DE1419173A1 - Process for dyeing and printing materials containing hydroxyl groups or amide groups - Google Patents

Description

Z n proceed to dyeing u n d # printing hydroxy or ru.ppen- Amirun = pen-containing Mat e rials. It has been found that valuable dyeings and prints are obtained on materials containing hydroxyl groups or amide groups if dyes which contain at least. once contain the following grouping applied to the material to be treated and subjected to the action of elevated temperature in the presence of acid-binding agents. In the general formula: R is an alkylene or Cycloalkyler_rest, R2 is an alkylene radical with 2 or 3 carbon atoms between the radicals R1 and Y, R1 is a nitrogen, oxygen or sulfur atom, X in the event that R1 is an oxygen or Represents a sulfur atom, a pair of electrons, and in the event that R1 represents a nitrogen atom, hydrogen or an aliphatic or cycloaliphatic substituent which can be part of a heterocyclic ring, and Y a substituent to be split off as a negative ion.

According to the process, dyeings and prints which are extremely washable and boil-fast are obtained on the materials mentioned, in particular on fibers and fabrics made from native and regenerated cellulose. For dyeing, the dyes are preferably used in an aqueous solution to which alkaline substances, such as alkali hydroxide or alkali carbonate, or compounds which change into alkaline substances, such as alkali bicarbonate, can be added. Further auxiliaries can be added to the solution, but these should not react in an undesired manner with the dyes. Such additives are, for example, surface-active substances, at . such as alkyl sulfates or preventing the migration of the dye Substances or auxiliary products for dyeing, such as urea (to improve tion of the solubility and the fixation of the dyes), or indifferent thickeners such as oil-water emulsions, tragacanth, Starch, alginate or methyl celulose. The solutions or pastes produced in this way are used towards this coloring material, for example by padding in a padder or applied by printing and then for some time heated to an elevated temperature, preferably 40-150o. That Heating can be done in the hot flue, in the steam apparatus Rolling or by placing in heated concentrated salt baths both on its own and in any order be executed one after the other. When using a dope or dye liquor without alkali is a passage of the dry goods through an alkaline reactive solution to which common salt or Glauber's salt is added is connected. The addition of salt reduces this ; Migration of the dye from the fiber. After the fixation has taken place, the dyed material is rinsed with hot water and, if the intended use of the dyed material requires it, finally soaped, whereby insufficiently fixed residues of the dyestuff are removed. The dyeings obtained are extremely fast to the wet, even if the dyes have little or no affinity for the material to be dyed.

For printing on materials containing hydroxyl groups or amide groups will. a printing paste made from the dye solution, a thickening agent such as sodium alginate and an alkali reacting compound or a compound which splits off alkali when heated, .as used as sodium carbonate, galium carbonate or sodium bicarbonate and the printed Material rinsed. The dyeing process is expediently followed by a wash in neutral or alkaline aqueous liquor.

Amide group-containing materials such as wool, silk and the like can in the same. Way to be stained in a neutral to slightly alkaline medium.

Dyes which are particularly advantageous for the dyeing process are those which have little or no affinity for the materials to be dyed. The use of these dyes enables the pigment molecules that are not firmly bound to the fiber in the course of the fixing process to be completely detached during the final washing treatment in neutral or alkaline aqueous liquor. The dyes to be used according to the process are prepared by introducing the grouping (I) into dyes at least once by processes known per se. For this purpose, dyes of the most varied classes of compounds can be used, for example azo, azomethine, anthradanone, triphenylmethane, oxazine and azaporphine dyes. The introduction of at least one substituent of the formula into the dyes is carried out by known processes, for example by reacting dye sulfonic acid or carboxylic acid chlorides with components, for example with the sulfuric acid ester of Ne-hydroxyethyl-N-methylpropylenediamine (1,3), which already have group (I) contain, or by combining a dye containing sulfonic acid chloride or carboxylic acid chloride groups with components, for example with N-ß = hydroxyethyl-N-methylpropylenediamine- (1,3), from which the grouping (I) by subsequent esterification - the aliphatic hydroxyl group with -e.g. .Sulfuric acid, phosphoric acid or with sulfonyl compounds can be obtained. In the event that Y in group (I) represents a halogen atom, dye sulfonic acid or carboxylic acid chlorides can be mixed with the! 9-halogen compounds corresponding to group (I), for example with N-ß-chloroethyl-N-methylpropylenediamine- (1,3) can be made to react.

