DE1795140C3 - Water-soluble phthalocyanine dyes, processes for their production and their use for dyeing or printing fiber materials made from native or regenerated cellulose, wool, silk, linear polyamides and leather - Google Patents

Description

in which Pc stands for a metal-free or copper, cobalt or nickel-containing phthalocyanine radical, the May contain phenyl groups or halogen atoms, B a divalent organic bridge member of the formula

-CH ₂ -CH ₂ -, -CH ₂ -CH ₂ -NH-,

CO — NH-,

SO ₂ -NH-

NH-

optionally substituted by phenyl, hydroxy, sulfo and carboxy alkyl group of 1 to 4 carbon atoms or a phenyl group optionally substituted by carboxy and sulfo, or R 1 and R ₂ together with the nitrogen atom form a piperidine or morpholine ring, A denotes the phenylene or naphthylene radical, which can be substituted by alkyl, alkoxy, nitro, carboxy, hydroxy or sulfonic acid groups or halogen atoms, π and / π for the number O or 1 are, a, b and c are the numbers from 1 to 4, the sum of a, b and c being at most 6.

The present invention further relates to a method of making the above and

-to defined phthalocyanine dyes of the general Formula (1), which is characterized in that one

(a) Phthalocyaninesulfonic acid chlorides of the general formula (2)

45 (HO ₃ S ^

(SO ₂ - Cl) ₀

means X is the group —CH ₂ —or —N -

Represents CH ₃ , Ri and R ₂ each represent a hydrogen atom or a in which Pc has the abovementioned meaning, ρ is a number from 0 to 3 and q is a number from 1 to 4, the sum of ρ and q being at most 4, with amines of the general formula (3)

HjN- (B) _n -A- (X ^ -SO ₂ -CHj-CH ₂ -O-PO ₃ H ₂

in which A, B, X, m and η have the abovementioned meanings, optionally with the addition of amines of the formula (4)

II-N (4)

in which Ri and R? have the meanings given above, in aqueous. watery-organic or

organic medium at pH values between about 4 and about 11, preferably between about 4 and about 9, and at temperatures between about 0 ⁰ C and about 100 ⁰ C, preferably between about 0 ⁰ C and about 30 ⁰ C, in the presence of acid-binding agents or

(b) Pbthalocyanine compounds of the general formula (5)

[SO ₂ -NH- (B) _n -A- (XL-SO ₁ -CH ₂ -CH ₂ -OH] ,,

SO ₂ -N

4th \

ISO ₃ H] ₁ -,

in which A, B, Ri, R ₂ , X, m, π, a, b and c have the abovementioned meanings, converted into the corresponding phosphoric acid monoesters using phosphorylating agents in a manner known per se

With procedure (a) success », the implementation depending according to the solubility properties of the reaction components in solution or in suspension. Should at Process (a) some of the sulfonic acid chloride groups of the starting compound of the formula (2) are converted into sulfonic acid groups, the condensation can be carried out simultaneously with the Reaction with amines of the formula (3) some of the sulfonic acid chloride groups are saponified, or that initially with an amount that is not sufficient for the complete conversion of all sulfonic acid chloride groups is reacted on amines of the formulas (3) and (4) and then the remaining sulfonic acid chloride groups be saponified by a special reaction step.

As phthalocyaninesulfonic acid chlorides of the formula (2), which are reacted according to procedure (a) are used, for example, sulfonic acid chlorides of metal-free phthalocyanine, but preferably sulfonic acid chlorides of the metal-containing ones mentioned Phthalocyanines such as

Copper phthalocyanine (3) tetrasulfonic acid chloride,

Copper phthalocyanine- (3} -trisulfonic acid chloride, Copper phthalocyanine (3) disulfonic acid chloride,

Nickel phthalocyanine (3) tetrasulfonic acid chloride,

Cobalt phthalocyanine (3) trisulfonic acid chloride,

Copper phthalocyanine- (4) -disulfonic acid chloride or

Copper phthalocyanine- (4) -tetrasulfone-

acid chloride,

likewise, for example, sulfonic acid chlorides of tetraphenyl copper phthalocyanine or of tetrachloride copper phthalocyanine or, for example, copper phthalocyanine- (3) -disulfonic acid chloride-disulfonic acid. The sulfonic acid chlorides mentioned are known according to Method produced, for example according to the method of German patent specification 8 91! 21.

