DED0015501MA - - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

Registration date: July 15, 1953. Advertised on January 26, 1956

^N GERMAN PATENT OFFICE

The invention relates to the production of new, water-soluble azophthalocyanine dyes which are derived from a phthalocyanine tetrasulfonic acid, contain at least one - SO ₂ -N Η group, at least one azo group and at least one salicylic acid group in the molecule and represent green to olive dyes, which are suitable for dyeing and printing textiles.

According to the present invention, there are the novel, water-soluble and accessory azophthalocyanine dyes produced by a process which is characterized in that ι moles of phthalocyanine sulfochloride of the general formula

- (SO ₃ H) ₄ _ "

where A represents a substituted or unsubstituted, metal-containing phthalocyanine molecule in which the - SO ₂ - Cl or the - SO ₃ H groups are either in the 3- or 4-position and η denotes the number 1 to 4 / with at least one, but preferably 2 to 4 moles of at least one aminoazo dye

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the general formula
χ

HO-HOOC-

μκ_ «4Τ

NH ₉

where x is H, halogen, CH ₃ , NO ₂ , OH or SO ₃ H, y'H, halogen, alkyl, alkoxy, NO ₂ , SO ₃ H or COOH and ζ H, halogen, alkyl or alkoxy and the NH ₂ -Group is in the m- or p-position to the azo group, brings it to reaction in an aqueous medium and in the presence of a mineral acid-neutralizing substance.

The new, water-soluble and licensing azophthalocyanine dyes obtained in this way are accordingly Represent compounds which are characterized by the general formula

-N = N-

(SO ₃ H) ₄

where A, n, x, y and ζ have the above meaning and the —SO ₂ · H N group is in the m or p position to the azo group.

Among those usable in the present process Sulfonic acid chlorides of phthalocyanine tetrasulfonic acids are to be understood as meaning those; which after the known methods can be produced. Suitable phthalocyanine sulfochlorides for the reaction there are especially those of the copper, nickel and cobalt phthalocyanines, then furthermore those of the iron, chromium and aluminum phthalocyanines in question. Depending on the chosen production method the sulfonic acid chloride groups in the phthalocyanine molecule are in the 4- or 3-position, depending on whether one starts with 4-sulfophthalic acid for their production or whether one proceeds by sulfonation or by direct sulfochlorination of the phthalocyanine introduces the sulfochloride groups. The number the sulfonic acid chloride groups in the molecule can vary from ι to 4. In the manufacture of sulfonic acid chlorides the phthalocyanine tetrasulfonic acids and in particular their isolation are mostly formed Mixtures of phthalocyanines with different numbers of sulfochloride groups.

Suitable aminoazo dyes of the general formula which are capable of conversion

■ N = N -! -

-NH,

where x, y and ζ have the above meaning and the NH ₂ group is in the m- or p-position to the azo group, are for example:

3-Amino-4'-oxy-i, i'-azobenzene-5'-carboxylic acid,

3-Amino-2'-methyl-4'-oxy-i, i'-azobenzöl-S'-carboxylic acid,

3-Amino-3'-methyl-4'-oxy-i, i'-azobenzene-5'-carboxylic acid,

3-Amino-4'-oxy-i, 1'-azobenzene-5'-carboxylic acid-6-sulfonic acid,

3-Amino-4'-oxy-i, 1'-azobenzene-5'-carboxylic acid-4-sulfonic acid,

. 3-Amino-4-methyl-4'-oxy-i, i'-azobenzene-5'-carboxylic acid,

3-Amino-6-methyl-4'-oxy-i, i'-azobenzene-5'-carboxylic acid,

3-Amino-6-methoxy-4'-oxy-i, 1 '-azobenzene-5'-carboxylic acid,

3-Amino-2 ', 4'-dioxy-i, i'-azobenzene-5'-carboxylic acid,

3-Amino-6-chloro-4'-oxy-i, i'-azobenzene-5'-carboxylic acid,

4-AminO "4'-oxy-i,. 1 '-azobenzene-5' -carboxylic acid, '

4-Amino-2'-methyl-4'-oxy-i, 1 '-azobenzene-5' -carboxylic acid,

4-Amino-3'-methyl-4'-oxy-i, i'-azobenzene-5'-carboxylic acid,

4-Amino-4'-oxy-i, i'-azobenzene-5'-carboxylic acid-5-sulfonic acid,

4-Amino-4'-oxy-i, 1'-azobenzene-5'-carboxylic acid-6-sulfonic acid,

4-Amino-2-methyl-4'-oxy-i, 1'-azobenzene-5'-carboxylic acid,

4-Amino-3-methyl-4'-oxy-i, 1'-azobenzene-5'-carboxylic acid,

4-Amino-2-methyl-3'-methyl-4'-oxy-i, i'-azobenzene-5'-carboxylic acid,

4-Amino-2-methoxy-4'-oxy-i, 1'-azobenzene-5'-carboxylic acid,

4-Amino-3-ethoxy-4'-oxy-i, i'-azobenzene-s'-carboxylic acid, .

4-Amino-2-methyl-5-methoxy-4'-oxy-i, 1 '-azobenzene-5'-carboxylic acid,

4-Amino-2, 5-dimethoxy-4'-oxy-i, i'-azobenzene-5'-carboxylic acid,

4-Amino72-chloro-4'-oxy-i, 1'-azobenzene-5'-carbon- ■ acid,

4-Amino-2-nitro-4'-oxy-i, 1'-azobenzene-5'-carboxylic acid,

4-Amino-4'-oxy-i, i'-azobenzene-2, 5'-dicarboxylic acid, 4-Amino-2 ', 4'-dioxy-i, 1'-azobenzene-5'-carboxylic acid,

4-Amino-2-methyl-3'-chloro-4'-oxy-i, i'-azobenzene-5'-carboxylic acid,

4-Amino-2-methyl-3'-nitro-4'-oxy-i, i'-azobenzene-5'-carboxylic acid,

4-Amino-2-methyl-5-methoxy-4'-oxy-i, i'-azo-

benzene-S'-carboxylic acid-s'-sulfonic acid,

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4-AminoT2-methyl-4'-oxy-1, ι'-azobenzene-5'-carbon- ' acid-3'-sulfonic acid,

4-Amino-3-methyl-4'-oxy-i, ι'-azobenzene-5'-carboxylic acid-3 '-sulfonic acid,

4-Amino-2-bromo-4'-oxy-i, i'-azobenzene-5'-carboxylic acid-6-sulfonic acid,

4-Amino-2, 6-dibromo-4'-oxy-i, i'-azobenzene-5'-carboxylic acid,

4-Amino-2-methyl-5-methoxy-2'-oxy-i, 1 '-azobenzene-ß'-carboxylic acid,

4-Amino-3-methyl-2'-oxy-i, i'-azobenzene-3'-carbon-. acid-5'-sulfonic acid,

4-Amino-2-methyl-5-methoxy-5'-nitro-2'-oxyi, i'-azobenzene-s'-carboxylic acid,.

