GB1568150A

GB1568150A - 1:2-cobalt complex dyestuffs

Info

Publication number: GB1568150A
Application number: GB1708377A
Authority: GB
Original assignee: Hoechst AG
Current assignee: Hoechst AG
Priority date: 1976-04-24
Filing date: 1977-04-25
Publication date: 1980-05-29
Also published as: FR2348952A1; CA1076105A; IT1078448B; FR2348952B1; JPS52130825A; BE853927A; AU2454477A; DE2618020A1; AU509686B2; CH606333A5

Description

(54) 1:2-COBALT COMPLEX DYESTUFFS (71) We, HOECHST AKTIENGESELLSCHAFT, a body corporate organized according to the laws of the Federal Republic of Germany, of 6230 Frank furt/Main 80, Postfach 80 03 20, Federal Republic of Germany, do hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed to be particularly described in and by the following statement: The present invention provides unsymmetrical 1:2-cobalt complex compounds each containing as dyestuff components an azomethine compound of the formula (1) and an azo compound of the formula (2).

wherein Rl represents a chlorine atom, a lower alkyl group, for example a methyl or ethyl, preferably a methyl, group, or a nitro group, R2 represents a hydrogen atom, a lower alkyl group, for example a methyl or ethyl, preferably a methyl, group, or a lower alkoxy group, for example a methoxy or ethoxy, preferably a methoxy, group, R8 represents a hydrogen or chlorine atom, a nitro group, or a lower alkyl group, for example a methyl or ethyl, preferably a methyl, group, and Z represents a group of the formula (3) or (4)

wherein R4 represents a hydrogen atom or a lower alkyl or lower alkoxy group, for example a methyl, ethyl, methoxy or ethoxy, preferably a methyl or methoxy, group, R5 represents a hydrogen atom or a lower alkyl or lower alkoxy group, for example a methyl, methoxy or ethoxy group, X represents a hydroxy group, a sulfoalkyl group having from 1 to 4 carbon atoms, for example a fi-sulfo-ethyl group or a group of the formula

wherein R9 represents a hydrogen atom or a lower alkyl group, for example a methyl group, and one of R,; and R7 represents a nitro group and the other represents a sulfo group, and salts thereof, preferably the alkali metal or alkaline earth metal salts, for example sodium, potassium or calcium salts, or the ammonium salts.

The term 'lower", used above in relation to alkyl or alkoxy groups, means that the group referred to has 1 to 4 carbon atoms.

The present invention also provides a process for preparing the above complexes, which comprises reacting the compounds of the above formulae (1) and (2), in a molar proportion of 1:1, with a cobalt-yielding compound, for example at a temperature from 60 to 1450C, preferably at from 600 to 100"--1050C at atmospheric pressure or from 105 to 145 C under elevated pressure, and at a pH in the range of from 5.0 to 10, preferably from 8.0 to 9.5. The metallization is preferably carried out in an aqueous medium.

According to a preferred embodiment of the process of the invention, an azomethine compound of the formula (1) is reacted with a cobalt-yielding compound, for example in aqueous solution at a pH in the range of from 7 to 10, preferably from 8.5 to 9.5, and at a temperature in the range of from 20 to 700 C, preferably from 50 to 600C, and the resulting compound is then reacted with an azo compound of the formula (2) at a pH in the range of from 7 to 10, preferably from 8.5 to and at a temperature in the range of from 60 to 130"C, preferably from 80 to 105 C. The azomethine compound and cobalt-yielding compound are preferably used in equimolar amounts.

Suitable cobalt yielding agents are cobalt salts of inorganic or organic acids, for xample cobalt carbonate, cobalt hydroxycarbonate, cobalt acetate and cobalt sulfate.

The metallization process may be carried out in the presence of an acid-binding agent, such an oxide or hydroxide of an alkali metal or alkaline earth metal, or in the presence of an alkaline earth metal or alkali metal salt having an alkaline reaction; for example sodium or potassium acetate, sodium or potassium carbonate, sodium or potassium bicarbonate, sodium or potassium hydroxide, calcium carbonate, or calcium oxide.

