CH629522A5 - Process for the preparation of concentrated, low-salt solutions of cobalt- and chromium-1:2 complex dyes which are free from sulphonic acid groups - Google Patents

Description

The invention relates to a process for the preparation of concentrated low-salt solutions of sulfonic acid group-free o, o'-dihydroxy or o, o'-hydroxycarboxy-cobalt and chromium 1: 2 complex azo dyes, which is characterized in that the metallization in water and a solvent of formula (1)

R (CO) mO (C2H3Q55

tate or propionate of the mono-, di- or triethylene glycol mono-methyl-, ethyl-, -propyl- or -butyl ether as well as the corresponding propylene glycol derivatives.

Individual connections are e.g.

H3COC2H4QCHO, HsC2OC2H4OCHO »H3COC2H4OCOCH3,

h5c, oc2h4ococh3, h7c3oc2h4ococh3, h9c4oc2h4o-coch3,

HaCOQ ^ OCOQHs, HsQOC ^ OCOQHs, H9C40C2H40-COC2Hs, H3C (OC2H4) 2OCOCH3, H3C (OC2H4) 3QCOCH3, HsQCOQH ^ OQHs, HgC4 (OC, H4) 2OC3H4H3H3C3H4H3

or H9C4OC2H4OCOC3H7 and the corresponding compounds with -CH (CH3) CH2- instead of C2H4.

For example, H5C20C2H40C0CH3 or H9C40-C2H4OCOCH3 used.

Other solvents that may be present during the metallization are e.g. Glycols, glycol monoethers and carboxamides, such as ethylene glycol, di- or triethylene glycol, propylene glycol, di- or tripropylene glycol, mono-, di- or tri-ethylene glycol monomethyl, ethyl, propyl or butyl ether, mono-, Di- or tripropylene glycol monomethyl, ethyl, propyl or butyl ether, dimethylformamide, dimethylacetamide or N-methylpyrrolidone.

Individual preferred solvents are e.g. Ethylene glycol, diethylene glycol, dipropylene glycol, ethylene glycol monoethyl ether or diethylene glycol mono-n-butyl ether.

Water-soluble salts in the presence of which the metallization is carried out are e.g. Alkali salts and magnesium salts, such as magnesium chloride and preferably sodium chloride, sodium formate, sodium acetate, sodium propionate, potassium chloride or potassium acetate.

Cobalt hydroxide is preferably used in the weakly acidic to weakly alkaline range for cobaltation, preferably in the vicinity of the neutral point. The chromation can be carried out with chromium-VI compound or preferably in organic solvents at elevated temperature with chromium-III hydroxide in the presence of alkanoic acids and salts, the chromium-III compound being the reaction product of chromium hydroxide which is formed in situ , Alkali hydroxide solution and excess Cr to C3 alkanoic acid and as a solvent compounds of the formula

H0- (C2H30

45

R2 R1

(1).

in the

A is hydrogen or methyl,

m the numbers 0 or 1,

n the numbers 1, 2 or 3 and

R and R1 independently of one another denote hydrogen or C 1 -C 4 -alkyl, in the presence of water-soluble salts and optionally in a mixture with other solvents.

Solvents of formula (1) are e.g. Glycol esters such as glycol acetate or diacetate and preferably glycol ether esters, in which the molecule simultaneously contains an ether and ester group. Glycol ether esters are, for example, the formates,

used, in which R1 is hydrogen or Cr to C4-alkyl,

R2 is hydrogen or methyl and n is 1, 2 or 3, and a carboxamide is optionally added after the chromating.

Suitable alkali lyes are e.g. Lithium hydroxide, potassium hydroxide and preferably sodium hydroxide.

Ci- to C3-alkanoic acids are formic acid, acetic acid and propionic acid and their substitution products, such as chloro-55-acetic acid, although the unsubstituted acids are preferred.

