DE1283997B - Process for the preparation of water-soluble phthalocyanine dyes - Google Patents

Description

It has been found that new, valuable, water-soluble phthalocyanine dyes of the general formula can be obtained

c-1

in which Pc for a substituted or unsubstituted Phthalocyanine nucleus, which is preferably metal-containing, B is a direct bond or a divalent one represents an organic bridge member, Ri and R2 hydrogen atoms or substituted or unsubstituted Mean alkyl or aryl groups, which are either the same or different or optionally can be linked to one another to form a ring, R3 is a hydrogen atom or an aliphatic atom Represents a radical which, optionally together with the bridge member B, is part of a heterocyclic R4 can be a hydrogen atom or an optionally substituted alkyl radical X represents the group then part of the sulfonic acid chloride groups saponified to sulfonic acid groups and

a) those dyes which contain groups of the formula (3) are isolated,

b) those dyestuffs which contain groups of the formula (2), isolated or through Treatment with acid-binding agents, for example sodium carbonate or sodium hydroxide, converted into dyes with groups of the formula (3) or

c) those dyes which contain groups of the formula (5), initially by treatment with inorganic or organic acids or derivatives thereof, for example sulfuric acid or acetic anhydride, converted into dyes with groups of the formula (2), then these isolated or by handling acid-binding agents, for example sodium carbonate or sodium hydroxide, irr dyes with groups of the formula (3).

Examples of a divalent organic radical B are the groups of the formulas

- (CH ₂ ), -

-CH ₂ -CH ₂ -Z

(2)

in which Z is a radical, which can be split off as an anion, of a monobasic or polybasic inorganic or organic Represents acid, or the group

-CH = CH ₂ (3)

denotes in which a, b and c also stand for numbers from 1 to 3, the sum of which should not exceed 5, η denotes the number 1 or 2 and in which finally the benzene nucleus A contains further substituents or is part of a polynuclear, condensed ring system can be prepared by mixing phthalocyaninesulfonic acid chlorides with amines of the general formula

in which ρ is an integer from 1 to 5 and R is a hydrogen atom or an alkyl group having 1 to S carbon atoms, which may optionally be linked together with R3 in the formulas (1) and (4) to form a ring, and furthermore the following Groupings called:

40

^ä \

N-B

-X '(4)

45

50

in which B, R3, R4 and η have the meanings given above and X 'in addition to the meanings mentioned for X also the group

CH ₂ -CH ₂ -OH

(5)

55

can mean and in which the benzene nucleus A is substituted as indicated above or is part of a polynuclear, condensed ring system, as well as with amines of the general formula

/ Ri

H-N

\ x

(6)

Ri and R * give way to the meaning mentioned above own, converts, possibly simultaneously or

- CO — NH-

SO ₂ -

SO ₂ -NH-

V Xs TVTlT ΓΤ \

The benzene nuclei in these groupings can optionally be replaced by water-solubilizing groups, for example sulfonic acid or carboxylic acid groups, may be substituted.

Phthalocyaninesulfonsäurechloride, the process according to Can be used as starting materials are, for example, di-, tri- or tetrasulfonic acid chlorides of preferably metal-containing phthalocyanines or mixtures of these, for example Copper phthalocyanine - (3) - tetrasulfonic acid chloride, copper phthalocyanine - (3) - trisulfonic acid chloride, Nickel phthalocyanine - (3) - tetrasulfonic acid chloride, cobalt phthalocyanine - (3) - trisulfonic acid chloride or copper phthalocyanine (4) tetrasulfonic acid chloride. However, there are also those for this purpose Suitable sulfonic acid chlorides which carry further substituents on the phthalocyanine nucleus, for example Sulfonic acid chlorides of tetraphenyl copper phthalocyanine or of tetrachloro nickel phthalocyanine, or for example copper phthalocyanine - (3) - trisulfonic acid chloride - monosulfonic acid, copper phthalocyanine- (3) -disulfonic acid chloride disulfonic acid or mixtures of these. The sulfonic acid chlorides mentioned are produced by known processes, for example according to the method of German patent specification 891121.