4-Amino-2-methyl-3'-oxy-i, i'-azobenzene ^ '- carbon-, acid,

4-Amino-3-methyl-3'-oxy-i, i'-azobenzene ^ '- carboxylic acid.

According to a further embodiment of the present In the invention one can also use a mixture of at least two different aminoazo dyes of the above general formula with the mentioned sulfonic acid chlorides of phthalocyanine tetrasulfonic acids bring to implementation.

The implementation of the sulfonic acid chlorides of the phthalocyanine sulfonic acids with the aminoazo dyes takes place in an aqueous medium and in the presence of at least one mineral acid neutralizing substance, such as B. alkali hydroxides, alkaline earth hydroxides, alkali carbonates, alkaline earth carbonates, alkali bicarbonates, Magnesium oxide, sodium acetate, ammonia, ammonium carbonate, dimethylformamide, triethanolamine, Pyridine and the like

The reaction temperature is of minor importance and can be varied within very wide limits, but it is advantageous to operate at low temperatures, preferably at temperatures between ο and 30 ⁰ .

Depending on the choice of reaction temperature and the mineral acid neutralizing substance, this can never completely avoidable saponification of the sulfonic acid chloride groups during the reaction to a greater or lesser extent be contained. It is not absolutely necessary that all sulfonic acid chloride groups with the Aminoazo dye are implemented. It is often an advantage if the dye in relation to its Solubility still contains one or more free sulfonic acid groups.

The various sulfonic acid chlorides used according to the invention can be mixed with with at least one, but preferably with several molecules of aminoazo dyes for reaction to be brought; so z. B. 1 mole of phthalocyanine tetrasulfonic acid chloride be reacted with 1, 2, 3 or 4 moles of an aminoazo dye.

In some cases it remains to be seen whether the

Sulfonic acid chloride groups completely or only partially converted into the sulfonic acid amides according to the invention will.

Depending on the choice of the phthalocyaninesulfonic acid chloride used and the number (1 to 4) of the moles of aminoazo dye used for the reaction, dyes with different coloring properties are formed. The more sulfonic acid dye molecule, the more pronounced the substantive nature of the dye, and the more salicylic acid is containing the dye molecule, the more pronounced ^is: pickling nature of the dye, which is clearly demonstrated by the increasing improvement of wet fastness properties. Green to olive shades are obtained, some of which are distinguished by excellent wet fastness properties and excellent light fastness.

The alkali salts of the azophthalocyanine dyes according to the invention are readily soluble in water and are suitable for dyeing as well as printing on vegetable, animal and fully synthetic fibers as well as for coloring oxidic protective layers on aluminum.

In addition, the new dyes, provided they contain sufficient components, can pass through Post-treatment with metal-releasing substances, if necessary. in connection with higher molecular weight basic substances, are fixed on textile fibers by known methods. In particular, one obtains by post-treating prints on cellulose fibers or fibers made from regenerated cellulose with copper-releasing substances in connection with ■ higher molecular weight basic condensation products green to olive colorations, the. are characterized by good wash and lightfastness.

The following examples illustrate the new process without, however, limiting it; the specified Parts mean parts by weight.

example 1

96.9 parts ( ¹ Z ₁₀ mol) of freshly prepared copper phthalo- 'cyanine tetrasulfochloride (crude product), obtained by the action of chlorosulfonic acid on copper phthalocyanine, are discharged onto ice and the separated reaction product is mixed as a moist paste with 300 parts of crushed ice. A solution of 27.9 parts ( ¹ Z ₁₀ mol) of the sodium salt of 3-amino-4'-oxy-i, i'-azobenzene-S'-carboxylic acid (obtained by the action of diazotized 3-N1 -traniline to salicylic acid and subsequent reduction of the nitro group with sodium sulphide) in 300 parts of water, to which 30 parts of calcium carbonate were added, quickly and allowed to ^{stir well at 15 to 20 0 for} 24 hours, acidify with dilute hydrochloric acid until the Congo acid reaction occurs, separates the precipitated dye off acid, subjects the dye obtained to purification, if necessary, and isolates it in the form of its sodium salt.

The dye thus obtained is a dark gray powder that turns greenish blue in water and dissolves in concentrated sulfuric acid with a yellow-green color and, dyed on pre-chromed cotton, gives strong green shades of good wet fastness and very good light fastness. In chrome print green shades with good fastness properties are obtained on cotton.

Instead of the sodium salt, the potassium, lithium or ammonium salt can also be used with the same success manufactured and used.

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Be in place of ¹ mol of 3-Z ₁₀ Amirio-4'-oxy-i, i'-azobenzene-S-carboxylic acid _^2/10 mole of _^3/10 moles or _^4/10 Mol3-Arhino-4'-oxy If i, i'-azobenzene-5 '~ carboxylic acid is brought to reaction, dyes are obtained which, for example in chrome printing on cotton, have different wet fastness properties;' thus, with an increasing number of salicylic acid groups in the dye molecule, the wet fastness properties generally experience a significant increase.

SO ₂ -HN

- SOoNa

copper phthalocyanine-3, 3 ', 3 ", 3"' -tetrasulfonic acid is a dark green powder that turns green-blue in water and in concentrated sulfuric acid with a yellow color. The chrome print on cotton turns a green from obtained very good wet fastness properties and excellent light fastness.