The cobalt complex compounds thus obtained may be isolated from their preparation solutions by salting out with sodium or potassium chloride, or by spray-drying.

The complexes of the invention may be used according to the invention as dyestuffs for dyeing or printing natural or synthetic polyamide fibres, for example wool, silk and polyamides made from B-caprolactam, from hexamethylene diamine and adipic acid, or from w-amino-undecanoic acid. They are especially suitable for dyeing or printing the aforesaid fibres in admixture with other hydrophobic fibres, for example wool in a mixture of wool and polyester fibres, with excellent resistibility of the hydrophobic fibres.

The complexes of the invention are preferably used in the form of the alkali metal salts, for example the sodium or potassium salts, or the ammonium salts.

Furthermore, they can be used in admixture with other 1:2-cobalt- or -chromium complex dyestuffs which contain one or two sulfonic acid groups per dyestuffs molecule.

Dyeing or printing may be performed in known manner under conditions usual for metal complex dyes. Dyeing is preferably effected from an acid or neutral bath, advantageously at a pH in the range of from 4.0 to 6.5 and at a temperature in the range of from 90" to 105 C with the addition of one or more of the usual dyeing auxiliaries, for example fatty amine or fatty alcohol oxethylation products, and one or more usual buffer substances, for example sodium phosphate, sodium acetate or sodium formate, optionally in admixture with the corresponding acids, to stabilize the pH of the dyeing bath.By adding an acid, for example formic or acetic acid, or even a mineral acid, to a dyeing bath containing an alkali metal salt of formic acid, acetic acid or another organic acid, the pH of the dyeing bath can be optimized with regard to the dyestuff concentration used and to the desired colour depth.

For printing, printing pastes are generally used which contain the usual thickeners and printing auxiliaries and a salt of a weak base and a strong mineral acid or an organic acid, for example ammonium sulfate or ammonium tartrate. The printed fabrics are generally dried and then treated with hot air or steam for a short period of time.

The dyestuffs of the invention thus yield on natural and synthetic polyamide fibres yellow, golden yellow or yellow brown colour shades having good to very good fastness to wet processing, for example to washing at 200 to 600 C, (for example at 400 and 600C according to DIN 54010 and 54014), to water (under severe conditions), and to alkaline and acid perspiration, a good fastness to decatizing, and excellent fastness to light under the xenotest (Registered Trade Mark) and daylight lamps.

The starting compounds of the formula (1) (azomethine compounds) may be obtained by condensing an amine of the formula (5)

wherein Rl is defined as above, with an aldehyde of the formula (6)

wherein R2 is defined as above, preferably in an aqueous solution, at a temperature in the range of from 200 to 800 C, preferably from 500 to 600 C, and at a pH in the range of from 8.0 to 9.5, preferably from 8.5 to 9.0.

The starting compounds of the formula (2) (azo compounds) may be obtained by coupling an amine, which has been diazotized in known manner and corresponds to the formula (7)

wherein R, is defined as above, with a coupling component of the formula (8)

wherein Z is defined as above, under usual coupling conditions, for example at a temperature in the range of from --5"C to +400C and at a pH in the range of from 6 to 10, preferably from 7 to 8.

The coupling components of the formula (8) used for the above reaction, in which Z represents a group of the formula (4) above, i.e. 2 - nitro - 4' - N - aceto acetylamino - diphenylamino - 4 - sulfonic acid or 4 - nitro - 4' - N - acetoacetylamino - diphenylamino - 2 - sulfonic acid, or a group of the formula (3), may be obtained by reacting a compound of the formula (9) or (10)

wherein R4, R5, Re, R7 and X are defined as above, with diketene, advantageously in an aqueous solution, at a temperature in the range of from 20 to 909C, preferably from 50 to 60"C, and at a pH in the range of from 3 to 9, preferably from 5 to 6.

The present invention also provides mixtures containing an unsymmetrical 1:2 cobalt complex compound as described above together with a 1:2 cobalt complex of a compound of the formula (1) and/or a 1:2 cobalt complex of a compound of the formula (2).

The following Examples illustrate the invention; the parts and percentages are by weight.

EXAMPLE 1.

