DE1795140A1 - Phthalocyanine dyes and process for their preparation - Google Patents

Description

FARBWERKE HOECHST AG formerly Master Lucius & Brüninj * File number: P 17 95 140.5-44 - HOE 68 / F 270 (Fw 5847)

Frankfurt (Main) -Hochst, August 4th 1970 Dr Mü / B

Phthalocyanine dyes and process for their preparation

The present invention relates to new, water-soluble phthalocyanine dyes of the general formula (1)

b-1

c-1

(D

in which Pc stands for a phthalocyanine radical, which preferably contains metal, such as copper, cobalt or nickel, and which may contain further substituents such as phenyl groups or halogen atoms, B is a divalent organic

New · Documents ιαπ ν 11 At ». 2 No. 1 sau 3 d * Xnd * n> ww «3. 209810 / U90

Pontic, for example

SO ₂ -NH-

CO-MH-

or —V 7— IH -,

means, X represents the group -CH ₂ - or -N-, R- and R _{2 represent} hydrogen atoms or optionally substituted alkyl or aryl groups or together with the nitrogen atom form an alkyleneimine ring, for example a piperidine or morpholine ring, which may contain heteroatoms, A a phenylene or Kaphthylenreet, which can contain further substituents, for example alkyl »alkoxy, nitro, carboxyl, hydroxyl or sulfonic acid groups or halogenatones, η and m represent the number 0 or, a, b and c are numbers are from 1 to 4, the sum of a, b and c being at most β, and a method for their preparation.

The new phthalocyanine dyes of the above general formula (1) can be produced by

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

(-SO ₂ -Cl ) ₍

in which Pc has the meaning given above, ρ 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 type Formula (3)

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

(S)

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in which A, B, X ₁ m and η have the meanings given above, optionally with the addition of amines of the formula (4)

H-N

(4)

in which R 1 and R 1 have the meaning given above, in aqueous, aqueous-organic or organic medium at pH values between about 4 and about 11, preferably between about 4 and about 9, at temperatures between about ⁰ and about 100 ° C, preferably between about 0 ° and about 30 ° C, in the presence of acid-binding agents or

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

(X) ₁₈ -SO ₂ -CH ₂ -CH ₂ -OH

b-1

in which A, B,

X, m,

a, b and c above

have the meanings mentioned, with phosphoryl relaxants in an is converted into the corresponding Phosphorstturemonoeeter in a known manner.

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In procedure (a), the reaction takes place depending on the solubility properties of the reaction components in solution or in suspension. If, in process (a), some of the sulfonic acid chloride groups of the starting compound of the formula (2) are converted into sulfonic acid groups, so the condensation be carried out so that at the same time n with the reaction with amines of the formula (3) a part of the sulfonic acid chloride groups is saponified, or that initially with a for the complete conversion of all sulfonic acid chlorine groups insufficient amount of amines of the form (3) and (4) is reacted and then the remaining sulfonic acid chloride groups are saponified by a special reaction step.

Phthalocyaninesulfonic acid chlorides of the formula (2) which are reacted according to procedure (a) include, for example, sulfonic acid chlorides of metal-free phthalocyanines Use, but preferably sulfonic acid chlorides, of metal-containing 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) phthalocyanine (3) phthalocyanine chloride. -trisulfonic acid chloride, Copper phthalocyanine (4) disulfonic acid chloride or copper phthalocyanine (4) tetrasulfonic acid chloride. However, there are too those sulfonic acid chlorides are suitable which have further substituents on the phthalocyanine nucleus, such as, for example, sulfonic acid chlorides of tetraphenyl copper phthalocyanine or of tetrachloro nickel phthalocyanine or, for example, copper phthalocyanine- (3) -dieulfonic acid chloride-disulfonic acid. The sulfonic acid chlorides mentioned are produced by known processes, for example according to the method of German patent specification 891 121.