Example 2

96.9 parts ( ¹ Z ₁₀ mol) copper phthalocyanine tetrasulfo-

. chloride, obtained according to Example 1, are unloaded on ice, and then the separated reaction product is mixed as a wet paste with 300 parts of crushed ice and with stirring, a 60 to 70 ⁰ heated solution of 83.7 parts _^(3/10 mole) of the sodium salt of 4-Amino-4'-oxy-i, 1 '-azobenzene-5'-carboxylic acid (obtained by the action of diazotized 4-nitroaniline on salicylic acid and subsequent reduction of the nitro group with sodium sulfide) in 2000 parts of water and 30 parts of sodium carbonate were quickly added and 2 to 3 hours at 60 ° and then stirred for a further 24 hours at room temperature. After acidification with dilute hydrochloric acid, the precipitated dye acid is separated off, optionally subjected to purification and isolated in the form of its sodium salt.
'. The new dye is a dark gray powder that dissolves in water with a green color and in concentrated sulfuric acid with a brownish-yellow color. The dye is suitable for dyeing cotton and viscose as well as for dyeing pre-chromed cotton and chromed wool. Green shades of good wet fastness and very good light fastness are obtained. In chrome printing on cotton, it provides green shades with very good fastness properties.

Instead of 30 parts of sodium carbonate, 50 parts of potassium carbonate can also be used with the same success or 30 parts of ammonium carbonate can be used.

Example 3

48.5 parts ( ¹ Z ₂₀ mol) of copper phthalocyanine tetrasulfochloride, obtained according to the information in Example 1, are discharged onto ice. The separated reaction mixture is mixed as a wet paste with 200 parts of crushed ice, and with stirring, a 30 ⁰ heated solution of 38.1 parts ⁽¹ Z ₁₀ MoI) also changes generally with increasing number of azo groups in the dye molecule of the color from blue-green to yellow-green or to olive.

Of particular interest is that dye 'is obtained when _^3/10 mol of 3-amino-4'-oxy-i, ι'-azobenzene-5'-carboxylic acid with ¹ mole of Z ₁₀ Kupferphthalocyanintetrasulfochlorid brings to implement.

The sodium salt of this dye of the formula

N = N

OH

COONa

of the sodium salt of 3-amino-4'-oxy-i, i'-azobenzene-S'-carboxylic acid-o-sulfonic acid (obtained by the action of 3-nitroaniline-6-sulfonic acid on salicylic acid and subsequent reduction of the nitro group with sodium sulfide) in 300 parts of water and 10 parts of sodium hydroxide (100 ⁰ Z ₀ ) were added quickly. The mixture is stirred for a further 24 hours at room temperature, the dyestuff acid is isolated by acidification with dilute hydrochloric acid and converted into its sodium salt, which is purified by repeated salting.

The dye obtained is a dark gray powder that turns turquoise and blue in water dissolves in concentrated sulfuric acid with a yellow-green color. -.

The new dye is suitable for dyeing cotton and viscose as well as for dyeing wool. Green shades of moderate wet fastness and medium light fastness are obtained. Will this After chroming dyeings on cotton or wool, you get much stronger shades of green, the good ones; Characterized by wet fastness and very good light fastness. In chrome print on cotton green shades with good fastness properties are obtained.

In place of 10 parts of sodium hydroxide (ioo ° / ₀₎ and 15 parts of potassium hydroxide can (100 ⁰ Z ₀₎ can be used.

Example 4

48.5 parts ( ¹ Z ₂₀ mol) of copper phthalocyanine tetrasulfonyl chloride are prepared analogously to the information in Example 1, and the paste thus obtained is dissolved in a solution consisting of 76.2 parts ( ² Z ₁₀ mol) of the sodium salt of the 4-amino 4'-oxy-i, 1'-azobenzene-5'-carboxylic acid-6-sulfonic acid (obtained by the action of 4-nitroaniline-6-sulfonic acid on salicylic acid and subsequent reduction of the nitro group with sodium sulfide) in 400 parts of water and 25 parts of pyridine , entered quickly and left to stir for 24 hours at ό to 10 °. As usual, the dye acid is separated off, freed from adhering impurities and the sodium salt is isolated.

The dye obtained is a dark gray powder that turns green in water and in concentrated sulfuric acid dissolves with a yellow-brown color and dyes nylon in yellowish green shades.

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In chrome printing on cotton, yellowish green shades have good fastness properties receive.

Instead of 25 parts of pyridine you can also use

5 the same success 25 parts of dimethylformamide or 50 Parts of triethanolamine are applied.

Leave according to the information in Examples 1 to 4
The 65 examples listed in the table below can also be carried out.

ι moles of copper phthalocyanine tetrasulfochloride obtained according to Example 1 are reacted with

\ 40 example Mole Water soluble salt the same the same the same the same. ., nuance ^ of the aminoazo dye 1 3-Amino-4-methyl-4'-oxy-i, ι'-azobenzene-5'-carboxylic acid 4-Amino-3-methyl-4'-oxy-i, 1'-azobenzene-5'-carboxylic acid 4-Amino-2-methyl-5-methoxy-4'-oxy-i, 1 '-azobenzene- in chrome print LO 5 I. 3-Amino-6-methyl-4'-oxy-i, 1 '-azobenzene-5' -carboxylic acid 3'-sulfonic acid 5'-carboxylic acid-3'-sulfonic acid on cotton 6th 3 3-Amino-2'-methyl-4'-oxy-i, i'-azobenzene-5'-carboxylic acid 3-Amino-6-methoxy-4'-oxy-i, 1'-azobenzene-5'-carboxylic acid the same bluish green 45 7th I. the same 3-Amino-6-methoxy-4'-oxy-i, 1'-azobenzene-5'-carboxylic acid 4-Amino-2-bromo-4'-oxy-i, 1 '-azobenzene-5' -carboxylic acid- . green 8th 2 3-Amino-4'-oxy-i, i'-azobenzene-5'-carboxylic acid-4-sulfonic acid, the same 6-sulfonic acid green ! 5 9 3 the same 4-Amino-3'-methyl-4'-oxy-i, 1'-azobenzene-5'-carboxylic acid 4-Amino-2-methyl-5-methoxy-2'-oxy-i, i'-azobenzene- green IO I. the same the same 3'-carboxylic acid yellowish green 50 3-Amino-3'-methyl-4'-oxy-i, i'-azobenzene-S'-carboxylic acid 4-Amino-4'-oxy-i, 1 '-azobenzene-5'-carboxylic acid-5-sulfonic acid II 3 4-sulfonic acid the same bluish green 20th 12th 2 the same green 13th 2 4-Amino-2-methyl-4'-oxy-i, 1'-azobenzene-5'-carboxylic acid grass green 14th I. the same bluish green 55 15th 2 4-Amino-2-methoxy-4'-oxy-i, 1 '-azobenzene-5' -carboxylic acid green l6 3 the same green I? I. 4-Amino-2,5-diethoxy-4'-oxy-i, 1'-azobenzene-5'-carboxylic acid green ■ l8 3 the same green 60 19th I. 4-Amino-2-chloro-4'-oxy-i, 1'-azobenzene-5'-carboxylic acid grass green 3D 20th 2 the same green 21 3 4-Amino-2-nitro-4'-oxy-i, 1'-azobenzene-5'-carboxylic acid yellowish green 22nd I. the same yellow-green . 23 3 4-Amino-4'-oxy-i, i'-azobenzene-2, 5'-dicarboxylic acid. · yellow-green 24 I. the same grass green OU 25th 3 4-Amino-2-methyl-4'-oxy-i, 1'-azobenzene-5'-carboxylic acid green 26th I. 3'-sulfonic acid olive green 27 3 green 28 I. green 29 3 green 30th I. yellowish green 31 3 bluish olive - 32 I. olive 33 3 turquoise blue 34 I. blue green 35 3 green 36 I. yellow-green 37 3 jade green 38 I. yellowish green 39 3 bluish green 40 2 olive green 41 I. green 42 3 bluish green olive