22.4 Parts of 4 - chloro - 2 - aminophenol - 6 - sulfonic acid were dissolved in 100 parts of water with the addition of 12.5 parts of an aqueous 33% sodium hydroxide solution. 12.2 Parts of 2-hydroxy-benzaldehyde in 200 parts of water and 34 parts of an aqueous 33% sodium hydroxide solution were then added, and the reaction mixture was heated to 60"C. The pH was adjusted to 9.2 with glacial acetic acid, the mixture was stirred for 1 to 2 hours at 60 C, and the pH was again adjusted to a value of 9.2. Then the reaction mixture was cooled to 25 C and 12.5 parts of cobalt hydroxy-carbonate were added.

Stirring was continued for 30 minutes, whereupon the solution of an azo compound, prepared as follows, was added.

30.9 Parts of 2 - nitro - 4' - aminodiphenylamino - 4 - sulfonic acid were dissolved at 50 to 600C and at a pH of from 6 to 7 in 100 parts of water and 12.1 parts of an aqueous 33% sodium hydroxide solution. 10.1 Parts of diketone were added dropwise with stirring over a period of 30 minutes; stirring of the reaction mixture was continued for another 2 hours at 50 to 60"C, whereupon the mixture was cooled to 200 C. - In a separate vessel, 15.4 parts of 4-nitro-2-aminophenol were dissolved in 150 parts of water and 25 parts of aqueous 31 % hydrochloric acid, 50 parts of ice were added and the aminophenol was diazotized by adding dropwise 17.3 parts of an aqueous 40% sodium nitrite solution.Stirring was continued for another 30 minutes, and the excess nitrous acid was decomposed by adding approximately 0.5 parts of amidosulfonic acid. The afore-described solution of the acetoacetyl coupling component was then added to the diazo solution obtained, the pH was adjusted with sodium carbonate to 8.5 to 9.0 and coupling was completed at 20"C while stirring for 4 hours.

The solution of the metal-free azo compound prepared in this manner was combined with the above solution of the cobalt complex-azomethine compound, and the reaction mixture was heated for 4 to 6 hours at 950C. The 1:2-cobalt complex compound formed was precipitated by salting out with sodium chloride or isolated by spray-drying. In the form of the free acid the dyestuff had the formula

100 Parts of a woollen fabric were introduced into a dyeing bath having a tem perature of 400 and containing 1.0 part of the above cobalt complex dyestuff, 0.15 parts of an addition product of 12 mols of ethylene oxide and 1 mol of stearyl amine, 2 parts of ammonium acetate and 2 parts of 60% acetic acid in 3,000 parts of water.

The temperature of the dyeing bath was increased within 30 minutes to boiling point, and dyeing was continued for 60 minutes at 1000C. The fabric was then after-treated in usual manner. A golden yellow coloration of good evenness was obtained, having good to very good fastness to wet processing and excellent fastness to light When, instead of the woollen fabric, 100 parts of a fabric of polycaprolactam fibres were dyed, a dyeing was obtained which also had good to very good fastness to use and processing and excellent fastness to light.

EXAMPLE 2.

The process described in Example 1 was carried out, but the 4-nit 2-aminophenol was replaced by 14.4 parts of 4-chloro-2-aminophenol in the plsparation of the azo compound. A 1:2-cobalt complex dyestuff was obtained which, in the form of the free acid, had the formula

100 Parts of a fabric of polycaprolactam fibres were introduced into a bath having a temperature of 40"C and containing 1.5 parts of the above cobalt complex dyestuff, 0.15 parts of an addition product of 12 mols of ethylene oxide and 1 mol of stearyl amine, 2.0 parts of ammonium acetate and 2.0 parts of aqueous 60 ' acetic acid in 3,000 parts of water.The temperature of this dyeing bath was raised to 980 to 100"C within 15 minutes, and the fabric was dyed for 60 minutes at 100"C. After a usual completion treatment, a golden yellow dyeing was obtained having good to very good fasmess to wet processing and excellent fastness to light.

When the fabric of polycaprolactam fibres was replaced by 100 parts of wool, the dyeing obtained had likewise good to very good fastness to use and processing and excellent fasmess to light.

