BE525737A - - Google Patents

Description

       

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  PROCESS FOR THE PREPARATION OF MORDANCABLE AZOPHTALOCYANINE COLORANTS, SOLUBLE IN WATER AND RESULTING NEW COLORS.



   In Belgian patent no. 516,774, a process has been described for the preparation of esters of water-soluble phthalocyanin-tetrasulfonic acids which contain at least one salicylic group in their molecule and constitute blue to green dyes suitable for dyeing and coloring. textile printing. These dyes are characterized by the fact that they are edible dyes and give, in particular, blue tints of very good strength.



   In addition, patent application No. 408,817, filed July 30, 1953 in the name of the Applicant, relating to a "Process for the preparation of azophthalocyanine dyes on water-soluble mordants and new dyes has been described. thus obtained ", a process for the preparation of such dyes., in which one reacts with a sulphonic acid chloride of phthalocyanine, derived from one of the phthalocyanine-tetrasulphonic acids, of 1-4 molecules, of at least one dye amino-azo, which contains a salicylic group. In this way dyes are obtained which give green to olive-green tints, exhibiting very good fastness in most cases.



     Gold.!' it has been found that new and very interesting water-soluble mordantable azophthalocyanine dyes are obtained when reacted in an aqueous medium and in the presence of a mineral acid neutralizing substance, simultaneously or in any order, 1 phthalocyanine sulfonic acid chloride molecule of general formula
 EMI1.1
 

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 EMI2.1
 in which A represents a substituted or unsubstituted phthalocyanine molecule, containing a metal, the groups -SO2Cl or SO3M being in position 3- or 4-, l! is a number between 1 and 4 and each M represents H, NH 4 or an alkali metal. with at least 1 molecule of an aminoazo dye of general formula:

   
 EMI2.2
 
 EMI2.3
 where x is hydrogen, halogen., CH 3, OH, NO2 or SO3M y is 1-hydrogen .. halogen, alkyl, alkoxy,
 EMI2.4
 NO 2 .. Soe or COOM, z is hydrogen, halogen, alkyl or alkoxy and each M represents H, NH4 or an alkali metal, and with at least 1 mol-
 EMI2.5
 cule of a dihydroxybenzene-oarboxylic acid of general formula-.
 EMI2.6
 
 EMI2.7
 wherein ¯% represents hydrogen, halogen, a t7t group, M3 or SO3M each M representing H, NH4 or an alkali metal.



  The novel water-soluble azophthalocyanine dyes thus obtained correspond to the following general formula:
 EMI2.8
 in which A represents a substituted or unsubstituted phthalocyanine molecule,
 EMI2.9
 containing a metal, the groups -so2 * 0- and -So2HU- or SOP- are found in the 3- or 4- position; and m represents Hp halogen, OHy CH3 or St13M x represents H, halogen, CH 3.9 oH.

   N02 or S3M

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 EMI3.1
 y represents Hç a halogen an alkyl group, an alcohol group - XTg NO29 S03M or COOM. z represents Hg a halogen, an alkyl or alkyl group a and b each represents a number between 1 and 3 c represents a number between 0 and 2,
 EMI3.2
 M represents H9 NIi4 or an alkali metal and sawne a + b + is equal to 4p the group -S 2oNH- located in position m- or p- relative to the azo group.



   The surprising finding has been made that the dyes obtained according to the present invention are superior in their dyeing properties to those of the two aforementioned patent applications. This is manifested by-
 EMI3.3
 particularly by improving strengths in general. Compared to the dyes prepared according to application PV 6520747 :; purer green to olive-green tints are obtained, especially when printing with a chrome mordant.



   All the sulfochlorides of phthalocyanine-tetrasulfonic acids which can be prepared by known methods are suitable for the present process.
The sulfochlorides of copper, nickel and cobalt phthalocyanines as well as of iron, chromium and aluminum phthalocyanines are particularly advantageous.



   Depending on the preparation method chosen, phthalocyanine sulfochlorides bearing the sulfochloride groups in position 3 or in position 4 will be obtained.



   Starting with 4-sulfophthalic acid, the sulfochloride groups will be obtained in position 4 and if one proceeds by direct sulfochlorination
 EMI3.4
 te of the phthalecyaulmes molecule, the sulfochloride groups enter Kosi in position 3. The number of chlorosulfonic groups in the molecule can vary from 1 to 4. When preparing the sulfochlorides of phthalocyanine-tetrasulfonic acids and in particular during their isolation there are in most cases mixtures of phthalocyanines having a different number of sulfochloride groups.
 EMI3.5
 



  Aminoazo dyes suitable for the reaction and corresponding to the general formula may be given as examples
 EMI3.6
 
 EMI3.7
 in which 9, and z have the aforementioned meanings and in which the group -NH is in the m- or p-position relative to the azo group, the following compounds 3-aminom acid, 9 hc 'ox 191sme, zobenzènem5caborlique 3 amino29netixyl acid .9Ahydx oy 191azo'benzènem59-earboxeylique 3maan3.n39th14mhrdroxy1g19azobenzene59-caz bolic Acid 3-amino-4S1 -hydroxy-l, \! Ls> -azobenzene-5 '-c arboxylic-6-s ulfroren19mazhenzobenzene-6-s ulfroren19mazhenzobenzene acid '-carboxylic-4-sulfonic acid 3-Amino-4-methyl-4' -hydroxy-ll J -azobenzene-5 '-carboxylic acid 3 amizoô mth3-t9 hdro 191azobenzenei9-oarbolic Acid 3aro..no6,

  etho 4ghYdoy lglsazobexazene59ay bolique Acid matn3..no-2ySl9mdihrdroa 1919azobenzèxe 'ex ^' boslic Acid 3 amiaohZ.orom49mhydroaear=lyla,zobenzènem59oarbolique

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 EMI4.1
 1r-mnirio- acid. ' 191'-azobenzene 5'-carboaylic acid 4-amino-2 '-methyl-4' -hydroxy-lal '-azobenzene-5' -carboxylic acid 4-Amino-J '= methyl-4' -hydroxy-lal ' -azobenzene-5 '-carboxylic 4-Amino-4'-hydroxy-1, la-azobenzene-5' -carboxylic-5-sulfonic acid 4-Amino0a4'-hydroxy-lal'-azobenzene-5'-carboxylic acid-6 -sulfonic Acid imamino 2ethyl.-4 'hydror 191'-azobenzene 5'-carboxylic acid 4-amin3.ethyl l' hydroxy lsl $ azobenzènem5'-earboxyl3que Acid ± -oedno-2-methyl-3 '+ éthfl-4'- hydroxp% 1'-azobenzene-5 '-carboxylic acid 4-amino-2ethoyl,. hydroy 1518-azobenzene 5'mcarboxylic Acid 1-amino nethoxy-1.,

  . ' hydroxyml'-azobenzene 5'-carboxylic acid 4-aino 3methoxy /. ' hydrox3r 1 $ 1'-azobenzene5'-carboxylic acid 4-Amino-2-methyl-5-methoig-4e-hydroxy-lile-azobenzene-5 -'-rarboxylic acid H, .momiro-25Fmàimethoxt 4'-hydror-191 ' -azobenzene-5'-carboxylic Acid .amino 2-chlorot ,. ' hydroey 191'-azobenzene-5'-carboaylic Acid 4-aminonitro -4 'hydroay 19l'-azobenzene 59-carboxylic acid, .- Amino-d ,.' hydror 11'-Azobenzene-s5'-dicarboxylic acid 4-Amino-2 ', 4' -dihydroxy-1,1 :;