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Example 43

48.5 parts ( ¹ Z ₂₀ mol) of copper phthalocyanine-4, 4 ', 4 ", 4"' -tetrasulfochloride, obtained by the action of chlorosulfonic acid on copper phthalocyanine-4, 4 ', 4 ", 4"' -tetrasulfonic acid, are with 250 parts of crushed ice, mixed well, and with stirring, a solution of 55,8Teüen _^(2/10 mole) of the sodium salt of 3 "amino-4'-oxy-i, 1'-azobenzene-5'-carboxylic acid in 300 parts of water and 35 parts of sodium acetate are quickly added and the mixture is stirred for about 60 hours at 20 ° to 25 ° The reaction product is made weakly acidic with dilute hydrochloric acid, the precipitated dye acid is separated off, dissolved in hot water and soda and the sodium salt is isolated by salting out with sodium chloride.

The dye obtained is a dark gray powder that turns green in water and in concentrated sulfuric acid with. dirty yellow paint dissolves.

The new dye is suitable for dyeing cotton, viscose, wool and natural silk. Through After treatment with metal salt, the wet fastness properties are in some cases considerably improved. In chrome print on Cotton will have a vivid green with very good wet fastness properties and excellent light fastness.

The same dye with the same coloring properties is obtained if, for. B. at

= / SO ₉ -HN

SO, well

which is based on copper phthalocyanine-4, 4 ', 4 ", 4"' - tetrasulfonic acid, represents a blue-black Powder which is green-blue in water and yellow-olive in concentrated sulfuric acid solves.

The dye thus obtained is particularly suitable

= / SO ₉ -HN

= (SO ₃ Na) ₂

which is based on copper phthalocyanine-4, 4 ', 4 ", 4"' - tetrasulfonic acid.

The sodium salt of this dye is a blue-black powder that dissolves in water with blue-green and in concentrated sulfuric acid with yellow-olive Color dissolves. In the chrome print on cotton, a rich blue-tinged green with very good results Obtained wet fastness properties and excellent light fastness.

Example 44

48.5 parts of copper phthalocyanine 4, 4 ', 4 ", 4".' - tetrasulfochlorid ⁽¹ Z ₂₀ mol) obtained as indicated in Example 43, are mixed with 250 parts of crushed ice, _s and with stirring, a solution of from 0 to 10 °, 50 ° to 60 ° or 80 to 90 instead of ⁰ as the above example at 20 to 25 operates ^0th

Example 43a

97 parts ( ¹ Z ₁₀ mol) of copper phthalocyanine-4, 4 ', 4 ", 4"' - tetrasulfochloride, obtained by the action of chlorosulfonic acid on copper phthalocyanine-4, 4 ', 4 ", 4"' - tetrasulfonic acid, are 400 parts Crushed ice and 150 parts of water mixed together to form a homogeneous paste. This paste is neutralized with calcium carbonate, and then a solution of 83.7 parts, with stirring _^(3/10 mole) of the sodium salt of 3-amino-4'-CiXy-I, I'-azobenzene-5'-carboxylic acid in 1000 parts of water, to which 40 parts of calcium carbonate were added, were quickly added and the mixture was stirred for 10 hours at 5 to 15 ° and then for a further 24 hours at room temperature. After the reaction has ended, the precipitated dye is filtered off with suction and made into a paste with 400 parts of water, acidified with 400 parts of concentrated hydrochloric acid, isolated, taken up in 300 parts of water, dissolved with sodium carbonate, filtered and the filtrate salted out with 300 parts of sodium chloride. The dye, separated off as the sodium salt, is dried and extracted with alcohol for further purification.

The dye of the formula thus obtained

N = N-

OH

COONa

N = N

OH

for chrome printing on cotton. The result is rich green tones with excellent wet fastness properties and excellent lightfastness.

Are ι'-azobenzene-5'-carboxylic acid put in place from _^3/10 mol only _^2/10 mole of 3-amino-4'-oxy-i for reaction, the result is a dye of the formula

COONa

27.9 parts ( ¹ Z ₁₀ mol) of the sodium salt of 4-amino-4'-oxy-i, 1'-azobenzene-5'-carboxylic acid in 600 parts of water and 25 parts of magnesium carbonate were added rapidly and for 60 hours at 20 to Let stir 30 ^0. The dyestuff is isolated and worked up as indicated in Example 43.

The dye obtained is a dark gray powder that turns green in water and in concentrated sulfuric acid with a greenish yellow color.

The dye dyes chromed cotton in a strong green and re-chromed wool in green and very lightfast colors.

A strong green with good fastness properties is obtained in chrome printing on cotton.

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Instead of 25 parts of magnesium carbonate, 12 parts of magnesium oxide and 30 parts of calcium carbonate can also be used or 60 parts of barium carbonate can be used.