As phosphoric acid monoesters of / Mydroxyethylsulfongruppe-containing amines of the formula (3) are the Phosphoric acid monoesters of the following compounds called:

/ I-hydroxyethyl- (3-aminophenyl) 'sulfone, 0-hydroxyethyl (4-aminophenyl) sulfone, O-hydroxyethyl- [4- (N-methylamino) phenyl] sulfone.

/? - HydroxyäthyI- (3-amino-4-hydroxy-phenyI) -

sulfone, /? - Hydroxyethyl- (3-amino-4-methoxyphenyl) - sulfone, / f-HydroxyäthyI- (3-hydroxy-4-aminophenyl) -

sulfone, /? - Hydroxyethyl- {3-methoxy-4-aminophenyl) - sulfone,

ß-hydroxyethyl (3-amino-4-methyl-phenyl) sulfone, 3-hydroxyethyl- (3-amino-4-sulfo-pheny!) -

sulfone, /? - Hydroxyethyl- (3-bromo-4-aminophenyl) - sulfone, ^ -Hydroxyethyl- (3-amino-4-carboxy-phenyI) -

sulfone, ^ -hydroxyethyl- (24-dimethoxy-4-aminophenyl) - sulfone,

^ -Hydroxyethyl- (2-methyl-4-amino-5-methoxyphenyl) -sulfone, /? - Hydroxyethyl- [3-mtro-4- (4'-aminophenyI-

amino) phenyl) sulfone, P-hydroxyethyl- [4-amino-naphthyl- {1)] - sulfone, ^ -Hydroxyäthyl- [5-amino-naphthyI-Ci)] - suffon, /? - Hydroxyethyl- [6-amino-naphthyl- (2)] - sulfone, ^ -HydroxyäthyI- [3- (4'-aminobenzoylamino) -

4-hydroxyphenyl] sulfone, ^ -hydroxyethyl- [3- (4'-aminobenzoylamino) -phenylj-sullon, ^ -Hydroxyäthyl- [3-amino-4-hydrüxy-5-πttro-

phenyl] sulfone, ^ -hydroxyethyl- [4- (3'-aminophenylsulfonyl amino) -phenyl] -sulfori, 3- (N-Methyl-N-isäthionylamino) -l-aminobenzene, 4- (N-methyl-N-isäthionylamino) -1 -aminobenzene, 2-methoxy-l (N-methyl-N-isäthionylamino) - 1 -aminobenzene or

^ -HydΓoxyäthyl (3-amino-4-methoxy-benzyl) - i, sulfone.

The phosphoric acid monoesters of the mentioned # -Hy-

Droxyäthylsulfone can according to known processes manufactured, for example according to the Houben

Weyl "Methods of Organic Chemistry", Volume 12/2, Page 147ff. described procedure.

Suitable amines of the formula (4) mentioned are, for example, the following:

Ammonia, methylamine, ethylamine, n-butylamine, benzylamine, aniline, Ethanolamine, dimethylamine, diethylamine, diisopropylamine, N-methylbenzylamine,

N-methylianiline, piperidine, morphioline,
Diethanolamine, 2-aminoethane-1-sulfonic acid,
2-aminoethane-1-carboxylic acid,
4-aminobenzenecarboxylic acid,

3-aminobenzenesulfonic acid or 4-aminobenzenesulfonic acid.