The reaction product formed in situ is e.g. from chromium III hydroxide, acetic acid and sodium hydroxide solution, probably a basic chromium III acetate. The amount of acid 60 is chosen so that a weakly acidic pH is established, for example in the range from 3 to 6.

The addition of a di- or oxycarboxylic acid is often advantageous.

The metallization is expediently carried out in such a way that the mixture of azo dye, solvent of the formula (1), optionally further solvent, water, water-soluble salt and metallizing agent is heated to the metallization temperature. Since the solvents of the

629 522

Formula (1) and the aqueous salt solution do not mix or do not mix completely, there is a two-phase system. The aqueous phase absorbs the salts, whereas the complex dye that forms is present in the organic phase. When the metallization has ended, the phases can be separated and a concentrated, low-salt solution of the metal complex dye in the organic medium is obtained.

A particularly preferred embodiment of the process according to the invention consists in combining the diazotization, coupling and metallization of the azo dye (s) in a one-pot process by carrying out all process steps in the solvent of the formula 1. Diazo-tion and coupling are carried out as usual. The use of the solvents already in the diazotization and coupling has the great advantage that it is possible to work much more concentrated than usual and, moreover, generally gives even better yields in the coupling. The use of solvents that are not completely miscible with water makes it possible to remove the salts introduced by diazotization and coupling after the metallization in a very simple manner by forming the two-phase system.

The solutions which can be prepared according to the invention generally contain 10 to 40, preferably 15 to 35 percent by weight 1: 2 complex dye, approximately 15 to 65, preferably 20 to 45 percent by weight solvent of the formula (1), 1 to 35, preferably 10 to 30 percent by weight, further solvents, 4 to 20, preferably 8 to 16 percent by weight, water and optionally up to 15% alkanoic acids, for example can be introduced by the process described above or by hydrolysis of the compounds of the formula (1).

The solutions prepared according to the invention are stable in storage and are suitable for the production of dyebaths and printing pastes for dyeing in particular nitrogen-containing fibers, such as wool, silk or synthetic polyamides. They are also suitable for the production of printing inks and wood stains, since their generally very low salt content means that they can be mixed with most organic solvents, e.g. Alcohols, glycols, ketones and esters are miscible.

In practice, it may be necessary to standardize the solutions produced according to the invention in terms of concentration and storage stability. For this purpose, solvents or other solvents already contained therein can be added.

As dyes in the solutions which can be prepared according to the invention, e.g. contain the sulfonic acid group-free o, o'-dihydroxy and o, o'-hydroxycarboxyazo-1: 2 metal complex compounds known from DT-OS 16 19 357 and DT-OS 24 44 736 (see in particular the literature information on page 3) .

Details of the new process can be found in the following examples, in which parts and percentages, unless stated otherwise, relate to the weight.

The formulas belonging to the examples are shown on the drawing sheets. Example and formula numbers match.

example 1

970 parts of dye paste, which 155 parts (0.5 mol) of the azo dye from diazotized l-amino-2-oxy ~ 5-nitro-benzene -> ß-naphthol and 155 parts (0.5 mol) of the azo dye from diazotized l-Amino-2-oxy-4-nitro-benzene - »ß-naphthol, are in a mixture of 835 parts of ethyl glycol acetate, 67 parts of 50 percent sodium hydroxide solution, 100 parts of acetic acid, 115 parts of water-moist chromium III hydroxide with a Content of 33% Cr203 and 50 parts of sodium chloride entered. It is then refluxed for 10 hours

(Temperature approx. 105 ° C) cooked. The mixture is then cooled to room temperature and the impurities are removed by filtration. The lower colorless layer is separated. The upper layer represents the low-salt, concentrated, stable stock solution 5. It dyes wool, polyamide or leather in black tones. Solutions of the corresponding 1: 2 chromium complex dyes can be prepared in an analogous manner, starting from the azo dyes in the table, see drawing nos. 1 and 2, examples 2 to 7.

