BE560105A - - Google Patents

Description

       

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   The present invention relates to novel water-soluble dyes of the phthalocyanine series, which have a halogenated triazin residue linked via a nitrogen bridge, it relates especially to the dyes of the phthalocyanine series which contain at least two sulfonic groups and at least one substituent

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 EMI2.1
 in which A represents a halogenated tri-azine residue, n a positive integer, preferably equal to unity, R a divalent organic residue and D an oxygen atom or a nitrogen bridge, for example the dyes of ser de phthalocyanine that meet the formula
 EMI2.2
 in which Q represents the residue of a phthalocyanine, R a divalent organic residue, preferably an alkyl or arylene residue, D an oxygen atom or a nitrogen bridge,

   X a remainder of formula
 EMI2.3
 in which m represents an integer, Z a chlorine atom, an etherified hydroxyl or an aminogenic group optionally bearing one or more substituents and n an integer of a value at most equal to 4, the residues Q and R and optionally Z containing together at least two sulfonic groups.



   For the preparation of these dyes, it is possible, in accordance with the invention, to condense with halogenated triazin compounds dyes of the phthalocyanine series which contain at least one acylable amino group of

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 such that the condensation product forms exhibits at least one mono- or di-halogenated triazine residue.



   As dyes of the phthalocyanine series of the genus Indicated, there should be mentioned as starting materials for the present process, preferably those which contain an amino group in an outer nucleus, i.e. in a nucleus which is bound. to the phthalocyanine ring via a linking member, for example via a -CO or -SO2 group, via a carboxyl-amidic or sulfonamide group or via of a -SO2-O- group. Instead of being in an outer ring, the acylable amino group can also be linked to an alkylenic chain linked to the phthalocyanine molecule, for example through a -SO2NH- group.

   Both metal-free phthalocyanin dyes and such metalliferous phthalocyanin dyes can be used. For example, it is possible to use complex compounds containing heavy metals in conjunction with phthalocyanines containing sulphonic groups, for example iron compounds, in particular however phthalocyanines having sulphonic groups and containing in complex bond cobalt, nickel, copper or zinc, which is one of the metals of atomic numbers 27 to 30 of the periodic system of the elements. As colorants providing particular results

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 Very good, it is worth mentioning here the copper phthalocyanines which contain sulphonic groups.



  Depending on the method of preparation chosen, the sulfonic groups can be found in position 4 or 3 of the phthalocyanine molecule depending on whether one starts to prepare them from 4-sulfophthalic acid or whether they are prepared by sulfonation or by sulfochlorination direct from phthalocyanine.



   The dyes of the phthalocyanine series which serve as starting materials in the present process can be prepared, for example, from halides of phthalocyaninesulfonic acids (which can be prepared, for example, by processing metal-free phthalocyanines or phthalooyanines. metallifers by sulfuric chlorohydrin or from phthalocyanine-di -, - tri- or tetrasulfonic acids, by reaction with halogenating agents such as phosphorus halides, thionyl chloride or sulfuric chlorohydrin), these are reacted 4'acid halides on organic compounds containing a hydroxyl or an acylable amino group and exhibiting, in addition to this Croup,

   an aminogenic group which can also be acylated or a substituent which can be transformed into such a group after reaction with the halide of the phthalocyaninesulphonic acid chosen. Examples of such organic compounds are functional organic compounds, such as hydroxyamines, for example hydroxyethylamine, or diamines, for example diamines.

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 EMI5.1
 cyclic, especially aromatic diam1je such as bzz "..

   diaminodiph6nYl.4 acid, '? iaainostilbne-2' '- d.sulfonic, 3., - or 1,3-disminobenzene and especially 1,4-diaminobenzene-2-sulfonic acid and acid 1 , 3diaa3nobenzene 4-sulfonic acid, it is also possible to use nitranilines or moncacylated organic diamines in which an -NH2 group is set free, by reduction, or saponification, once the reaction with the chloride of phthalocyaninesulfonic acid is terminated. choice of starting substances care must be taken that the product formed must contain at least two sulfonic groups and at least one acylable amino group;

   as a result, n reacts, for example,
 EMI5.2
 phta'1 oyata3nieues dyes having at least two halogenated sulphonic groups on hydroxyamines or on diamines having sulphonic groups, if hydroxyamines or diamines free of sulphonic groups are used, they must be reacted with at most one of the groups sulfonic
 EMI5.3
 ha10genea of a phthalocyanine having at least three such groups.

   Thus, for example, from one molecule of the chloride of a phthalooyanin-tetraxulfonic acid and one to two molecules at most of one of the diamines free of sulfonic groups which have been mentioned, or with their monoacylated derivatives, very valuable dyes of the phthalocyanine series are obtained which serve as starting substances in the present process and which, after

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 hydrolysis of unreacted sulfochlorides, contain at least two SO3H groups and at least one amino group.

     acylable, while when hydroxyamines containing sulfonic groups, such as 1-amino-3-hydroxybenzene-6-sulfonic acid or diamines containing sulfonic groups, such as 1,3-diaminobenzene-4-sulfo acid, are used -, nique, 1,4-diaminobenzèn3-2-sulfonic acid, diamino-monoazo dyes containing sulfonic groups or their monoacyl derivatives, more than two 'of the halogenated sulfonic groups present in the starting phthalocyanine can be reacted.



   In accordance with the invention, the dyes of the phthalocyanine series of this type which contain acylable amino groups are condensed with di- or tri-halogenated triazin compounds. Among the latter, in addition to cyanuryl chloride (2,4,6-trichloro 1,3,5-triazine), the triazines of formula
 EMI6.1
 in which A represents a residue which is preferably organic, in particular the residue of an organic amine.



   Triazines of this kind can be prepared, according to methods known per se, from

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 cyanuryl halides, such as cyanuric bromide or chloride, for example by reacting a cyanuryl chloride molecule with a molecule of an amine or a hydroxyl compound which may be a dye.

   As a dye of this kind, there may be mentioned, for example, aminoazo dyes such as those which can be prepared by coupling.
 EMI7.1
 dlazoic acids (eg azotex-benzene-sultonic or aminonaphthene-xulionic acids) with couplers containing aminogenic groups (such as crdsine, meta-toluidine, m-aoylamino-anilines etc.) can be prepared by coupling barbituric acids or pyrazolones, especially 1-plaenyl-µ-methyl-5pyrazolone-2'-, -3'- or -4'-sulfonic acid with disazos derived from monoacyldic aromatic diamines (such as actylarino-ani3ise.su.fonic acids) and saponifying the acylamino-azo dyes obtained.

   As compounds which do not have the character of a dye, there may be mentioned, for example, ammonia, aliphatic or aromatic hydroxyl compounds such as methyl alcohol, ethyl alcohol or butyl alcohol, phenol, ortho-, meta- or para-cresol, the phenol carrying in the para position a secondary butyl residue
 EMI7.2
 or tertiary amyl, dialkylphenols, pchlorophno., and especially nitrogenous organic compounds such as methylamine, dlmethylamine, ethylamine, diethylamine, isopropylamine, butylamine, hexylamine, aniline, tolylamine ,

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 4-chloraniline, N-methylaniline or N-methylcyclohexylamine, in addition ss-chlorethylamine, methoxy-ethylamine,

   [gamma] -methoxypropylamine, ethanolamines, acetamide, butyric acid amide, urea, thiourea, toluenesulfonic acid amide, glycine, acid esters aminocarbonic, such as methyl or ethyl carbamate, ethyl aminoacetate, aminoacetamide, aminoethanesulfonic acids, aminobenzene-2- or -4methylsulfone, l acid -aminobenzene-2,5-disulfonic acid, aminobenzoic acids and their sulfonic acids, l-aminobenzene-2-, -3- or -4-sulfonic acid and its sulfonamides or sulfones, phenylhydrazine and its sulfonic derivatives.