Example 45

48.5 parts ( ¹ Z ₂₀ mol) of copper phthalocyanine-4, 4 ', 4 ", 4"' - tetrasulfochloride are stirred with ice and water to form a homogeneous paste. Then it sets a solution of 57.1 parts _^(3/20 mole) of the sodium salt of 3-amino-4'-oxy-i, 1'-azobenzene-5'-carboxylic acid-6-sulfonic acid in 400 parts of water and 25 parts of Ammonia (20 ° / ₀ ) is added and the mixture is stirred for 60 hours at 0 to 5 °. The reaction product is salted out directly with common salt, the resulting dye is separated off and isolated as the sodium salt by redissolving twice.

The dye obtained is a dark green powder that changes in water with green and in concentrated sulfuric acid with a greenish yellow color dissolves and chromed cotton in lively, dyes bluish green shades of good wet fastness and very good light fastness.

The chrome print on cotton produces a strong green with good wet fastness properties and very good light fastness receive.

Dyed on anodically oxidized aluminum, the dye gives a clear green.

In place of 25 parts of ammonia (20 ⁰ Z ₀₎ 10 parts of sodium hydroxide (100%) or 15 parts of potassium hydroxide can (ioo ° / ₀₎ can be used with equal success.

Example 46

48.5 parts of (Z ¹ ₂₀ mol) of copper phthalocyanine 4, 4 ', 4 ", 4"' are -tetrasulfochloride with 250 parts of ice, mixed well, the paste obtained and washed with ice cold dilute sodium hydroxide to a _pH value of 6 , 9 and a solution of 57.1 parts ( ³ Z ₂₀ mol) of the sodium salt of 4-amino-4'-oxy-i, i'-azobenzene-5'-carboxylic acid-6-sulfonic acid in 400 parts of water and 20 Parts of sodium bicarbonate were added rapidly. The mixture is heated under good stirring to 40 ^0, this temperature is maintained for several hours upright and allowed to stir for an additional 50 to 60 hours at room temperature. The dye is salted out from the litmus-alkaline solution with table salt and cleaned.

The dye obtained is a blue-gray powder that is greener in water and concentrated in Sulfuric acid dissolves with a yellow-brown color and a yellowish green in the chrome print on cotton of good fastness properties.

Instead of 20 parts of sodium bicarbonate, 15 parts of sodium carbonate or 25 parts of potassium carbonate can also be used can be applied.

In accordance with the information in Examples 43 to 46, those in the table below can also be found run the examples listed.

ι mol of copper phthalocyanine-4, 4 ', 4 ", 4"' - tetrasulfochloride, obtained according to Example 43, is reacted with _g j

example Mole Water soluble salt
of the aminoazo dye nuance
in chrome print
on cotton 47 I. 3-Amino-4-methyl-4'-oxy-i, 1 '-azobenzene-5' -carboxylic acid bluish green 48 2 the same green 49 3 the same yellowish green 50 4th the same yellow-green 51 I. 3-Amino-6-methyl-4'-oxy-i, 1'-azobenzene-5'-carboxylic acid grass green 52 2 the same yellowish green 53 3 the same yellow-green « ⁵⁴ 2 3-Amino-4'-oxy-i, i'-azobenzene-5'-carboxylic acid-4-sulfonic acid yellow-green "''55 ■ 2 4-Amino-4'-oxy-i, 1'-azobenzene-5'-carboxylic acid-5-sulfonic acid yellow-green 56 3 4-Amino-2-methoxy-4'-oxy-i, 1 '-azobenzene-5' -carboxylic acid olive green 57 ■ I. 4-Amino-2-chloro-4'-oxy-i, 1'-azobenzene-5'-carboxylic acid bluish green 58. I. 4-Amino-2-methyl-5-methoxy-5'-nitro-2'-oxy-i, 1 '-azobenzene-
3'-carboxylic acid blue green 59 I. 4-Amino-2-methyl-3'-oxy-i, i '.- azobenzene ^' - carboxylic acid blue green 60 2 4 "Amino-2,6-dibromo-4'-oxy-i, i'-azobenzene-s'-carboxylic acid blue green 61 3 4-Amino-2-nitrO "4'-oxy-i, 1 '-azobenzene-S'-carboxylic acid olive green 62 3 4-Amino-2-bromo-4'-oxy-i, i'-azobenzene-S'-carboxylic acid
6-sulfonic acid green 63 4th 4-Amino-2 ', 4'-dioxy-i, i'-azobenzene-5'-carboxylic acid olive green

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Example 64

An ice-cold paste of 45.7 parts ( ¹ I ₂₀ mol) of copper phthalocyanine - monosulfochloridetrisulfonic acid (obtained by partial saponification of the copper phthalocyanine 4, 4 ', 4 ", 4"' - tetrasulfochlorides described according to the information in Example 43) are used at ο to 5 ° mixed with a solution of 14 parts ( ¹ Z ₂₀ mol) of the sodium salt of 4-amino-4'-0Xy-I ₁ i'-azobenzene-5'-carboxylic acid in 400 parts of water and 15 parts of calcium carbonate. The mixture is stirred for 24 hours at 0 to ⁵⁰ and the dye is isolated in the usual way. The dye obtained is a dark gray powder which dissolves in water with green and in concentrated sulfuric acid with a yellow-brown color.

t5 The dye delivers in chrome printing on cotton Green tones with good fastness properties.

Example 65

64 parts (i / ₂₀ mol) brominated copper phthalocyanine 4, .4 ', 4 ", 4"' - tetrasulfochlorid, obtained by the action of chlorosulfonic acid and thionyl chloride to brominated Kupferphthalocyamn-4, 4 ', 4 ", 4"' - tetrasulfonic (according to analysis, contains 9.4% bromine), are unloaded onto ice, the suctioned off reaction product. is mixed with 250 parts of crushed ice and with stirring, a solution of 42 parts _^(3/20 mole) of the sodium salt of 3-amino-4'-oxy-i, i'-azobenzene-5'-carboxylic acid in 300 parts of water, the 20 parts of calcium carbonate were added, added quickly.

The mixture is stirred at room temperature for 50 hours and the dye is isolated as the sodium salt.