When carrying out process variant (a) in an aqueous or aqueous-organic medium, it is expedient to use hydroxides as acid-binding agents. Carbonates or hydrogen carbonates. secondary or tertiary phosphates. Borates or acetates of the metals of the first to third groups of the periodic table, preferably the sodium or potassium compounds, and / or tertiary organic bases, such as η, for example, pyridine. When reacting in an organic medium, the acid-binding agents used are preferably tertiary organic bases, such as, for example, wpiep nim «> thvlgnilin PvriHin nAs * r Pirnlinp

Suitable, according to procedure (b) for application: n Phosphorylating agents used are, for example, concentrated phosphoric acid. Pyrophosphoric acid, Metaphosphoric acid, polyphosphoric acid. Alkyl esters or acidic alkyl esters of condensed phosphoric acids. Mixtures of phosphoric acid and Phos-> -. phosphorus (V) oxide or phosphorus oxychloride.

The reaction of the phthalocyanine compounds of the formula (5) with phosphoric acid or with the mentioned condensed phosphoric acids or their alkyl esters or acidic alkyl esters is expediently carried out at an elevated temperature, preferably between about 50 "and about 150 ^° C. and also with an excess of the mentioned phosphorylating agents In order to reduce the formation of phosphoric acid diesters as much as possible. The esterification can also be carried out in the presence of inert solvents or diluents, such as, for example, toluene, chlorobenzene or chloronaphthalene. When using condensed phosphoric acids or their alkyl esters or acidic alkyl esters It may be advantageous to then subject the resulting reaction mixture to a mild hydrolysis, for example by means of hot water, in order to convert pyro- or polyphosphoric monoesters formed in the process into phosphoric acid monoesters.

The implementation of the phthalocyanine compounds i; Formula (5) with phosphorus oxychloride is expediently carried out with exclusion of moisture with an excess of phosphorus oxychloride with cooling or moderate heating, if appropriate in the presence of a tertiary amine such as pyridine. Lutidin cxler damsel- v> thylaniline. and / or pines (other solvents or diluents, such as benzene or chlorobenzene.

It is useful to use the resulting from the reaction Hydrogen chloride by gently evacuating the -> 5 Reaction vessel or by passing an inert gas through the reaction mixture continuously remove.

Natural hazards ta measured initially formed in the reaction of the phthalocyanine compounds of the formula (5) with phosphorous oxychloride gave the phosphoric acid monoester-dichloride of these compounds, optionally in admixture with phosphoric acid diester chlorides, which must then be hydrolyzed in a second reaction step. The hydrolysis is conveniently, for example, ^ water, dilute acids or bases, with cooling, at room temperature or under heating.

The phthalocyanine compounds of the formula (5) are

obtainable by known processes, for example by the processes of German patents 11 79 317 or 12 38 136 or according to the procedure of Belgian patent 6 74 683.

The isolation of the new phthalocyanine dyes obtained by the two processes described above takes place by salting out, for example with sodium or potassium chloride and / or by Acidification with a mineral acid or by evaporation of the neutral or weakly acidic, aqueous Dye solutions, preferably at moderately elevated temperature and reduced pressure.

The new phthalocyanine dyes are suitable for dyeing and printing fiber materials made of wool. Silk, linear polyamides, but especially made from native or regenerated cellulose, for example Linen and especially cotton and also leather.

The preparation of the dyeings is effected for example Hnrrh direct dyeing from a dyeing liquor contains the alkaline agent and optionally inorganic salts such as alkali metal chlorides or alkali metal sulfates, at room temperature or at elevated temperature, for example between about 50 'and etwn 100 ⁰ C.

However, if the dyes have little or no affinity for the fiber, this is the best way to work. that the fiber material with the aqueous solutions of the dye ' ^f e. which optionally contain alkaline agents and inorganic salts, impregnated cold or at a moderate temperature, squeezed off and the applied dyes, optionally after intermediate drying, fixed.

If the padding liquor used contains an alkaline agent, the subsequent one takes place Fixation, for example, by steaming, by heat setting or by leaving it for several hours of the impregnated goods. The type and quantity are decisive for the selection of the fixing method of the alkali used.