  The primary condensation products thus obtained still contain two reactive halogen atoms. Those which do not present sulphonic groups are condensed, according to the present process, only with phthalocyanines which contain at least two sulphonic groups while the primary condensation products of formula (2), which contain in the residue A one or two sulfonic groups, are also suitable for reaction on dyes of the phthalocyanine series which do not contain sulfonic groups, for example on phthalocyanines containing aminogenic groups which are mentioned in US Patents 2,479,491 of August 16, 1949 or 2,430,052 of November 4, 1947 and 2,761,868 of May 13, 1953.

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   The condensation of cyanuryl chloride or of the dihalogenated triazin compounds of formula (2) with the dyes of the phthalocyanine series is preferably carried out in the presence of agents capable of fixing acids, such as sodium carbonate for example, and in conditions such that at least one exchangeable halogen atom still remains in the finished product, that is to say, for example, in organic solvents or at relatively low temperatures in an aqueous medium.



   Instead of using the compounds of formula (2), cyanuryl chloride can in general be used with the same success and, after condensation with the dye of the phthalocyanine series, replace one of the chlorine atoms. of the primary condensation product formed by one of the amines mentioned for the preparation of the compounds of formula (2) amine which may optionally have a coloring character.



   The particularly interesting dyes of formula (1) can also be prepared according to a variant of the process which has just been described. This variant consists in condensing phthalocyaninesulfonic acid halides with condensation products of formula
 EMI9.1
 

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 in which the symbols R, X and Z have the meaning given in the explanation of formula (1), DH representing a hydroxyl or an acylable amino group;

   in this case, it is necessary to choose the starting substances so that at least two SO3H groups are present in the condensation product formedµ it is necessary for example to choose compounds of formula (3) which contain groups of this kind in the residues R and / or Z, or react in the direction indicated only one of the halogenated sulphonic groups of the phthalocyanine used and hydrolyze after condensation the halogenated sulphonic groups mainly sulphochlorides which remain, into free sulphonic groups.



   The dyes of the phthalocyanine series which are obtained by the indicated process and its variant are new. They are valuable water-soluble dyes which are suitable for dyeing and printing a wide variety of materials, especially for dyeing and printing polyhydroxy materials with a fibrous structure and, indeed, as well. synthetic fibers of regenerated cellulose or viscose for example, that of natural materials such as for example linen and especially cotton.



   After having been applied to the fiber by padding, printing or direct dyeing, the dyes of the present invention can be fixed, by alkali treatment, for example with sodium carbonate, hydroxide

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 sodium, alkaline earth metal hydroxides, trisome phosphate, etc. attached to heat treatment.



  The dyeing can be carried out, for example, at a more or less high temperature, that is to say at 50-100, or even cold, for example at 20-50 approximately when dichlorotriazine dyes are used. In order to exhaust the bath, it is recommended to add to the dye bath at the same time as the dyes or during the dyeing operation, possibly in portions, more or less neutral salts, especially inorganic salts such as chlorides of alkali metals or sulfates. During the dyeing operation, the dyes react with the polyhydroxy material to be dyed, presumably fixing by chemical bonding.

   The addition to the dye bath of agents capable of fixing the acids can take place from the start of the dyeing operation; The alkaline agents are advantageously added so that the pH of the dyeing bath, which initially exhibits a weakly acidic to neutral or weakly alkaline reaction, increases little by little during the dyeing.



   Instead of preparing the dye baths by dissolving in water, simultaneously or one after the other, the indicated dyes and, where appropriate, more or less neutral mineral salts, it is also possible to treat the dyes and salts so as to obtain pasty preparations or, preferably, dry preparations. Since a

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 Many of the dyes of the invention exhibit, due to their content of labile substituents, a certain sensitivity to strong acids and alkalis, it is advantageous to add, to the preparations as few salts as possible exhibiting a strongly alkaline reaction in water.

   On the other hand, it has proved to be advantageous to isolate the colorates in the presence of salts exhibiting a weakly alkaline reaction, for example in the presence of a mixture of mono and disodium phosphate, then to dry them.
 EMI12.1
 



  With the phthalosnines according to the invention which contain at least two sulphonic groups and have a halogenated triazine residue, one obtains on polyhydroxylated materials, especially on cellulosic textiles, very precious, vivid and mostly nourished dyes and prints, which have remarkable fastness to wet treatments and very good light fastness.



   In some cases, it may be advantageous to subject the dyes obtained by the indicated dyeing and printing processes to further processing.



   This is how it is advantageous to soap the dyes obtained; thanks to this subsequent treatment, the amounts of dye which are not completely fixed are eliminated.



   The invention is described in more detail in the

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 non-limiting examples which follow. Unless otherwise indicated, the parts and percentages given in these examples are understood to be by weight and the temperatures in degrees centigrade.



  Between a part by weight and a part by volume, there is the same ratio as between the gram and the cubic centimeter.



   Example 1
60 parts of copper phthalocyanine are introduced into 720 parts by volume of sulfuric chlorohydrin, followed by heating for two hours at 140-141. After cooling, the reaction mixture is poured into ice and the precipitated sulfochloride is isolated by filtration. Washed well with ice water and made into a wet paste.



   The thus obtained sulfochloride (crude product) is stirred with 300 parts of crushed ice, and at 0-3 the pH is adjusted to a value of 6.5 with dilute sodium hydroxide solution, While stirring, add quickly sulfo-
 EMI13.1
 chloride 15 parts of 1-anino-4-acetylamînobenzene dissolved in 580 parts by volume of acetone then 50 parts by volume of pyridine The mixture is stirred for 20 hours at room temperature; after which, the pyridine is completely removed by steam distillation of water in alkaline solution.



  By acidifying with dilute hydrochloric acid until acidic reaction with congo, the dye is separated. We heat

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 for one hour at 1000 the residue in 1250 parts of water and 50 to 60 parts of concentrated sulfuric acid, then filtered, The dye obtained is dissolved in 1000 parts of hot water by adding alkali and distilled at water vapor at a pH of 8.5 until no more volatile amine can be detected, then it is separated in the usual manner with sodium chloride, after making the reaction mixture weakly alkaline at bright yellow. We are very likely
 EMI14.1
 easily in the presence of a mono- (p-amino-phenyl) -amiàe-tetrasulfonic acid of a cuprophthalocyanine acid.



   The monosulfamide trisulfonic acid thus obtained is dissolved in the sodium salt form in 2000 parts of water, and the pH is precisely adjusted to a value of 7.0. Condensed at 0-4 with 18.5 parts of cyanuryl chloride which has been reprecipitated from acetone, the pH value of the reaction solution being maintained between 7.5 and 5 by adding a solution. normal sodium hydroxide.



  When the condensation is complete, 50 parts of sodium bicarbonate are added and stirred cold for half an hour, the dye separated by the addition of sodium chloride, filtered and dried under vacuum at 40-45.



   The dye obtained dyes the cotton in an aqueous alkaline bath, preferably in a salt bath, for example according to the process described in Example 26, in very pure shades, of a greenish-blue, which are solid in the light and in the heat. washing.

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   An analogous dye is obtained by preparing cuprophthalocyanine sulfochloride according to the first paragraph of Example 3.



   Example 2
With cuprophthalocyanine acid chloride-. sulfonic acid (crude product) which is obtained according to the first paragraph of Example 1 and 300 parts of crushed ice is formed into a fine paste which is adjusted to a pH of 7.5 by means of a dilute solution of sodium hydroxide, 0-3. 30 parts of sodium carbonate are then quickly added and 15 per-
 EMI15.1
 parts of 1-amino-soêvylaminobenàne dissolved in 580 parts by volume of acetone, then the reaction mixture is stirred for 20 to 24 hours at room temperature. Then acidified until acidic reaction with congo by adding 35-40 dilute hydrochloric acid, then filtered to separate the dye formed.