As amines of the general formula (4), according to the process The following compounds can be used, for example called:

/? - Hydroxyethyl (3-aminophenyl) sulfone,
/ 3-HydroxyäthyI- (4-aminophenyl sulfone,
/? - Hydroxyethyl- [4- (N-methylamino) -phenyl] -sulfone,

/ f-Hydroxyethyl- (3-amino-4-hydroxyphenyl) -

sulfone,
/ 3-hydroxyethyl (3-amino-4-methoxyphenyl) sulfone,
/ J-hydroxyethyl- (3-hydroxy-4-aminophenyl) -

sulfone,
/ 3-hydroxyethyl (3-methoxy-4-aminophenyl) sulfone,

£ -hydroxyethyl (3-amino-4-methylphenyl) sulfone,

/? - Hydroxyethyl- (3-amino-4-sulfo-phenyl) -

sulfone,
^ -Hydroxyethyl (3-bromo-4-aminophenyl) sulfone,

/ 5-hydroxyethyl- (3-amino-4-carboxy-phenyl) -. sulfone,
ß-hydroxyethyl (2,5-dimethoxy-4-aminophenyl) sulfone,

/ i-hydroxyethyl (2-methyl-4-amino-5-methoxyphenyl) sulfone,

/ 3-Hydroxyethyl-r3-nitro-4- (4'-aminophenylamino) -pheny J-sulfone,

^ -Hydroxyethyl- [4-amino-naphthyl- (l)] - sulfone, ^ -Hydroxyethyl- '5-amino-naphthyl- (l) J-sulfone, ^ -Hydroxyethyl- | 6-amino-naphthyl- (2)] - sulfone, / I-hydroxyethyl- [3- (4'-aminobenzoylamino) -

4-hydroxyphenyl] sulfone,
^ -Hydroxyethyl- [3- (4'-aminobenzoylamino) -

phenyl] sulfone,
_j 5-hydroxyethyl- (3-amino-4-hydroxy-5-nitro-

phenyl) sulfone,
/? - Hydroxyethyl- [4- (3'-aminophenylsulfonyl-

amino) -phenylj-sulfone.

The / 3-hydroxyäthylsulfongruppen-containing Amines can optionally also in the form of their esters with mineral acids or organic acids, can be used, for example, in the form of their acidic sulfuric acid esters or their acetic acid esters.

The following compounds, for example, may also be mentioned as amines of the general formula (4): β- chloroethyl (3-aminophenyl) sulfone, vinyl (4-amino; phenyl) sulfone, / 9-hydroxyethyl [4 - (/? - amino-ethyl) -phenyl] -sulfone of the formula

HO

CH ₂ SOj ■ CH ₂ -CH ₂ -NH ₂

l '[4' - (ß-HydroxyäthylsuIfonyl) phenyl] piperazine d _he formula

CH ₂

HN

- CH ₂ - CH ₂ - OH

N- [2-Nitro-4 - (/ 5 (-hydroxyethylsulfonyl) -phenyl] -ethylenediamine of the formula

H ₂ N - CH ₂ - CH ₂ - NH

or the compounds of the formulas below NH ₂

HO ₃ S

SO ₂ -CH ₂ -CH ₂ -OH

NH-

SO ₃ H

Η, Ν

Η, Ν

HO ₃ S

The following compounds, for example, can also be used as amines of the general formula (4) which can optionally be used in the form of their alkali salts:

3- (N-Ethionylammo) -l-aminobenzene,
3- (N-methyl-N-ethionylamino) -

1-aminobenzene,
4- (N-methyl-N-ethionylamino) -

1-aminobenzene,
2-methoxy-4- (N-methyl-N-ethionylamino) -

1-aminobenzene,
3- (N - ^ - cyanoethyl-N-ethionylamino) -l-amino-

benzene,
^ N- ^ cyanoethyl-N-ethionylaminoH-amino-

benzene,
3- <N - ^ - cyanoethyl-N-ethionylamino) -4-methoxy-

1-aminobenzene,
5- (N- / K ^ chloroethyl-N-ethionylamino) -2-methyl-

1-aminobenzene,

H ₂ N-

CO -NH

Amines of the general formula (4) are also those of the abovementioned compounds suitable, which contain an N-isethionylamino group in place of the N-Äthionylamino group.

Representatives of amines of the general formula (6), which are available for the preparation of the process according to the Phthalocyanine dyes are used, for example, are the following compounds: Ammonia, methylamine, ethylamine, n-butylamine, benzylamine, aniline, ethanolamine, dimethylamine, Diethylamine, di-iso-propylamine, N-methylbenzylamine, N-methylaniline, piperidine, morpholine, diethanolamine, 2-aminoethane-l-sulfonic acid, 2-aminoethane -1 - carboxylic acid, 4 - aminobenzenecarboxylic acid, 3-aminobenzenesulfonic acid or 4-aminobenzenesulfonic acid.

The amines of the general formulas (4) and (6) can be used when carrying out the present process either as free bases or in the form of their water-soluble salts with hydrohalic acids can be used.

