DE4442291B4 - Triphendioxazine compounds - Google Patents

Abstract

wobei die mit A bezeichneten Kerne, unabhängig voneinander, linear, in 2,3- und 9,10-Stellung, oder angular, in 1,2- und 8,9- oder in 3,4- und 10,11-Stellung, anelliert Ringe mit den Restgliedern der Formeln -NR₁-(CO)_m-NH-, -CR₁=CH-CO-NH-, -O-CH₂-CO-NH-, -NR₁-(CO)_m-O-, -CO-CH=CR₁-NH-, -CO-NH-CO-NH-, -CO-NH-CR₂=N-, -CR₂=N-CO-NH- oder -NH-CR₁=N- enthalten,
R₁ Wasserstoff, C_1-4-Alkyl oder Phenyl,
R₂ Wasserstoff, C_1-4-Alkyl oder Phenyl
und m 1 oder 2 bedeuten,
wobei die angulären Moleküle in 3- und 10-Stellung, bzw. in 2- und 9-Stellung je eine C_1-2-Alkoxygruppe tragen können.The triphendioxazine compounds of the general formula I

the cores designated A being, independently of one another, linear, in the 2,3 and 9,10 position, or angular, in the 1,2 and 8,9 or in the 3,4 and 10,11 position, anneals rings with the residues of the formulas -NR ₁ - (CO) _m -NH-, -CR ₁ = CH-CO-NH-, -O-CH ₂ -CO-NH-, -NR ₁ - (CO) _m - O, -CO-CH = CR ₁ -NH-, -CO-NH-CO-NH-, -CO-NH-CR ₂ = N-, -CR ₂ = N-CO-NH- or -NH-CR ₁ = N- contained,
R _{1 is} hydrogen, C _1-4 -alkyl or phenyl,
R _{2 is} hydrogen, C _1-4 alkyl or phenyl
and m is 1 or 2,
wherein the angular molecules in the 3- and 10-position, respectively in the 2- and 9-position each carry a C _1-2 alkoxy group.

Description

wobei die mit A bezeichneten Kerne, unabhängig voneinander, linear, in 2,3- und 9,10-Stellung, oder angular, in 1,2- und 8,9- oder in 3,4- und 10,11-Stellung, anelliert Ringe mit der Restgliedern der Formeln -NR₁-(CO)_m-NH-, -CR₁=CH-CO-NH-, -O-CH₂-CO-NH-, -CO-CH=CR₁-NH-, -CO-NH-CO-NH-, -CO-NH-CR₂=N-, -CR₂=N-CO-NH-, -NR₁-(CO)_m-O- oder -NH-CR₁=N- enthalten,
R₁ Wasserstoff, C_1-4-Alkyl oder Phenyl,
R₂ Wasserstoff, C_1-4-Alkyl oder Phenyl
und m 1 oder 2 bedeuten,
wobei die angulären Moleküle in 3- und 10-Stellung, bzw. in 2- und 9-Stellung je eine C_1-2-Alkoxygruppe tragen können.The invention relates to the triphendioxazine compounds of general formula I.

the cores designated A being, independently of one another, linear, in the 2,3 and 9,10 position, or angular, in the 1,2 and 8,9 or in the 3,4 and 10,11 position, anneals rings with the residues of the formulas -NR ₁ - (CO) _m -NH-, -CR ₁ = CH-CO-NH-, -O-CH ₂ -CO-NH-, -CO-CH = CR ₁ -NH -, -CO-NH-CO-NH-, -CO-NH-CR ₂ = N-, -CR ₂ = N-CO-NH-, -NR ₁ - (CO) _m -O- or -NH-CR ₁ = N- contained,
R _{1 is} hydrogen, C _1-4 -alkyl or phenyl,
R _{2 is} hydrogen, C _1-4 alkyl or phenyl
and m is 1 or 2,
wherein the angular molecules in the 3- and 10-position, respectively in the 2- and 9-position each carry a C _1-2 alkoxy group.

Under the said alkyl and alkoxy radicals are those with 1 or 2 carbon atoms preferred.

worin n 1, 2 oder 3 bedeutet,
kondensiert. Falls die an den Ringen A annelierten Heterocyclen verschieden sind, müssen unterschiedliche Verbindungen der Formel II eingesetzt und Massnahmen für eine asymmetrische Kondensation getroffen werden.The preparation of these compounds is characterized in that one mole of 2,3,5,6-tetrachloro-1,4-benzoquinone with 2 moles of a compound of general formula II

where n is 1, 2 or 3,
condensed. If the heterocycles annealed at rings A are different, different compounds of formula II must be used and measures for asymmetric condensation must be taken.