   The latter is stirred with 1000 parts of water, the pH is adjusted to a value of 7.5 to 8 using a dilute solution of sodium hydroxide, the total volume having to reach about 1500 parts. After adding 90 parts of solid sodium hydroxide, heat for two hours at 85-90. While stirring well at 40, the alkalinity is brought back to a pH of 8.5 with the aid of concentrated hydrochloric acid, then it is distilled with water vapor.



   To further purify, acidify again with

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 hydrochloric acid until acidic reaction with congo, filtered and the dye is suspended in water :, basified with a dilute solution of sodium hydroxide, then the dye is isolated in the form of its sodium salt by salting out with sodium chloride.



   The condensation of this aminophthalocyaninesulfonic acid with cyanuric chloride, which condensation is carried out according to the indications given in the third paragraph of Example 1, provides a dye which substantially corresponds to the product described in said example.



   If cuprophthalocyanine sulfochloride prepared according to the first paragraph of Example 3 is used, a similar dye is obtained. Example 3
While stirring, 57.5 parts of cuprophthalocyanine are introduced into 537 parts of chlorosulphonic acid, so that the temperature does not rise above 30.



  Then stirred for half an hour at room temperature.



  The reaction mixture is brought over the course of an hour and a half to a temperature of 130-133, then it is maintained for 4 hours at this temperature. Stirred while cooling, poured, still stirring, onto a mixture of 500 parts of water, 280 parts of sodium chloride and 3000 parts of crushed ice, continues to stir for a short time, filter and wash

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 with 600 parts by volume of a saturated solution of sodium chloride and 200 parts of gace. In this way, a cuprophalocyanine sulfochloride is obtained which can be transformed into a wet paste (crude product), which very probably consists of a mixture of disulfochloride and tri-
 EMI17.1
 Cuprophtaiocyanine-3,3t, 3 ", 3" -tetrasulfonic acid sulfochloride.



   The mixture of sulfochlorides thus obtained is stirred, in the form of an acid paste, with 300 parts of crushed ice and it is maintained, using a cold dilute solution of sodium hydroxide, at 0-3, at a pH value of 6.5 to 7.0. 5 parts of sodium carbonate and a solution of 14 parts of 4-aminoformylanilide in 500 parts of water and immediately after 15 parts of sodium carbonate are added to the sulphochloride paste thus neutralized. The reaction mixture is stirred for 24 hours at 20-25. After acidification with hydrochloric acid, the dye which has precipitated is filtered off.

   For saponification, this product is suspended in 1000 parts of water, dilute sulfuric acid (containing 60 parts of concentrated H2SO4) is added, so that the total volume does not reach more than 1500 parts, then we heat for one hour at 100. After cooling, the product is filtered and again suspended in water. It is made alkaline with sodium hydroxide solution, the volatile amine is removed by steam

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 of water, then the dye is separated off in the sodium salt state, at a pH of 7 to 7.5 using sodium chloride.



   This dye is dissolved in 2000 parts of water and the pH is precisely adjusted to 7.0. Condensed at 0-4 with 18.5 parts of cyanuryl chloride dissolved in acetone. By addition of normal sodium hydroxide solution, the mixture is maintained at a pH of between 5.0 and 7.5 during the condensation. When the condensation is complete, 200 parts by volume of a normal ammonia solution are added to the cold reaction mixture, heated for two hours to 35-40, then the dye is separated from the alkaline solution to bright yellow.
The dye thus obtained dyes the cellulosic fibers, according to the dyeing process indicated in Example 24, in shades of a brilliant blue, which are solid in washing.



   If the dichlorotriazine dye is to be obtained, when the condensation with cyanuric chloride is complete, 25 to 50 parts of sodium bicarbonate are added, stirred for half an hour at 0-5, then the dye is isolated by salting out with sodium chloride.



   The dye obtained in this way dyes the cellulosic fibers, following the dyeing procedures given in Examples 24 and 26, in shades of brilliant blue, which are solid in washing.

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 Analogous dyes are obtained by transforming
 EMI19.1
 mant sulfochloride cuprophthalocyanine-3,4 ', 4 ", 4tt .... sulfonic acid and proceeding, for the rest, in a similar manner.



   Example 4
The mixture of sulfochlorides (crude product) obtained according to the first paragraph of Example 3 is stirred with 300 parts of crushed ice, then, at 0-3, the pH is adjusted to a value of 6.5 to 7.0 using dilute sodium hydroxide solution. 25 parts by volume of a sodium carbonate solution prepared by dissolving 20 parts of calcined sodium carbonate in 100 parts of water are added to the sulfochloride thus neutralized. Then stirred for a short time and immediately added a neutral solution of 47.5 parts of the secondary condensation product obtained from a molecule of cyanuryl chloride, a molecule of acid
 EMI19.2
 Z, 3-diaminobenzene-4-sulfonic acid and one molecule of ammonia in 1200 parts of water, then continues to stir at room temperature.

   By gradually adding sodium carbonate, the pH value of the reaction mixture is maintained between 6.5 and 7.8. Stir for 24 hours, then heat to 35-40. When the pH value remains constant for one to two hours without the need to add alkali, the dye is separated with sodium chloride. The dye as well

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 obtained dyes the cellulosic fibers, according to the method indicated in Example 25, in shades of a brilliant blue, which are solid in washing.



   Analogous dyes are obtained by reacting the sulfochloride with lesser amounts, eg, about 31 parts, but also larger amounts, eg, 60 parts, of the secondary condensation product used in the present example.



   Instead of the secondary condensation product obtained from cyanuryl chloride, 1,3-diaminobenzene-4-sulfonic acid and ammonia, one can use that which can be obtained from a chloride molecule of cyanuryl, one molecule of 1,4-diaminobenzene-2-sultonic acid and one molecule of ammonia, and an analogous dye is obtained.



   Example 5
To a sulphochloride paste obtained according to the first paragraph of Example 3 from 57.5 parts of cuprophtalocyanine, and neutralized as indicated in the first paragraph of Example 4, 13.6 parts of 4-amino- are added. formylamide dissolved in 500 parts of water, then 20 parts of sodium carbonate are added. This reaction mixture is stirred for 24 hours at room temperature. The dye is then separated cold, by acidification with acid

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 hydrochloric acid, then filtered.



   To saponify the formyl group, form the sodium salt of the dye and add enough water to have a total volume of up to 1500 parts; 60 parts of caustic soda are added to the cold solution and finally heated for 3/4 hour to one hour at 85-90. The excess alkali is neutralized with hydrochloric acid, entrained with water vapor in an alkaline solution, then the dye is isolated, in the sodium salt state, by adding chloride. sodium, at a pH of 7.5.



   For condensation with cyanuric chloride, the dye thus obtained is dissolved in 2000 parts of water and the solution is brought to a pH of 7.0. Condensed with 17.0 parts of finely divided cyanuryl chloride, at 0-4, as described in Example 1. When the condensation is complete, 25 parts of sodium bicarbonate are added and stirring continued for a half. hour. The dye is isolated as described in the previous examples, and it is dried at 45. The dye thus obtained dyes the cellulosic fibers, by the dyeing method given in Example 24 and Example 26, in shades of a brilliant blue which are solid in washing.



   By treating this dye with ammonia, a new, analogous dye is obtained which, following the dyeing procedures given in Example 24 and Example 25,

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 provides very similar blue shades on cellulosic fibers. For this ammonia treatment, the following can be done:
About 118 parts of dye (i.e. 1/10 of a molecule) are dissolved in 2000 parts of cold water, 200 parts by volume of a normal ammonia solution are added to it, then, while stirring, the mixture is heated for two hours at 35-40. The dye thus formed is isolated in the usual manner.