The dye thus obtained is a dark green powder that turns bluish green in water and dissolves in concentrated sulfuric acid with olive paint and in chrome print on cotton strong green tones provides very good fastness properties.

Example 66

A moist paste of copper phthalocyanine tetrasulfonyl chloride, which was prepared by the action of chlorosulfonic acid on 45 parts ( ¹ Z ₂₀ mol) of copper phthalocyanine tetrasulfonic acid (obtained by sulfonating copper phthalocyanine with oleum), discharging onto crushed ice and separating off the reaction product, is mixed with 100 parts of ice and 100 Share water. A solution of 42 parts ( ⁸ × ₂₀ mol) of the sodium salt of 4-amino-4'-oxy-i, i'-azobenzene-5'-carboxylic acid in 1000 parts of water and 15 parts of calcium carbonate is quickly added with stirring 30 hours with ο to 5 ⁰ . The dye is precipitated from its solution by the usual method and isolated as the sodium salt.

The dye thus obtained is a dark gray powder that turns greenish blue in water and dissolves in concentrated sulfuric acid with yellow-green color and in its coloring properties is identical to the dye described in Example 2.

Example 67 '

24.2 parts ( ¹ Z ₄₀ mol) of copper phthalocyanine tetrasulfochloride, obtained according to the details of Example 1, are unloaded onto ice, and the sulfochloride separated off is stirred as a moist paste with 150 parts of crushed ice. While stirring, a solution of 22.2 parts _^(3/40 mole) of the sodium salt of 4-amino-2 ', 4'-dioxy-i, i'-azobenzene-5'-carboxylic acid (prepared by coupling diazotized p -Aminoacetanilide on 2,4-dioxybenzoic acid and subsequent saponification) in 400 parts of water and 15 parts of magnesium carbonate quickly and allowed to stir for 24 hours at room temperature. The dye isolated by acidification with dilute hydrochloric acid is purified by dissolving and washing out and isolated as the sodium salt.

The dye thus obtained is a dark gray powder that turns dark green and in water dissolves in concentrated sulfuric acid with a yellow-brown color.

The new dye dyes cotton directly in strong, greenish gray and chromed cotton in strong gray-green tones. Nylon is found in olive and anodized aluminum in stained green hues. In the chrome print on cotton an olive becomes remarkable Retain authenticity properties. -

Example 68

96.9 parts ( ¹ Z ₁₀ mol) of copper phthalocyanine tetrasulfochloride, obtained according to Example 1, are mixed as a moist paste with 350 parts of crushed ice, and a solution of 27.9 parts ( ¹ Z ₁₀ mol) of the sodium salt of 4-amino-4 '-oxy-i, i'-azobenzene-5'-carboxylic acid, 29.3 parts ( ¹ Z ₁₀ mol) of the sodium salt of the 3-amino-2' -methyl-4 '-ο xy-i, 1' -azobenzene -s'-carboxylic acid (prepared by coupling diazotized 3-nitroaniline to 4-methyl-2-oxybenzoic acid and subsequent reduction with sodium sulfide) in 2000 parts of water and 30 parts of sodium carbonate is added too quickly and stirred for 30 hours at 0 °. The azophthalocyanine dye is isolated and worked up as indicated in Example 2.

The dye obtained is a greenish-tinged, dark-gray powder that turns blue-green in water and dissolves in concentrated sulfuric acid with a brownish-yellow color and lively in the chrome print on cotton Provides green tones with very good fastness properties. .

. Example 69 '<

29 parts ( ³ zioo mol) of nickel phthalocyanine tetrasulfochloride, obtained by the action of chlorosulfonic acid on nickel phthalocyanine, are discharged onto ice. The separated reaction product is mixed as a wet paste with 150 parts of crushed ice and a solution of 25.1 parts _^(9/100 mol) of the sodium salt of 3-amino-4'-oxy-i, i'-azobenzene-5'- carboxylic acid in 300 parts of water and 15 parts of calcium carbonate is added. The mixture is stirred for 24 hours at ⁰ to 50 °, the reaction mixture is made slightly alkaline with sodium carbonate while warming to 50 °, nitrated from calcium carbonate and the dye is isolated by salting out with sodium chloride.

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The obtained dye of the formula

N = N

OH

COONa

- SOsNa,

which the nickel phthalocyanine ^, 3 ', 3 ", 3"' - tetrasulfonic acid underlying. is a dark gray powder that turns green and in water dissolves in concentrated sulfuric acid with a greenish yellow color.

The new dye is suitable for dyeing chromed cotton, with strong green tones of good lightfastness can be obtained. In chrome printing on cotton, a vivid green turns out to be very good Obtained wet fastness properties and good light fastness.

If instead of _^9/100 mole only _^3/100 mol "the sodium salt of 3-amino-4'-oxy-i, i'-azobenzene-5 '-carboxylic acid put to use, the result is a dye with some blaustichigerem hue and significantly lower wet fastness properties.

In accordance with the information in Example 68, the examples listed in the table below can also be used To run. .

ι moles of nickel phthalocyanine tetrasulfochloride obtained according to Example 68, is reacted with

example Mole Water soluble salt
, the aminoazo dye nuance
in chrome print
on cotton 70
71
72
73
74
75 OJ H OJ H OJ H 3-Amino-4'-oxy-i, 1 '-azobenzene-5'-carboxylic acid-4-sulfonic acid
the same
3-Amino-6-methoxy-4'-oxy-i, i'-azobenzene-s'-carboxylic acid
the same
4-Amino-2-chloro-4'-oxy-i, 1 '-azobenzene-5' -carboxylic acid
the same blue-green ¹
yellow-green
green
olive green
blue green
green

Example 76

96.4 parts ( ¹ Z ₁₀ mol) of nickel phthalocyanine-4, 4 ', 4 ", 4"' - tetrasulfochloride, obtained by the action of chlorosulfonic acid on nickel phthalocyanine-4, 4 ', 4 ", 4"' - tetrasulfonic acid thoroughly mixed with 350 parts of crushed ice, and with stirring, a solution of 83.7 parts _^(3/10 mole) of the sodium salt of 3-amino-4'-oxy-i, i'-azobenzene-5'-carboxylic acid in 500 Parts of water, to which 30 parts of calcium carbonate were added, were quickly added. The mixture is then left to stir at 25 ° for about 50 hours, the reaction mixture is slightly acidified with dilute hydrochloric acid, the precipitated dye is separated off from acid, it is dissolved in water and sodium carbonate and the dye is salted out.