The process according to the reaction of Phthalocyaninsulfonsäurechloriden with amines of the general formula (4) and with amines of the general formula (6) can in aqueous or non-aqueous medium, depending on the solubility properties in solution or suspension, in the presence of acid-SO ₂ -CH ₂ -CH ₂ -Cl

SO ₂ - CH ₂ - CH ₂ - O - SO ₃ H

SO ₂ - CH ₂ - CH ₂ - O - SO ₃ H

3- (N-0-chloroethyl-N- / f-cMoiMiyIsulfonyl-

amino) -l-aminobenzene,
. 3- (N- / 8-cyanoethyl-N-vinylsulfonylamino) -

1-aminobenzoL
3- (N - /? - Carboxyethyl-N-äthionyIamino) -

1-aminobenzene,
3- (N- / 3-carbethoxyethyl-N-ethionylammo) -

1-aminobenzene,

4- (N- / 3-carbethoxymethyl-N-ethionylamino) -1-aminobenzene,

5- (N - /? - cyanoethyl-N-ethionylamino) -2-chloro-

1-aminobenzene,
4- (N- / S-cyanoethyI-N-aetmonylamino) -6-amino-

1,3-dimethylbenzene,
3- (N - ^ - Hydroxyäthyl-N-äthionyIamino) -

1-aminobenzene,

3- (Ni? -Hydroxyethyl-N-isoäthionyIamino) -1-aminobenzene-disulfuric acid ester or
4- (N-carbomethoxymethyl-N-ethionylamino) -1- (4'-aminobenzoylamino) benzene of the formula

CH ₂ - CO - OCH ₃

- CH ₂ - CH ₂ - OSO ₃ H

the means to be carried out. For example, methanol or dimethylformamide can be used as solvents to carry out the reaction in a non-aqueous medium. Acid-binding agents which can be used are, for example, sodium bicarbonate _→ sodium carbonate or sodium hydroxide, furthermore tertiary organic bases, for example pyridine or triethylamine, or else an excess of the amine of the general formula (6). The reaction is carried out at weakly acidic to weakly alkaline pH values. If amines of the general formula (4) are used which contain a group of the formula (2) or a group of the formula (3), it is advisable to work in a neutral to weakly acidic medium in order to avoid side reactions. The reaction can be carried out over a wide temperature range. It is expedient to work at temperatures between about -5 and _; + 10O ⁰ C.

If the process according to the reaction with such amines of the general formula (4) carried out, the contain a group of the formula (S), the first reaction step of the condensation follows according to the process a further stage in which the dyes initially obtained with groups of Formula (S) by treatment with inorganic

or organic acids or derivatives thereof converted into dyes with groups of the formula (2) will. From the class of inorganic or organic acids or derivatives thereof which are used for This second reaction step can be used, for example, the following are listed: Sulfuric acid, phosphoric acid, acetic anhydride, acetyl chloride, p-toluenesulfonic acid chloride, chlorosulfonic acid and sulfamic acid. While the reaction with the acids mentioned is preferred made without a solvent or in an excess of these acids, which serves as a solvent is, the reaction with the acid derivatives mentioned takes place preferably in the presence of anhydrous Solvents or diluents instead, which are also effective as acid-binding agents, for example Pyridine, a-picoline or triethylamine.

The starting compounds necessary for carrying out the process of the present invention are expediently selected in such a way that the resulting phthalocyanine dye of the general Formula (1) the number of solubilizers necessary to achieve sufficient solubility in water Contains groups such as sulfonic acid and / or carboxylic acid groups.

The phthalocyanine dyes obtainable according to the process are isolated by salting out, for example with sodium or potassium chloride, and / or by acidification with a mineral acid or by evaporating the neutral, aqueous dye solutions, preferably at a moderately elevated temperature and reduced pressure.

The new phthalocyanine dyes obtainable according to the process are suitable for dyeing and printing of various materials, such as wool, silk, leather and linear polyamides, in particular however, materials containing hydroxyl groups and having a fibrous structure, for example linen, regenerated cellulose and especially cotton. The new dyes are applied to the fiber by treating the Material with an aqueous solution of the dye, for example by direct coloring from a long liquor, made by padding or by printing using an aqueous printing paste, the Dyeings or prints at the same time or after an alkali treatment, for example with trisodium phosphate, Sodium carbonate or sodium hydroxide, or subjected to a heat treatment will. The coloring can take place at normal or at elevated temperature, for example at 50 to 100 C, and in the presence of neutral, inorganic salts such as sodium sulfate.