   -azobenzene-5 '-carboxylic Acid ± -adno-2 + ethyl-3' -chloro-4'-hydroxy-1,1'-azobenzene-5 '-csrboxylic acid 4-Amino -2 = methyL-3 itro /. ' L 91'a.zobenzene-5'arboxylic acid 1, .amino-2nethylm5n.etho-1 ,. ' hydroay 19I9-a, zobenzene-5'-carboxylic-3'-su? 'onic 1,1 .-. no-2ethylm /' hyd o 191'-azobenzene-5'-csr'bouylic acid 3'-sulfo-
 EMI4.2
 fuck
 EMI4.3
 T, .- mninca-aethyl-hydroey 191a-azobenzene 5'-earboaylic '-sulfo-
 EMI4.4
 fuck
 EMI4.5
 4 amixm2 bromom4 'y'oxY lyl'aZObenzene 5'-cax borlic-6-sulfoni- acid
 EMI4.6
 than
 EMI4.7
 4-Amin0-2, 6-dibromo-4 '-hydroxy-1, l' -azobenzene-5 '-carboxylic acid t, .- Amino-2ethyl5ethoxy 2'hhydroy 191' = azobenzene 3'-carboxylic Acid 1, i .no 3nethyl 29 hyûroa lal'ma,

  5'-sulfo- arbocyl zobenzene
 EMI4.8
 fuck
 EMI4.9
 L amine2ethyl 5n3rthoxy 5 'nitro 2' hydroxy 1S1'-azobenzene 3'- acid
 EMI4.10
 carboxylic
 EMI4.11
 4-aBdno-2-methyl-3 Hydroylal'-azobenzene4'mearboxylic acid ± -aàno + 3-methyl-3 '-wdroxy-1,1'-azobenzene- ±? -Esrboxylic acid. dihydroxy-benzene- acids
 EMI4.12
 carboxylic acids suitable for the reaction the following acids
 EMI4.13
 Lp4-dihydroxybeBzeBe-5-carboxylic acid (gentisic acid), 3-ehloromlsCc3ihydroxybenzene-5carboxylic acid .3-Bromo-1,4-dihydroxybenzene-5-carboxylic acid, 3-ethyl-1,4-dihoxy-carboxylic acid, 3-ethyl-1,4-dihoxy-carboxy-carboxylic acid ls ± -dihydroxybenzene-5-aarboxylic-3-sulfonic acid, ly3-dihydroxybenzeBe-4-carboxylic acid (fl resorcylic acid)

  '6blorcla3-d3.hydroaybenzene4-carboylic acid9 6 <=' brcmo-ly 3-dihydroxybecz ene-4-c arboxylic acid, 5.ethyl lg3mdihydroxybenzene - /. Arboaeylique9 Acid 129mtt ihyda oscybenzenear'boo ..



  1,24> flroxybenzene-3-earboxylic acid, i2âihydrozcybenzene arboylic-5msulfonic acid etc.



  The reaction of phthalocyanine sulfochlorides with aminoazo dyes and hydroxybenzenecarboxylic acids takes place.
 EMI4.14
 in aqueous medium and in the presence of at least one substance which neutralizes mineral acids, such as, for example, alkaline hydroxides., hydroxides
 EMI4.15
 sLcalinterreux9 alkaline carbonates carbonates alea7.inca-earths alkaline bi-carbonates., 1-magnesium oxide, sodium 1-acetate, ammonia, ammonium carbonate, dimethyl-formamide., triethanolaBai -
 EMI4.16
 ne, pyridine and analogous compounds.



  The reaction of sulfochloride on the aminoazo dye and on

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 EMI5.1
 dihydroxybenzenecarboxylic acid can take place simultaneously or in any order. o
The reaction temperature is of secondary importance and can vary within very wide limits, but the reaction is advantageously carried out at low temperatures, preferably at temperatures between 0 and 30 ° C.



   By judiciously choosing the reaction temperature and the substance neutralizing the mineral acids, it is possible to more or less completely prevent the saponification of the cblorosulphonic groups without however being able to avoid it completely. It is not absolutely necessary that all
 EMI5.2
 chlorosulphonic groups react with the aminoazo dye and dihydroxybenzenecarboxylic acid. It is often advantageous that the dye contains in view of its solubility!)

   another one or two sulphonic groups free
The sulfochlorides obtained in one way or another for use according to the invention? are reacted with at least one
 EMI5.3
 aa.noazo dye molecule and at least one molecule of a dihydroxybenzenecarboxylic acid o One can thus react 1 molecule of phthalocyanine tetrasulchloride with 1 molecule of aminoazo dye and 1 or 2 molecules of dihydroxybenzenecarboxylic acid or with 2 molecules of aminoazo dye and 1 molecule of dihydroxybenzenecarboxylic acid or with 3 molecules of aminoazo dye and 1 molecule of dihydroxybenzenecarboxylic acid.
 EMI5.4
 hydroxybenzenecarboxylic,

  9 or with 1 molecule of aminoazo dye and 3 molecules of dihydroxybenzene arbor.3.que or alternatively with 2 molecules of aminoazo dye and 2 molecules of dihydroxybenzenecarboxylic acid.



   It is also possible, according to another variant of the process, to react with the phthalocyanine tetrasulfochlorides a mixture of at least two different aminoazoic dyes and of a dihydroxybenzenecar- acid.
 EMI5.5
 boxylic8 corresponding to the aforementioned general formula, or a mixture of at least two dihydroxybenzenecarboxylic acids and an aminoazo dye, or a mixture of two different aminoazo dyes and two acids.
 EMI5.6
 different dihydroxybenzenecarboxylics.



   Sulfochloride groups can? during the reaction to be converted wholly or only partly into the corresponding sulfonamides.



   Depending on the choice of the phthalocyanine sulfochloride used and depending on the number of azo dye molecules (1-3) and of dihydroxybenzenecarboxylic acid molecules (3-1) used in the reaction,!) Dyes endowed with different dyeing properties.



   Due to the presence of at least two salicylic groups in the dye molecule, it is possible to fix the dye ,? The novel dyes are particularly suitable for chromium printing on coton. The mordant character of the azophthalocyanine dyestuffs prepared according to the invention is also growing. the number of salicylic groups? this is clearly manifested by the increasing improvement in the fastness to washing and soaping. Green to olive-green tints are obtained which are distinguished by very good and even excellent fastnesses.
 EMI5.7
 



  The new dyes? as long as they contain sufficient bite-size groups,!) furthermore, they can be fixed on the textile fibers in a known manner by subsequent treatment with metal-yielding substances. \) optionally in combination with high basic substances. molecular weight. In particular by printing on cellulose or cellulose fibers regenerated by means of substances which yield copper in association with basic condensation products of high molecular weight., Green to olive-green tints which are distinguished by

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 good resistance to washing and light.



   The alkali salts of azophthalocyanine dyes prepared according to the invention are readily soluble in water and are suitable for dyeing and printing vegetable, animal and synthetic fibers,
 EMI6.1
 same as in the dyeing of the protective layers of oxides on the aluminum.



   The following examples illustrate the new process, without however limiting it; parts are given by weight.
 EMI6.2
 



  Ismn7.e 9699 parts (1 mole) of freshly prepared cuprophthalocyanine tetrasulfochloride obtained by the action of dichloro-sulfonic acid on copper phthalocyanine are poured onto ice and the reaction product separated as a wet paste is mixed with 350 parts of crushed ice. A cold solution is added rapidly with stirring,
 EMI6.3
 containing 27.9 parts (1/10 mol.) of sodium salt of 3-aaino-4'-hydro- xy-1,1'-azobenzene-5 '-crboxylic acid and 59s4 parts (3/10 mole ) disodic salt of lg3dihdrobenzene,.-carboatylic acid in 600 parts of water, added with 20 parts of calcium carbonate, stirred for 5 hours at 5-10 C and a further 24 hours at room temperature.