   Example 6
0.1 gram molecule of cuprophthalocyanine sulfonic acid containing 2.5 to 3 sulfonic groups in the molecule and obtained by sulfonating cuprophthalocyanine in solid phase (for example following the indications given in French patent 1,031,720 of December 15, 1950). The temperature should not rise above 30.



  Stirred for half an hour at 80-82; after which, 180 parts of thionyl chloride are added dropwise over the course of 3/4 of an hour. Stirred at 820 until formation of sulfochloride is complete, then poured into a mixture. of ice and water. The precipitated sulfochloride is isolated by filtration and then washed with water.



   By stirring with 300 parts of crushed ice, a paste of sultochloride is prepared to which is added 18.8

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 EMI23.1
 parts of acid., iu, .yiô: 1'.l.'3 1.Re -'- sodium in solution in 400 parts of water: and, in 3fif..âi 'timep 100 parts by volume of a solution' normal sodium hydroxide. 50 parts by volume of pyridine are added to the reaction mixture, followed by stirring for 24 hours at room temperature. The pyridine is completely removed by steam stripping in an alkaline solution, then the dye is isolated in the usual manner as a sodium salt. This dye is condensed, as described in Example 3, at 0-5, with 18.5 parts of cyanuryl chloride.

   When the condensation is complete, the mixture is stirred cold with 50 parts of sodium bicarbonate at 20, the dye is released to a pH of 7.3 with sodium chloride, then dried at 45. A dye is thus obtained which, following the dyeing process indicated in Example 24, dyes the cellulosic fibers in shades of a brilliant blue which are solid in washing.



   Example 7
As described in the first paragraph of Example 4, the sulfochloride obtained according to the first paragraph of Example 3 is neutralized, at 0-3, from 28.75 parts of cuprophthalocyanine.



   35.5 parts of the product of formula are dissolved in water
 EMI23.2
 

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 adding, at a pH of 7.5, 550 parts by volume of a normal sodium hydroxide solution. This aminochlorotriazine solution is added to the neutralized, well-stirred suspension of sulfochloride. By adding 8 parts of anhydrous sodium carbonate in 4 portions, the pH value is constantly maintained above 7.0. After allowing to react for 8 hours at 18-21, 10 parts by volume of concentrated ammonia are added, and stirring continues for 10 hours at room temperature. The mixture is heated for one hour at 35-40, at a pH of 7.5 to 7.7, then the dye is isolated in the usual manner.



   If one uses for the condensation, instead of the product of the formula indicated in the second paragraph, 25.5 parts of the product of the formula
 EMI24.1
 after release with potassium chloride, a dye is obtained which, according to the process described in Example 27, dyes the cotton in shades of brilliant blue, which are solid in washing.



   Example 8 ----------
Starting from 30 parts of copper phthalocyanine, we prepare, following the indications of the first paragraph

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 of Example 3, the mixture of copper-containing phthaloayanine sulfochloride, which is mentioned in this example.



   The sulfochloride thus obtained (crude product) is stirred with 50 parts of crushed ice and 50 parts of water until a very fine distribution is obtained, then the pH of the mixture is adjusted to 0-5, to a value 7.3 using dilute sodium hydroxide solution.



   At the same time, 7.15 parts of N-formyl-p-aminophenol are dissolved in the cold in 250 parts of water, adding 52 parts by volume of a normal solution of sodium hydroxide. The solution thus prepared is added all at once to neutralized sulfochloride, and then 4 to 5 parts of calcined sodium carbonate are added. The reaction mixture is stirred at 20-22 for 24 hours. Hydrochloric acid is then added until a distinctly acidic congo reaction, followed by filtration of the dye formed. For the saponification of the formylaminogen group, the still wet dye paste is stirred with 400 parts by volume of normal hydrochloric acid, then heated for 2 hours at 85-90 with good stirring.

   After cooling, the dye is again isolated by filtration, suspended while hot in 1000 parts of water and basified (to a pH of 7.8) with a dilute solution of sodium hydroxide. The dye solution is heated to 35-40. When this remains for an hour and a half at a pH value of 7.6 without

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 that it is necessary to add further quantities of alkali, the dye is released again with sodium chloride.



   The dye thus obtained is dissolved in 1200 parts of water and it is condensed at 0-4, with 9.3 parts of cyanuryl chloride previously reprecipitated from acetone., Maintaining the pH at a value between 5, 5 and 7.8 by addition of normal sodium hydroxide solution.



   When the condensation is complete, 12.5 parts of sodium bicarbonate are added, then stirred for half an hour at 2-3. The dye is then isolated by salting out with sodium chloride, then dried under vacuum at 45-50.



   Example 9
To a fusion of 250 parts of anhydrous aluminum chloride and 40 parts of sodium chloride, are added dropwise with good stirring, at 10, over 15 minutes, 28 parts of sulfuric chlorohydrin, then the mixture is continued. stir for 10 minutes. During 25 minutes, 19.7 parts of the dry tetrasodium salt of cupro- acid are introduced.
 EMI26.1
 pnthalocyanin-tetrasulfonic acid (prepared by alkaline saponification of 3,3 ', 3 ", 3 -rasu-copper phthalocyanine phthalocyanine chloride). The temperature of the reaction mixture is brought to 160-161 in 45-50 minutes, then stirred for three hours at this temperature. While stirring, it is allowed to cool to

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   125-130 and pour over a mixture of ice and water.

   Washed with 500 parts by volume of a 5% solution of sodium chloride, then dried under vacuum at 70. A chlorinated cuprophthalocyanine-tetrasulfonic acid is obtained.



   For the formation of the sulfochloride, the product thus obtained is introduced with stirring into 320 parts of chlorosulfonic acid, followed by heating for 4 to 5 hours at 100-1030. The cooled reaction mixture is poured onto sodium chloride and crushed ice, then stirred for a short time, and filter. Washed with 200 parts by volume of a 10% sodium chloride solution. The sulfochloride thus obtained is stirred with 60 parts of ice until a fine paste is obtained, then it is adjusted, at 0-3, to a pH of 7.0 to 7.5 using a dilute solution of sodium hydroxide. 4 parts of calcined sodium carbonate and 2.8 parts of p-aminoformylanilide dissolved in 100 parts of water are added to the neutralized sulfochloride.

   Stirred for 20 to 24 hours at room temperature and acidified to 40 with dilute hydrochloric acid until acid reaction with congo. For saponification, the wet dye is put into a paste in 200 parts of water, 10 to 12 parts of concentrated sulfuric acid in 50 parts of water are added to it, and the whole is heated for one hour at 1000 with stirring well. The dye is then isolated in the sodium salt state according to the indications given in the second paragraph of Example 1.

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 EMI28.1
 



  The chlorinated -aminophni-amidosulionyi-eupropa3o-cyaninesulfonic acid thus obtained is condensed with cyanuryl chloride in a manner analogous to that described in the third paragraph of Example 1. When the condensation is complete, the pH is adjusted to In order to have an alkaline reaction with sodium bicarbonate, stirring is continued for half an hour at 5, the dye is separated by the addition of sodium chloride, then it is dried under vacuum at 45-50.



   The dichlorotriazine dye thus obtained dyes the cellulosic fibers, according to the dyeing process indicated in Example 24 or in Example 26, in shades of a blue-green, which are solid in washing.



   By treating this dye with ammonia, a monochlorotriazine dye is obtained. 0.01 gram molecule of dye is dissolved in 500 cubic centimeters of water, 20 cm3 of a binormal ammonia solution is added, then, while stirring, the mixture is heated for about 5 hours at 35-40.



  The dye is isolated and dried in the usual manner.