10th

Color hue color hue color hue

2 scarlet 4 blue 6 green

15 3 violet 5 olive 7 brown

Example 8

1550 parts of dye paste containing 322 parts (1.0 mol) of the azo-20 dye from diazotized 1-amino-benzene-2-carboxylic acid and 1-phenyl-3-methyl-pyrazolone-5 are mixed in a mixture of 830 parts Ethyl glycol acetate, 107 parts of 50 percent sodium hydroxide solution, 152 parts of acetic acid, 115 parts of water-moist chromium III hydroxide with a content of 33% 25 Cr203 and 40 parts of sodium chloride. The mixture is then boiled under reflux (temperature about 105 ° C) for 12 hours. It is then cooled to room temperature and contaminants are filtered off. The filtrate consists of two liquid phases. The top is the watery, colorless, salt-rich layer. The lower one is separated off and, after adding 60 parts of ethylene glycol, it is the low-salt, concentrated, stable stock solution. It dyes wool, polyamide or leather in yellow tones.

35 Example 9

400 parts of dye paste containing 132 parts (0.41 mol) of the azo dye from diazotized 1-amino-benzene-2-carboxylic acid and 1-phenyl-3-methyl-pyrazolone-5 and 600 parts of dye paste containing 200 parts (0, 59 mol) of the azo dye from diazo-40 tiert l-amino-2-oxy ~ 5-nitrobenzoI and l-PhenyI-3-methyl-pyrazolon-5, are in a mixture of 930 parts of ethyl glycol acetate, 107 parts of 50 percent sodium hydroxide solution, 152 Parts of acetic acid, 14 parts of oxalic acid (krist.), 115 parts of water-moist chromium III hydroxide with a content of 33% 45 Cr203 and 40 parts of sodium chloride. The mixture is then boiled under reflux (approx. 105 ° C.) for 6 hours. It is then cooled to room temperature and contaminants are filtered off. The filtrate consists of two liquid phases. The lower colorless, salt-rich, aqueous phase is separated off. After the addition of 60 parts of ethylene glycol-monoethyl ether, the upper one is the low-salt, concentrated, stable stock solution. It dyes wool, polyamide or leather in orange tones.

55 Example 10

950 parts of dye paste containing 339 parts (1.0 mol) of the azo dye from diazotized 1-amino-2-oxy-4-nitro-benzene and 1-phenyl-3-methyl-pyrazolone-5 are mixed in a mixture of 830 Parts of ethyl glycol acetate, 107 parts of 50 percent 60% sodium hydroxide solution, 185 parts of propionic acid, 14 parts of oxalic acid (crystalline), 115 parts of water-moist chromium III hydroxide with a content of 33% Cr203 and 40 parts of sodium chloride. The mixture is then boiled under reflux (temperature 105 ° C.) for 10 hours. It is then cooled to room temperature and filtered to remove impurities. The filtrate consists of two liquid phases. The top is the watery, colorless, salty layer. The lower one is separated off and, after adding 60 parts of diethylene glycol mono-n-bu-

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4th

tyl ether is the low-salt, concentrated, stable stock solution. It dyes wool, polyamide or leather in red tones.

Example 11

A mixture of 835 parts of ethyl glycol acetate (ethylene-5 glycol monoethyl ether acetate), 80 parts of l-amino-2-oxy-4-nitrobenzene, 74 parts of l-amino-2-oxy-5-nitro-benzene and 142 parts of 30 percent hydrochloric acid heated to 70 ° C and then cooled to 0 to 5 ° C. A solution of 69 10 parts of NaNO 2 and 260 parts of water is run into this solution at 0 to 5 ° C. with stirring in about 1 hour. The mixture is stirred for about 1 hour at 0 to 5 ° C, then 154 parts of β-naphthol and then 80 parts of 50 percent sodium hydroxide solution are added at 0 to 5 ° C within 1 hour. After stirring for one hour, 40 parts of 15 5% sodium hydroxide solution are again added within 1 hour. The mixture is then stirred for 20 hours, 27 parts of 85 percent formic acid and 115 parts of water-moist chromium III hydroxide with a content of 33% Cr203 are added and the mixture is boiled under reflux (about 103 ° C.) for 7 hours. After cooling to room temperature, the 20 minor precipitates are removed by filtration. The filtrate consists of two liquid layers. The lower colorless, salt-rich, aqueous layer is separated off. The upper one represents the low-salt, concentrated, stable stock solution. It dyes wool, polyamide or leather in black tones. 25th