EXAMPLE 3.

22.4 Parts of 4 - chloro - 2 - aminophenol - 6 - sulfonic acid were dissolved in 100 parts of water with the addition of 12.5 parts of an aqueous 33% sodium hydroxide solution. 12.2 Parts of 2-hydroxy-benzaldehyde in 200 parts of water and 34 parts of an aqueous 33% sodium hydroxide solution were then added, and the reaction mixture was heated to 600 C. The pH was adjusted to 9.2 with glacial acetic acid, and the mixture was stirred for 1 to 2 hours at 60"C and ar the pH of 9.2. Then the mixture was cooled to 25"C, and 12.5 parts of cobalt hydroxy-carbonate were added.

After stirring for 30 minutes, the solution of a disazo compound, prepared as follows, was added.

27.7 Parts of 4 - amino - azobenzene - 4' - sulfonic acid were dissolved in 200 parts of water and 12.1 parts of an aqueous 33% sodium hydroxide solution, at a pH of from 6 to 7 and a temperature of from 500 to 600C. 10.1 Parts of diketone were then added dropwise over a period of 30 minutes, and the reaction mixture was stirred for 2 hours at 50 to 600 C; it was then cooled to 200 C. - In a separate vessel, 15.4 parts of 4-nitro-2-aminophenol were dissolved in 150 parts of water and 25 parts of 31% hydrochloric acid; 50 parts of ice were added and the phenol was diazotized by slowly adding 17.3 parts of an aqueous 40 /* sodium nitrite solution.

After 30 minutes, about 0.5 parts of amidosulfonic acid were added to decompose the excess nitrous acid. Then the solution of the acetoacetyl compound described above was added to the diazo solution obtained, the pH was adjusted to 8.5 to 9.0 by adding sodium carbonate and coupling was completed after stirring at room temperature for 4 hours.

The solution of the diazo compound obtained was combined with the solution of the cobalt complex azomethine compound described above, and the reaction mixture was heated to 95"C for 4 to 6 hours. The 1:2-cobalt complex dyestuff obtained was precipitated by salting out with sodium chloride or isolated by spray drying. In the form of the free acid it has the formula

Polyamide carpet yarn was padded with an aqueous padding liquor containing 10 parts of the above dyestuff, 5 parts of a locust bean flour preparation, 4 parts of an addition product of 8 mols of ethylene oxide and 1 mol of isotridecyl alcohol, and 10 parts of aqueous 60% acetic acid in 1,000 parts of the padding liquor, to a liquor pickup of 100%; the yarn was steamed for 6 minutes at 100" to 1020C and then rinsed with cold water. The golden yellow dyeing obtained had good fastness to use and excellent fastness to daylight.

EXAMPLE 4.

The process described in Example 3 was carried out, but the 4-amino-azobenzene4'-sulfonic acid was replaced by 41.3 parts of 4 - amino - 6 - methyl - 3 - methoxyazobenzene - 4' - ss - sulfoethyl - sulfone. The 1:2-cobalt complex compound obtained had, in the form of the free acid, the formula

100 Parts of wool flock were introduced into a dyeing bath having a temperature of 40"C and containing 1.0 part of the above cobalt complex dyestuff, 0.15 parts of an addition product of 12 mols of ethylene oxide and 1 mol of stearyl amine, 2 parts of ammonium acetate and 2 parts of aqueous 60% acetic acid in 3,000 parts of water.

The temperature of the dye bath was raised to boiling point within 30 minutes, and dyeing was continued for 60 minutes at 100"C.

After a usual after-treatment and completion, an even golden yellow dyeing was obtained having good to very good fastness to wet processing and excellent fastness to light When, instead of 100 parts of wool flock, the same amount of woolen yarn in hanks was dyed, a very good and even dyeing having good to very good fastness to wet processing and excellent fastness to light was likewise obtained.

EXAMPLES 5 to 12.

The following Table gives further dyestuffs according to the invention which were prepared under the conditions specified in the preceding Examples. They yielded golden yellow dyeings on wool.

EXAMPLE 13.