   Example 10 While stirring and cooling, one introduces,
 EMI28.2
 in 200 parts by volume of chlorosulfonic acid, 19.7 parts of cuprophthalocyanine-4 "1p, 4116411-sodium tetrasulphonate. The mixture is then stirred for a quarter of an hour at temperature.

 <Desc / Clms Page number 29>

 ordinary ture. In one hour, the reaction mixture is brought to an internal temperature of 130-132 and stirring is continued for 3/4 of an hour to one hour at this temperature. After cooling, the sulfochloride formed is poured onto 1400 parts of crushed ice, 200 parts of water and 170 parts of sodium chloride, filtered, and washed with a mixture of 300 parts by volume of a saturated solution of sodium chloride and about 100 parts of ice.



   The sulfochloride thus obtained is stirred well, in the form of a wet and acidic paste, with 30 parts of water and 30 parts of ice, then at 0-3, it is adjusted to a pH of 7.5 using 'a dilute solution of sodium hydroxide. To the sulfochloride neutralized in this way, an aqueous suspension, neutral, at 20, the total volume of which is 180 parts by volume and which contains 9.5 parts of the secondary condensation product of a molecule of cyanuryl chloride, is immediately added, with one molecule of 1,3-diamiobenzene-4sulfonic acid and one molecule of ammonia.

   The reaction mixture was stirred at 20, added in 5 portions a total of 6 parts of calcined sodium carbonate, so that the pH of the reaction mixture did not drop below 7.0. After allowing to react, for 8 to 9 hours at 20, 5 parts by volume of concentrated ammonia are added and stirring continues for 14 hours at room temperature, which causes partial amidification of the unhydrolyzed sulfochloruen groups.

 <Desc / Clms Page number 30>

 Using dilute hydrochloric acid, the alkalinity is reduced to 7.7, heated to 35 and the dye separated with sodium chloride.



   On cotton, brilliant blue prints are obtained which, once set, resist washing.



   Example 11 While stirring, introduced into 160 parts
 EMI30.1
 by volume of chlorosulfonic acid, 19.7 parts of cupro-. p? talooyan.ne-3 s' a s f 'g ^' sodium etrasuiforate so that the temperature does not rise above 20. Stirred and brought in one hour to an internal temperature of 130-132.



  This temperature is maintained for one hour, allowed to cool, and the sulfochlorination mixture is poured into 1400 parts of ice, 170 parts of sodium chloride and 200 parts of water. The sulfochloride formed is isolated by filtration, then washed with a mixture of 300 parts by volume of a saturated solution of sodium chloride and 100 parts of ice.



     The sulfochloride is stirred with 30 parts of water and 30 parts of ice until a very fine distribution is obtained, then the solution is adjusted to 0-3 to a pH of 7e5 with a solution. dilute sodium hydroxide. A neutral aqueous suspension, at 20, the total volume of which is 180 parts by volume, is added to the neutralized sulfochloride and

 <Desc / Clms Page number 31>

 which contains 9.5 parts of the secondary condensation product of a cyanuryl chloride molecule with one molecule
 EMI31.1
 of l-iaminobenzene-4-aulfonic acid and an ammonia molecule.

   The reaction mixture is stirred for 7 hours at room temperature, introducing in 5 portions 6 parts of calcined sodium carbonate, so that the pH value does not fall below 7.0. At the end of this time, 5 parts by volume of concentrated ammonia are added, then stirring is continued for 12 hours at room temperature.



  The alkalinity is reduced to 7.7 pcr by addition of dilute hydrochloric acid, the dye is isolated by the addition of sodium chloride, and dried under vacuum at 60.



   The dye thus obtained provides on cotton prints of a brilliant blue which, once fixed, resist washing.



   Example 12
While stirring, 40.8 parts of cuprophthalo acid are introduced into 250 parts of chlorosulphonic acid.
 EMI31.2
 oyanine-5,5 ', 5 "-trisulphonic (obtained by making oleum act on copper-containing phthalocanine), so that the temperature does not rise above 25 to 30. Then heat to 80, then the mixture is stirred for half an hour at this temperature. 56 parts by volume of thionyl chloride are then added dropwise over one hour, so that the

 <Desc / Clms Page number 32>

 temperature drops to 73. When all the thionyl chloride has been added, heat for a quarter of an hour at 80-82.



   The cooled reaction mass is poured onto ice, the sulfochloride formed is isolated by filtration and washed well with water.



   Half of the sulfochloride thus obtained is stirred well with 25 parts of ice and 25 parts of water, then adjusted to 0-4 to a pH of 7.5 with a dilute solution of sodium hydroxide.



   At the same time, an aqueous suspension of 11.8 parts of the secondary condensation product of a cyanuryl chloride molecule with a 1,3-diamino-benzene-4-sulfonic dibasic acid molecule and an ammonia molecule is prepared. , suspension which was carefully neutralized with a volume sodium hydroxide solution, then brought to a total volume of 250 parts in
2 parts of calcined sodium carbonate are added to the neutralized sulfochloride, then at once the suspension of the aminochlorotriazin compound is stirred for 20 hours at 30 and as soon as the pH value of the reaction mixture has fallen to 7.0, the mixture is stirred. add 3 to 4 parts of calcined sodium carbonate in 3 portions.

   When the pH remains constant for one hour at 30-35, the dye is separated with sodium chloride, washed with brine and dried in vacuo at 60.



   The dye thus obtained dyes the cotton, according to the method indicated in Example 27, in shades of a brilliant blue.

 <Desc / Clms Page number 33>

 



   Example 13.



   Stirred, with 50 parts of water and 50 parts of ice, the sulfochloride (crude product) obtained according to the first paragraph of Example 3 from 30 parts of cuprophthalocyanine, then neutralized with a dilute solution of hydroxide. sodium.



   By stirring, with 200 parts of water, 19.6 parts of the secondary condensation product of a molecule of cyanuryl chloride, a molecule of 1,3-diaminobenzene-4sulfonic acid and a molecule of aniline, one prepares a suspension which is adjusted to a pH of 7.5 by adding a normal solution of sodium hydroxide. The final volume should, at 20, be about 450 parts by volume.



   While stirring well, are introduced into the neutralized suspension of sulfochloride, 13.5 parts of calcined sodium carbonate, and simultaneously the suspension of the aminochlorotriazine compound. Stirred for 24 hours at 20-22, then heat at 35-40 and isolate the dye as described in the first paragraph of Example 4.



   A dye is thus obtained which, according to the dyeing process described in Example 25, dyes the cellulosic fibers in brilliant shades of a blue-green, which, once fixed, resist washing.



   Example 14.



   Has a sulfochloride paste obtained according to

 <Desc / Clms Page number 34>

 first paragraph of Example 3 from 60 parts of cuprophalocyanine and neutralized according to the first paragraph of Example 4, 15 parts of 1-amino-4-acetethylaminobenzene are added in solution in 580 parts of acetone and 50 parts of pyridine. After leaving to react for 24 hours at room temperature, the pyridine is completely entrained in water vapor in an alkaline medium. Acidified to 40 with concentrated hydrochloric acid until acidic reaction with congo, filter, suspend the precipitated dye in approximately 900 parts of water, then, by addition of a sodium hydroxide solution, it is It is dissolved and made alkaline to bright yellow.

   For saponification, 90 parts of caustic soda are added, the volume is adjusted to 1500 parts and heated for two hours at 90. It is again separated by adding concentrated hydrochloric acid; it is redissolved while basifying, then water vapor is passed through until complete elimination of the volatile amine. By adding sodium chloride, the dye is separated in a weakly alkaline medium to bright yellow. We are very likely in the presence of the mono-aminoanilide of cuprophthalooyanine-tetrasulfoic acid.