Phosphoric acid monoesters are selenium as phosphoric acid monoesters of amines of the formula (3) containing ft-hydroxyethylsulfonic groups of the following compounds:

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ß-Hydroxyethyl- (3-aminophenyl) -sulfone, ß-Hydroxyethyl- (4-aminophenyD-sulfone, ß-Hydroxyäthyl-T4- (N-methylamino) -phenyij -sulfon, ß-Hydroxyäthyl- (3-amino- 4-hydroxyphenyl) sulfone, ß-hydroxyethyl (3-amino-4-methoxy-pheny1) sulfone, ß-hydroxyethyl (3-hydroxy-4-araino-phenyD-sulfone, ß-hydroxyethyl (3 -methoxy-4-aminophenyl) sulfone, ß-hydroxyethyl (3-amino-4-methy1-pheny1) sulfone, ß-hydroxyethyl (3-amino-4-sulfo - phenyl) «sulfone, ß- Hydroxyethyl- (3-bromo-4-aminophenyl) -sulfone, ß-hydroxyethyl- (3-aaiino-4-carboxy-phenyl) -sulfone, ß-hydroxyethyl- (2,5-dimethoxy ~ 4-aniinophenyD-sulfone , ß-hydroxyethyl (2-methyl-4-amino-5-methoxy-phenyl) -sulfone, ß-hydroxyethyl- £ 3-nitro ~ 4- (4 ^t -a »inophenylai» ino) -phenyi | -sulfone, ß-hydroxyethyl- £ 4-amino-naphthyl- (l) | -sulfone, ß-hydroxyethyl- £ 5-amino-naphthyl- (l) j-sulfone, ß-hydroxyethyl-

6-amino-naphthyl- (2) j -sulfone, ß-hydroxyethyl-T3- (4'-aaino-

J-i Γ

benzoylainino) -4-hydroxyphenyl sulfone, ß-hydroxyethyl-j 3- (4 * -

aminobenzoylamino) -phenyl "] - sulfone, ß-hydroxyethyl-T3 ~ aiaino ~ 4-hydroxy-S-nitrophenyl / sulfone, ß-hydroxyethyl- [4- (3'-aminophenylsulfonylamino) -phenyl | -sulfone, 3- (N -Methyl-N-isftthionylamino) -l-aminobenzene, 4- (N-methyl-N-lsäthlonylamino) -l-aminobenzene, 2-methoxy-4- (N-methyl-N-isethionylamino) -l-aminobenzene or β-hydroxyethyl (3-amino-4-methoxy-benzyl) sulfone.

The phosphoric acid monoesters of the ß-hydroxyethyl sulfones mentioned can be prepared by known processes, for example by the "Methods of Organic Chemistry" in Houben-Weyl, Volume 12/2, page 147 ff. Procedure described.

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

Ammonia, methylamine, ethylarain, n-butylamine, benzylamine, Aniline, ethanolamine, dimethylamine, diethylamine, diisopropylamine, N-methylbenzylamine, N-methylaniline, piperidine, Morpholine, diethanolamine, 2-aminoethane-l-eulfonic acid, 2-Aminoethane-l-carboxylic acid, 4-aminobenzenecarboxylic acid, 3-aminobenzenesulfonic acid or 4-aminobenzenesulfonic acid,

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When carrying out process variant (a) in an aqueous or aqueous-organic medium, nan uses as süv: rebindcri ';. 3 Medium expediently hydroxides, carbonates or hydrogen carbonates, secondary or tertiary phosphates, borates or acetates of the metals the first to third groups of the periodic table, preferably the sodium or potassium compounds, and / or tertiary organic Bases such as pyridine. When implementing in organic Medium is preferably used as acid-binding agent tertiary organic bases, such as dimethylaniline, pyridine or Picoline.

Suitable according to procedure (b) used Phosphorylating agents 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 phosphorus (V) oxide or Phosphorus oxychloride.

The reaction of the phthalocyanine compounds of the formula (5) with phosphoric acid or with the condensed phosphoric acids mentioned or their alkyl esters or acidic alkyl esters are advantageously carried out at an elevated temperature, preferably between about 50 ° and about 150 ° C and also with an excess of said phosphorylating agents to prevent the formation of phosphoric acid diesters to reduce 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, to subjugate incidentally formed pyro- or polyphosphoric acid monoesters in phosphoric acid e-monoest he Convict.

The reaction of the phthalocyanine compounds of the formula (5) with phosphorus oxychloride is expediently carried out with the exclusion of Moisture with an excess of phosphorus oxychloride with cooling or moderate heating, optionally in the presence of one tertiary amine, such as pyridine, lutidine or dimethylaniline, and / or a (further solvent or diluent, such as benzene or chlorobenzene.