32.8 Parts of the azomethine compound prepared according to Example 1 and 55.8 parts of the azo compound prepared according to Example 1 were mixed in the form of the solution or suspension obtained, 12.5 parts of cobalt hydroxycarbonate were added and the mixture was stirred for 30 minutes at 200 to 300 C, heated to boiling temperature and then refluxed for 4 to 6 hours. After isolation by precipitation with sodium chloride or by spray drying, a dye was obtained containing, besides the unsymmetrical 1:2-cobalt complex dyestuff of Example 1 as main component, also the 1:2-cobalt complex dyestuff of the azomethine compound and the 1:2-cobalt complex dyestuff of the azo compound. It had the same tinctorial properties as the dyestuff of Example 1 alone.

EXAMPLE 14.

32.8 Parts of the azomethine compound according to Example 3 and 52.6 parts of the disazo compound according to Example 3 were mixed in the form of the solution or suspension obtained. 12.5 Parts of cobalt hydroxy-carbonate were added, the mixture was stirred for 30 minutes at 20 to 30"C, and then heated to boiling temperature. The reaction mixture was then refluxed for 4 to 6 hours. The dye obtained contained as the main component the unsymmetrical 1:2-cobalt complex dyestuff of Example 3, together with the 1:2-cobalt complex dyestuff of the azomethine compound and the 1:2-cobalt complex dyestuff of the disazo compound. It had the same good tinctorial properties as the unsymmetrical 1:2-cobalt complex dyestuff of Example 3 alone.

WHAT WE CLAIM IS: 1. A 1:2cobalt complex compound wherein each cobalt atom is complexed with one molecule of a compound of the formula (1) and one molecule of a compound of the formula (2)

wherein Rl represents a chlorine atom or a lower alkyl or nitro group, R, represents a hydrogen atom or a lower alkyl or lower alkoxy group,

**WARNING** end of DESC field may overlap start of CLMS **.

Claims

**WARNING** start of CLMS field may overlap end of DESC **. EXAMPLE 13. 32.8 Parts of the azomethine compound prepared according to Example 1 and 55.8 parts of the azo compound prepared according to Example 1 were mixed in the form of the solution or suspension obtained, 12.5 parts of cobalt hydroxycarbonate were added and the mixture was stirred for 30 minutes at 200 to 300 C, heated to boiling temperature and then refluxed for 4 to 6 hours. After isolation by precipitation with sodium chloride or by spray drying, a dye was obtained containing, besides the unsymmetrical 1:2-cobalt complex dyestuff of Example 1 as main component, also the 1:2-cobalt complex dyestuff of the azomethine compound and the 1:2-cobalt complex dyestuff of the azo compound. It had the same tinctorial properties as the dyestuff of Example 1 alone. EXAMPLE 14. 32.8 Parts of the azomethine compound according to Example 3 and 52.6 parts of the disazo compound according to Example 3 were mixed in the form of the solution or suspension obtained. 12.5 Parts of cobalt hydroxy-carbonate were added, the mixture was stirred for 30 minutes at 20 to 30"C, and then heated to boiling temperature. The reaction mixture was then refluxed for 4 to 6 hours. The dye obtained contained as the main component the unsymmetrical 1:2-cobalt complex dyestuff of Example 3, together with the 1:2-cobalt complex dyestuff of the azomethine compound and the 1:2-cobalt complex dyestuff of the disazo compound. It had the same good tinctorial properties as the unsymmetrical 1:2-cobalt complex dyestuff of Example 3 alone. WHAT WE CLAIM IS:

1. A 1:2cobalt complex compound wherein each cobalt atom is complexed with one molecule of a compound of the formula (1) and one molecule of a compound of the formula (2)

R, represents a hydrogen or chlorine atom or a nitro or lower alkyl group, and Z represents a group of the formula (3) or (4)

wherein R4 represents a hydrogen atom or a lower alkyl or lower alkoxy group, R5 represents a hydrogen atom or a lower alkyl or lower alkoxy group, X represents a hydroxy group, a sulfoalkyl group having from 1 to 4 carbon atoms, or a group of the formula

wherein R, represents a hydrogen atom or a lower alkyl group, and one of R6 and R7 represents a nitro group and the other represents a sulfo group, or a salt thereof.

