Trisazo Compounds for Ink-jet Printing

Abstract

Novel trisazo compounds are disclosed. The compounds are well suited for the dyeing and printing of natural and synthetic materials, especially as recording liquids for inkjet printing.

Claims

1. A trisazo compound of formula (I) ##STR00025## in which R.sup.1 is SO.sub.3M or COOM, and R.sup.2 is hydrogen, SO.sub.3M or COOM, with the proviso that R.sup.1 is SO.sub.3M when R.sup.2 is hydrogen, R.sup.3 and R.sup.4 independently of one another are hydrogen or CH.sub.3, R.sup.5 and R.sup.6 independently of one another are SO.sub.3M, COOM or NO.sub.2, and M is hydrogen, a monovalent metal cation, ammonium or alkylammonium which is mono- or polysubstituted identically or differently by C.sub.1-C.sub.4-alkyl.

2. The trisazo compound according to claim 1, wherein R.sup.1 is SO.sub.3M or COOM, and R.sup.2 is hydrogen, SO.sub.3M or COOM, with the proviso that R.sup.1 is SO.sub.3M when R.sup.2 is hydrogen, R.sup.3 and R.sup.4 independently of one another are hydrogen or CH.sub.3, and R.sup.5 and R.sup.6 independently of one another are SO.sub.3M, COOM or NO.sub.2, with the proviso that one of the radicals R.sup.5 or R.sup.6 is NO.sub.2, and M is hydrogen, sodium, potassium, lithium, ammonium or alkylammonium which is mono- or polysubstituted identically or differently by C.sub.1-C.sub.2-alkyl.

3. The trisazo compound according to claim 1, wherein R1 is SO.sub.3M or COOM, and R.sup.2 is hydrogen, SO.sub.3M or COOM, with the proviso that R.sup.1 is SO.sub.3M when R.sup.2 is hydrogen, R.sup.3 and R.sup.4 independently of one another are hydrogen or CH.sub.3, and R.sup.5 and R.sup.6 independently of one another are SO.sub.3M, COOM or NO.sub.2, with the proviso that one of the radicals R.sup.5 or R.sup.6 is NO.sub.2, and M is hydrogen, sodium, potassium, lithium, ammonium, trimethylammonium or triethylammonium.

4. The trisazo compound according to claim 1, wherein R.sup.1 is SO.sub.3M or COOM, and R.sup.2 is hydrogen, SO.sub.3M or COOM, with the proviso that R.sup.1 is SO.sub.3M when R.sup.2 is hydrogen, R.sup.3 and R.sup.4 are hydrogen or CH.sub.3, with the proviso that R.sup.3 and R.sup.4 are not both simultaneously hydrogen and are not both simultaneously CH.sub.3, R.sup.5 and R.sup.6 are SO.sub.3M, COOM or NO.sub.2, with the proviso that one of the radicals R.sup.5 or R.sup.6 is NO.sub.2, and M is hydrogen, sodium, potassium, lithium, ammonium, trimethylammonium or triethylammonium.

5. The trisazo compound according to claim 1, wherein the compound is of formula (Ia) or (Ib) ##STR00026## in which R.sup.1 is SO.sub.3M or COOM, and R.sup.2 is hydrogen, SO.sub.3M or COOM, with the proviso that R.sup.1 is SO.sub.3M when R.sup.2 is hydrogen, R.sup.3 and R.sup.4 are hydrogen or CH.sub.3, with the proviso that R.sup.3 and R.sup.4 are not both simultaneously hydrogen and are not both simultaneously CH.sub.3, R.sup.5 and R.sup.6 are SO.sub.3M, COOM or NO.sub.2, with the proviso that one of the radicals R.sup.5 or R.sup.6 is NO.sub.2, and M is hydrogen, sodium, potassium, lithium, ammonium, trimethylammonium or triethylammonium.