When using impregnation baths that do not contain an alkaline agent, the The impregnated goods are then first placed in a salty AiKaimaa, for example, and subjected to them then one of the fixing processes described above.

Alkali metal hydroxides, carbonates, bicarbonates, phosphates, borates or silicates or alkali metal salts of trichloroacetic acid or mixtures of the above Connections used.

For use in textile printing, the new dyes are, optionally with the addition of ^1-to-use '■ chen auxiliaries such as urea or dispersants, dissolved in water and thickening agents. such as methyl cellulose or alginate thickenings. stirred together. The above-described alkaline agents are added to the pastes thus obtained and the goods are printed in the customary manner. The fixation is then carried out by steaming or heat setting in a known manner.

You can also choose the fiber material with neutral or slightly acidic printing pastes that do not contain any alkaline agents. In In this case, the fiber material is either in front of or after printing with alkaline agents, treated for example by means of a short passage by a salty, alkaline solution, and then one of the above-mentioned fixing methods subject. The fixation can be done in a very simple way

but can also be done in such a way that the printed goods are allowed to pass through a hot, salty, alkaline solution.

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

Compared to those from the German patents Il'9 317 and 12 38136 and from the Belgian Patent 6 74 683 known, structurally closest comparable dyes are characterized by the new ones Phthalocyanine dyes by a better solubility and by a better resistance wedge of their alkaline Dye liquors and printing pastes.

Furthermore, the phihalocyanine dyes according to the invention have compared to the French patent specification 14 83 639 and the US patent specification 32 23 470 known dyes, which also have a / I-Phosphatoäthylsulfonyl-Reaklivgruppc, a clear superiority in the water right (difficult), in alkaline and acidic perspiration resistance as well as in the sulfuric acid overstaining fastness. Furthermore, the dyes according to the invention are inherent in comparison the well-known Phosphatoäthylsulfonylformazan dyestuff from the Belgian patent 7 10 871 a much better sulfuric acid Überfärbeechlheil and significantly better alkaline perspiration fastness.

Example I.

11.2 parts by weight of the phosphoric acid monoester of 0-hydroxyethyl (4-aminophenyl) sulfone are dissolved in 50 parts by weight of water by carefully adding 20 parts by volume of 2 η sodium hydroxide solution. 19.4 parts by weight of copper phthalocyanine are added -tetrasulfonsäurechlorid a moist filter cake in the form (3) into the obtained solution at 20 ⁰ C with good stirring. Then 1 part by weight of pyridine is added, and as the reaction now begins, the pH of the reaction mixture is kept at 5.5-1.7 by sprinkling in about 9 parts by weight of sodium carbonate. After the reaction has ended, the dye solution obtained is brought to pH with hydrochloric acid 2, and the dye is deposited by salting out with sodium chloride and potassium chloride, film it off and washed with sodium chloride solution. After drying, 44 parts by weight of a salty, turquoise-blue dye, the consumption of which, according to analysis, roughly corresponds to the formula

C'ti IV

S ()> -NII

[SO ₁ HI,

SO, - CH. CM, -O-PO

, N, J

is equivalent to. The dye yield! on cotton fabric in The presence of alkaline agents gives bright turquoise-blue dyeings of good laundry detergents. Friction and l. lightness.