2. A complex compound as claimed in claim 1, wherein a lower alkyl group is a methyl group and a lower alkoxy group is a methoxy group.

3. A complex compound as claimed in claim 1 or claim 2, wherein the sulfoalkyl group represented by X is a p-sulfoethyl group.

4. A complex compound as claimed in any one of claims 1 to 3, wherein the salt is an alkali metal, alkaline earth metal or ammonium salt.

5. A complex compound as claimed in claim 4, wherein the salt is a sodium, potassium, calcium or ammonium salt

6. A complex compound as claimed in claim 1 and described herein.

7. A complex compound as claimed in claim 1 and described in any one of Examples 1 to 12.

8. A 1:2-cobalt complex compound which, in the form of the free acid, has the formula

9. A 1:2-cobalt complex compound which, in the form of the free acid, has the formula

10. Al :2-cobalt complex compound which, in the form of the free acid, has the formula

11. A process for preparing a 1:2 cobalt complex compound as claimed in claim 1, which comprises reacting equimolar amounts of the compounds of the formulae (1) and (2), given in claim 1, with a cobalt yielding agent at a pH in the range of from 5tolO.

12. A process as claimed in claim 11, wherein the pH is in the range of from 8.0to9.5.

13. A process as claimed in claim 11 or claim 12, wherein the reaction is carried out at a temrerature in the range of from 600 to 145"C at atmospheric pressure or at 105 to 1450C under elevated pressure.

14. A process as claimed in any one of claims 11 to 13, wherein the reaction is carried out in an aqueous medium.

15. A process as claimed in claim 11, wherein an azomethine compound of the formula (1), given in claim 1, is reacted with a cobalt yielding agent at a pH in the range of from 7 to 10 and at a temperature in the range of from 200 to 700 C, and the resulting compound is reacted with an azo compound of the formula (2), given in claim 1, at a pH in the range of from 7 to 10 and at a temperature in the range of from 600 to 1300C.

16. A process as claimed in claim 15, wherein the azomethine compound and the cobalt-vielding compound are used in equimolecular amounts.

17. A process as claimed in any one of claims 11 to 16, wherein the cobalt vielding agent is cobalt carbonate, cobalt hydroxycarbonate, cobalt acetate or cobalt sulfate.

18. A process as claimed in any one of claims 11 to 17, wherein the reaction is carried out in the presence of an acid-binding agent or an alkali or alkaline earth metal salt having an alkaline reaction.

19. A process as claimed in claim 11, conducted substantially as described herein.

20. A process as claimed in claim 11, conducted substantially as described in Example I or Example 3.

21. A complex compound as claimed in any one of claims 1 to lû, whenever prepared by a process as claimed in any one of claims 11 to 20.

22. A mixture comprising a complex compound as claimed in any one of claims 1 to 10 and 21 together with a 1:2 cobalt complex compound of a compound of the formula (1) given in claim 1 and/or a 1:2 cobalt complex compound of a compound of the formula (2) given in claim 1.

23. A process for preparing a mixture as claimed in claim 22, which comprises reacting a mixture of compounds of the formulae (1) and (2) simultaneously with a cobalt-yielding agent.

24. A process as claimed in claim 23, conducted substantially as described in Example 13 or Example 14.

25. A process for dyeing or printing natural or synthetic polyamide fibres, wllerein a complex compound as claimed in any one of claims 1 to 10 or 21, or a mixture as claimed in claim 22, is used.

26. A process as claimed in claim 25, wherein wool, silk or fibres of a polymer made from e-caprolactam, hexamethylene-diamine and adipic acid, or amino undecanoic acid are dyed or printed.

27. A dyeing or printing process as claimed in claim 25, conducted substantially as described herein.

28. A dyeing process as claimed in claim 25, conducted substantially as described in any one of Examples 1 to 4.

29. Natural or svnthetic polyamide fibres, whenever dyed or printed by a process as claimed in claim 25.

30. A dyeing or printing preparation which contains a complex compound as claimed in any one of claims 1 to 10 and 21 or a mixture as claimed in claim 22.