   3.78 parts of cyanuryl chloride are dissolved in 100 parts of acetone then, while stirring well and cooling, the whole is added at 0-2 to a solution of 3.46 parts of the 4-amino acid -sodium benzene sulfonate

 <Desc / Clms Page number 35>

 in 200 parts of water. At the same time, 20 parts by volume of a normal sodium hydroxide solution are added dropwise to 0-2, so that the pH of the reaction mixture has a value of 5 to 7. Condensation takes place. unfolds very quickly.



   The condensation product is added to a neutral solution of 0.02 molecules of p-aminophenyl-amidosulfonylcuprophthalocyanine-sulfonic acid in 500 parts of water. The mixture is heated to 35-40 and, as in the first condensation, maintains alkalinity between 5 and 7.5 by adding normal sodium hydroxide solution dropwise.



  After one and a half to two hours the condensation is complete and, by adding sodium chloride, the dye is separated in a weakly alkaline medium to bright yellow.



   According to the method indicated in Example 27, pure blue shades are obtained on cotton which are resistant to washing.



   Example 15.



   In 200 parts of water and 100 parts of acetone, 5.15 parts of acid are dissolved in the sodium salt form
 EMI35.1
 -amino- -hydroy-I, i'¯azobenzne-5 -ca.rboy, fue, then cooled to 0-2. The solution obtained is added to 3.78 parts of cyanuryl chloride dissolved in 100 parts of acetone. While stirring well, add dropwise to 0-2.20 parts by volume of a normal solution.

 <Desc / Clms Page number 36>

   of sodium hydroxide, the pH being thus maintained between 5 and 7.0.

   When the condensation is complete and the free amine can no longer be detected, a neutral solution of 0.02 molecules of mono-N- (p-aminophenyl) -amide of cuprophatalocyanine-tetrasulfonic acid in 500 parts is added. of water, then heat to 40. By adding 18 to 20 parts by volume of a normal sodium hydroxide solution drop by drop as described during the first condensation, the pH value is maintained between 6 and 7. When the condensation is complete, the dye is released. with sodium chloride in a weakly alkaline medium to bright yellow, then dried under vacuum at 60-65.



   The dye thus obtained dyes the cotton, according to the method given in Example 27, in shades of a brilliant green, which are resistant to washing.



   By printing with subsequent chrome plating on cotton, green prints are obtained.



   Example 16.



   Cuprophthalocyanine sulfochloride is prepared according to the first paragraph of Example 3, starting with 60 parts of copper-containing phthalocyanine. A quarter of the product thus obtained is stirred (approximately 0.025 molecules with 50 parts of ice until a very fine distribution is obtained, then, at 0-3, it is adjusted to a pH of 7.5 using of a dilute solution of sodium hydroxide.

 <Desc / Clms Page number 37>

 6.9 parts of 4,4'-diaminodipheyl-3-sulfonic acid in 200 parts of water by adding 26.5 parts by volume of a normal solution of sodium hydroxide. This solution is added to the neutralized sulfochloride and 5 parts of calcined sodium carbonate are introduced. The reaction mixture is stirred for twenty hours at 20 minutes.

   Then heated to 60-63, then stirred for some time at this temperature and at a pH such that a strongly alkaline reaction to bright yellow occurs. The alkalinity is brought back to 7.5 and the dye is separated as completely as possible by adding sodium chlorine.



   4.6 parts of cyanuric chloride are dissolved hot in acetone, taken over ice-cold water, isolated by filtration and then suspended in crushed ice.



  To this cyanuryl chloride suspension, the dye described above is added, dissolved in 700 parts of water. By adding dropwise to 4-6.23 parts by volume of a normal solution of sodium hydroxide, the pH value is maintained between 5 and 7.2. When the condensation is complete, 27.5 parts by volume of binormal ammonia is added to the dye solution and heated two and a half to three hours at 30-35. At a pH of
7.5 the dye is separated by adding sodium chloride and dried under vacuum at 50-55
The dye thus obtained provides, according to the process

 <Desc / Clms Page number 38>

 of the dye described in Example 27, brilliant blue dyes which are wash solid.



   Example 17.



   According to the first paragraph of Example 3, cuprophthalocyanis sulfoahloride is prepared starting from 60 parts of pigment. Half of the product thus obtained (approximately 0.05 molecules) is stirred with 75 parts of crushed ice and 75 parts of water then, at 0-3, adjusted to a pH of 7.5 using a solution. dilute sodium hydroxide. To the suspension of sulfochloride obtained, there is added a suspension, weakly alkaline to brilliant yellow of 37 parts of the monoazo dye of formula
 EMI38.1
 in 1000 parts of water.

   While stirring well, the reaction mixture is immediately heated to 30-33. Adding in portions a total of 12 parts of calcined sodium carbonate, the pH value is prevented from falling below 7, and the mixture is stirred d. 'first for six hours at 30-33 Then for twelve hours at room temperature. Then heated to 35-380. When the pH of the reaction mixture remains constant for one hour, the dye is separated off using sodium chloride.

 <Desc / Clms Page number 39>

 



   A dye is thus obtained which, according to the dyeing processes indicated in Examples 24, 25 and 27, provides the cellulosic fibers with shiny shades, which are solid in washing, of a green tending to blue.



   Example 18.



   According to the first paragraph of Example 3, 60 parts of cuprophthalocyanine are converted into sulfochloride.



  A quarter of the product thus obtained is stirred at 0-3 with 25 parts of water and 25 parts of crushed ice, then the pH is adjusted to a value of 7.3 to 7.5 using a dilute sodium hydroxide solution.



   In 15 parts by volume of pyridine and 30 parts of water, 5.7 parts of 1- (3'-aminophenyl) -5-pyrazolone-3-carboxylic acid are dissolved. Then, while stirring well, is added. this solution with neutralized sulfochloride. After allowing to react for 24 hours at room temperature, 50 parts by volume of a saturated sodium chloride solution are added to the reaction mixture and then, using pentanormal hydrochloric acid, the mixture is acidified in the cold until an acid reaction. in Congo. By filtration the precipitated dye is isolated, suspended in water and heated to 60 in a strongly alkaline solution to brilliant yellow until saponification of the sulfochloride groups which are not yet hydrolyzed.

   To remove the pyridine, entrained in an alkaline medium with water vapor then, at

 <Desc / Clms Page number 40>

 a pH of 7.3, separates the dye as completely as possible using potassium chloride and a saturated solution of sodium chloride.



   In 300 parts of water and ice, 11.8 parts of the product of formula are stirred
 EMI40.1
 until a fine paste is obtained, then it is adjusted to a pH of 7.5 using normal sodium hydroxide solution.



  To the resulting solution is added 12.5 parts by volume of a binormal aqueous solution of sodium nitrite, cooled to 5 and, while stirring well, added 7.5 parts by volume of concentrated hydrochloric acid. Stir at 10-120 until the diazotization is complete and add the diazo formed to an alkaline solution of the dye described above in 200 parts by volume of water and 12 parts of calcined sodium carbonate. When the population is complete, the dye is separated with sodium chloride, washed with 200 parts of brine saturated with sodium chloride, then dried in vacuo at 55-60.
The dye thus obtained provides Impressions of a brilliant greenish yellow tint on cotton which, when fixed, resist washing.

 <Desc / Clms Page number 41>

 



     --- Example 19.



   According to the first paragraph of Example 3, 60 parts of ouprophthalooyanine are converted into sulfochloride. As described in the first paragraph of Example 4, half of the product thus obtained is neutralized at 0-3.



   6.78 parts of mono-acetyl-ethylenediamine are dissolved in 250 parts of water. In the well-stirred neutral suspension of sulfochloride, 11 parts of calcined sodium carbonate are added first, followed by the amine solution.