Example 12

A mixture of 625 parts of ethylene glycol acetate (ethyl-englykolmonoäthylätherätetat), 210 parts of ethyl glycol (Äthyl-englykolmonoäthyläther), 80 parts of 1-amino-2-oxy-4-nitro-30 benzene, 74 parts of l-amino-2-oxy-5- nitro-benzene, 142 parts of 30 percent hydrochloric acid is heated to 70 ° C and then cooled to 0 to 5 ° C A solution of 69 parts of NaNOz and 260 parts of water is run into this solution at 0 to 5 ° C. with stirring in about 1 hour. The mixture is stirred for 1 35 hours at 0 to 5 ° C, then 8 parts of amidosulfonic acid are added. The mixture is stirred for a further hour at 0 to 5 ° C. Then 154 parts of β-naphthol and 87 parts of 50 percent sodium hydroxide solution are added within 1 hour and, after stirring for an hour, another 45 parts of 50 percent sodium hydroxide solution. The mixture is then stirred for a further 20 hours, 150 parts of acetic acid and 115 parts of water-moist chromium III hydroxide with a content of 33% Cr203 are added and the mixture is boiled under reflux (about 103 ° C.) for 7 hours. After cooling to room temperature, the minor precipitations are removed by filtration. The filtrate consists of two liquid layers. The lower colorless, salt-rich, aqueous layer is separated off. After the addition of 67 parts of ethylene glycol, the upper one is the low-salt, concentrated, stable stock solution. It dyes wool, polyamide or leather in black tones. so

If you take 210 parts of ethylene glycol instead of 210 parts of ethylene glycol, you get a stock solution with similar properties.

Example 13 55

A mixture of 625 parts of ethyl glycol acetate, 210 parts of ethyl glycol, 80 parts of 1-amino-2-oxy-4-nitro-benzene, 74 parts of 1-amino-2-oxy-5-nitro-benzene and 142 parts of 30 percent hydrochloric acid stirred at room temperature for 6 hours. A solution of 69 parts of NaNO.sub.2 and 260 parts of water is then run into this mixture 60 at about 0 to 5.degree. C. in about 1 hour. The mixture is stirred for about 1 hour at 0 to 5 ° C., then 154 parts of β-naphthol and then 89 parts of 50 percent sodium hydroxide solution are added at 0 to 5 ° C. within 1 hour. After stirring for one hour, 44 parts of 50 percent sodium hydroxide solution are again added within 1 hour. Then stir for 20 hours,

gives 185 parts propionic acid and 115 parts water moist

Chromium III hydroxide containing 33% Cr203 and boiled under reflux for 7 hours (approx. 103 ° C). After cooling to room temperature, the minor precipitations are removed by filtration. The filtrate consists of two liquid layers. The lower colorless, salt-rich, aqueous layer is separated off. After the addition of 67 parts of ethylene glycol, the upper one is the low-salt, concentrated, stable stock solution. It dyes wool, polyamide or leather in black tones.