   When the reaction is complete, the mixture is weakly acidified with dilute hydrochloric acid, the dye precipitated in the diacid form is filtered off, washed with dilute hydrochloric acid, dissolved in water containing sodium carbonate and isolated. the dye in the form of the sodium salt of its weakly alkaline medium by salting out with sodium chloride.



   The dye thus obtained is a green powder, which dissolves
 EMI6.4
 in water with a veit-blue color and in concentrated sulfuric acid with a yellow-green color.



   In chrome printing on cotton, a solid green with yellow reflections is obtained with remarkable fastnesses.
If instead of 27.9 parts (1/10 mol.) 55.8 parts are used
 EMI6.5
 (2/10 mol,) of sodium salt of 3-emino-4'-ydroxy-1,1'-azobenzene-5'-carboxylic acid and instead of 5994 parts (3/10 mol) is used 39.6 parts (2/10 mole) of the disodium salt of l3mdihydroxybenzéteml.car'6-xylic acid, a dye is obtained which in chromium printing on cotton gives a grass-colored green having remarkable fastnesses to cotton. washing, soaping and light. The dye is also suitable for tinting the protective oxide layers on aluminum and gives a pure green-blue.
 EMI6.6
 



  IF instead of 55 parts (2 / lot), 83.7 parts (3/10 mol) of disodium salt of the acid: 3-amino-4'-hydroxy-1,1'-azobenzene-5 are used '-carboxylic acid and instead of 399.6 parts (2/10 mol.) 19.8 parts (1/10 mol) of disodium salt of 1,3-dihydroxy-benzene-4-arboxyiiqn3, one obtains a dye suitable for dyeing cotton and viscose. On pre-chrome cotton we obtain an intense green-blue. The dye is particularly suitable for chrome printing on cotton; green-blue prints with good wash and soap fastnesses and very good light fastness are obtained.
 EMI6.7
 



  & xa, 7.e 2.



  96.9 parts (1/10 mol.) Of 4, 4 ', 4 ", 4'w-tetrasulfochloride of eupro-phtaleyanine are poured onto ice, freshly prepared and obtained by the action of chlorosulfonic acid on cnprophthalocyanine acid. -4, 4 ', 4 "", 4, w-tetrasulfonic acid (obtained from 4, sulfophthalic acid) and the separated reaction product is mixed as a wet paste with 350 parts of crushed ice. .

   A cold solution containing 27.9 parts (1/10 mol) of the sodium salt of 3-amino acid is quickly added with stirring.
 EMI6.8
 l ,. ' hydror 191'aobene 59-carborlique and 59.4 parts (3/10 mol.) of disodium salt of 13-di hyâro, ybenzene, .mcax boylique in 600 parts of water, to which was added 15 parts of calcium carbonate,

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 EMI7.1
 stir for 3-4 hours at 5-100C. then for 48 hours at room temperature.

   When the reaction is complete, it is acidified with dilute hydrochloric acid until acidic reaction with Congog red separates the precipitated dye in the diacid form and transforms it into sodium salt.
The dye thus obtained appears as a dark violet powder, which dissolves in 1-water with a blue-turquoise coloration and in
 EMI7.2
 Concentrated sulfuric acid with a green-yellow color.



  The dye is suitable for the. tea-cture of cotton, viscose ,? "Nylon" and wool, By subsequent chrome plating of the dyes on wool a green with blue reflections is obtained and on cotton an intense blue-green, dyes which are distinguished by good fastness to washing and soaping and very good light fastness. The colourant is particularly suitable for 1-chromium printing on cotton, it gives a strong and luminous green-blue with remarkable fastness to washing and soaping and exceptional fastness to light.

   The dye is further suitable for coloring.
 EMI7.3
 tion of protective layers of oxides on aluminum Si â. instead of 27? 9 parts (1/10 mole) 5598 parts (2/10 mole) of sodium salt of 3.no 4 'ydrsr 1919masobenm zene5 sarboslic acid are used and instead of 54.9 parts (3/10 mol .) 39s 6 parts (2/10 mole) of 1- * 1? 3-dihydroxybenzene-4-oarboxylic acid disodium salt? a dye is obtained which, by printing with chromium on cotton, gives a green of exceptional fastness to washing and soaping and of remarkable fastness to light.
 EMI7.4
 



  If instead of 558 parts (2/10 molo) 83.7 parts (8/10 mol) of the sodium salt of 3-mino-4'-hydroxy-1,1? -Azobenzene-5 'acid are used - carboxylic acid and instead of 39y6 parts (2/10 mol.) 1998 parts (1/10 mol) of disodium salt of 1-acid 193dihdroacbenene L, .arbolic one obtains a dye. \) which in 19: printing in chrome on cotton gives a strong, bright yellow-green with very good wash and soap fastness and excellent lightfastness.



    Horseshoe crab
 EMI7.5
 Stirred in 350 parts of ice resulting in the formation of a homogeneous paste 96.9 parts (.3 / 10 mol) of cupro-phthalocyanineg tetrasulfochloride obtained according to the data of Example 1. A solution containing 39.6 is added with stirring. parts (2/10 mol) of disodium salt of 19 avid 3-di-hydroxybenzene-4-carboxylic acid in 200 parts of ice-cold water (solution I) and stirred for one hour.
 EMI7.6
 lution. 9 containing 27 to 9 parts (1/10 mol.) of sodium salt of 3-amino acid ,. 19.9aobenzene59a bori, ic in 250 parts of water (solution II), to which 10 parts of calcium carbonate were added, and stirred for 24 hours at 15-20 C.

   The reaction finished? it is acidified with dilute hydrochloric acid until an acid reaction with Congo red, sepa-
 EMI7.7
 The dye precipitated as acid dissolves it in water and sodium carbonate and the dye is released with sodium chloride.



   The dye thus obtained appears as a green-blue powder, which dissolves in water with a blue coloration and in concentrated SO 4H2 with a green-yellow coloration.
 EMI7.8
 The colourant gives the chrome print on cotton a sustained grass green possessing very good wash and soap fastness and remarkable lightfastness.



   If solution 119 is used instead of solution I, first of all, left to stir for 1 hour and then solution I is added, a dye identical to the aforementioned dye is obtained. If solutions I and II are added simultaneously (in the form of mixture), we still get the same colorant

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 Example 4
Mix with 200 parts of ice 48.5 parts (1/20 mol.)
 EMI8.1
 from tetrasu:

  Cupro-phthalooyanine chloride and rapidly add with stirring a solution containing 9.8 parts (1/20 mol) of disodium salt of lp3-dihydroxybenzene-4-carboxylic acid and 14 parts (1/20 mol) of sodium salt. 3-SO1 acid. ' yCiro lala-azo'benzene 5'-carborlique in 350 parts of ice-water, to which 10 parts of calcium carbonate were added and the mixture was stirred for 2 hours at room temperature, then for 2 hours at 70 Ce When the reaction is complete, the mixture is acidified with dilute hydrochloric acid until a weakly acidic reaction with Congo red, the dye precipitated in the form of an acid is separated off, dissolved in water and sodium carbonate and released. dye with sodium chloride.



   The dye thus obtained appears as a dark green-blue powder which dissolves in water with a blue color with green reflections and in concentrated sulfuric acid with a green-yellow color.



   The dyeing in an acid medium on wool gives a green-blues, which passes to a sustained green after chrome plating. On viscose and cotton we get a
 EMI8.2
 blue green and on pre-chrome cotton an intense green. Anodically oxidized aluminum is dyed green-blue.