The compounds of the formula II are known (see, for example DE-OS 28 55 883 ) or can be prepared without difficulty in analogy to known, described processes, or in another method familiar to the person skilled in the art.

vorzugsweise den Formeln a bis o.

wobei die mit * bezeichnete Bindung zum Stickstoffatom führt und
R₁ Wasserstoff, C_1-4-Alkyl oder Phenyl, vorzugsweise Wasserstoff, Methyl oder Aethyl und
R₂ Wasserstoff, C_1-4-Alkyl oder Phenyl vorzugsweise Wasserstoff, Methyl oder Aethyl bedeuten.In preferred pigments of the formula I, the formula parts correspond

preferably the formulas a to o.

where the bond denoted by * leads to the nitrogen atom and
R _{1 is} hydrogen, C _1-4 alkyl or phenyl, preferably hydrogen, methyl or ethyl and
R _{2 is} hydrogen, C _1-4 alkyl or phenyl, preferably hydrogen, methyl or ethyl.

At the Most preferred compounds of formula I are those in which both rings A correspond to the formula parts a) or j). The novel pigments of formula I are excellent for dyeing plastic compounds, among which solventless and solvent-containing Be understood masses of plastics or synthetic resins (in paints on oily or aqueous Basis, in paints of various kinds, for spin dyeing of Viscose or cellulose acetate, for pigmenting polyethylene, Polystyrene, polyvinyl chloride, rubber and artificial leather). You can also in printing inks for the graphic arts, for the pulp coloring, for the Coating of textiles or for pigment printing use.

The obtained dyeings are characterized by their excellent heat, light and weather fastness, chemical resistance, their color strength and the very good applicative properties, e.g. Flockulationsechtheit, Crystallization and dispersing fastness and in particular by their migrant, efflorescent, Overpainting and solvent fastness out.

By the aftertreatment of the crude pigments in organic solvents at elevated Temperatures, e.g. 110 ° -200 ° C can the Pigment properties are often further improved. As organic solvent (but in which the pigments themselves are not dissolved) come e.g. chlorobenzene (Mixture), nitrobenzene, dimethylformamide, dimethylacetamide, glacial acetic acid, Ethylene glycol or quinoline into consideration. This aftertreatment will preferably combined with a grinding or kneading operation.

In In the following examples, the parts parts by weight and the Percentages by weight. The temperatures are in degrees Celsius specified. One part by volume corresponds to the volume of one part by weight of water.

example 1

In 250 parts by volume of ethanol are 22 parts of 6-methoxy-5-amino-benzimidazolone- (2), 15 parts of chloranil (2,3,5,6-tetrachlorobenzoquinone) and 10 parts anhydrous sodium acetate registered. The mixture is heated with stirring to the boil, lets cooling down, filtered from the crystallized intermediate, it washed with Ethanol, then with water and dried.

26 parts of this intermediate are in 150 parts by volume H ₂ SO ₄ conc. and stirred for 12 hours at room temperature. It is then poured out on ice, the resulting pigment is filtered, washed with water until acid-free and dried, for example at 60 ° in vacuo. It is also possible to dilute the condensation mixture to 80%, filter off the pigment obtained and wash acid-free with 300 parts of 80% H ₂ SO ₄ , then with 150 parts of 50% H ₂ SO ₄ and with 2000 parts of water. The moist presscake is then suspended in 250 parts of dimethylacetamide and the remaining water distilled off at 100-150 °. After cooling to 120 °, the pigment is filtered, washed with 200 parts of cold dimethylacetamide and then with 100 parts of isopropanol and dried at 60 ° in vacuo.

Kunststoffe in violetten Tönen mit ausgezeichneter Migrier- und Lösungsmittelechtheit.The resulting pigment corresponds to the formula

Violet-colored plastics with excellent migration and solvent resistance.

After treatment:

In one heated to 75-78 ° Kneaders are 20 parts of the pigment prepared according to Example 1, with 23 parts of ethylene glycol and 160 parts of NaCl at 0.6 bar for 2 Kneaded for hours. Thereafter, it is suspended in 1500 parts of water and for Heated to 80 ° for 2 hours. Subsequently is filtered hot and salt-free with 4000 parts of hot water washed. The pigment is dried at 80 ° in vacuo.

Example 2

In 300 parts by volume of ethanol are 24 parts of 4-methyl-5,8-dimethoxy-6-amino-quinolone (2), 12 parts of chloranil and 8.5 parts of anhydrous sodium acetate added, with stirring and Reflux cooling 6 Cooked hours, cooled to room temperature, the precipitate formed filtered off, with ethanol, then with water and again with ethanol washed. The ethanol-wet intermediate is in 300 vol. Dissolve o-dichlorobenzene to a finely divided suspension, stirring stir Cooked 8 hours, with the distilled ethanol / dichlorobenzene mixture is replaced by o-dichlorobenzene. It is allowed to cool to 100 °, filtered, washed Residue first with hot o-dichlorobenzene, then with hot ethanol, then with hot and finally with cold water and dry it.

das Kunststoffe in blauen Tönen mit ausgezeichneter Migrier- und Lösungsmittelechtheit färbt.This gives the pigment of the formula

which dyes plastics in blue tones with excellent migration and solvent fastness.