Example 14

A mixture of 415 parts of ethyl glycol acetate, 415 parts of ethyl glycol, 137 parts of 1-amino-2-carboxy-benzene and 130 parts of 30 percent hydrochloric acid is mixed at 0 ° C. in the course of 30 minutes with a solution of 69 parts of NaNOz in 260 parts of water. After stirring for 1 hour at 0 ° C., 6 parts of amidosulfonic acid are added, stirring is continued at 0 ° C. for 30 minutes, 179 parts of 1-phenyI-3-methyIpyrazolon-5 and then 40 parts of 50 percent within 30 minutes at 0 ° C. Caustic soda. The mixture is then stirred for 10 hours at room temperature, 45 parts of 85 percent formic acid, 69 parts of anhydrous sodium acetate and 115 parts of water-moist chromium III hydroxide with a content of 33% Cr203 are added and the mixture is boiled under reflux (temperature approx. 103 ° C.) for 10 hours. Then 67 parts of sodium hydroxide solution (50 percent) and 17 parts of table salt are added. The minor precipitates are removed by filtration at room temperature. The lower colorless, aqueous layer is separated off. After adding 100 parts of ethyl glycol, the upper layer is the low-salt, concentrated, stable stock solution. It dyes wool, polyamide or leather in yellow tones.

Example 15

A mixture of 415 parts of ethyl glycol acetate, 415 parts of ethyl glycol, 154 parts of l-amino-2-oxy-4-nitro-benzene and 142 parts of 30 percent hydrochloric acid is stirred at room temperature for 6 hours. A solution of 69 parts of NaNQ2 in 260 parts of water is then run in at 0 to 5 ° C. in about 1 hour. The mixture is stirred at 0 to 5 ° C for one hour. Then 6 parts of amidosulfonic acid are added, the mixture is stirred for 30 minutes and then 179 parts of l-phenyl-3-methyl-pyrazolone and 40 parts of 50 percent sodium hydroxide solution are added in 30 minutes. After stirring for two hours at 0 to 5 ° C., 83 parts of acetic acid, 69 parts of anhydrous sodium acetate and 115 parts of water-moist chromium III hydroxide with a content of 33% Cr203 are added. The mixture is boiled under reflux (temperature approx. 103 ° C.) for 10 hours. After cooling to room temperature, the minor precipitations are removed by filtration. The filtrate consists of two liquid layers. The lower colorless, salt-rich, aqueous layer is separated off. After 67 parts of ethylene glycol have been added, the upper one is the low-salt, concentrated, stable stock solution. It dyes wool, polyamide or leather in red tones.

Solutions of other 1: 2 chromium complex and chromium mixed complex dyes can be prepared in an analogous manner from the dyes in the table, see drawing sheet No. 3, examples No. 16 to 20.

At

hue

At

hue

For example

game

game

16

blue-gray

18th

orange

20th

17th

Scarlet fever

19th

olive

red

Example 21

A mixture of 625 parts of ethyl glycol acetate, 210 parts of ethyl glycol, 188 parts of l-amino-2-oxy-5-sulfamido-ben-

5

629 522

zol and 142 parts of 30 percent hydrochloric acid is heated to 70 ° C and then cooled to 0 to 5 ° C. A solution of 69 parts of NaNOz in 260 parts of water is run into this mixture at 0 to 5 ° C. with stirring in about 1 hour. The mixture is stirred at 0 to 5 ° C for 1 hour, then 8 parts of amidosulfonic acid are added. The mixture is stirred for a further hour at 0 to 5 ° C., then 188 parts of acetoacetanilide and 152 parts of 50 percent sodium hydroxide solution are introduced within 1 hour. The mixture is then stirred for 2 hours, 125 parts of water-moist cobalt-H-hydroxide io with a content of 25% cobalt are added and the mixture is boiled under reflux (temperature approx. 103 ° C.) for 3 hours. After cooling to room temperature, the minor precipitations are removed by filtration. The filtrate consists of two liquid layers. The lower colorless, salt-rich aqueous layer is separated off. The upper one represents the low-salt, concentrated, stable stock solution. It dyes wool, polyamide or leather in yellow tones.

Solutions 20 of other 1: 2 cobalt complex dyes can be prepared in an analogous manner from the dyes in the table, see drawing sheet No. 4, examples 22 to 25.