   In chrome printing on cotton, a light grass-green of good strength is obtained.
 EMI8.3
 



  Exemtite 50 46g6 parts (1/20 mole) dry cupro-phthalocyanine disulfo-chloride disulfonic acid (mole weight 9329?) Responding to analysis CU8 found 4g99% 88 found 981% Cl g found 5s49% Or? hold. / +. 985% S ô cale. 9.79% Vl Cal. 59% is added over 5 minutes to a solution cooled to 50% containing 1299 parts of 3-mino-4'-hydrozy-1gl'-azobenzene-5-cerboxylic acid, 78 parts 1,34ihydroxy-benzene-4-carboxylic acid and 12.5 parts sodium hydroxide (100%) in 500 parts water and stirred for 14 hours. When the reaction is complete, the dye is salted out with 180 parts of sodium chloride and separated as the sodium salt.



   The dye thus obtained appears as a blue green powder, which dissolves in water with a blue coloration and in SO4H2 cone. with a green-yellow coloration.



   By printing with chromium on cotton, a green with blue reflections is obtained which has good fastness to washing and soaping and very good fastness to light.



    Example
44.6 parts (1/20 mol.) Of cupro-phthalocyanine tetrasulfonic acid, obtained by sulfonation of cupro-phthalocyanine with 14% oleum.,
 EMI8.4
 are converted by obloro-sulfomic acid and thionyl chloride to cupro-phthalocyaaine tetrasulfochloride;

   the reaction mixture is poured onto ice and water, filtered and the residue washed with aqueous sodium chloride solution? then mix the filter cake with
 EMI8.5
 200 parts of ice p.3 ... made until a homogeneous paste is formed and add this to a cold solution, containing 25s, 7 parts of 3-mino-4'-kdt W-lsl'-azobenzene acid -5 'srboxylic (1/10 mol.) 7.8 parts of 193-dihydroxy-benzen-4-carboxylic acid (1/20 mol.) And 19 parts of sodium hydroxide (100%) in 450 parts of water. The mixture is stirred for 24 hours and the dye is released, once the reaction is complete, with 180 parts of sodium chloride. The dye is purified by dissolving it in water and releasing it twice in succession.



   The dye thus obtained appears as a green powder, which dissolves in water with a green-blue coloration and in SO4h2 cone. with

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 green coloring = yellow.



   By chrome printing on cotton, an intense green of very good strength is obtained.



  Example 7
 EMI9.1
 48s5 parts (3/20 mole) of ophthalocrine cup tetrasulfochloride obtained according to the data of Example 19 are poured onto ice and the separated reaction product as a wet paste is thoroughly mixed with 250 parts of ice; quickly add a cold solution. \! containing 19.8 parts (1/10 mol.) of disodium salt of 1,3- acid
 EMI9.2
 di = hydroxybenzene = 4-carboxylic acid and 71.97 parts (1/20 mol.) of sodium salt of 1.ino39a & t149hdrol91 ° maobenêne59arboxylic acid in 450 parts of water, to which 5 parts of calcium carbonate have been added, and stirred for 24 hours at room temperature.

   After acidification with dilute hydrochloric acid, the precipitated dye is separated off as acid and converted into the sodium salt.



     The dye thus obtained appears as a green-blue powder which dissolves in water with a blue color with green reflections and in cone SO4H2. with an olive-green coloring.



   By chrome printing on cotton a light green-blue is obtained with good fastness to washing and soaping and to the lunière o Example 8
We mix with 150 parts of crushed ice 29 parts (3/100
 EMI9.3
 mole) of cupro-phthalocyanine tetrasultochloride, 9 obtained according to the data of Example 1Q and rapidly added with stirring (in a nitrogen atmosphere) a solution containing 11 ,, 8 parts (6/100 mole) of disodium salt. lalvd3.hydrrbensènem5arborl3qme acid and 899 parts (3/100 mol) of sodium salt of 4anincxm219mdâ.Iola.9maObenene59m carboxylic acid in 300 parts of water, to which was added 5 parts of calcium carbonate.

   Stirred for 10 hours at 5 = 10 C and 15 hours at
 EMI9.4
 the room temperature and the isolation of the dye is done as shown in Example 19 60
The dye obtained appears as a dark gray powder which
 EMI9.5
 dissolves in water with a green coloration and in SO E oonc. with an olive-green coloring. -
Chrome printing on cotton gives a dark olive green of good strength.



  Example 9
 EMI9.6
 9 parts (1/10 mol.) Of frankly prepared oupro-phthalocyanine tetrasulfochloride, obtained by the action of chlorosulfonic acid on cuprC) c => phthalocyanine9 are poured onto ice, and the reaction product is mixed. separated in the form of a wet paste with 350 parts of crushed ice. A cold solution is quickly added with stirring, containing
 EMI9.7
 39a g parts (2/10 mole) of sodium salt of 19 acid 1 $ 3 # odihydroxybenzene, carboxylic and 762 parts (2/10 mole) of sodium salt of 1 acid 4 = amino- 4Ioc, y191pmasobenêne5 pca boli. 6sulfonic acid in 600 parts of water to which 20 parts of calcium carbonate have been added and stirred for 30 hours at 20-25 C.

   When the reaction is complete, it is weakly acidified with dilute hydrochloric acid to separate the dye precipitated in for-
 EMI9.8
 me d5'acid., dissolved in 10 water and sodium carbonate and isolated the dye by salting out with sodium chloride.



   The dye thus obtained is in the form of a black-blue powder, which dissolves in water with a green = blue color and in cone SO4H2. with brown coloring.

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   By dyeing in an acid medium on wool., We obtain a pure green with faun reflections? and after chrome plating an olive green. Dyeing on pre-chrome cotton gives an intense and sustained grass-green, while on "Nylon" a green-yellow is obtained and on viscose a blue with green reflections.



   By printing with chromium on cotton, a green-yellow is obtained with good fastness to washing and soaping and very good fastness to light.



  Example 10.
 EMI10.1
 



  Stirred until obtaining a homogeneous paste 48.5 parts (1 / 20molo) of cupro-phthalocyanine tetrasulfochloride and 250 parts of ice water, add this paste to a solution, containing 9.9 parts (1/20 mol)
 EMI10.2
 ig3mdihydroarbenene diacid disodium salt l, .mcarboylique9 42 parts of disodium salt (1/10 mol.) of 4 ani.nom2methyl acid 5.ethoxy ,. ' 1-hydroxy, 1'-azobenzene-511-carboxylic-32-sulfonic acid and 5 parts of sodium carbonate in 500 parts of water and stirred for 24 hours at 15 ° C. The isolation of the sodium salt from the dye is carried out as usual.



   The dye obtained appears as an olive-green powder, which dissolves in water with a green coloration and in SO4H2 conc. with a pink coloring.



   By chrome printing on cotton .. a green-yellow is obtained.
 EMI10.3
 



  ExesnIl 11
4895 parts (1/20 mol) of cupro-phthalocyanine tetrasulfochloride are mixed with 250 parts of ice and a solution containing 31.1 parts (1/10 mole) of dipotassium salt is rapidly added with stirring.
 EMI10.4
 1-6 bra! No-lp3-dihydroxy-benzene-4-carboxylic acid and 1496 parts (1/2 mole) of sodium salt of emino 2ttethyl l9mhye7x o 191'a, sobensem ne-5? -Asrboxyuque in 500 parts of water9 to which 8 parts of calicum carbonate water was added, and stirred for 24 hours at 20 ° C. The dye is isolated according to the data in Example 6.



   The dye obtained appears as an olive-gray powder, which dissolves in water with a green color and in cone SO4H2. with an orange-dirty coloring.