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It is advantageous to use the hydrogen chloride formed in the reaction by gently evacuating the reaction vessel

or by passing an inert gas \ through the reaction mixture continuously to remove "

In the reaction of the phthalocyanine compounds of the formula (5) naturally, with phosphorus oxychloride, the next are formed Phosphoric acid monoester dichlorides of these compounds, optionally mixed with phosphoric acid diester chlorides, which then have to be saponified in a second reaction step. The saponification is expedient, for example with water, dilute acids or bases with cooling, at room temperature or with heating.

The phthalocyanine compounds of the formula (5) can be obtained by known processes, for example by the Method of German patents 1 179 317 or 1 233 136 or according to the method of Belgian patent specification 674 683.

The isolation of the two processes described above The new phthalocyanine dyes obtained are carried out 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 obtainable by the processes described above are suitable for dyeing and printing of fiber materials made from wool, silk, linear polyamides, but especially from materials containing hydroxyl groups, such as cellulose, for example linen, regenerated cellulose and especially cotton and also leather.

The dyeings are produced, for example, by direct dyeing from a dye liquor which has an alkaline effect Contains agents and, if appropriate, inorganic salts, such as, for example, alkali metal chlorides or alkali metal sulfates, at room temperature or at an elevated temperature, for example between about 50 ° and about 100 ° C.

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- β - - ^: ■ ■■■■■■ '■: ■' ■. '■ ....

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However, if the dyes have little or no dyes Affinity to fiber, one works advantageously eo that »on that Fiber material with the aqueous solutions of the dye, the optionally alkaline agents and inorganic Contain salts, impregnated cold or at a moderate temperature, squeezed off and the applied dyes, if necessary an intermediate drying fixed.

If the padding liquor used contains an alkaline agent, the subsequent fixation takes place, for example, by steaming, by heat setting or else by leaving the impregnated goods lying around for several hours. Decisive for the selection of the fixing method are Type and amount of alkali used.

When using impregnation baths that do not contain an alkaline agent, the impregnated material is brought in Then first of all, for example, in a salty one Alkali bath and then subject it to one of the fixing processes described above.

Alkali metal hydroxides, carbonates, bicarbonates, phosphates, borates or silicates or alkali metal salts of triehloroacetic acid or mixtures of the compounds mentioned are used.

For use in textile printing, the new dyes, if necessary with the addition of customary auxiliaries, such as urea or dispersants, dissolved in water and mixed with thickeners such as methyl cellulose or alginate thickeners. To the Pastes obtained in this way are given the alkaline agents described above and the goods are printed in the usual way Way. The fixation is then carried out by steaming or heat setting in the known catfish.

The fiber material can also be mixed with neutral or slightly acidic printing pastes that are not alkaline

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contain active agent, print. In this case, the fiber material is either before or after printing with treated with alkaline agents, for example by means of a short passage through a salty, alkaline solution, and then subjected to one of the above-mentioned fixing processes. In a very simple way, however, the fixation can also be carried out in such a way that the printed goods are exposed to a hot, salty, allows alkaline solution to pass.

The new dyes give very valuable, strong colors and colors on the fiber materials mentioned above Prints that are characterized by very good wet fastness and very good light fastness.

Compared to those from German patents 1,179,317 and 1 238 136 and from the Belgian patent 674 683, structurally closest comparable dyes the new phthalocyanine dyes are characterized by better solubility and better stability of their alkaline dye liquors and printing pastes,

example 1

11.2 parts by weight of the phosphoric acid monoester of β-hydroxyethyl (4-aminophenyl) sulfone are dissolved in 50 parts by weight of water by carefully adding 20 parts by volume 2N sodium hydroxide solution dissolved. 19.4 parts by weight of copper phthalocyanine- (3) -tetrasulfonic acid chloride are added to the solution obtained at 20 ° C. with thorough stirring entered in the form of a moist filter cake. Then 1 part by weight of pyridine is added, and As the reaction now begins, the pH of the reaction mixture is set by sprinkling in about 9 parts by weight of sodium bicarbonate held at 5.5-5.7. After the reaction has ended, the dye solution obtained is adjusted to pH 2 with hydrochloric acid, and the dye deposited by salting out with sodium chloride and potassium chloride, filtered off and washed with sodium chloride solution washed. After drying, 44 parts by weight are obtained of a salty, turquoise-blue dye, the constitution of which, according to the analysis, corresponds to the formula

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SO ₂ -NH

... ^) SO ₂ CH ₂ CH ₂ OPO ₃ H ₂ CuPc

is equivalent to. The dye yields on cotton fabric in the presence alkaline agents bright turquoise blue dyeings with good wash, rub and light fastness properties.