The new dyes produce very valuable, strong colors on the above-mentioned materials and prints that are characterized by very good wet fastness properties and very good light fastness properties.

The dyes obtainable according to the process, each having a similar structure, are distinguished from the from Example 3 of British Patent 969 033 known dye in the dyeing of cotton fabric by a better yield compared to that known from Example 3 of Belgian patent 611053 Dye when dyeing cotton fabric using the Klotz short-dwell process a better color yield and compared to that from Example 1 of the German Auslegeschrift 1 179 317 known dye when dyeing cotton fabrics due to better wash and bleeding fastness and when printing cotton fabrics due to less soiling of those that are differently or not colored Fabric or enclosed white goods.

example 1

In an ice-cold, neutralized solution of 84.3 parts by weight of the acid sulfuric acid ester of / i-hydroxyethyl (4-aminophenyl) sulfone in 300 parts by weight of water 97 parts by weight of copper phthalocyanine (3) tetrasulfonic acid chloride in the form of a moist Paste entered. Then 10 parts by weight of pyridine are added and the mixture is stirred at 5 ^° C., a pH of 6.5 to 7 being maintained by continuously adding 20% strength aqueous ammonia. After about 3 hours, when the reaction has practically come to a standstill, the reaction mixture is allowed to warm to room temperature and is stirred for a further 15 hours at this temperature. The solution obtained is then filtered and the dye formed is isolated by salting out with sodium chloride and potassium chloride. To clean it, you can dissolve the dye again in water and salt it out again. After drying, 229 parts by weight of a salty, blue dye are obtained which dissolves very easily in water and dyes wool and cotton in turquoise-blue shades of very good fastness properties.

Dyes with similar properties are obtained by following the above reaction instead of copper phthalocyanine (3) tetrasulfonic acid chloride, equivalent amounts of nickel phthalocyanine (3) tetrasulfonic acid chloride or the sulfonic acid chlorides of cobalt phthalocyanine, tetraphenyl copper phthalocyanine or of metal-free phthalocyanine, the preparation of which is described in German Patent 891 121, is used.

Example 2

12.8 parts by weight of 20% strength aqueous ammonia are slowly added dropwise to a suspension of 97 parts by weight of copper phthalocyanine (3) tetrasulfonic acid chloride in 300 parts by weight of water, which has been rendered neutral by adding dilute sodium hydroxide solution. This mixture is now stirred at 20 ^° C. until it reacts neutrally again and a neutral solution of 56.2 parts by weight of the acidic sulfuric acid ester of i-hydroxyethyl (4-aminophenyl) sulfone in 200 parts by weight of water is then added. 5 parts by weight of pyridine are then added to the reaction mixture and the mixture is stirred at a temperature of 20 ° C., a pH of 6.5 to 7 being maintained by adding 38 parts by weight of sodium bicarbonate in portions. As soon as the reaction has ended and bicarbonate is no longer consumed, the solution obtained is filtered and the dye formed is isolated by salting out with sodium chloride and potassium chloride. After the dryer, 190 parts by weight of a blue powder are obtained which dissolves in water with a turquoise-blue color. The dye can be fixed to cotton under the action of alkaline agents and provides turquoise-blue dyeings and prints of good fastness to washing and good fastness to light.

Dyes with similar properties are obtained if in the previous example instead of of the acid sulfuric acid ester of / i-hydroxyethyl

809 639/1519

(4-Amino-phenyl) -sulphone equivalent amounts of the acidic sulfuric acid esters of the following / i-hydroxyethylsulphone groups Amines are used:

/ 3-hydroxyethyl (3-aminophenyl) sulfone, /? - Hydroxyethyl- (3-amino-4-methoxyphenyl) -