   By chrome printing on cotton, a green-yellow of good strength is obtained.
 EMI10.5
 



  ExEm'Q} -e12 96p9 parts (1/10 mol 0) of freshly prepared supro-phthalocyanine tetrasulfochloride (crude product) are poured onto ice, obtained by the action of chlorosulfonic acid on the phthalocyanine of copper and the separated reaction product as a wet paste is mixed with 300 parts of crushed ice. A solution containing 31.1 parts (1/10 mol.) Of the dipotassium salt of 1.11 acid 6-brcmo- is rapidly added with stirring.
 EMI10.6
 a3 = d3.hydroybenénemlcarborlique8 59 parts (2/10 molo) of the potassium salt of 3ino acid = 4, $ hy o ilgmazobenènea5'mcarboxyïique and 15 parts d9hràroyd potassium (100%) in 600 parts of water 10 hours at 5L0 G, then 15 hours at room temperature.

   The reaction ended, \! the dye precipitated in acid form is weakly atlidified with 1 dilute hydrochloric acid, separated from it, redissolved in water and potassium carbonate and the dye is released in a weakly alkaline medium by means of potassium chloride.



   The dye obtained is in the form of a green powder.
 EMI10.7
 dissolved in l.11 water with a green = blue color and in Sa4H2 cone. with a green-yellow coloration.

 <Desc / Clms Page number 11>

 



   If we dye wool with this dye in an acidic medium, we obtain a green-blue and by subsequent chrome plating an intense green with yellow reflections. Direct dyeing on viscose gives an intense green with blue reflections.



   By chrome printing on cotton? a light grass-green of remarkable solidity is obtained Example 13
48.5 parts (1/20 molo) of tetrasulfo are poured onto ice.
 EMI11.1
 Cupro <-> phthalocyanine chloride. 9 obtained according to the data of Example 119, the drained reaction product is mixed with 200 parts of ice and rapidly added with stirring a solution containing 31.1 parts (1 / mol.)
 EMI11.2
 of the dipotassium salt of 1,3-dihydroxybenzene- ± rc8rboxyUque and 39.8 parts (1 / .0 mole) of the potassium salt of 3arninol acid,. 'hydroxy hle = azobenzene-5-1-carboxyl: Lque-6- -oulfonique in 400 parts of water, to which 10 parts of calcium carbonate have been added, and stirred for 24 hours at 10-20 C.

   The isolation of the dye is carried out according to the data of example il *
The dye thus obtained appears as a green-blue powder which dissolves in water with a blue coloration and in S04H2 cone. with a green-yellow coloration.



   By chrome printing on cotton, the dye gives a grass green of good fastness.



  Example 14
48.5 parts (1/20 mol.) Of 4., 4 ', 4 "are poured onto ice.
 EMI11.3
 



  Prepared according to the data of Example 2, the reaction product separated as a wet paste is mixed with 250 parts of crushed ice, and a solution is quickly added to the metatx asu7.foohloride cuprophthaloeyanine9.
 EMI11.4
 ice cream containing 1998 parts (1/10 mol.) of the disodium salt of 183-dihydroxybenzene-4-carboxylic acid and 42s5 parts (1/10 mol.) of the sodium salt of 1.no2ethyl5n.ethoy 4'hàroxyl9l acid Azobsnzene 5'carbo xl3.que 3 pmsulnic in 350 parts of water to which was added 10 parts of calcium carbonate, and stirred for 48 hours at 15-20 C, The isolation of the dye is made according to the data of example Se
The dye obtained appears as a black-blue powder.

     which dissolves in water with a green coloration and in SO4H2 cone. with a dirty red-brown coloration.



   The dyeing in an acid medium on wool gives a beautiful olive-yellow and the dyeing on pre-chromed cotton an intense olive-green.
By chrome printing on cottons, an olive-yellow is obtained with good washing and soap fastness and medium fastness to light.



  Example 15
 EMI11.5
 Treated in the same manner as in Example 248.5 parts (1/20 mol) of 494e 4 "j <4-tetrasulfochloride of cuprophthalocyanine and open to the paste thus obtained a cold solution, containing 99 parts (1/20 mol.) Of the disodium salt of ly3-dihydroxybenzene-4-carbosylic acid and 44 parts (3/20 mol.) Of the sodium salt of 1..i.no2, ethyl I3. hl'-azobenzene-5'-carboxylic acid in 400 parts of water, to which 10 parts of calcium carbonate were added, and stirred for 48 hours at room temperature. Reaction weakly acid Congo red with dilute hydrochloric acid and convert the precipitated acid dye to the sodium salt in the usual manner.



   The dye thus obtained appears as a dark green powder. which dissolves in water with a green color and in SO4H2 conco with an orange-salty color.



   By chrome printing on cotton, the dye gives a green-

 <Desc / Clms Page number 12>

 yellow with remarkable fastness to washing and soaping and good light fastness.



  Example 16
29 parts (3/100 mol.) Of ice are mixed with 150 parts
 EMI12.1
 4., t ,. ', 4us 4 "' - cupro-phthalocyanine tetrasulfochloride obtained according to the data of Example 2, and an ice-cold solution, containing 11.9 parts (6/100 mol.) Is added rapidly with stirring. 1,3-dihydroxybenzene-4-carboxylic acid disodium salt, 17.7 parts (6/100 mol.) of sodium salt of
 EMI12.2
 l am.no-z'-f'-d3.hydro 1,1'-asobenzene-5'-carboxylic acid and 8 parts of sodium acetate in 400 parts of water at 0-5 C, stirred for 5 hours at this temperature, then for 40 hours at room temperature. The isolation of the dye is carried out according to the data of Example 14.



   The dye thus obtained appears as a violet-blue powder, which dissolves in water with an olive coloration and in SO4H2 conc. with an olive-green coloring.



   By chrome printing on cotton, an olive is obtained with very good fastness to washing and soaping and of medium fastness to light.



  Example 17
48.5 parts (1/20 mol.) Of 4.4 ', 4 "are poured onto ice,
 EMI12.3
 Freshly prepared 41f'-cupro-phthaloeyanine tetrasulfochloride obtained according to the data of Example 2, and the separated reaction product was mixed as a wet paste with 200 parts of ice;

   a cold solution containing 9.9 parts (1/20 mol.) of 1,4- acid is quickly added with stirring
 EMI12.4
 dihydroxybenene-5-carboxy3ic (disodium salt) and 38.1 parts (1/10 mol.) of the sodium salt of 3-amir.ol 'hydrcy l, 1'-azobenzene-5'-aarboxylic-6-sulfonic acid (obtained by the action of 3-nitraniline-6-sulfonic acid on salicylic acid followed by reduction of the nitro group with sodium sulfide) in 300 parts of water, to which 10 parts have been added of calcium carbonate and stirred for 48 hours at room temperature. The color is separated by acidification with dilute sulfuric acid and converted to the sodium salt.



   The dye thus obtained appears as a dark purple powder, which dissolves in water with a bluish green coloration and in
 EMI12.5
 804Hz Conc with a brown-yellow coloration.



   The dye is suitable for chrome printing on cotton and gives a good green fastness.



   Instead of the sodium salt, it is also possible to use the potassium salt or. lithium.



    Example 18
200 arties of ice are added according to the example data
 EMI12.6
 2 salt 48.5 parts (1/20 mole) of 4.4 ', 41f, y 4 "' - cuprophthalocyanine tetra-sulfochloride freshly prepared, a solution, containing II. ., 8 parts (1/20 mol.) Of 1,2,3-trihydroxy-benzene-4-carboxylic acid (trisodium salt) and 27.9 parts (1/10 mol.) Of sodium salt.
 EMI12.7
 dique of 3-aaino-4'-hydroxy-1,1'-azobenzene-5'-carboxylic acid in 400 parts of water, to which 15 parts of magnesia have been added, and stirred for 10 hours at 0-5 G, then for another 30 hours at room temperature. The reaction finished,

   the procedure is carried out as usual and the sodium salt is separated from the dye.



