the} same or different and denote hydrogen or alkyl, and b) 99 to 1% by weight of one or more compounds of the formula 2

in which n 0 or 1, X is an oxygen or sulfur atom, _R3 and R 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, Are sulfonic acid, sulfonic acid amide or sulfonic acid alkyl esters, where two adjacent radicals R ₃ and R ₄ together can also represent a benzo ring, a lower alkylene or a 1,3-dioxapropylene group, B cyano, a group of the formula -COOR ₅ or CONR ₅ R ₅ , where R _{5 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 below the meaning of R ₅ together with the nitrogen atom can also form a morpholine, piperidine or piperazine ring; means or B is a group of formulas

or

means, - wherein R _{6 is} a straight-chain or branched alkyl group having 1 to 18 carbon atoms, preferably 1 to 6 carbon atoms, which is substituted by hydroxyl groups, halogen atoms, alkoxy, dialkylamino, alkylmercapto, chloroaryloxy, aryloxy, arylmercapto or aryl radicals can be substituted, where in the case of the dialkylaminoalkyl groups the two alkyl groups together can also form a morpholine, piperidine or piperazine ring, or R _{6 is} a group of the formula - (CH ₂ CH ₂ 0) _n -R with n 1, 2 or 3 and R = H, alkyl, a dialkylaminoalkoxyalkyl or alkylthioalkoxyalkyl group, where the dialkyl groups in the dialkylaminoalkoxyalkyl together can form a piperidine, pyrrolidine, hexamethyleneimene, morpholine or piperazine ring, or R _{6 is} a radical of the formula

means in which R ₉ and R _{10 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 ₉ and R ₁₀ together also represent an alkylene group can be fused benzo ring or a 1,3-dioxapropylene group, means pure 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 _{8 is} one Cyan group or a group of formulas

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, Y = O, S or NR with R = H or (C ₁ to C ₄ ) alkyl, or B is a group of the formula

means where X is an oxygen or sulfur atom, R _{11 is} a phenyl ring through one or two chlorine atoms, one or two alkyl or alkoxyalkyl groups, a phenyl, cyano, carboxy, carboalkoxy, carboxylic acid amide, sulfonic acid, sulfonic acid amide - Or sulfonic acid alkyl ester group can be substituted. 2) Mixtures of optical brighteners according to claim ₁ , characterized in that they are a compound of formula 1 as a compound of formula

contain, wherein R ₁ and R2 1ie have the meanings given in claim 1. 3) Mixtures of optical brighteners according to claim 1, characterized in that they are a compound of formula 2 as a compound of formula

contain, wherein R ' ₃ and R' ₄ together a fused phenyl ring or in the 5- and 7-position hydrogen or chlorine, alkyl, phenyl, X oxygen or sulfur and B 'a group of the formulas

is where R ' _{6 is} alkyl, chloroalkyl, alkoxyalkyl, hydroxyalkyl or a group of the formula - (CH ₂ CH ₂ 0) _n -R, where ₁ , 2 or 3 and R is hydrogen or alkyl, R' _{11 is} phenyl, 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 ' _{3 is} cyano or carboalkoxy and R' _{7 is} alkyl. 4) Mixtures of optical brighteners according to claim 1, characterized in that they are a compound of formula 2 as a compound of formula

contain, wherein R " ₃ and R" _{4 are} hydrogen or alkyl n O or 1 and B "a group of the formulas

-CN or -COOalkyl and R " _{6 means} alkyl or methyl ethyl. ₅ ) Mixtures of optical brighteners according to claim 1 to 4, characterized in that they contain 50 to 99% by weight of a compound of formula 1 and 50 to 1% by weight of a compound of formula 2.