The dye thus obtained is a blue-black powder that turns blue-green in water and in concentrated sulfuric acid with a yellow-olive color.

In chrome printing on cotton, the new dye provides a rich green of excellent quality Authenticity properties.

Example 77

48.3 parts ( ¹ Z ₂₀ mol) of freshly prepared cobalt phthalocyanine tetrasulfochloride, obtained by the action of chlorosulfonic acid on cobalt phthalocyanine, are discharged onto ice. The separated reaction product is mixed as a wet paste with 250 parts of crushed ice, a solution of 41.7 parts _^(3/30 mole) of the sodium salt of 3-amino-4'-oxyi, ι'-azobenzene-5'-carboxylic acid in 400 Share water

and 20 parts of calcium carbonate were quickly added and ^{left to stir at 30 to 40 0 for} 3 hours and then at room temperature for a further 24 hours. The dye is isolated as indicated in Example 68.

The dye obtained is a blue-gray powder which dissolves in water with a greenish blue color and in concentrated sulfuric acid with a greenish yellow color.

In the chrome print on cotton, strong green tones with very good wet fastness properties and excellent Preserved lightfastness. The color on anodically oxidized aluminum is intense Shades of green.

Instead of calcium carbonate, other alkalis can easily be used will.

Example 78

48.3 parts ( ¹ Z ₂₀ mol) of cobalt phthalocyanine tetrasulfo ¹ chloride, obtained according to Example 77, are mixed with 250 parts of crushed ice, and a solution of 32.4 parts ( ¹ Z ₁₀ mol) of the sodium salt of the 4-amino-2- Nitro-4'-oxy-i, 1'-azobenzene-5'-carboxylic acid (prepared by coupling diazotized 4-acetylamino-2-nitraniline to salicylic acid and subsequent saponification) in 1000 parts of water and 20 parts of calcium carbonate is quickly added. The mixture is stirred for 15 hours at room temperature and the dye is isolated in the usual way,

The dye obtained is a dark gray powder that turns olive green in water and in

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concentrated sulfuric acid dissolves with a gray-brown color and is interesting in chrome printing on cotton Provides green tones with good fastness properties. If you replace the 4-amino-2-nitro-4'-0Xy-I in the above example, i'-azobenzene-S'-carboxylic acid .by the corresponding Amount of 4-amino-2-chloro-4'-oxy-i, i'-azobenzene-5'-carboxylic acid or 3-amino-4'-oxy-i, i'-azobenzene-S'-carboxylic acid-o-sulfonic acid, in this way dyes are obtained which have a similar hue and good fastness properties.

Example 79

96.5 parts (V ₁₀ mol) of cobalt phthalocyanine-4, 4 ', 4 ", 4"' - tetrasulfochloride, obtained by the action of chlorosulfonic acid on cobalt phthalocyanine-4, 4 ', 4 "-4"' - tetrasulfonic acid, are considered moist Paste at io °. in a solution of 29.3 parts ( ¹ Z ₁₀ mol) of the sodium salt of 3-amino-2'-methyl-4'-oxy-i, i'-azobenzene-5'-carboxylic acid in 800 parts of water and 45 parts Potassium hydroxide (100 ° / ₀ ) entered quickly. The mixture is stirred for 50 hours at 10 ° and the dye is isolated by one of the customary methods.

The dye is a dark gray powder that turns blue-green in water and in concentrated Dissolves sulfuric acid with a greenish yellow color.

In chrome printing on cotton, vivid green tones with good fastness properties are obtained.

Example 80

48.1 parts ⁽¹ mole Z ₂₀₎ Eisenphthalocyanintetrasulfochlorid, obtained by the action of chlorosulfonic acid on iron phthalocyanine are mixed well with 250 parts of crushed ice, and with stirring a solution of 57.1 parts _^(3/20 mol) of the 3 Natriumsälzes -Amino-4'-oxy-i, i'-azobenzene-S'-carboxylic acid-6-sulfonic acid in 400 parts of water and 15 parts of potassium hydroxide (100 ⁰ Z ₀ ) were added. The mixture is stirred for 24 hours at room temperature and the dye is isolated as the potassium salt.

The dye is a dark gray powder that turns green in water and concentrated in Sulfuric acid with a brownish yellow color dissolves.

This dye stains anodically oxidized aluminum in green tones.

In chrome printing on cotton, olive green shades are obtained with this new dye.

If instead of _^3/20 mol of 3-amino-4'-oxy-i, ι'-azobenzene-5'-carboxylic acid-6-sulfonic acid ³ Z ₂₀ moles of 3-amino-4'-oxy-i, I ' When azobenzbl-5'-carboxylic acid is reacted, a dye is obtained which dyes cotton in olive green shades using chrome printing.

Example 81

24.1 parts ( ¹ Z ₄₀ mol) of iron phthalocyanine tetrasulfochloride, obtained according to Example 80, are mixed with 150 parts of crushed ice and quickly poured into a solution of 30.9 parts ( ¹ Z ₁₀ mol) of the sodium salt of 4-amino-3-methoxy -4'-oxy-i, i'-azobenzene-5'-carboxylic acid in 800 parts of water to which 15 parts of magnesium carbonate were added. The mixture is stirred for 40 hours at 5 to 10 ° and the dye is isolated in the usual way.

The dye is a dark gray powder that turns olive green in water and concentrated in Dissolves sulfuric acid with a purple-brown color.

The chrome print on cotton produces olive-brown shades.

When using ¹ Z ₁₀ mol of 4-amino-2 ', 4'-dioxybenzene-i, i'-azobenzene-5'-carboxylic acid instead of 4-amino-3-methoxy-4'-oxy-i, i'-azobenzene-5'-carboxylic acid, a dye is obtained which dyes cotton in olive green tones using chrome printing.