Dyes with similar properties are obtained when one in the above example instead of the phosphoric acid monoester of Ö-Hydroxyäthyl- (4-amino) -phenylsulfon equivalents Amounts of phosphoric acid monoesters of the following ß-hydroxyethyl sulfones are used:

ß-Hydroxyethyl- (3-aminophenyl) -sulfone, ß-Hydroxyethyl- (2-aminophenyl) -sulfone, ß-Hydroxyäthy 1-f4- (N-methylanino) -phenyl] -sulfone, ß-Hydroxyäthy1 - (3-amino-4-hydroxypheny1) -eulfone, ß-hydroxyethy 1- (3-amino-4-methoxyphenyl) -sulfone, ß-hydroxyethyl- (3-hydroxy-4-aminopheny1) - sulfone, ß-Hydroxyäthy1- (3-methoxy-4-aminopheny1) -sulfon, ß-Hydroxyäthyl- (3-amino-4-raethy1-phenyl) -sulfon, ß-Hydroxyäthyl- (3-amino-4- sulf ο -phenyl) -sulfone, ß-IIydroxyäthyl- (3-bron ~ 4-aminophenyl) -sulfone, ß-hydroxyethyl- (3-amino-4-carboxy-phenyD-sulfon, ß-hydroxyethyl- ( 2,5-dimethoxy-4-aminophenyD-eulfon, ß-hydroxy ethyl- (2-methy l-4-a «ino-5-methoxy-phenyl) -sulfone, ß-hydroxyäthy 1-j 3-nitro- 4- (4'-aainophenylaiBino) -phenyl | -sulfone, ß-hydroxyethyl- [4-'-naphthyl- (in -sulfone, ß-hydroxyethyl- [δ-amino-naphthyl- (I)] -sulfone, ß- Hydroxyäthyl-r6-aaino ~ naphthyl- (2) l -sulfone, ß-Hydroxyäthyl-f3- (4 ^t -aminobenzoylamlno) -4-hydroxyphenyl-sulfone, ß-Hydroxyäthyl- j3- (4'-aminobenzoylaiaino) -phenyl! -sulfone, ß-hydroxyä ethyl- (3-amino-4-hydroxy-5-nitrophenyD-sulfone, ß-hydroxyethyl- r ^ -O'-aminophenylsulfoaylaeino) -phenylj-eulfon or ß-hydroxyethyl- (3-araino-4-methoxy-benzyl) - Bulfon.

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Example 2

16.9 parts by weight of the phosphoric acid monoester of ß-hydroxyethyl (4-aminophenyl) sulfone are in 50 parts by weight of water by carefully adding 30 parts by volume of 2N sodium hydroxide solution solved. In the solution obtained are at 20 ° C under good Stir 19.3 parts by weight of nickel phthalocyanine- (3) -tetrasulfonic acid chloride entered in the form of a moist filter cake. After adding 1 part by weight of pyridine, the now starting Reaction the pH of the reaction mixture by sprinkling about 8 parts by weight of sodium bicarbonate 5.5 to 6 held. After the reaction has ended, the dye solution obtained is dried to dryness in a spray dryer evaporated. 40 parts by weight of a salty, turquoise-blue dye, the constitution of which is roughly of the formula

NiPc

SO ₂ -CH ₂ -CH ₂ -O-PO ₃ H ₂

J ^,

is equivalent to. The dye gives excellent green-blue dyeings on cotton fabric in the presence of alkaline agents Wash, rub and light fastness.

Is used in the above example instead of nickel phthalocyanine- (3) -tetrasulfonic acid chloride the equivalent amount of cobalt phthalocyanine- (3) -tetrasulfonic acid chloride or Copper phthalocyanine- (3) -tetrasulfonic acid chloride, so obtained one dyes with similar properties.