  Stir the whole for 24 hours at 20-22. For saponification, 60 parts of 100% sodium hydroxide are added, the volume is brought to 1000 parts, and heated for two and a half hours at 85-90. At 40, the alkalinity is brought back to a pH of 8.5 using concentrated hydrochloric acid, then steam is carried out to remove the volatile amine.



  The dye can, in weakly alkaline solution to bright yellow, be separated by the addition of sodium chloride.



  Half of the dye thus obtained is dissolved in water, cooled to 0-2, then condensed at 6-8 with 4.6 parts of cyanuryl chloride which has been dissolved in aoetone, poured over ice water and filtered off. By adding 25 parts of a normal sodium hydroxide solution dropwise, the reaction solution is maintained at a pH between 5.5 and 7.5. When the condensation is complete, 27.5 parts by volume of binormal ammonia are added,

 <Desc / Clms Page number 42>

 then we heat two and a half to three hours at 35-40.



  By adding a little hydrochloric acid, the alkalinity is reduced to 7.5, the dye is separated with sodium chloride, then it is dried at 55-60 under a water pump vacuum.



   The dye thus prepared dyes the cotton, according to the method given in Example 25, in shades of brilliant blue, which are wash solid.



   Example 20.



   11.5 parts of cobalt-containing phthalocyanine are introduced into 115 parts of chlorosulphonic acid, followed by stirring for 15 minutes at room temperature. The reaction mixture is heated to 130-132 and stirred for two hours at this temperature. After cooling, 56 parts of sodium chloride are poured, 100 parts of water and 600 parts of crushed ice, filtered, then washed with a mixture of 60 parts of ice and 120 parts by volume of a brine saturated with sodium chloride. sodium. The sulfochloride obtained is stirred with 55 parts of ice until a very fine division is obtained, then, at 0-3, the pH is adjusted to the value of 7.0 using a dilute solution of sodium hydroxide.



  To the sulfochloride paste thus prepared are added 5.0 parts of calcined sodium carbonate and almost simultaneously a neutral suspension of 9.5 parts of 2-chloro-4- acid.
 EMI42.1
 amino-6- (31-am: inophenyl) -amino-1.3e5-triazine-41-sultonic in 150 parts of water. The reaction mixture is stirred

 <Desc / Clms Page number 43>

 for 20-22 hours at room temperature, then heat it to 35-37, and hold for two hours at this temperature. The dye is separated at a pH of 7.5 to 7.6 by the addition of sodium chloride.



   The dye thus obtained dyes the cotton, according to Example 25, in shades of a blue-green.



   An analogous dye is obtained by using 11.8 parts of nickel phthalocyanine instead of 11.5 parts of cobalt-containing phthalocyanine.



   Example 21.



   In a manner analogous to the first paragraph of Example 3, cuprophthalocyanine sulfochloride is prepared by causing chlorosulfonic acid to act on 57.5 parts of cuprophthaloayanine.



   The paste thus obtained is stirred with 100 parts of ice and 100 parts of water, then neutralized, to 0-3, with a dilute solution of sodium hydroxide, so as to have a weakly alkaline reaction to the bright yellow paper. . 20 parts by volume of a solution of 20 parts of sodium carbonate in 100 parts of water are added to the neutralized sulfochloride paste. A neutral solution of 43 parts of the secondary condensation product of a moléoule of oyanuryl chloride with one molecule of methanol and one molecule of 1,3-diaminobonzene-4-sulfonic acid in 900 to 1000 parts of water is immediately added. . In

 <Desc / Clms Page number 44>

 adding the remainder of the sodium carbonate solution dropwise to maintain the reaction mixture at a pH between 6.8 and 7.8.

   After stirring for 24 hours at room temperature, heat to 35-40. When the dye solution, at 35, remains alkaline to bright yellow for one to two hours without the need to add further amounts of the sodium carbonate solution, the dye is separated with sodium chloride and dried. .



   The dye thus obtained dyes the cellulosic fibers, according to the dyeing process indicated in Example 25, in shades which are solid in the light and in washing.



     Example 22.



   Starting from 60 parts of cuprophthalocyanine, described in the first paragraph of Example 3, the sulfochloride is prepared. A quarter of the product thus obtained is stirred with 25 parts of water and 25 parts of ice until a very fine division is obtained, then, at 0-3, the well-stirred paste is neutralized with a cold 15% solution. approximately sodium hydroxide to have a pH of 7.3. Stir with water to obtain a thin, weakly alkaline, bright yellow paste and a volume of 650 parts.



   To the well-stirred neutralized solution of sulfochloride, two parts of calcined sodium carbonate and 21.0 parts of the monoazo dye of formula are added.

 <Desc / Clms Page number 45>

 
 EMI45.1
 prepared by coupling in alkalinized solution with carbonate of
 EMI45.2
 sodium 1- (3'-aminophenyl) -5-PYrazolone-µ-oarboxylic acid with 2-chloro-4- (4 "-sulfophenyl) -amino-6- (4'-sulfo-3'aminophenyl) Amino-1,3p5-trlazlne, diazotized, the reaction mixture is heated to 30-35. The pH value drops rapidly to 7.0, after which a part of sodium carbonate is added again. The alkali is consumed, again 1 to 1.5 parts of sodium carbonate are added, in total the mixture is stirred for 6 to 7 hours at 30-35, then overnight at room temperature.

   At 350, and when the pH remains constant, at a value of 7.5 to 7.7, the dye is separated by addition of sodium chloride, then it is dried at 60 under vacuum.



   The product obtained dyes the cotton, according to the method given in Example 25, in shades of a green tending to yellow.



   Example 23.



   While stirring well, introduce 20 parts of
 EMI45.3
 cuprophthalocyanine in 282 parts of oleum at 1.0. We heat

 <Desc / Clms Page number 46>

 slowly the reaction mixture to 80 and, over 5 to 10 minutes,
 EMI46.1
 15 parts of # -hydroxymethyl-phthalimide are introduced. Heat to 95-100 and stir for 4 hours at this temperature. After cooling, it is poured onto water and ice and the resulting dye is isolated by filtration, which is washed with brine.



   The still wet product is suspended in water, adjusted to pH 7.5 with dilute sodium hydroxide solution, so that the volume is about 400 parts. After adding 200 parts by volume of a binormal solution of sodium hydroxide, heat to the boil for an hour and a half at reflux, then carefully drop by drop, add over half an hour and at temperature boiling, 65 parts by volume of decanormal hydrochloric acid. Heating is then continued for two to two and a half hours at 100, with vigorous stirring.

   With cooling, neutralized with sodium hydroxide solution until weakly alkaline reaction to bright yellow, then the dye is separated by addition of sodium chloride. To purify the amino acid
 EMI46.2
 methylouprophthalocyanine sulfonic acid formed, dissolved in water, entrained in an alkaline solution with water vapor and released again.



   In 500 parts of water, half the dye thus obtained is dissolved in the sodium salt form, then

 <Desc / Clms Page number 47>

 cooled to 0-2. In addition, 3.7 parts of cyenuryl chloride are dissolved hot in 1 Pans and this solution is added at 1-4 to the well-stirred solution of the dye.



  20.5 parts by volume are then added dropwise
 EMI47.1
 of a normal solution of laydyezyde to neutralize $ so that the aleu of pE rOB44 ranges between 6 and i. aulfoniue in solution in pou dlcauo We add again drop by drop 20 on i7oJ, \: even 9 Ul'aC Gol1 "tion nor2! o.le due soâra this tiul brings the fold to the value of 7. At the same time, we heat up to 16-18 o When the condensation is good, add 5 to 6 parts of sodium bicarbonate, add a little time to 209, and separate the dye by diluting this sodium chloride. vacuum at 45 - 5doo and obtains a product which dyes the cotton, following the method
 EMI47.2
 indicated at 1 # exeùipie 25, in blue lines.