sulfone,
/? - Hydroxyethyl- [4- (N-methylamino) -phenyl] -

sulfone,
/? - Hydroxyethyl (3-methoxy-4-aminophenyI) - ι ο

sulfone,
/? - Hydroxyethyl- (3-amino- £ methyl-phenyl) -

sulfone,
/? - Hydroxyethyl- (3-amino-4-sulfo-phenyl) -sulfone,

/? - Hydroxyethyl- (3-bromo-4-aminophenyl) -

sulfone,
j3-hydroxyethyl- (3-amino-4-carboxy-phenyl) -

sulfone,
/ S-hydroxyethyl- (3-amino-4-hydroxyphenyl) -

sulfone,
/? - Hydroxyethyl (3-hydroxy-4-aminophenyl) sulfone,

/ i-hydroxyethyl- (2,5-dimethoxy-4-amino-

phenyl) sulfone,
/ i-hydroxyethyl- (i-methyl-4-amino-5-methoxy-

phenyl) sulfone,
/? - Hydroxyethyl- [3-nitro-4- (4'-aminophenyl-

amino) -phenyl] -sulfone,
ß-hydroxyethyl- [3- (4'-aminobenzoylamino) -

4-hydroxyphenyl] sulfone,

/ i-Hydroxyäthyl- / I-Hydroxyäthyl - /? - Hydroxyäthyl- / i-Hydroxyäthyl-

_t 4-amino-naphthyl- (l)] - sulfone,] 5-amino-naphthyl- (1)] - sulfone, ° 6-amino-naphthyl- (2)] - sulfone, 3- (4'-aminobenzoylamino) -

HO - CH ₂ - CH ₂ - SO ₂

are dissolved in 250 parts by weight of water. 40 parts by volume of 2N sodium hydroxide solution are added to this solution and 38.8 parts by weight of copper phthalocyanine- (3) -tetrasulfonic acid chloride are then introduced in the form of a moist paste with thorough stirring. The reaction mixture is then heated to 50 ⁰ C and held at this temperature to give / pc alcohol by continuous addition of aqueous ammonia 2O ° maintains a pH value of 9 to 9.5. The reaction has ended after about 2 hours. Now is filtered off the resulting condensation product, thoroughly washed with warm water and dried in vacuum at 6O ⁰ C.

The dry and ground condensation product is concentrated in 490 parts by weight Entered sulfuric acid and stirred for 12 hours at room temperature. Then you pour the obtained Solution on ice, the precipitated ester dye is filtered off and washed with sodium chloride solution. The moist filter cake is dissolved by adding sodium bicarbonate until it is neutral Reaction in 2000 parts by volume of water and then isolating the dye by salting out with sodium chloride. After drying, 82 parts by weight of a salty, turquoise-blue dye are obtained, which dissolves easily in water and which is used for dyeing and printing fiber materials made of native and regenerated cellulose can be used. This is obtained in the presence of acid-binding agents Dyeings and prints of excellent washfastness.

Example 4

To a solution of 8.5 parts by weight of the hydrochloride of /? - hydroxyethyl [4 - (/? - aminoethyl) phenyl] sulfone of the formula given in Example 3 in 250 parts by weight of water, 15 parts by volume of 2 η sodium hydroxide solution and 15 parts by volume of 2 n -Ammonia added. 19.4 parts by weight of copper phthalocyanine- (3) -tetrasulfonsät.'rechlorid are then added to this solution with thorough stirring, heated to phenyl sulfone,
/ i-hydroxyethyl- (3-amino-4-hydroxy-5-nitro-

.phenyl) sulfone,
^ -Hydroxyethyl- [4- (3'-aminophenylsulfonyl-

amino) -phenylj-sulfone.

Example 3

22.7 parts by weight of the hydrochloride of ß-hydroxyethyl - [4 - (ß - aminoethyl) phenyl] sulfone of the formula

CH, - CH, - NH, · HCl · H, O

50 ^° C. and stirring is continued for a few hours at this temperature, a pH of 9 to 9.5 being maintained by the continuous addition of 2η sodium hydroxide solution. After completion of the reaction the solution is allowed to cool to room temperature, the reaction product is precipitated by acidification with hydrochloric acid, filtration it off, it is washed with dilute hydrochloric acid and dried at 6O ⁰ C.

The dry and ground condensation product is poured into 200 parts by weight with thorough stirring concentrated sulfuric acid and stirred for 12 hours at room temperature. Then you pour the resulting solution on ice, the precipitated ester dye is filtered off and washed with it Saline solution. The moist filter residue is dissolved in 1000 parts by volume of water with the addition of Sodium bicarbonate to a neutral reaction and then isolates the dye by salting out with Sodium chloride. After drying, 33 parts by weight of a salty, turquoise-blue dye obtained, which is very washfast on cotton fabric with the help of alkaline agents can fix.

Example 5

31.4 parts by weight of 3- (N - ^ - cyanoethyl-N-ethionylamino) -l-aminobenzene the formula

55

60 H, N

, CH, -CH, -CN

SO ₂ - CH ₂ - CH ₂ - O - SO ₃ H

are in 250 parts by weight of water with the addition of 7.5 parts by weight of sodium bicarbonate up to neutral reaction resolved. In the solution obtained one contributes -: - 5 ° C with thorough stirring 29.1 parts by weight Kiipferphthalocyanm- (3) -tetrasulfonsäurechloriä a, then adds 3 parts by weight of pyridine and. Provides by adding 20% aqueous

Ammonia has a pH of 6.5 to 7. The reaction mixture is then stirred at + 5 ° C, whereby a pH of 6.5 to 7 is maintained by continuously adding aqueous ammonia. As soon as the reaction has ended and ammonia is no longer consumed, the obtained solution and isolated the dye formed by salting out with sodium chloride and Potassium chloride. For further purification, the isolated dye can be dissolved again in water and salt out again. After drying, 85 parts by weight of a salty, blue dye which dissolves easily in water and wool and cotton in turquoise-blue tones from dyes very good fastness properties.