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Example 3

1β, 9 parts by weight of the phosphoric acid monoester of ß-Hydroxyäthyl- (3-aminophenyl) -sulfon are in 50 parts by weight of water by carefully adding 30 parts by volume 2N sodium hydroxide solution dissolved. In the solution obtained in this way, 15.9 parts by weight of one are added at 20 ° C. with thorough stirring Copper phthalocyanine (3) sulfonic acid chloride, which contains an average of 2.2 sulfonic acid chloride groups, than moist Filter cake entered. After the addition of 1 part by weight of pyridine, the pH value is set in the reaction that now begins the reaction mixture kept at 5.5 to 6 by sprinkling about 5 parts by weight of sodium bicarbonate. After the reaction has ended, the dye solution obtained is with Sodium chloride is added, and the deposited dye is filtered off, washed with sodium chloride solution and dried. 57 parts by weight of a salty, turquoise-blue dye are obtained, the constitution of which roughly corresponds to the formula -

CuPc

So ₂ -CH ₂ -CH ₂ -O-PO ₃ H ₂

is equivalent to. The dye is suitable for dyeing and printing fabrics made from natural or regenerated cellulose in the presence of alkaline agents and provides dyeings and Prints of high brilliance and very good wash and lightfastness.

If, in the above example, instead of the phosphoric acid monoester of α-hydroxyethyl-O-aminophenyl) sulfone, the same amount of the phosphoric acid ester of S-hydroxyethyl- (4-aminophenyl) -sulfone is obtained turquoise blue dye with similar properties.

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Example 4

16.8 parts by weight of the phosphoric acid monoester of ß-hydroxyethyl (4-aminophenyl) sulfone are in 50 parts by weight of water by carefully adding 30 parts by volume of 2N sodium hydroxide solution solved. 19.4 parts by weight of copper phthalocyanine (3) -tetrasulfonic acid chloride are added to this solution at 15 ° C. with thorough stirring entered in the form of a moist filter cake. After adding 1 part by weight of pyridine, the now the onset of the reaction, the pH of the reaction mixture through Dropping a total of about 75 parts by weight of 2N aqueous ammonia kept at 5.5 to 5.7. When the reaction is complete, the dye solution obtained is adjusted to pH 3 with hydrochloric acid and the dye is isolated by salting out with potassium chloride and sodium chloride. The dye obtained can be used for purification Dissolve again in water and salt out again. After drying, 59 parts by weight of a salty, turquoise blue. Dye obtained, its constitution roughly of the formula

is equivalent to. The dye yields on cotton fabric in the presence alkaline agent deep, luminous, turquoise-blue colorations with very good lightfastness.

In the above example, instead of the phosphoric acid monoester of ß-hydroxyethyl (4-aminophenyl) sulfone equivalent amounts of phosphoric acid monoesters of 3- (N-Methy1-N-i8äthionylamino) -l-aminobenzene, 4- (N-M-methyl-N-isethionylamino) -1-aminobenzene or of 2-methoxy-4 <- (N-methyl-N-isethionylamino) -1-aminobenzene one, then one obtains dyes with similar properties.

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Example 5

10 parts by weight of the phthalocyanine dye of the formula

are introduced into 30 parts by weight of pyrophosphoric acid with thorough stirring. The resulting mixture is one hour stirred at 100 ° C. Then the still hot reaction mixture is stirred into a mixture of sodium chloride solution and sis, the temperature should not exceed + 10 ° C. The phosphoric acid ester separates out. One stirs for a while after, then filtered off the ester dye and washes it with sodium chloride solution. The moist filter cake is dissolved in 300 parts by weight of water and the pH of the solution is adjusted by adding about 4 parts by weight of crystallized, tertiary sodium phosphate to 4.5 and separating the ester dye again by salting out with sodium chloride. After filtering off and drying, 27 parts by weight of the salt-containing dye of the formula are obtained

CuPc -4- SO ₂ -NH-CH ₂ -CH ₂ - / ^

The dye is very soluble in water and gives up Cotton fabric made using the two-bath process suitable for reactive dyes, turquoise-blue dyeings of excellent washfastness. It is particularly suitable for printing.