6. The trisazo compound according to claim 1, wherein R.sup.1 is SO.sub.3M, R.sup.2 is SO.sub.3M, R.sup.3 and R.sup.4 are hydrogen or CH.sub.3, with the proviso that R.sup.3 and R.sup.4 are not both simultaneously hydrogen and are not both simultaneously CH.sub.3, R.sup.5 and R.sup.6 are SO.sub.3M, COOM or NO.sub.2, with the proviso that one of the radicals R.sup.5 or R.sup.6 is NO.sub.2, and M is hydrogen, sodium, potassium, lithium, ammonium or triethylammonium.

7. The trisazo compound according to claim 1, wherein R.sup.1 is COOM, R.sup.2 is COOM, R.sup.3 and R.sup.4 are hydrogen or CH.sub.3, with the proviso that R.sup.3 and R.sup.4 are not both simultaneously hydrogen and are not both simultaneously CH.sub.3, R.sup.5 and R.sup.6 are SO.sub.3M, COOM or NO.sub.2, with the proviso that one of the radicals R.sup.5 or R.sup.6 is NO.sub.2, and M is hydrogen, sodium, potassium, lithium, ammonium or triethylammonium.

8. The trisazo compound according to claim 1, wherein the compound is of the formula ##STR00027## ##STR00028## ##STR00029##

9. A process for the dyeing and printing of cellulose-containing materials, animal hides, animal hair, eggshells, porous materials, or metals, comprising applying a dye containing at least one trisazo compound according to claim 1.

10. A formulation containing at least one trisazo compound according to claim 1.

11. The formulation according to claim 10, wherein the formulation is a liquid.

12. The formulation according to claim 10, containing 0.5% to 25% by weight of at least one trisazo compound according to claim 1, based on the overall formulation.

13. The formulation according to claim 10, containing 40% to 99% by weight of water and optionally one or more additives from the group of N-methyl-2-pyrrolidone, 2-pyrrolidone, 2-hexylpyrrolidone, hydroxyethylpyrrolidone, 2-propanol, ethanediol, hexane-1,2-diol, butane-1,2-diol, trimethylolpropane, diethylene glycol, diethylene glycol monobutyl ether, triethylene glycol monobutyl ether, dipropylene glycol monobutyl ether, glycerol, butyl lactate, urea, sulfolane, glycol ethers and biocides in a total amount of from 0.01% to 50% by weight, based on the overall formulation.

14. The formulation according to claim 10, containing 40% to 99% by weight of at least one solvent from the group of N-methyl-2-pyrrolidone, 2-pyrrolidone, 2-hexylpyrrolidone, hydroxyethylpyrrolidone, 2-propanol, ethanediol, hexane-1,2-diol, butane-1,2-diol, trimethylolpropane, diethylene glycol, diethylene glycol monobutyl ether, triethylene glycol monobutyl ether, dipropylene glycol monobutyl ether, glycerol, butyl lactate and optionally one or more additives from the group of urea, sulfolane, glycol ethers, biocides in a total amount of from 0.01% to 50% by weight, based on the overall formulation.

15. (canceled)

16. A process for preparing trisazo compounds according to claim 1, comprising reacting at least one compound of formula (II) ##STR00030## in which R.sup.1 and R.sup.2 have the definitions specified in claim 1, with a diazotization reagent, and reacting the reaction mixture thus obtained with at least one compound of formula (III) ##STR00031## in which R.sup.3 and R.sup.4 have the definitions specified in claim 1, to give the intermediate of formula (IV) ##STR00032## in which R.sup.1, R.sup.2, R.sup.3 and R.sup.4 have the definitions specified in claim 1, and reacting the intermediate of formula (IV) with a diazotization reagent, and reacting the reaction mixture thus obtained with a compound of formula (V) ##STR00033## to give the intermediate of formula (VI) ##STR00034## in which R.sup.1, R.sup.2, R.sup.3 and R.sup.4 have the definitions specified in claim 1, and reacting the intermediate of formula (VI) with a reaction product obtainable by reacting a compound of formula (VII) ##STR00035## in which R.sup.5 and R.sup.6 have the definitions specified in claim 1, with a diazotization reagent, to form the trisazo compound of formula (I), and isolating the trisazo compound by filtration of the reaction mixture.