Dyes with similar properties can be used obtained if you place in the previous example of the phosphoric acid monoester of / I-hydroxyethyl- (4-

phosphoric acid monoesters of the following / i-hydroxyethyl sulfones used:

,: f-Hydroxväthyl- (3-aminophenyl) -sulion.
^ -Hydroxyethyl (2-aminophenyl) sulfone.
f? -Hydroxyethyl- [4- (N-methylamino) -phenyl] -

sulfone,
p-hydroxyethyl- (3-amino-4-hydroxyphenyl) -

suifon.
;? - Hydroxyethyl- (3-amino-4-methoxy-phenv!) -

sulfone. β hydroxyethyl- (3-hydroxy-4-aminophenyl) -

sulfone,
# -Hydroxyethyl- (3-methoxy-4-aminophenyl) -

sulfone.
/? - Hydroxyethyl- (3-amino-4-methyl-phenyl) -

su I hair dryer. /} - Hydroxyethyl- (3-amino-4-sulfo-phenyl) -

sulfone, /? - Hydroxyethyl- {3-bromo-4-aminophenyl) -

sulfone, /? - Hydroxyethyl- {3-amino-4-carboxy-phenyl) -

sulfone,

/? - Hydroxyethyl- {2Jj-dimethoxy-4-aminophenyl) sulfone.

/? - Hydroxyethyl- (2-methyl-4-amino-5-methoxy-

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

amino) phenyl] sulfone.
/? - Hydroxyethyl- [4-amino-naphthyl- (1)] -

sulfone.
/} - Hydroxyethyl [5-amino-naphthyl- (l)] sulfone.

I HllrhVl

yp

/? - Hydroxyethyl- [3- (4'-aminobenzoylamino) -

4-hydroxyphenyl sulfone.
/ f-Hydroxyethyl- [3- (4'-aminobenzoylamino) -

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

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

amino) phenyl] sulfone or
/ J-hydroxyethyl- (3-amino-4-methoxy-benzyl) -

sulfone.

Example 2

163 parts by weight of the phosphoric acid monoester of ^ -Hydroxyäthyl- (4-aminophenyl) sulfone are in

so dissolved 50 parts by weight of water by carefully adding 30 parts by volume of 2N sodium hydroxide solution. 193 parts by weight of nickel phthalocyanine pVtetrasulfonsäurechlorid be entered in the form of a moist filter cake into the obtained solution at 20 ⁰ C with good stirring. After adding 1 part by weight of pyridine, the pH of the reaction mixture is kept at 53 to 6 by sprinkling about 8 parts by weight of sodium bicarbonate in the reaction that now begins.

(I.

th. After the reaction has ended, the salt-containing, turquoise-blue dye obtained becomes its constituent dye solution in a spray dryer to dry lion roughly the formula evaporated. 40 parts by weight of one are obtained

I SOi-Nil - <^ \ - SO, —CII, -CH, -Ο —PO ₁ HjJ _1- ,

NiPc

[SO ₁ Hl,.,

is equivalent to. The dye yields on Biiumwollgewebc in In the presence of alkaline agents, green-blue dyeings of excellent washability. Friction and l. non-authentic.

If the above example is used instead of the nickel phthalocyanine-pj-tetrasulfonic acid chloride, the equivalent amount of cobalt phthalocyanine - (}) - tctrastilfuiisäuicCliiuilu t'nici 'ΚαμίθΓρ! ϊϊ! ~ ι «ϊί <Μ.'νίΐΠίΠ- (jJ-iCirüViilfonsäurechlorid. this gives dyes with similar properties.

Example J

16.9 parts by weight of the phosphoric acid monoester of / I-hydroxyethyl (3-aminophenyl) sulfone are dissolved in 50 parts by weight of water by carefully adding 30 parts by volume of 2N sodium hydroxide solution. Be in the solution thus obtained at 20 ⁰ C with good stirring 15.9 parts by weight of copper phthalocyanine (3) -sulfonsäurechlorids containing 2.2 sulfonyl chloride groups on the average as a moist filter cake. After adding 1 part by weight of pyridine, the pH of the reaction

Sodium bicarbonate kept at 5.5 to 6. After completion of the reaction, the dye solution obtained becomes mixed with sodium chloride, and the deposited dye is filtered off, with sodium chloride solution washed and dried. 57 parts by weight of a salt-containing, turquoise-blue dye, its Constitution roughly of the formula

SOj-NII

SO. C ll - dl O - PO, I

CuPc

| SO, H],,

corresponds The dye is suitable for dyeing and printing fabrics from native or regenerated Cellulose in the presence of alkaline agents and provides dyeings and prints of high brilliance and very good wash and light fastness properties.