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Example 6

6.1 parts by weight of phosphorus oxychloride are below 10 ° C added dropwise to 20 parts by weight of pyridine. In the received Mix with good stirring at 10 ° to 20 ° C 12.2 Ge * parts by weight of the phthalocyanine dyes of the formula

CuPc

registered. The resulting mixture is stirred at 70 ° C. for 3 hours. The resulting melt is then stirred into 300 weight parts of crushed ice, the temperature not to exceed +5 ^0C. The mixture is then stirred for a few more hours while cooling with ice and for a few hours at room temperature and the dyestuff which has separated out is then filtered off. For cleaning, the moist filter cake is dissolved in about 500 parts by weight of water and the dye is isolated by salting out. After drying, 22 parts by weight of the salty, blue dye of the formula are obtained

CuPc

SO ₂ -NH-CH ₂ -CH ₂ -V _- y- SO ₂ -CH ₂ -CH ₂ -O-PO ₃ H ₂

2.2

which provides dyeings with very good fastness properties on cotton and rayon under the action of alkaline agents and results in very strong and washfast prints, especially in textile printing according to the two-phase process. A dye with similar properties is obtained if the above example is used as the starting dye 11.6 parts by weight of the dye of the formula

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- ie -

1795-0

CuPc

begins.

Example 7

13.5 parts by weight of the phthalocyanine dye of the formula

CuPc -J- SOg-NH-CHg-CHg-NH

y - SO ₃ -CHg-CHg-OH

2.2

are added to 100 parts by weight of pyrophosphoric acid. The mixture is heated to 100 ° C, stirred for one hour at this temperature and then it was placed in a Mix in ice and saturated sodium chloride solution, the temperature should not exceed + 5 ° C. The mixture is stirred for some time, then the precipitated ester dye is filtered off and washed with a saturated sodium chloride solution. Then dissolves the moist filter cake in 500 parts by weight of water, adjusts the pH of the solution to 5 by adding sodium phosphate and isolates the dye by salting out with sodium chloride, after drying 27 parts by weight of the salt-containing dyestuff of the formula are obtained

CuPc

O ₂ K

SO ₂ -KH-CH ₂ -CH ₂ -KH

flo _e -

2.2

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Under the action of alkaline agents, the dye produces blue-gray dyeings of very high on cotton fabric good moisture fastness and good lightfastness.

A dye with similar properties and something A more yellowish shade is obtained if 19.8 parts by weight of the dye of the formula are used as the starting compound in the above example

SO ₂ -NH-CH ₂ -CH ₂ -NH ~ ^ _y ~ SO ₂ -CH ₂ -CH ₂ -OH

begins. Example 8

16.9 parts by weight of the phosphoric acid monoester of β-hydroxyethyl (3-aminophenyl) sulfone of the formula

SO ₂ -CH ₂ -CH ₂ -O-PO ₃ H ₂

are in 50 parts by weight of water by adding 30 volumes share 2N sodium hydroxide solution dissolved. 19.4 parts by weight of copper phthalocyanine- (3) -tetrasulfonic acid chloride in the form of a moist filter cake are added to this solution with thorough stirring at 15 ° C., 1 part by weight of pyridine is then added and then drop 10 parts by volume of 2N ammonia solution in such a way that the pH of the reaction mixture is kept at 8 to 3.5 will.

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As soon as the ammonia solution is used up, nan drips up to terminate the reaction at the same pH 2N sodium hydroxide solution. The dye solution obtained is then weakly acidified and the dye by salting out with sodium chloride deposited, filtered off and dried. 58 parts by weight of a salt-containing, turquoise-blue dye, the is suitable for dyeing and printing native or regenerated cellulose in the presence of alkaline agents. the Dyes and prints produced therewith have very good wet fastness properties and do not stain.

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

Methylamine, xthylamine, n-butylamine, benzylamine, aniline, Xthanolamine, dimethylamine, diethylamine, di-isopropylamine, N-methylbenzylamine, N-methylaniline, piperidine, Morpholine, diethanolamine, 2-aminoethane-l-carboxylic acid, 2-aminoethane-l-sulfonic acid, 4-aminobenzenecarboxylic acid, 3-aminobenzenesulfonic acid or 4-aminobenzenesulfonic acid.

If, in the above example, the equivalent is substituted for the copper phthalocyanine- (3) -tetrasulfonic acid chloride Amount of tetraphenyl copper phthalocyanine tetrasulfonic acid chloride, a bluish green dye is obtained similar coloring properties.