Description

EXAMPLES

Example A

[0043] Example A is the dye C.I. Acid Black 1 (not according to the invention) corresponding to the formula

##STR00009##

[0044] Product from TCI Chemicals.

Example B

[0045] Example B is the dye C.I. Direct Black 19 (not according to the invention) corresponding to the formula

##STR00010##

[0046] Product from Dystar under the trade name Jettex Direct Black 19.

Example 1

[0047] 1.00 mmol of 5-aminoisophthalic acid were suspended in 80 equivalents of water. Next, 2.50 equivalents of hydrochloric acid in the form of a 37% aqueous solution were added and the reaction mixture was cooled down to 2° C. A 40% aqueous sodium nitrite solution was added in an equimolar amount and the mixture was stirred for 1 hour at 3° C. The nitrite excess was removed by adding amidosulfonic acid. An equimolar amount of m-toluidine was subsequently suspended in water and added to the reaction mixture within 60 minutes. Subsequently, the pH of the reaction mixture was adjusted using hydrochloric acid to pH 1.8 and the mixture was stirred for 30 minutes. The black precipitate was isolated by filtration and washed with aqueous hydrochloric acid (1% aqueous HCl solution).

[0048] The filter cake was suspended in 80 equivalents of water and the suspension was stirred for 40 minutes at 4° C. 2.75 equivalents of HCl were subsequently added and an equimolar amount of a 40% aqueous sodium nitrite solution was then metered in over a period of 60 minutes. The nitrite excess was removed by adding amidosulfonic acid. Next, an equimolar amount of 4-amino-5-hydroxynaphthalene-1,7-disulfonic acid was added and the suspension was stirred for 2 hours. The suspension was warmed to 15° C. and the pH adjusted to 1.1 by adding aqueous HCl solution. The reaction mixture was subsequently stirred for 12 hours and the pH set to 7.7 using an aqueous NaOH solution (suspension 1). An equimolar amount of 4-[(4-amino-3-nitrophenyl)amino]-4-oxobutanoic acid was suspended in 70 equivalents of water and 4 equivalents of hydrochloric acid were added. An equimolar amount of an aqueous sodium nitrite solution was then added. The nitrite excess was removed by adding amidosulfonic acid. Suspension 1 was metered into this suspension at a temperature of 3° C. The pH was adjusted to 8.8 using an aqueous NaOH solution. Subsequently, the reaction mixture was warmed to room temperature. For further purification, filtering was performed over an SiO.sub.2 bed (Celite®).

[0049] 0.42 mmol of the dye of the formula

##STR00011##

was obtained. Yield: 42%

Example 2

[0050] The dye of example 2 was prepared analogously to example 1, with the difference that instead of 5-aminoisophthalic acid an equimolar amounts of p-aminobenzoic acid were used. 0.44 mmol of the dye of the formula

##STR00012##

was obtained. Yield: 44%

Example 3

[0051] The dye of example 3 was prepared analogously to example 1, with the difference that instead of 5-aminoisophthalic acid an equimolar amount of aniline-2,4-disulfonic acid was used and instead of 4-[(4-amino-3-nitrophenyl)amino]-4-oxobutanoic acid an equimolar amount of 4-nitroaniline-2-sulfonic acid was used. 0.49 mmol of the dye of the formula

##STR00013##

was obtained. Yield 49%

Example 4

[0052] The dye of example 4 was prepared analogously to example 1, with the difference that instead of 5-aminoisophthalic acid an equimolar amount of aniline-2,4-disulfonic acid was used and instead of 4-[(4-amino-3-nitrophenyl)amino]-4-oxobutanoic acid an equimolar amount of 2-nitroaniline-4-sulfonic acid was used. 0.50 mmol of the dye of the formula