Is used in the above example instead of the phosphoric acid monoester of j9-hydroxyethyl (3-aminophenyl) sulfone the same amount of the phosphoric acid ester of ^ -Hydroxyäthyl- (4-aminophenyl) -suifon. this gives a turquoise-blue dye with similar properties.

Example 4

163 parts by weight of the phosphoric acid monoester of 0-hydroxyethyl (4-aminophenyl) sulfone are in Dissolve 50 parts by weight of water by carefully adding 30 parts by volume of 2N sodium hydroxide solution. In these Solution are at 15 "C with thorough stirring 19.4 Parts by weight of copper phthalocyanine (3) tetrasulfonic acid chloride entered in the form of a moist filter cake. After adding 1 part by weight of pyridine is at the now onset of the reaction the pH of the reaction mixture by dropping in total held about 75 parts by weight of 2N aqueous ammonia at 5.5 to 5.7. After the reaction has ended, the obtained dye solution adjusted to pH 3 with hydrochloric acid and the dye by salting out with Potassium chloride and sodium chloride isolated. The dye obtained can be purified again in Dissolve the water and salt out again. After drying, 59 parts by weight of a salty, obtained turquoise-blue dye, its constitution roughly of the formula

CuPc-

SO ₂ -NH

ISO ₂ -NH ₂ I,.,

-SO ₂ -CH ₂ -CH ₂ -O-PO ₁ I

ISO ₃ H] ₂₅

The dye yields on woven in cotton Presence of alkaline agents deep, luminous, turquoise-blue dyeings of very good lightfastness

If in the above example, instead of the phosphoric acid monoester of p-hydroxyäihyi- (4-aminophenyl) sulfone, equivalent amounts of the phosphor

phosphoric acid monoester of 3- (N-methyl-N-isäthionylamino) -1 -aminobenzene, 4- (N-Metr; yl-N-isäthionylamino) -l-aminohenzene or of 2-methoxy-4- (N-methyl- N- isäthionylamino) -f-aminobenzene. so Dyes with similar properties.

you get

Example 5 10 parts by weight of the phthalocyanine dye of the formula

CuPc

-J-SO ₂ - NU - CMj- CH ₂ - <ζ ^ - SO, - CH ₂ - CH ₂ - Oll J ₂₂

are introduced into 50 Cicwichisteile pyrophosphoric acid with thorough stirring. The mixture obtained is stirred at 100 ° C. for one hour. Then stir the still hot reaction mixture is poured into a mixture of sodium chloride solution and ice, the Temperature should not exceed + IO ° C. The phosphoric acid ester separates out. One stirs for a while after, then filtered off the ester dye and washed it with sodium chloride solution. The moist filter cake is dissolved in 300 parts by weight of water, the pH of the solution to 4.5 by adding about 4 parts by weight of crystallized, tertiary sodium phosphate and separating the ester dye again by salting out with sodium chloride. After filtering off and drying, 27 parts by weight are obtained of the salty hydrogen of the formula

C u Pc—

c — J-SO ₂ -

NH - -CH, -CH,

- <f ^ N-SO, - Cll · - CH., - O -PO, H ₂ J ₇₂

The dye is very soluble in water and has excellent washfastness. It is suitable in

on cotton fabric according to the special dimensions for reactive dyes also for printing, suitable two-bath process turquoise-blue dyeings

Example 6

6.1 parts by weight of phosphorus oxychloride are lower to 20 ⁰ C 12.2 Cewichtsteile of the phthalocyanine dye

half 10 "C in 20 parts by weight of pyridine. Into that of the formula

The mixture obtained are stirred at 10 ° r.