Is used in the above example instead of 3- (N - /? - Cyanäthyl-N-äthionylamino) -1 -aminobenzenes equivalent amounts of the following amines result in dyes with similar properties:

4-chloro-3- (N - /? - cyanoethyl-N-ethionylamino) -

1-aminobenzene,
4- (N- / i-cyanoethyl-N-ethionylamino) -l-amino-

benzene,
2-methyl-5- (N-ß-cyanoethyl-N-ethionylamino) -

1-aminobenzene,
3- (N-carbomethoxymethyl-N-ethionylamino) -

1-aminobenzene,
3- (N-Carbomethoxyäthyl-N-äthionylarnino) -

1-aminobenzene,
3- (N - // - cyanoethyl-N-vinylsulfonylamino) -

1-aminobenzene,
4- (N- / i-chloroethyl-N-ethionylamino) -1 -amino-

benzene,

4- (N-methyl-N-ethionylamino) -1 -aminobenzene,
3- (N-methyl-N-ethionylamino) -l-aminobenzene,
3-methoxy-4- (N-methyl-N-ethionylamino) -

1-aminobenzene or
4- (N-methyl-N-ethionylamino) -l- (4'-amino-

benzoylamino) benzene.

Example 6

In a solution of 20.1 parts by weight ß-hydroxyethyl (3-amino-phenyl) sulfone are dissolved in 500 parts by weight of water at 15 to 20 ⁰ C with good stirring 48.5 parts by weight of copper phthalocyanine (3) in the form of a moist -tetrasulfonsäurechlorid Paste entered. By adding sodium hydroxide solution to this suspension, then the pH value 8 a, heated to 50 ⁰ C and further stirred the reaction mixture at this temperature, with 2 η-ammonia solution, the pH is maintained 8 by dropwise addition of 25 parts by volume. As soon as the amount of ammonia solution has been used up, the pH value of 8 is kept constant by adding dropwise 2 η sodium hydroxide solution. After about lOstündigem stirring at 50 to 55 ⁰ C 130 parts by volume 2 N sodium hydroxide solution are about been consumed, and the reaction is stopped. The solution is now allowed to cool to room temperature, the reaction product is completely precipitated with hydrochloric acid, filtered off, washed with dilute hydrochloric acid and dried. The dry and ground condensation product is introduced into 600 parts by weight of concentrated sulfuric acid and stirred for 12 hours at room temperature. The resulting solution is then poured onto ice, the precipitated ester dye is filtered off and washed with sodium chloride solution. The moist filter cake is dissolved in 2000 parts by volume of water with the addition of sodium bicarbonate until the reaction is neutral, and the dye is then isolated by salting out with sodium chloride. After drying, 83.5 parts by weight of a salt-containing, turquoise-blue dye are obtained, which can be used for dyeing and printing fiber materials made from native and regenerated cellulose. In the presence of acid-binding agents, dyeings and prints of excellent washfastness are produced.

Dyes with similar properties are obtained if one in the preceding example in place of the / i-hydroxyethyl (3-aminophenyl) sulfone the same amount of / i-hydroxyethyl (4-aminophenyl) sul fön or equivalent amounts of those listed at the end of Example 2, containing ß-hydroxyethylsulphone groups Amines used.

If, in the above example, equivalent amounts of the following amines are used instead of ammonia one, you also get dyes with similarly good coloring properties: methylamine, ethylamine, n-butylamine, benzylamine, aniline, ethanolamine, dimethylamine, diethylamine, di-isopropylamine, N-methylbenzylamine, N-methylaniline, piperidine, Morpholine, diethanolamine, 2-ammoethari-1-carboxylic acid, 2-aminoethane-l-sulfonic acid, 4-aminobenzenecarboxylic acid, 3 - aminobenzenesulfonic acid or 4-aminobenzenesulfonic acid.