   Example 24.



   With 80 parts of trisodium phosphate, two parts of the monochlorotriazine odorant obtained according to the first three paragraphs of Example 3 are dissolved in 400 parts of water, then diluted to 4000 parts. After having added 80 parts of sodium chloride, one enters with 100 parts of a cotton cloth in the dye bath thus prepared, which one carries in half an hour 4 60; we add

 <Desc / Clms Page number 48>

 again 80 parts of sodium chloride, heat in a quarter of an hour to 80 and maintain for half an hour at this temperature. The resulting blue dye is then rinsed and soaped for 15 minutes in a boiling solution containing 0.3% of a nonionic detergent.



   Example 25.



   In 100 parts of water, one part of the dye obtained according to the first three paragraphs of Example 4 is dissolved. With the solution obtained, a scarf is printed at 80, a cotton fabric which is expressed in such a way that it retains the dye solution in the proportion of about 75% of its own weight. The article thus impregnated is dried, impregnated at room temperature with a solution containing pax liter 10 grams of sodium hydroxide and 300 grams of sodium chloride, then expressed until absorption of 75% of liquid and vaporized for 60 seconds. at 100-101. It is then rinsed, treated in a 0.5% solution of sodium bicarbonate, rinsed again, soaped for a quarter of an hour at the boil in a 0.3% solution of a nonionic detergent, rinsed again, then dry.

   The result is a brilliant blue dye, which is fixed and resists boiling.
Example 26.



   In 2000 parts of water, two parts of the primary phthalocyanino-triazine condensation product obtained according to Example 1 are dissolved. In the dye bath as well.

 <Desc / Clms Page number 49>

 obtained, we enter, at 20-45, with 100 parts of a well soiled cotton yarn. Over thirty minutes, 500 parts of a 20% solution of sodium chloride and 125 parts of a 10% solution of sodium carbonate are added in portions.



  Ten minutes later, 30 parts of a sodium hydroxide solution are added, the mixture is dyed for 60 minutes at 20-45. After rinsing with cold water, the resulting dye is soaped for 15 minutes at 85-100, rinsed thoroughly with cold water, and then dried. A pure blue dye is obtained, with very good fastness to light and to leavening.



   Instead of sodium carbonate, it is also possible to use tri-carbonate phosphate.



   Example 27.



   In 25 parts of urea and 75 parts of water, 3 parts of the dye obtained according to Example 18 and two parts of sodium carbonate are dissolved. With the solution thus obtained, a cotton fabric is impregnated, squeezed to have a weight increase of 75% and dries, to 80.



   The fabric is then subjected to the action of dry heat at about 140 for about 5 minutes, rinsed and soaped at the boil. The result of these operations is a green dye, which is solid on boiling.

 <Desc / Clms Page number 50>

 



   Example 28.



   In 339 parts of water, 30 parts of the dye obtained according to Example 19 are dissolved, 150 parts of urea are added, the whole is poured into 450 parts of a sodium alginate thickener and 30 parts of sodium carbonate are added. potassium and part of a 40% by volume sodium hydroxide solution. With the printing color thus obtained, a cotton fabric is printed in the usual way which is dried.



  Then sprayed for 5 minutes at 100-101, rinsed, soaped, rinsed again, then dried. This gives a brilliant blue impression.


    

Claims (1)

Claims. I.) A process for the preparation of dyes of the phthalocyanine series, characterized by the fact that it condenses, EMI51.1 with at least halogen-containing triazine compounds, water-soluble dyes of the phthalocyanine series which exhibit at least one acylable amino group, such that the condensation product formed contains at least one acylable amino group. EMI51.2 minus one mono- or dl-halogenotriazine residue. The present process can be further characterized by the following points @ 1) As at least dihalogenated triazine compounds, cyanuryl chloride or a triazine of formula EMI51.3 in which A represents a hydrogen atom or a preferably organic residue, in particular the residue of an organic amine which may or may not have the character of a dye. 2) We use a sum of dyes from the phthalocyanine series of dyes of formula EMI51.4 <Desc / Clms Page number 52> in which Q represents the residue of a metal phthalocyanine preferably containing sulphonic groups, R a divalent organic residue, preferably a residue EMI52.1 lcoylén1que or arylénlquet X an aminogenic group of formula EMI52.2 m an integer and n an integer with a value at most equal to 4. 3) The colorants of the series of the EMI52.3 phthalcoyanine dop òrwule dyes EMI52.4 wherein Q represents the residue of a copper-containing phthalocyanine, one of Y is a sulfonic group and the other Y is hydrogen or a sulfonic group. 4) As a variant of the process defined above, we EMI52.5 condenses phthalocyanin sulfonic acid halides with condensation products of the formula EMI52.6 in which X represents a group of formula m an integer, Z a chlorine atom, EMI52.7 an etherified hydroxyl or an aminogenic group optionally carrying one or more substituents, and R an organic residue, especially an alkylenic or arylenic residue, in <Desc / Clms Page number 53> choosing the starting substances so that the product.1 condensation formed contains at least two sulphonic groups, or else leaving only one sulphohalide group to react EMI53.1 of an oolde piztal, oianineoopoly-Jialfonique and hydrolysing after condensation the groups, -, s suliohalides which have not reacted in groups Inulfonlquoso II.) As a product "41ts 1i. '.! du3t: r.iQls new 5) The dyes of the phthalocyanine series obtained by carrying out the above process. 6) The water-soluble dyes of the series of EMI53.2 p4% taloc27anine, which contains at least one halogen trlazinlque residue. 7) The water-soluble dyes of the series of EMI53.3 phthalooyanine which contains a trîazînîque resta of formula EMI53.4 in which Z represents a chlorine atom, an atom EMI53.5 hydrogen or a preferably organic residue, for example an etherified hydroxyl, or an aminogenic group optionally bearing one or more substituents. 8) The water soluble dyes of the phthalocyanine series which meet the formula <Desc / Clms Page number 54> EMI54.1 in which Q represents the residue of a metalliferous phthalocyanine containing, preferably, sulphonic groups R an organic residue would say, preferably an alkyl residue or an arylene residue, X an aminogenic group of formula -N-, m a number integer, Z a chlorine atom @ Cm-1H2m-1 or an etherified hydroxyl or an aminogenic group optionally carrying a substituent, and n an integer of a value at most equal to 4, the remainder Q, R and, where appropriate, Z together having at least two sulfonic groups. . 9) Water-soluble dyes of the phthalocyanine series which meet the formula EMI54.2 in which Q represents the residue of a copper-containing phthalocyanine containing sulphonic groups, Z a chlorine atom or an aminogenic group optionally bearing a substituent, and n a positive integer of a value at most equal to 2. III.) A characterized dyeing and printing process <Desc / Clms Page number 55> EMI55.1 by the fact 1n y we use: i.se p:. sa 11m: .oe using the dyes obtained according to the process e0fini-de3U50 and tft proceeds do% o.; i sir'4.5 '' .. c & rcté1sé by the fact o.,% 2'on dyed 8dn4YJVa.ayü. Ct nf Ji cr? Ls'Wd airvia..riv1 of fibrous structure with the dyes defined above des3usp in aqueous bath, preferably in bath: saline in jount an alca11 # by operating followed the method @ of eeinye cliCt0 or following the method of Printing or following the dyeing called "Pad" The 3 '^ -..''- The process wants ciico7,? o be characterized by the fact that the Qolcrnnts defined above in ml3.t & '1 are used, using the p ,, "' océ <\ 2é ci 0 1mprel.:isiol1 or the pE'oeë <ïë de"., Oad "V.) As new 3.d .L products, matlèrez dyed or improved by the implementation of iio (" ..a3 defined under III.) And 17.) o EMI55.2 Note: Added a word.