CuPc-J-SO ₂ -Nil -CH ₂

SO, —CH ₂ -CH ₂ -OH J _2- ,

registered. The resulting mixture is 3 hours at

Stir in parts by weight of crushed ice, whereby the temperature should not exceed + 5 ° C. One stirs then after a few hours with ice cooling and a few hours at room temperature and filtered

CuPc -J-SO ₂ -NH-CH ₂ -

CH,

then the excreted dye from. For cleaning

i-- »~ cr. de "? S * _! ch? °" pilt <* rlriu * hi »n in ptwa SOO

Parts by weight of water and isolates the dye off Salting out. After drying, 22 parts by weight of the salty, blue dye are obtained formula

), —CH ₂ -CH ₂ -Q-PO ₃ H ₂ J ₂₂

that on cotton and rayon stains under the influence of alkaline agents with very good stains Fastnesses provide very strong and washable fastness properties, especially in textile printing using the two-phase process Prints results

A dye with received when one

Starting dye 11.6 parts by weight of the dye formula

similar properties is shown in the previous example as

[_SO ₂ -NH-CH ₂ -CH ₂ - / ~ ^> - SO ₂ -CH ₂ -CH ₂ -OhJ ₃

CuPc

[SO ₃ H]

begins.

Example 7

13.5 parts by weight of the phthalocyanine dye of the formula

O-.N

CuPc - SO ₂ -NH-CH ₂ -CH ₂ -NH- <f> - SO ₂ -CH ₂ -CH ₂ -OH

2.2

are added to 100 parts by weight of pyrophosphoric acid. The mixture is heated to 100 ° C, a Stirred hour at this temperature and then still warm in a mixture of ice and Stir in saturated sodium chloride solution, whereby the temperature should not exceed + 5 ° C. One stirs some time after, then filtered the excreted Ester dye off and washes it with saturated Sodium chloride solution. Then you solve the moist filter cake in 500 parts by weight of water, adjusts the pH by adding sodium phosphate of the solution to 5 and the dye is isolated by salting out with sodium chloride. After drying 27 parts by weight of the salt-containing dye of the formula are obtained

O, N

CuPc SO ₂ -NH-CH ₂ -CH ₂ -NH- <f> - SO ₂ -CH ₂ -CH ₂ -O-PO ₃ H ₂

2.2

The dye gives blue-green on cotton fabric under the action of alkaline agents Dyeings of very good wet fastness and good light fastness.

CuPc-

O ₂ N

--SO ₂ -NH-CH ₂ -CH ₂ -NH- ^

A dye with similar properties and a slightly more yellowish shade is obtained if you use the above example as starting compound 193 parts by weight of the dye of the formula

SO ₂ -CH ₂ -CH ₂ -OH

begins

Example 8

163 parts by weight of the phosphoric acid monoester of /? - Hydroxyethyl (3-aminophenyl) sulfone of the formula

NH ₂

SO ₂ -CH ₂ -CH ₂ -O-PO ₃ H

₃ H ₂

are dissolved in 50 parts by weight of water by adding 30 parts by volume of 2N sodium hydroxide solution. In these The solution is carried at 19.4 ° C. with thorough stirring Parts by weight of copper phthalocyanine - ^ - tetrasulfonic acid chloride in the form of a moist filter cake, adds then 1 part by weight of pyridine is added and then 10 parts by volume of 2N ammonia solution are added dropwise one that the pH of the reaction mixture is kept at 8 to 83.

As soon as the ammonia solution has been used up, it is added dropwise until the reaction has ended pH value 2N sodium hydroxide solution. The dye solution obtained is then weakly acidified and the dye deposited by salting out with sodium chloride.

filtered off and dried 58 parts by weight of a salt-containing, turquoise-blue dye, which is used for Dyeing and printing of native or regenerated Cellulose in the presence of alkaline agents suitable The dyeings and prints produced with it have very good wet fastness properties and do not stain.