Example 7

58 parts by weight of /? - hydroxyethyl [3-nitro-4 - (/? - aminoethylamino) phenyl] sulfone the formula

H> N ■

NH

are suspended in 1000 parts by weight of water. This suspension is heated to 50 ° C. and 97 parts by weight of copper phthalocyanine- (3) -tetrasulfonic acid chloride are introduced in the form of a moist paste with thorough stirring. The mixture is then stirred at 50 ° C., a pH of 8.5 to 9 being constantly maintained by adding dropwise 2N sodium hydroxide solution. As soon as 100 parts by volume of 2N sodium hydroxide solution have been consumed (after about 2 1/2 hours ), one adds a solution of 36.6 parts by weight of ethanolamine in 100 parts by weight of water and CH ₂ - OH

The reaction mixture is stirred for a further 10 hours at 50 ^° C. The resulting condensation product is then filtered off, washed thoroughly with warm water and dried at 40 ° C. in vacuo.

The dry and ground condensation product is then prepared according to the method described in the second paragraph of Example 6 described procedure with 1250 parts by weight of concentrated sulfuric acid in the acidic sulfuric acid ester converted. This gives 310 parts by weight of a salt-containing, blue-green Dye, which under the action of alkali

Lisch-acting agent on cotton fabric supplies washable and lightfast dyeings.

If the ethanolamine used is replaced in the above example by a corresponding one Amount of diethanolamine, a dye with similar properties is obtained. If you put under Use of the different amines instead of copper phthalocyanine- (3) -tetrasulfonic acid chloride the equivalent amount of nickel phthalocyanine- (3) -tetrasulfonic acid chloride is formed in in both cases dyes which have a slightly more yellow shade, but otherwise the same coloring Have properties.

Example 8

29 parts by weight of /? - hydroxyethyl [3-nitro-4 - (// - aminoäthylamino) phenyl] sulfone of the formula given in Example 7 are suspended in 500 parts by weight of water. The mixture is heated this suspension at 50 ¹ C and wears with good stirring 48.3 parts by weight Nickelphthalocyanin- -tetrasulfonsäurechlorid (3) in the form of a wet paste a. The mixture is then stirred at 50 ° C., a pH of 9 to 9.5 being constantly maintained by adding dropwise 2η sodium hydroxide solution. After 50 parts by volume of 2N sodium hydroxide solution have been consumed, a solution of 12.5 parts by weight of 1-aminoethane-2-sulfonic acid in 200 parts by weight of water is added and the reaction mixture is stirred for a further 5 hours at 50.degree - Sodium hydroxide solution is maintained at a pH of 9 to 9.5. As soon as the condensation has ended, one leaves

cool to room temperature, the condensation product is precipitated by acidification with dilute hydrochloric acid and dry it.

The dry and ground condensation product is then prepared according to the method described in the second paragraph of Example 6 described procedure with 700 parts by weight of concentrated sulfuric acid in the acidic sulfuric acid ester converted. This gives 113 parts by weight of a salty, blue-green Dye, the cotton in the presence of acid-binding agents such as sodium bicarbonate or Sodium carbonate, dyes in blue-green shades with very good wet fastness properties.

Dyes with similar properties but a much more yellow hue are obtained if, in the above example, instead of 12.5 parts by weight of 1-aminoethane-2-sulfonic acid, 26.1 parts by weight of 2- {ß- aminoethylamino) - 5 - nitrobenzene -1 - sulfonic acid of the formula

H ₂ N - CH ₂ - CH ₂ - NH

NO ₂

SO ₃ H

or the same amount by weight of 4 - (/ f-aminoethylamino) -3-nitrobenzene-1 sulfonic acid is used.

If, in the preceding examples, the β - hydroxyethyl - [3 - nitro -A- (β- aminoäthylamino) phenyl] sulfone is replaced by the equivalent amount of 1 - Γ2 '- nitro - A' - (β - hydroxyäthylsulfonyl) - phenylj-piperazine of the formula

SO, - CH, - CH, - OH

this also creates blue-green to green dyes with excellent fastness properties.

Example 9

57.6 parts by weight of copper phthalocyanine are gradually introduced into 260 parts by weight of chlorosulfonic acid with thorough stirring. The sulfonation mixture is slowly heated to 125 ° C. and stirred for a further 4 hours at this temperature. Then allowed to 9O ⁰ C to cool, dropped at 80 to 90 C slowly 115 parts by weight of thionyl chloride and stir for 4 hours at 90 C after. After cooling to room temperature, the reaction mixture is poured onto ice, the precipitated copper phthalocyanine sulfonic acid chloride is filtered off and washed neutral with ice water.