##STR00014##

was obtained. Yield 50%

Example 5

[0053] The dye of example 5 was prepared analogously to example 1, with the difference that instead of 5-aminoisophthalic acid an equimolar amount of aniline-2,4-disulfonic acid was used, instead of 4-[(4-amino-3-nitrophenyl)amino]-4-oxobutanoic acid an equimolar amount of 2-nitroaniline-4-sulfonic acid was used and instead of m-toluidine an equimolar amount of o-toluidine was used. 0.53 mmol of the dye of the formula

##STR00015##

was obtained. Yield 53%

Example 6

[0054] The dye of example 6 was prepared analogously to example 1, with the difference that instead of 5-aminoisophthalic acid an equimolar amount of aniline-2,4-disulfonic acid was used, instead of 4-[(4-amino-3-nitrophenyl)amino]-4-oxobutanoic acid an equimolar amount of 4-nitroaniline-2-sulfonic acid was used and instead of m-toluidine an equimolar amount of o-toluidine was used. 0.48 mmol of the dye of the formula

##STR00016##

was obtained. Yield 48%

Example 7

[0055] The dye of example 7 was prepared analogously to example 1, with the difference that instead of 5-aminoisophthalic acid an equimolar amount of aniline-2,5-disulfonic acid was used and instead of 4-[(4-amino-3-nitrophenyl)amino]-4-oxobutanoic acid an equimolar amount of 4-nitroaniline-2-sulfonic acid was used. 0.42 mmol of the dye of the formula

##STR00017##

was obtained. Yield 42%

Example 8

[0056] The dye of example 8 was prepared analogously to example 1, with the difference that instead of 5-aminoisophthalic acid an equimolar amount of aniline-2,5-disulfonic acid was used and instead of 4-[(4-amino-3-nitrophenyl)amino]-4-oxobutanoic acid an equimolar amount of 2-nitroaniline-4-sulfonic acid was used. 0.49 mmol of the dye of the formula

##STR00018##

was obtained. Yield 49%

Example 9

[0057] The dye of example 9 was prepared analogously to example 1, with the difference that instead of 5-aminoisophthalic acid an equimolar amount of aniline-2,5-disulfonic acid was used, instead of 4-[(4-amino-3-nitrophenyl)amino]-4-oxobutanoic acid an equimolar amount of 2-nitroaniline-4-sulfonic acid was used and instead of m-toluidine an equimolar amount of o-toluidine was used. 0.53 mmol of the dye of the formula

##STR00019##

was obtained. Yield 53%

Example 10

[0058] The dye of example 10 was prepared analogously to example 1, with the difference that instead of 5-aminoisophthalic acid an equimolar amount of aniline-2,5-disulfonic acid was used, instead of 4-[(4-amino-3-nitrophenyl)amino]-4-oxobutanoic acid an equimolar amount of 4-nitroaniline-2-sulfonic acid was used and instead of m-toluidine an equimolar amount of o-toluidine was used. 0.50 mmol of the dye of the formula

##STR00020##

was obtained. Yield 50%

Example 11

[0059] The dye of example 11 was prepared analogously to example 1, with the difference that instead of 5-aminoisophthalic acid an equimolar amount of aniline-2,5-disulfonic acid was used, instead of 4-[(4-amino-3-nitrophenyl)amino]-4-oxobutanoic acid an equimolar amount of 4-nitroaniline-2-sulfonic acid was used and instead of m-toluidine an equimolar amount of o-toluidine was used. Following the synthesis, 10.0 equivalents of ammonium chloride were added and the reaction mixture was stirred for 2 h at room temperature. For further purification, filtering was performed over an SiO.sub.2 bed (Celite®). 0.49 mmol of the dye of the formula