   The dye thus obtained appears in the form of a dark purple powder, which dissolves in water with a green-blue color and in conc. SO4H2. with a green-yellow coloration.



   By chrome printing on cotton, we obtain a green-blue of

 <Desc / Clms Page number 13>

 remarkable fastness to washing and soaping and good fastness to light.



   Example 19
48.5 parts (1/20 mol.) Of 4.4 ', 4 "are poured onto ice,
4 '"- cupro-phthalocyanine tetrasulphochloride, obtained according to the data of Example 2, the reaction product, which is drained, is mixed with 250 parts of ice and a solution containing 46.7 parts (3 / 20 mol.) Of the dipotassium salt of 6-bromo-1,3-dihydroxy-benzene-4-carboxylic acid and 14.17 parts (1/20 mol) of the sodium salt of 4-amino acid. 3'-methyl-4'-hydroxy-1,1'-azobenzene-5'-carboxylic acid in 350 parts of water, to which 10 parts of magnesium carbonate have been added, and the mixture is stirred for 50 hours at the ambient temperature.

   After acidification with dilute hydrochloric acid, the precipitated acid dye is separated off and converted as usual to the sodium salt.



   The dye thus obtained appears as a violet-blue powder, which dissolves in water with a bright green-blue color and in conc. SO4H2 with a brown-yellow color.



   Printing with chrome on cotton gives a solid green-blue, exceptionally fast to washing and soaping and remarkable to light.



  Example 20
48.5 parts (1/20 mol.) Of 4.4 ', 4 ", 4'" - freshly prepared cupro-phthalocyanine tetrasulfochloride, obtained according to the data of Example 2, are poured onto ice. and mixing the reaction product as a wet paste with 250 parts of ice; an ice-cold solution containing 19.8 parts (1/10 mol.) of the disodium salt of 1,4-dihydroxybenzene-5-carboxylic acid and 14 parts (1/10 mol.) is added rapidly under a nitrogen atmosphere with stirring. 20 mole) of the sodium salt of 4-amino-4'hydroxy-1,1'-azobenzene-5'-carboxylic acid in 350 parts of water, to which 10 parts of sodium bicarbonate were added and stirred for 10 hours at 5-10 C and 30 hours at room temperature.

   The dye is separated by acidification with dilute hydrochloric acid and converted into the sodium salt.



   The dye thus obtained appears as a violet-blue powder, which dissolves in water with a green-blue coloration and in SO4H2 conc. with green coloring.



   The colourant dyes the protective oxide layers on the aluminum in olive green tints. In chrome printing on cotton, a green of remarkable solidity is obtained.



  Example 21
29 parts (3/100 mol.) Of 4.4 ', 4 ", 4"' - cupro-phthalocyanine tetrasulfochloride, obtained according to the data of Example 2, are mixed with 200 parts (3/100 mol.) And added with stirring. a cold solution, containing 10.6 parts of the disodium salt of 3-methyl-1,4-dihydroxybenzene-5-carboxylic acid, 57.2 parts (3/20 mol.) of the sodium salt of the acid 4-amino-4'-hydroxy-1,1'-azobenzene-5'-carboxylic-6-sulfonic acid and 6 parts of triethanolamine in 300 parts of water, and stirred for 48 hours at 15-20 C. When the reaction is complete, the dye is separated off in the form of sodium salt according to the data of Example 18.



   The dye thus obtained appears as a violet-blue powder, which dissolves in water with a green coloration and in SO4H2 conc. with brown-gray coloration.



   By chrome printing on cotton, an olive green is obtained.

 <Desc / Clms Page number 14>

 



  Example 22
 EMI14.1
 48.5 parts (1/20 mol.) Of 4.4 ', 4 ", 4'" -tetraSLllfochloride of freshly prepared cupro-phthalocyanine, obtained according to the data of Example 2, are poured onto ice. the reaction product as a wet paste with 250 parts of ice and rapidly added with stirring a cold solution containing 19.8 parts (1/10 mol.) of the disodium salt.
 EMI14.2
 as 1,3-d.3.h; acid, drobenzene-1 carboxsl3.que and 36, $ parts (1/10 mol.) of the sodium salt of l., .- amin-2- acid 5-methyl-5'-nitro-2'-hydro l, 1'-azobenzene-3'-carboxylic in 1000 parts of water, to which 10 parts of calcium carbonate were added, and stirred for 55 hours at 15-20 C.



  The dye is separated off as an acid by acidifying the reaction mixture and converted, as usual, to the sodium salt.



   The dye thus obtained appears as a dark purple powder, which dissolves in water with a green color and in SO4H2 conc. with red-brown coloring.



   By chrome printing on cotton, a sustained olive green is obtained.



    Example 23
 EMI14.3
 48.5 parts (1/20 mol.) Of 4.4 ', 4fit, 4' "- freshly prepared cupro-phthalocyanine tetrasulfochloride, obtained according to the data of Example 2, are poured onto ice. mixing the reaction product separated in a wet paste with 200 parts of ice;

  an ice-cold solution containing 9.9 parts (1/20 mol.) of the disodium salt is added rapidly with stirring
 EMI14.4
 of 1.3-dihydroxybenzene-4-carboxylic acid and 9.9 parts of sodium salt of 1,4'-dihydroxybenzene-5-carboxylic acid (1/20 mol.) and 27.9 parts (1/10 mol. .) sodium salt of 3-amino-4'-hydroxy-1,1'-azobenzene-5'-carboxylic acid in 450 parts of water, to which 10 parts of calcium carbonate have been added, and stirred for 10 hours at 5-10 C and 35 hours at room temperature. When the reaction is complete, the mixture is weakly acidified with dilute hydrochloric acid, the precipitated acid dye separated off and converted into the sodium salt.



   The dye thus obtained appears as a dark purple powder, which dissolves in water with a green-blue coloration and in SO4H2 conc. with an olive coloring.



   By chrome printing on cotton, the dye gives a grass green of remarkable fastness to washing and soaping and exceptional to light.



  Example 24
48.5 parts (1/20 mole) of 4.4 ', 4 "are poured onto ice,
 EMI14.5
 4'ft-cupro-phthalocyanine tetrasulfochloride, obtained according to the data of Example 2, and mixes the separated reaction product as a wet paste with 200 parts of ice;

   a cold solution containing 19.8 parts (1/10 mol.) of the disodium salt of the acid is quickly added with stirring.
 EMI14.6
 1,3-Dihzirobenzene-f-carboxylic acid and 14 parts (1/20 mol.) Of the sodium salt of 3-ai.no-1'-hydrox- l, -azobenzene-5'-carboxylic acid and 19 parts (1/20 mol.) of the sodium salt of 3-am.no-l'-hydroxy-1,1'-azobenzene-5 'carboxylic-6-sulfonic acid in 400 parts of water, to which one 10 parts of calcium carbonate were added, and the mixture was stirred for 48 hours at room temperature. The dye was isolated according to the data of Example 16.



   The dye thus obtained appears as a blue-gray powder, which dissolves in water with a greenish blue coloration and in SO4H2 conc. with a greenish-yellow coloration.



   By chrome printing on cotton, a grass green is obtained which is very fast to washing and soaping and is exceptionally fast to light.

 <Desc / Clms Page number 15>

 



    Example 25
48.5 parts (1/20 mol.) Of 4, 4 ', 4 ", 4"' - cupro-phthalocyanine tetrasulfochloride are poured onto ice, the precipitated reaction product is mixed with 200 parts of ice. and rapidly add with stirring an ice-cold solution, containing 9.9 parts (1/20 mol.) of the disodium salt.
 EMI15.1
 as l, 3-dihydroxy-benzene-4'-carboxylic acid, 14 parts (1/20 mol.) of the sodium salt of 3-amino-4-hydroxy-l, 1'-azobenzene-5 '-carboxylic acid and 15.5 parts (1/20 mol.) of the sodium salt of 3-amino-6-methoxy-4'-hydroxy-1,1'-azobenzene-5'-carbexylic acid in 500 parts of water, to which 10 parts of calcium carbonate was added, and stirred at room temperature for 48 hours.