Color hue color hue color hue

25th

22 violet 24 blue-violet 25 yellow

23 bordo

Example 26

The following two reaction mixtures I and II are prepared by diazotization and coupling in the solvent mixture of butyl diglycol (diethylene glycol mono-n-butyl ether) or ethyl glycol and ethyl glycol acetate:

Reaction mixture I:

A mixture of 415 parts of butyl diglycol, 415 parts of ethyl glycol acetate, 154 parts of 1-amino-2-oxy-5-nitro-benzoI and 142 parts of 30 percent hydrochloric acid is stirred at room temperature for 6 hours. A solution of 69 parts of NaNOz in 260 parts of water is run into this mixture at 0 to 5 ° C. with stirring in about one hour. The mixture is stirred for 1 hour at 0 to 5 ° C, 6 parts of amidosulfonic acid, stirred for 30 minutes, then 179 parts of l-phenyl-3-methyl-pyrazo-ion-5 and then 40 parts of 50 percent sodium hydroxide solution at 0 to 5 ° C within 30 minutes and stir for 2 hours.

Reaction mixture II:

A mixture of 415 parts of ethyl glycol, 415 parts of ethyl glycol acetate, 154 parts of l-amino-2-oxy-4-nitro-benzene and 142 parts of 30 percent hydrochloric acid is stirred at room temperature for 6 hours. A solution of 69 parts of NaNO 2 in 260 parts of water is run into this mixture at 0 to 5 ° C. with stirring in about 1 hour. The mixture is stirred for 1 hour at 0 to 5 ° C, 6 parts of amidosulfonic acid, stirred for 30 minutes, then 154 parts of ß-naphthol and then 120 parts of 50 percent sodium hydroxide solution at 0 to 5 ° C within 1 hour and stirred for 15 hours at room temperature after.

The reaction mixtures I and II are mixed, mixed with 230 parts of aqueous cobalt-II-hydroxide paste with a cobalt content of 27% and heated under reflux (temperature about 103 ° C.) for 1 hour. After cooling to room temperature, the minor precipitations are removed by filtration. The filtrate consists of two liquid layers. The lower colorless, salt-rich, aqueous layer is separated off. The upper one represents the low-salt, concentrated, stable stock solution. It dyes wool, polyamide or leather in brown tones.

C.

4 sheets of drawings

Claims (7)

629 522 PATENT CLAIMS 1. Process for the preparation of concentrated, low-salt solutions of sulfonic acid group-free o, o'-dihydroxy or o, o'-hydroxycarboxy cobalt and chromium 1: 2 complexazo dyes, characterized in that the metallisie - 5 tion in water and a solvent of formula 1 R (C0) m0 (C2H30 ^ - -JÒ (1), in the 10th A is hydrogen or methyl, m the numbers 0 or 1, n the numbers 1, 2 or 3 and R and R1 independently of one another are hydrogen or Cr to C4-alkyl 15 mean, in the presence of water-soluble salt. 2. The method according to claim 1, characterized in that that you metallize in a mixture with other solvents. 3. The method according to claim 1, characterized in that as compounds of formula 1 solvents of formula 20 ROCyt ^ OCOR1 used, where R and R1 have the meaning given. 25th 4. The method according to claim 2, characterized in that ethylene glycol, diethylene glycol dipropylene glycol or ethylene glycol Cx to C4 monoether are used as further solvents. 5. The method according to claim 1, characterized in that one uses sodium chloride, sodium formate, acetate or propionate as water-soluble salts. 6. The method according to claim 1, characterized in that that the reaction mixture is used for the metallization, which is obtained in the preparation of the azo dye to be metallized by diazotization and coupling in the presence of the solvents of formula 1 and optionally further solvents. 7. Use of the solutions prepared according to claim 1 for the preparation of dye baths and printing pastes from outside the textile industry.