The moist filter cake obtained is transferred to a neutral one at 5 ° C. with thorough stirring Solution of 84.5 parts by weight of the acidic sulfuric acid ester of / i-hydroxyethyl- (4-aminophenyl) -sul-

NH

HO ₃ S

NH-CO fön in 300 parts by weight of water, stir the Mix for a short time, then add 10 parts by weight of pyridine and hold by adding dropwise 20% aqueous ammonia solution maintains a pH of 6.5 to 7. During the entire duration of the reaction the temperature of the condensation mixture should not exceed + 5 C. After about The reaction has ended in 6 hours. The solution obtained is then filtered, and the dye formed is isolated by salting out with sodium chloride. By repeated dissolving in water and again The dye can be cleaned by salting out.

After drying, 269 parts by weight of a salt-containing dye are obtained, the cotton in Presence of acid binding agents, such as sodium bicarbonate or sodium carbonate, in turquoise blue Töneri dyes with very good wet fastness properties.

In the above example, if the acid sulfuric acid ester is replaced by i-hydroxyethyl (4-aminophenyl) sulfone by equivalent amounts of the following compounds

SO, - CH ₂ - CH, - O - CO - CH ₃

SO2 _CH2 CH2 Cl

SO ₃ H

SO, - CH, - CH, - O - SO, H

NH

HO ₃ S

NH-CO-NH

this also creates turquoise-blue dyes with excellent properties Authenticity properties.

Example 10

In a neutralized solution of 84.3 parts by weight of the acid sulfuric acid ester of / i-hydroxyethyl- (3-aminophenyl) -sulfone in 300 parts by weight of water with good stirring at 15 ¹ C 97 parts by weight of copper phthalocyanine- (3) -tetrasulfonic acid chloride in the form entered a moist paste. 10 parts by weight of pyridine are then added and the mixture is stirred at 15 ° C., a pH of 6.5 to 7 being maintained by continuously adding 20% strength aqueous ammonia. After about 2 hours, when the reaction has practically come to a standstill, 33% sodium hydroxide solution is added to the resulting solution until a pH value of 12 is reached, and the dye is then salted out by adding sodium chloride, filtered off and dried. This gives 230 parts by weight of a salt-containing dye which can be fixed to native and regenerated cellulose fibers from salt-containing dye liquors with the aid of acid-binding agents. In addition to good wet and rubbing fastness properties, these dyeings also show very good light fastness.

Claims (1)

Claim: Process for the preparation of water-soluble phthalocyanine dyes of the general formula SO ₁ - N - BIA / R ₁ " SO ₁ -N SO, —X (I] 50 55 [SO ₃ H],., in which Pc represents a substituted or unsubstituted phthalocyanine nucleus, B represents a direct bond or a divalent organic bridge member, Ri and Ro represent hydrogen atoms or substituted or unsubstituted alkyl or aryl groups, which can be either identical or different or optionally linked to form a ring, R _{; i represents} a hydrogen atom or an aliphatic radical which, optionally together with the CH ₂ - CH ₂ - O - SO ₃ H Bridge member B can be part of a heterocyclic ring, R4 is a hydrogen atom or represents an optionally substituted alkyl radical, X represents the group -CH ₂ -CH ₂ -Z (2) in which Z is a radical, which can be split off as an anion, of a monobasic or polybasic inorganic or represents organic acid, or the group - CH = CH ₂ (3) denotes in which a, b and c also stand for numbers in the range from 1 to 3, the sum of which should not exceed 5, "denotes the number 1 or 2 and in which finally the benzene nucleus A contains further substituents or is part of a polynuclear, condensed ring system can be, characterized in that phthalocyaninesulfonic acid chlorides with amines of the general formula SO ₂ -X ' n-l in which B, Ra, Ri and «the above Have meanings and X 'in addition to the meanings given for X also have the group -CH ₂ -CHo-OH '(5) can mean and in which the benzene nucleus A is substituted or constituent as indicated above a polynuclear, condensed ring system, as well as with amines of the general formula Η —Ν in which Ri and R _{2 have} the abovementioned meaning, converts, optionally simultaneously or subsequently saponifying some of the sulfonic acid chloride groups to sulfonic acid groups and a) those dyes which contain groups of the formula (3) are isolated, b) those dyestuffs which contain groups of the formula (2), isolated or through Treat with acid-binding agents in 809639/1519 17 18 Dyes with groups of the formula (3) via acids or derivatives thereof into dyes leads or converted with groups of the formula (2), these c) those dyes, the groups of which are then isolated or treated with Formula (5) contain, initially by means of tannic acid binding agents in dyes your with inorganic or organic 5 groups of the formula (3) converted.