   After acidification of the reaction mixture with dilute hydrochloric acid, the dye is separated off as acid and converted in the usual manner to the sodium salt.
The dye thus obtained appears as a dark purple powder, which dissolves in water with a green-blue coloration and in SO4H2 conc. with brown coloring.



   By chrome printing on cotton, a yellowish green is obtained with very good fastness to washing and soaping and remarkable fastness to light.



  Example 26
64 parts (1/20 mol.) Of 4.4 ', 4 ", 4'" - brominated cupro-phthalocyanine tetrasulfochloride, obtained by the action of a- are poured onto ice.
 EMI15.2
 cblorosulfonic acid on brominated cuprophthalocyanine 4,4 ', 4 ", 4" 1-tetrasulfonic acid (containing 11.5% bromine when analyzed), and the filtered reaction product is mixed through a filter. suction with 300 parts of crushed ice; a solution containing 19.8 parts (1/10 mol.) of the disodium salt of 1,3-di-hydroxybenzene-4-carboxylic acid and 14 parts (1/20 mol.) is rapidly added with stirring. 3-amino-4'- sodium salt
 EMI15.3
 hydroxy-1,1-azobenzene-5'-carboxyliqus in 300 parts of water, to which 10 parts of calcium carbonate were added.

   Stirred for 48 hours at room temperature and the dye separated in the form of sodium salt.



   The dye thus obtained appears as a black-blue powder, which dissolves in water with a bright blue coloration and in SO4H2 conc. with a green-yellow coloration.



   The dye is particularly suitable for chrome printing on cotton; a luminous grass-green is obtained with exceptional fastness to washing and soaping and having excellent fastness to light.



  Example 27
96.5 parts (1/10 mol) of freshly prepared cobaltophthalocyanine tetrasulphochloride obtained by the action of chlorosulphonic acid on cobalt phthalocyanine are poured onto ice and the separated reaction product mixed as wet dough with 350 parts of crushed ice; quickly add a solution containing 19.8 parts (1/10 mol.) of the salt
 EMI15.4
 1,3-dihydroxy-benzene-carboxylic acid disodium and 61.8 parts (2/10 mol.) of the sodium salt of 3-amino-6-methoxy-4'-hydrozy-1,1 -azo-benzene-5'-carboxylic acid, to which 15 parts of calcium carbonate were added and stirred for 26 hours at 15-20 C.

   Isolation of the sodium salt from the dye is carried out according to the data of Example 24.



   The dye thus obtained appears as a green-blue powder, which dissolves in water with a green-blue coloration and in SO4H2 conc. with dark gray coloring.



   By chrome printing on cotton, a green of very good strength is obtained.

 <Desc / Clms Page number 16>

 



  Example 28
96.5 parts (1/10 mol.) Of 4.4 ', 4 ", 4"' - freshly prepared cobaltophthalocyanine tetrasulfochloride, obtained, are poured onto ice.
 EMI16.1
 by action of chlorosaLionic acid on 1? l ', 4 ", 4"' t-tetrasuif or cobaltophthalocyanine acid and the separated reaction product is mixed in the form of a wet paste with 350 parts of crushed ice .

   A solution containing 46.2 parts (3/10 mol.) Of the disodium salt of the acid is quickly added.
 EMI16.2
 1,3-dihydrosybenzene-4-carboxylic acid and 30.9 parts (1/10 mol.) of the sodium salt of 3-amino-6-methoxy-4'-hydrozy-1,1'-azobenzene- 5'-aarboxylic in 500 parts of water, to which 10 parts of calcium carbonate have been added, stirred for 48 hours at room temperature and the dye separated in the usual manner as the sodium salt.



   The dye thus obtained appears as a black-blue powder, which dissolves in water with a green-blue coloration and in SO4H2 conc. with an olive coloring.



   The dye is suitable for dyeing pre-chromed wool and an intense green-gray tint is obtained.



   This dye can be used to dye chrome-etched cotton.



  We thus obtain intense gray-green shades,
By dyeing the protective layers of oxides on the aluminum, pure green tints are obtained. By chromium printing on cotton, the dye gives a somewhat dull green having remarkable fastnesses to washing and soaping, Example 29
48.2 parts (1/20 mol.) Of nickel-phthalocyanine tetrasulfochloride, obtained by the action of chlorosulfonic acid on nickel phthalocyanine, are poured onto ice, and the separated reaction product is mixed. in the form of a wet paste with 200 parts of ice;

   a solution containing 19.8 parts (1/10 mol.) of the disodium salt of a-
 EMI16.3
 1,3-dihdroxy-benzene-l.-carboxylic acid and 27.9 parts (1/10 mol.) of the sodium salt of 3-amino-4'-hydroxy-l, 1'-azobenzene-5 ' -carboxylic in 450 parts of water, to which 10 parts of calcium carbonate have been added., and the mixture is stirred for 24 hours at 20 ° C. When the reaction is complete, the mixture is acidified to a weakly acid reaction with Congo red. dilute hydrochloric acid separates the acid dye and isolates it as the sodium salt.



   The dye thus obtained appears as a green powder, which dissolves in water with a green-blue color and in SO4H2 conc. with a green-yellow coloration.



   By dyeing on wool in an acidic medium, a green-blue is obtained which gives, after chromium-plating, a full blue-green. Dyeing on pre-chromed cotton gives an intense green-blue, like direct dyeing on viscose. The dye is particularly suitable for chrome printing on cotton.



  The result is a lively green grass with remarkable fastness to washing and soaping and exceptional fastness to light.



  Example 30
Intimately mixed with 350 parts of ice 96.4 parts
 EMI16.4
 (1/10 mol.) Of 4.4 ', 4 ", 4'" - nickelo-phthalocyanine tetrasulfochloride, obtained by the action of chlorosulfonic acid on 4,4 ', 4', 4 '"- tetrasul- acid - nickelo-phthalocyanine fonic, and a solution containing 62.2 parts (2/10 mol.) of 6-bromo-l, 3-dihydroxybenzene-4-carboxylic acid (dipotassium salt) is added rapidly with stirring and 75.4 parts of potassium salt
 EMI16.5
 4 amino-2-carboxy-4'-hydroxy-l,l'-azo-benzene-2,5'-dicarboxylic acid (2/10 mol.) in 650 parts of water, to which was added 15 parts of card-
 EMI16.6
 calcium bonate, and stirred for 50 hours at 15-20 0 ..

   When the reaction is complete, the reaction mixture is weakly acidified with dilute hydrochloric acid, the precipitated acid dye is separated off, dissolved in water and sodium hydroxide.

 <Desc / Clms Page number 17>

 sodium carbonate and release the dye.



   The dye thus obtained appears as a dark violet powder which dissolves in water with a blue coloration and in conc. SO4H2. with an olive coloring.



   By chrome printing on cotton, a sustained green-blue is obtained with very good solidity.



  Example 31
47.9 parts (1/20 mol.) Of chromophthalocyanine tetrasulfo chloride, obtained by the action of chlorosulfonic acid on chromophthalocyanine, are poured onto ice and the separated reaction product is processed into a paste. moist to a homogeneous paste by stirring with 200 parts of cold water; a solution heated to 40-50 C, containing 19.8 parts (1 / mol) of the disodium salt of 1,3-dihydroxyben-
 EMI17.1
 4-zene-carbozylic acid and 14 parts (1/20 mol.) of the sodium salt 'of 4-adno-4'-hydroxy - 1,1'-azobenzene-5'-carboxylic acid in 450 parts of water , to which was added 10 parts of calcium carbonate, and stirred for 6 hours at 45 C.