##STR00021##

was obtained. Yield 49%

Example 12

[0060] The dye of example 11 was prepared analogously to example 1, with the difference that instead of 5-aminoisophthalic acid an equimolar amount of aniline-2,5-disulfonic acid was used, instead of 4-[(4-amino-3-nitrophenyl)amino]-4-oxobutanoic acid an equimolar amount of 4-nitroaniline-2-sulfonic acid was used and instead of m-toluidine an equimolar amount of o-toluidine was used. Following the synthesis, 10.0 equivalents of triethylamine were added and the reaction mixture was stirred for 2 h at room temperature. For further purification, filtering was performed over an SiO.sub.2 bed (Celite®). 0.47 mmol of the dye of the formula

##STR00022##

was obtained. Yield 47%

Example 13

[0061] The dye of example 13 was prepared analogously to example 1, with the difference that instead of 5-aminoisophthalic acid an equimolar amount of 4-aminophthalic acid was used and instead of 4-[(4-amino-3-nitrophenyl)amino]-4-oxobutanoic acid an equimolar amount of 2-amino-4-nitrobenzoic acid was used. 0.50 mmol of the dye of the formula

##STR00023##

was obtained. Yield 50%

Example 14

[0062] The dye of example 13 was prepared analogously to example 1, with the difference that instead of 5-aminoisophthalic acid an equimolar amount of 4-aminophthalic acid was used and instead of 4-[(4-amino-3-nitrophenyl)amino]-4-oxobutanoic acid an equimolar amount of 4-nitroaniline-2-sulfonic acid was used. 0.52 mmol of the dye of the formula

##STR00024##

was obtained. Yield 52%
Determining the storage stability of an aqueous dye solution:

[0063] The E1/1 value specified is a hypothetical absorbance value which would be obtained if a 1 percent by weight solution of the respective compound (dissolved in water) were to be measured in a cuvette with a 1 cm path length.

[0064] The change in the E1/1 value, and the change in λ.sub.max, serve as a measure for the storage stability of an aqueous dye solution. For the determination of the storage stability of the dyes according to the invention and not according to the invention of examples A and B and 1 to 14, aqueous dye solutions having a concentration of 19% by weight were in each case produced and these dye solutions were stored in a closed glass vessel for 28 days at 45° C. The E1/1 value was determined in each case after 0 days and after 28 days in accordance with the procedure described above. The change in the E1/1 value over this period amounts to the value ΔE1/1=E1/1 (28 days)−E1/1 (0 days). The change in Amax over this period amounts to the value Δλ.sub.max=λ.sub.max (28 days)−λ.sub.max (0 days).

[0065] Here, the change in the E1/1 value is a measure for the loss of colour strength over the storage period, the change in Amax is a measure for the shift of the colour locus over the storage period.

[0066] The results are reproduced in table 1.

TABLE-US-00001 TABLE 1 according to the λ.sub.max Δ λ.sub.max Example invention [nm] Δ E1/1 at λ.sub.max [nm] A no 619 −14 5 B no 618 −11 −6 1 no 621 −7 −8 2 no 622 −9 −5 3 yes 596 <−1 0 4 yes 615 −3 −1 5 yes 616 <−1 1 6 yes 595 −3 0 7 yes 596 <−1 1 8 yes 613 −3 −1 9 yes 613 −2 1 10 yes 598 −3 1 11 yes 598 −2 −1 12 yes 600 −2 0 13 yes 625 −3 1 14 yes 619 <−1 −1

[0067] Conclusion: As can be seen from table 1, the aqueous solutions of the trisazo compounds according to the invention of examples 3 to 14 display a markedly smaller change in the absorbance values and in Amax compared to the dyes not according to the invention of examples A and B and 1 and 2 of the prior art, even after relatively long storage over a period of 28 days at an elevated temperature of 45° C. This means that for the aqueous solutions of the trisazo compounds according to the invention the colour strength and colour locus remain virtually unchanged over a period of 28 days, whereas in contrast for the dyes not according to the invention marked deviations can be detected.