Example 82 Example 83 Example 84

96.2 parts ( ^x / ₁₀ mol) of iron phthalocyanine-4, 4 ', 4 ", 4"' - tetrasulfochloride, obtained by the action of chlorosulfonic acid on iron phthalocyanine-4, 4 ', 4 ", 4" - tetrasulfonic acid are used as wet paste in a solution of 51.4 parts ( ² Z ₁₀ mol) of the sodium salt of 4-amino-4'-oxy-i, i'-azobenzene-5'-carboxylic acid in 1000 parts of water and 30 parts of sodium carbonate. The mixture is stirred for 60 hours at .20 to -25 ⁰ and the dye is isolated in the usual way.

The dye is a dark gray powder, ® ⁵ which dissolves in water with a yellow-green color and in concentrated sulfuric acid with a red-brown color and dyes cotton in olive hues using chrome printing.

47.9 parts ( ¹ Z ₂₀ mol) of chromium phthalocyanine tetrasuliochloride, obtained by the action of chlorosulfonic acid on chromium phthalocyanine, are discharged onto ice. The separated reaction product is called ". wet paste with 200 parts of ice is mixed, a solution of 41.8 parts _^(3/20 mole) of the sodium salt of 3 - amino - 4 '- oxy -1, ι' - azobenzene - 5 '- carboxylic acid in 400 parts of water and 10 Parts of sodium hydroxide (100%) were added rapidly and the mixture was left to stir at 10 to 20 ° for 24 hours.

The dye is isolated as the sodium salt in the usual way.

The dye obtained is a gray-green powder which dissolves in water with green and in concentrated ₁₀ g of sulfuric acid with a yellow color and dyes cotton in chrome printing in yellow-green shades of very good wet fastness properties.

95.8 parts ⁽¹ mole Z ₁₀₎ Chromphthalocyanintetrasulfochlorid obtained in Example 83, are mixed as a wet paste with 200 parts ice and 200 parts of water, and a solution of 73.6 parts _^(2/10 mole) of the sodium salt of 4- Amino-2-methyl-5-methoxy-2'-oxy-5'-nitro-i, i'-azobenzene-3'-carboxylic acid (obtained by acetic acid coupling of diazotized 5-nitro-3-amino-2-oxybenzoic acid 5-methyl-2-methoxyaniline) in 1200 parts of water and 30 parts of sodium carbonate is added quickly. The mixture is stirred for 24 hours at room temperature and the dye is isolated in the usual way. ■

The dye obtained is a dark gray powder that turns green in water and concentrated in Sulfuric acid dissolves with a reddish brown color and dyes cotton in chrome print in olive green tones.

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Example 85

47.9 parts ( ¹ Z ₂₀ mol) of chromophthalocyanine-4, 4 ', 4 ", 4"' - tetrasulfochloride, obtained by the action of chlorosulfonic acid on chromophthalocyanine-4, 4 ', 4 ", 4"' - tetrasulfonic acid are obtained ice unloaded, and the separated reaction product is as a moist paste of a solution of 42 parts of _^(3/20 mole) of the sodium salt of 3-amino-4'-oxy-i, i'-azobenzene-5'-carboxylic acid in 300 parts of water, to which 20 parts of calcium carbonate were added, added quickly. The mixture is allowed first for 10 hours at 10 ° and afterwards for 40 hours at 20 to 25 ⁰ stir. The dye is isolated in the usual way in the form of its sodium salt.

The dye obtained in this way is a dark green powder that changes in water with green and in concentrated sulfuric acid with a yellow-brown color.

^{1 In} chrome printing on cotton, the new dye provides olive green shades with very good fastness properties.

Example 86

93.3 parts ( ^× / ₁₀ mol) of aluminum phthalocyanine tetrasulfochloride, obtained by the action of chlorosulfonic acid on aluminum phthalocyanine, are discharged onto ice. The isolated reaction product is mixed as a wet paste with 400 parts of crushed ice, a solution of 83.7 parts _^(3/10 mole) of the sodium salt of 3-amino-4'-oxy-i, i'-azobenzene-5'-carboxylic acid added in 500 parts of water and 20 parts of sodium hydroxide (100 ° / ₀₎ quickly and for 24 hours at 20 ⁰ allowed to stir. Sodium chloride is added to the solution obtained, and the dyestuff which has precipitated out is isolated and purified by salting twice.

The dye obtained is a greenish-tinged dark gray powder that dissolves in water with green and dissolved in concentrated sulfuric acid with green-yellow color and cotton in chrome print in dyes vivid green tones with very good wet fastness properties.

When colored on anodically oxidized aluminum, the dye gives a beautiful bluish green.

Instead of the 3-amino-4'-oxy-i, i'-azobenzene-5'-carboxylic acid 3-Amino-4'-oxy-i, i'-azobenzene-s'-carboxylic acid-o-sulsonic acid can also be used with the same success can be applied.

Example 87

Parts _^(3/100 mol) of aluminum phthalocyanine-4, 4 ', 4 ", 4"' - tetrasulfochlorid, obtained by the action of chlorosulfonic acid to aluminum phthalocyanine 4, 4 ', 4 ", 4"' - tetrasulfonic acid, are mixed with 150 parts of crushed Stirred ice and 200 parts of water. To this paste 50 is added a solution of 23.1 parts ⁽³ / ioo mole) of the sodium salt of 4-amino-4'-oxyi, ι'-azobenzene-5'-carboxylic acid in 700 parts of water and 20 parts of potassium carbonate and stirred Hours at room temperature. The dye is isolated in the usual way.

The dye is a greenish dark gray powder that turns yellow-green in water and in concentrated Sulfuric acid with a brown color, dissolves and dyes cotton with chrome printing in green tones.

Claims (1)

PATENT CLAIM: Process for the production of water-soluble and associated azophthalocyanine dyes, characterized in that 1 mole of phthalocyaninesulfonic acid chloride the general formula (SO ₂ - Cl) _n
(SO ₃ H) ₄ _ " where A represents a substituted or unsubstituted, metal-containing phthalocyanine molecule in which the —SO ₂ Cl or —SO ₈ H groups are either in the 3- or 4-position and η denotes the number ι to 4, with at least one, but preferably 2 to 4 mol of at least one aminoazo dye of the general formula where χ H, halogen, CH ₃ , OH, NO ₂ or SO ₃ H, y H, "halogen, alkyl, alkoxy, NO ₂ , SO ₃ H or COOH and ζ H, halogen, alkyl or alkoxy means, in aqueous · Brings medium and in the presence of a mineral acid neutralizing substance to implement. I 509 630/132 1. 56