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Claims (15)

1795U0 PATENT CLAIMS 1. Water-soluble phthalocyanine dyes of the general Formula 1) IsO ₂ -NH- (B) _n -A- (X) _1n -SO ₂ -CH ₂ -CH ₂ -O-PO ₃ H ₂ (D b-1 -1 in which Pc stands for a phthalocyanine radical which is preferably metal-containing and which contains further substituents can, B is a divalent organic bridge member, X for the group or -N- R and R _{2 are} hydrogen atoms or optionally substituted alkyl or aryl groups or together with the nitrogen atom form an alkyleneimine ring containing optionally heteroatoms, A is a phenylene or naphthylene radical, which may contain further substituents, η and m for the number 0 or 1, a, b and c denote numbers from 1 to 4, the sum of a, b and c being at most 6. 2. The dye of the formula / [ ^S0 2- ^NH ~ VV ~ ^SO 2 " ^CH 2- ^CH 2- ° - ^PO 3 ^H 2 CuPc 2 0 9 8 1 0 / 14.9 0 3. The dye of the formula SO ₂ -KH 1795H0 J, 4. The dye of the formula 5. The dye of the formula 6. The dye of the formula IsO ₂ -NH- / y - SO ₂ -CH ₂ -CH ₂ -O-PO ₃ H ₂ J 209810/1490 1795H0 7. The dye of the formula CuPc SO ₂ -CH ₂ -CH ₂ -O-PO ₃ H ₂ [ ^S0 3 ^H J: 8. The dye of the formula SO ₂ -CH ₂ -CHj ₁ -O-PO ₃ H ₂ NiPc [ ^S0 3 ^H ] 9. The dye of the formula SO ₂ - ₂ -CHg-CH ₂ -O-PO ₃ Hg NiPC [ ⁸⁰ S ⁸ ]: 10. The dye of the formula CuPc -J- SOg-NH-CH ₂ -CHg- ^ y ~ SOg-CHg-CHg-O-PO ₃ Hg 209810 / U90 11. The dye of the formula 1795H0 - S. CuPc- SO ₂ -NH-CH ₂ -CH ₂ - / ^ \ ₂ . 12. The dye of the formula CuPc -T y- SO ₂ -CH ₂ -CH ₂ -O-PO ₃ H ₂ 13. Process for the production of new, water-soluble Phthalocyanine dyes !! of the general formula (1) J ^ SO ₂ -NH- (B) _n -A- (X) _n -SO ₂ -CH ₂ -CH ₂ -O-PO ₃ H ₂ I. b-1 [ ^Μ 3 ^Η ] CI in which Pc stands for a phthalocyanine radical which is preferably metal-containing and which contains further substituents can, B is a divalent organic bridge member, X for the group CH ₂ - or ^H 3 N - stands, 209810 / U90 R, and R ₂ denote hydrogen atoms or optionally substituted alkyl or aryl groups or together with the nitrogen atom form an alkyleneimine ring optionally containing heteroatoms, A represents a phenylene or naphthylene radical which may contain further substituents, η and m for the number O or 1 stand, a, b and c are numbers from 1 to 4, the sum of a, b and c being at most 6, characterized in that one a) Phthalocyaninesulfonic acid chlorides of the formula (2) (HO ₃ S) _p - Pc- (SO ₂ -Cl) _q (2) in which Pc is as defined above, 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 type Formula (3) H ₂ N- (B) _n -A- (X), J ₁ -SO ₂ -CH ₂ -CH ₂ -OPO ₃ H ₂ (3) in which A, B, X, m and η have the meanings given above, optionally with the addition of amines Formula (4) H-N (4) «2 in which R _{1 and R 2 have} the meaning given above, in aqueous, aqueous-organic or organic medium at pH values between about 4 and about 11 at temperatures between about 0 and about 100 ° C. in the presence of acid-binding agents 209810/1490 Means UMCtEt, or b) phthalocyanine compounds of the general formula (5) [8O ₂ -KH- (B) _n -A- (X) ₁₁ -SO ₂ -CH ₂ -GH ₂ -OHJ _& (5) SO ₂ -H b-1 [ ⁸⁰ S = Jc-I in which A, B, R-, R ₂ , X, m, η, a, b and c the further have the above meanings, alt phosphorylating agents converted in a manner known per se into the corresponding phosphoric acid monoesters. , 14. fiber materials made of natural or regenerated cellulose, Wool, silk or polyamides and leather that have been dyed or printed with the dyes mentioned in claim 1 are. 15. Use of the dyes mentioned in claim 1 to Dyeing or printing of fiber materials made from native or regenerated cellulose, silk or polyamides and leather. 209810 / U90