Dyes with similar good properties are obtained if in the preceding example instead of aqueous ammonia, aqueous solutions of equivalent amounts of the following amines are used:

Methylamine, ethylamine, n-butylamine, Benzylamine, aniline, ethanolamine, Dimethylamine, diethylamine, di-isopropylamine, N-methylbenzylamine, N-methylaniline, piperidine, Morpholine, diethanolamine, 2-aminoethane-1-carboxylic acid, 2-aminoethane-1-sulfonic acid, 4-aminobenzenecarboxylic acid, 3-aminobenzenesulfonic acid or 4-aminobenzenesulfonic acid.

If, in the above example, the copper phthalocyanine- (3) -tetrasulfonic acid chloride is substituted an equivalent amount of tetraphenyl copper phthalocyanine tetrasulfonic acid chloride, one obtains one bluish green dye with similar coloring properties.

130 2SO / 6

Claims (3)

Patent claims: K Water-soluble phthalocyanine dyes of the general formula (I) [SO ₂ -NH- (B) ₁ , -Α- (X) _m -SO, -CHj-CHi-O-PO ₃ HJ ₀ Pc SO ₂ -N [SO ₃ H], -, in which Pc stands for a metal-free or a copper, cobalt or nickel-containing phthalocyanine residue, which can contain phenyl groups or halogen atoms, B a divalent organic bridge member the formula -CH ₂ -CH ₂ - -CH ₂ -CH ₂ -NH- ^ CO-NH- 20th SO ₂ -NH- or NH- means X is the group —CH ₂ —or —N - CH ₃ 30th 40 an alkyl group of 1 to 4 carbon atoms optionally substituted by phenyl, hydroxyl, sulfo and carboxy, or a phenyl group optionally substituted by carboxy and sulfo, or R 1 and R 2 together with the nitrogen atom form a piperidine or morpholine ring, A the phenylene or naphthylene radical means which can be substituted by alkyl, alkoxy, nitro, carboxy, hydroxyl or sulfonic acid groups or halogen atoms, π and m stand for the number O or t, a, b and c mean the numbers from 1 to 4, where the sum of a, b and c is at most 6 2. Process for the preparation of the phthalocyanine dyes mentioned and defined in claim 1, characterized in that one (a) Phthalocyaninesulfonic acid chlorides of the general formula (2) (HO ₃ S (SO ₂ -CI), represents, R _t and R ₂ each represent a hydrogen atom or H ₂ N- (B), - Λ- (X) _m -SO ₂ -CH ₂ -CH ₂ -O-PO ₃ H ₂ in which Pc has the meaning given in claim 1, ρ is a number from 0 to 3 and q is a number from 1 to 4, the sum of ρ and q being at most 4, with amines of the general formula (3) (3) in which A, B, X, m and π have the meanings given in claim 1, optionally with the addition of amines of the formula (4) R,
/ H-N ₍₄₎ R2 in which Ri and R _{2 have} the in claim 1 [SO ₂ -NH- (B) _n - Λ - (X) _m - have the meanings mentioned, in an aqueous, aqueous-organic or organic medium at pH values between about 4 and about 11 and temperatures between about O ⁰ C and about 100 ° C in the presence of acid-binding agents or (b) Phthalocyanine compounds of the general formula (5) ₂ -CH ₂ -CH ₂ -OHL Pc SO ₂ -N in which A, B. Ri. R). X, / 7>. H. & / j and c the complete! have the meanings mentioned, mil Phosphorylating agents in per se known Manner converted into the corresponding phosphoric acid monoesters, 3. Use of the dyes mentioned and defined in claim 1 or of the dyes produced according to claim 2 for dyeing or printing fiber materials made from native or regenerated cellulose, wool, silk, linear polyamides and leather. The present invention relates to new water-soluble phthalocyanine dyes of the general formula (1) [SO ₂ -NH- (B), -A- (X) _m -SO ₂ -CH ₂ -CH ₂ -O-POjH ₂ ] "Ri" Pc SO ₂ -N [SO ₃ H],., (D