   When the reaction is complete, the reaction mixture is acidified and the acid dye is precipitated with dilute hydrochloric acid, separating it and converting it to the sodium salt.



   The dye thus obtained appears as a green powder, which dissolves in water with a blue green color and in conc SO4H2, with a brown color.



   By chrome printing on cotton, a green-yellow of good strength is obtained.



  Example 32
 EMI17.2
 47.9 parts of 4e4 '., 4 ", 4'" - chromo-piitalocyanin tetrasulfochloride, obtained by the action of chlorosulfonic acid on 4,4 ', 4 acid, are poured onto ice. ", 4 '" - chromophthalocyanine tetrasulfonic acid, and mix the separated reaction product as a wet paste with 250 parts of ice; quickly add a solution containing 31.1 parts
 EMI17.3
 (1/10 molo) of 6-bromo-1,3-dihydroçrbenzene-4-carboxylic acid and 39.5 parts of the potassium salt of 3-am3..no-1., .'-- hydroT 1,1-azobenzene-5'-carboxylic-6-sulfonic acid in 400 parts of water, to which 10 parts of calcium carbonate were added.

   After stirring for 10 hours at 10 ° C., the temperature is slowly allowed to rise to 25-30 ° C. and stirred at this temperature for a further 30 hours. The dye is separated in the form of potassium salt according to the data of Example 11.



   The dye thus obtained appears as a green-blue powder, which dissolves in water with a green color and in SO4H2 conc. with an olive coloring.



   By chrome printing on cotton, the dye gives a grass-green of very good fastness Example 33
The mixture is converted into a homogeneous paste by stirring with 300 parts of ice 96.2 parts (1/10 mol.) Of ferro-phthalocyanine tetrasulfochloride, obtained by the action of chlorosulfonic acid on ferro-phthalocyanine, and quickly added with stirring, under a nitrogen atmosphere, a solution
 EMI17.4
 containing 23.6 parts (1/10 word) of the trisodium salt of 1,2,3-tri-hjr-drozybenzene-4-arboxylic acid and '5.4 parts (2/10 mol.) of the potassium salt of 4-amino-4'-hydroxy-1,2-azobenzene-2,5 '-di carboxylic acid in 600 parts of water, to which 15 parts of calcium carbonate have been added; stirred for 10 hours at 5-10 C, then for 20 hours at room temperature.

   The reaction mixture is brought to a weakly acidic reaction in Congo red by means of dilute hydrochloric acid. The precipitated acid dye is separated, dissolved in water and potassium carbonate and released.

 <Desc / Clms Page number 18>

 gue the dye with potassium chloride.



   The dye thus obtained appears as an olive-gray powder, which dissolves in water with an olive coloration and in SO4H2 conc. with brown coloring.



   By chrome printing on cotton, the dye gives an olive-yellow Example 34
Intimately mixed with 250 parts of ice 48.1 parts
 EMI18.1
 (1/20 mol.) Of z4 "5 4", 4 '"- ferro-phthalocyanine tetrasuliochloride, obtained by the action of chlorosulfonic acid on the barium salt of the acid., 1', 4", 4 "" ferro-phthaloeyanine tetrasulphonic acid and rapidly added with stirring a solution containing 19.8 parts (1/10 mol.) Of the disodium salt of 1,3-dihydroxy-benzene-4-carboxylic acid and 30, 9 parts (1/10 mol.) Of salt
 EMI18.2
 -am3no-3 metho / '- hydroxy-1,1'-azobenzene-5'-carbohydrate sodium in 500 parts of water, to which 10 parts of calcium carbonate were added.

   The mixture is stirred for 24 hours at room temperature and the colourant is separated in the form of the sodium salt,
The dye thus obtained appears as a green-gray powder, which dissolves in water with a green coloration and in conc SO4H2, with a pink coloration.



   By chrome printing on cotton, the dye gives a dull green of good fastness.



  Example 35
93.3 parts (1/10 mol.) Of alumino-phthalocyanine tetrasulfochloride, obtained by the action of chlorosulfonic acid on alumino-phthalocyanine, are poured onto ice, and the separated reaction product is mixed as of a moist paste with 300 parts of ice; a solution containing 39.6 parts (2/10 mol.) of the disodium salt of 1,3-dihydroxy-benzene-4'-carboxylic acid and 30.9 parts (1/10 mol.) of the salt is quickly added. sodium
 EMI18.3
 4-amino-3-methoxy-4'-hydroxy-1,1'-azobenzene-5'-carboxylic acid in 600 parts of water, to which 15 parts of calcium carbonate have been added, the mixture is stirred for 24 hours at room temperature and isolates the dye as sodium salt.



   The dye thus obtained appears as a green powder, which dissolves in water with a green color and in SO4H2 conc. with brown coloring,
By chrome printing on cotton, a grass green is obtained with good washing and soap fastness and medium fastness to light.



   Of course, the invention is not limited to the working methods described which have been given only by way of examples.



   CLAIMS.

** ATTENTION ** end of DESC field can contain start of CLMS **.


    

Claims (1)

The main objects of the invention are 1) A process for the preparation of mor- dangable and water-soluble azophthalocyanine dyes, said process being characterized in particular by the following points considered separately or in combination: a) the reaction is carried out in an aqueous medium and in the presence of a acid neutralizing substance, 1 molecule of phthalocyanine sulfonic acid chloride of general formula: EMI18.4 <Desc / Clms Page number 19> in which A represents a substituted or unsubstituted phthalocyanine molecule containing a metal, the groups -SO2Cl or SO.M are in the 3- or 4- position, each M represents H, NH4 or an alkali metal and n is a number between 1 and 4 with at least 1 molecule of an aminoazo dye of general formula EMI19.1 where x is hydrogen, halogen, CH3, OH, NO2 or SO3M, v is hydrogen, halogen, alkyl, alkoxy, NO2, SO3M or COOM, z is hydrogen, halogen, an alkyl or alkoxy group and each M represents H, NH4 or an alkali metal, and with at least 1 molecule of a dihydroxybenzene-carboxylic acid of the general formula: EMI19.2 wherein m represents hydrogen, halogen, OH, CH3 or SO3M, each M representing H, NH4 or an alkali metal .; b) the reaction of a molecule of phthalocyanine sulfonic acid chloride with at least one molecule of aminoazoic dye and at least one molecule of dihydroxybenzenecarboxylic acid takes place simultaneously or in any order. 2) The new azophthalocyanine dyes which can be mordanted and soluble in water, corresponding to the following general formula: EMI19.3 <Desc / Clms Page number 20> in which A represents a substituted or unsubstituted phthalocyanine molecule containing a metal, the groups SO2.0 and -SO2NH- or -SO3M are in the 3- or 4- position, and m represents H, a halogen, OH, CH3 or SO3M x represents H, a halogen, CH3, OH, NO2 or SO3M represents H, a halogen, an alkyl group, an alkoxy group, NO2, SO3M or COOM z represents H, a halogen, an alkyl or alkoxy group each M ′ represents H, NH or an alkali metal a and b each represent a number between 1 and 3 c represents a number between 0 and 2 and the sum a + b + c is equal to 4, the -SO2NH- group being in the m- or p- position relative to the azo group; dyes prepared according to the above process. N.R. attached to be valid as of 23-3-1954 Page 16, line 52, replace: "4-amino-2-carboxy-4'-hydroxy-", by: "4-amino-4'hydroxy- ".