After treatment:

10 Parts of the pigment prepared according to Example 2 are in the presence of 30 parts NaCl and 150 parts acetone in a ball mill of 0.5 l capacity milled with 1 kg steel balls of 4 mm diameter for 72 hours. The millbase obtained is separated from the balls with a sieve, filtered and washed salt-free with 2000 parts of water. The pigment is at 80 ° in Vacuum dried.

By analogy with the statements in Examples 1 and 2, the pigments of the formula I in which the rings A correspond to the following formulas a to m are prepared. Table I Ex. Ring A 3 a 4 b 5 c 6 d 7 e 8th f 9 G 10 H 11 i 12 j 13 k 14 l 15 m

Anwendungsbeispiel 1 4 Teile des Pigments gemäss Beispiel 1 werden mit 96 Teilen einer Mischung aus 50 Teilen einer 60-prozentigen Lösung von Kokos-Aldehyd-Melaminharzlösung in Butanol, 10 Teile Xylol und 10 Teile Aethylenglykolmonoäthyläther 24 Stunden in einer Kugelmühle gemahlen. Die dabei erhaltene Dispersion wird auf Aluminiumblech gespritzt, 30 Minuten an der Luft trocknen gelassen und dann 30 Minuten bei 120°C eingebrannt. Man erhält so einen brillant rotstichig violetten Film mit sehr guter Migrierechtheit sowie guter Licht- und Wetterbeständigkeit. Anwendungsbeispiel 2 Beispiel für die Herstellung einer 0,1% gefärbten PVC-Folie (Verschnitt Buntpigment zu Weisspigment 1 : 5): 16,5 Teile eines Weichmachergemisches, bestehend aus gleichen Teilen Dioctylphthalat und Dibutylphthalat, werden mit 0,05 Teilen Pigmentfarbstoff gemäss Beispiel 1 und 0,25 Teilen Titandioxyd gemischt. Dann werden 33,5 Teile Polyvinylchlorid zugegeben. Das Gemisch wird 10 Minuten auf einem Zweiwalzenstuhl mit Friktion gewalzt, wobei das sich bildende Fell mit einem Spatel fortlaufend zerschnitten und zusammengerollt wird. Dabei wird die eine Walze auf einer Temperatur von 40°, die andere auf einer Temperatur von 140° gehalten. Anschliessend wird das Gemisch als Fell abgezogen und 5 Minuten bei 160° zwischen zwei polierten Metallplatten gepresst.The groups a-m are as follows:

Application example 1 4 Parts of the pigment according to Example 1 are with 96 Split a mixture 50 A 60% solution of coconut-aldehyde-melamine resin solution in butanol, 10 Parts xylene and 10 Parts of ethylene glycol monoethyl ether 24 Milled in a ball mill for hours. The resulting dispersion is sprayed on aluminum sheet, allowed to air dry for 30 minutes and then baked at 120 ° C for 30 minutes. This gives a brilliant reddish violet film with very good migration fastness and good light and weather resistance. Example of Application 2 Example of the Production of a 0.1% Colored PVC Film (Blend of Colored Pigment to White Pigment 1: 5): 16.5 parts a plasticizer mixture consisting of equal parts of dioctyl phthalate and dibutyl phthalate are with 0.05 parts Pigment dye according to Example 1 and 0.25 parts Mixed titanium dioxide. Then be 33.5 parts Polyvinyl chloride added. The mixture is rolled for 10 minutes on a two-roll mill with friction, wherein the forming coat is cut with a spatula continuously and rolled up. The one roller is kept at a temperature of 40 °, the other at a temperature of 140 °. The mixture is then stripped off as a coat and pressed for 5 minutes at 160 ° between two polished metal plates.

So receives one reddish violet colored PVC film of high brilliance and very good migration and light fastness.

Claims (3)

The triphendioxazine compounds of the general formula I

the cores designated A being, independently of one another, linear, in the 2,3 and 9,10 position, or angular, in the 1,2 and 8,9 or in the 3,4 and 10,11 position, anneals rings with the residues of the formulas -NR ₁ - (CO) _m -NH-, -CR ₁ = CH-CO-NH-, -O-CH ₂ -CO-NH-, -NR ₁ - (CO) _m - O, -CO-CH = CR ₁ -NH-, -CO-NH-CO-NH-, -CO-NH-CR ₂ = N-, -CR ₂ = N-CO-NH- or -NH-CR ₁ = N-, R _{1 is} hydrogen, C _1-4 -alkyl or phenyl, R _{2 is} hydrogen, C _1-4 -alkyl or phenyl and m is 1 or 2, wherein the angular molecules in the 3- and 10-position, or can each carry a C _1-2 alkoxy group in the 2- and 9-position. A process for preparing the triphendioxazine compounds of the formula I, according to claim 1, characterized in that 1 mol of 2,3,5,6-tetrachloro-1,4-benzoquinone is reacted with 2 mol of a compound of the general formula II

wherein n is 1, 2 or 3, condensed. Use of the compounds of the formula I according to claim 1 as pigments, for dyeing of plastic materials.