The conversions can of course be varied very widely. The grouping (I) can also be introduced into the dyes in several process steps, for example by reacting the chloromethyl compound of the dye with β-hydroxyethyl methylamine and then esterifying the terminal hydroxyl group with sulfuric acid, phosphoric acid or sulfonyl compounds. If one starts with the preparation of the new dyes from the dye precursors, and one already leads into these,. for example after a. of the procedures outlined above, the grouping a, so the precursors substituted in this way by known processes, for example. in the preparation of the azo dyes by diazotization and / or coupling, converted into the corresponding dyes. Dyes of this type can, for example, by coupling twice the molar amount of the diazotized. Sulfuric acid ester of 3-aminobenzyl-B-hydroxyethyl-methylamine with 1,8 - dihydroxynaphthalene-3,6-disulfonic acid can be obtained.

It is also possible to proceed in such a way that the grouping mentioned is modeled in the dye precursors and the grouping (I) is only finally formed after conversion of the dye precursors. For example, by coupling diazotized 4-aminobenzyl-13-hydroxyethyl-methylamine with 1-phenyl-3-methylpyrazolone- (5), a monoazo dye can be produced which does not yet contain the radical Y in group (I). This residue can then be introduced subsequently by esterification of the aliphatic hydroxyl group by one of the aforementioned processes, for example by treatment with the reaction product of chlorosulfonic acid and pyridine. The above-mentioned manufacturing processes result in numerous possibilities for binding the grouping to the aromatic or heterocyclic ring systems of the dye. Some of these possibilities are shown below: Residues in which the sub stituent X of the general formula I is an aliphatis.chen oder.cycloaliphatic substituent. and is part of a heterocyclic ring can be constructed as follows, for example: In addition, as an aliphatic substituent, X can also represent a group identical to R2. The radical R2 can be either straight-chain or branched, but should not have more than 2 or 3 carbon atoms in a straight chain between R1 and Y. Among the radical Y, which is split off as a negative ion e.g. can, are / sulfuric acid ester groups, phosphoric acid ester groups, Understand halogen atoms and sulfonyloay groups. The dyes to be used according to the process can, in addition to the grouping (I), also. other common substituents, including solubilizing groups, such as sulfonic acid and carboxylic acid groups.

Example 1: -12.4 g of the sulfuric acid ester of 3-aminobenzyl-n.-hydroxyethyl-methylamine are dissolved in 50 ml of 1N sodium hydroxide solution, 31 ml of a 10 c / .igen sodium nitrite solution are added and the solution is at 0-3 0 in 80 ml of 2N hydrochloric acid are stirred in. The diazonium salt solution is stirred into a solution of 7.7 g of 1-phenyl-3-methyl-pyrazolone- (5) in 45 ml of 1N sodium hydroxide solution and 50 ml of water and a pH of 9-10 is maintained by adding soda at the same time. After the coupling has ended, the dye is salted out, filtered off with suction and dried.

2 g of the dye thus obtained are dissolved in 100 ml of water with the addition of 3.2 g of sodium hydroxide, 0.3 g of Turkish red oil and 10 g of urea. The solution is padded onto cotton and the soaked fabric is heated to 110 o for 10 minutes. It is then rinsed and soaped at the boil. A very wet-fast yellow coloration is obtained.

Example 2:

10.5 g of 3-aminobenzyl-di-ß-hydroxyethyl-amine are dissolved in 150 ml of 2N hydrochloric acid and diazotized at 0-5 ° with 35 ml of 70% nitrite solution. The obtained diazonium salt solution is stirred into a solution of 8,? g -1-2henyl = -3-methyl-pyrazolone- (5) in 50 ml 1N sodium hydroxide solution and 50 ml water and at the same time slowly add 20 g soda. After the coupling is complete, the dye is filtered off with suction and dried at 70 ° to 8.2 g of the dye thus obtained are dissolved in 60 ml of pyridine and 5.4 g of chlorosulfonic acid are added dropwise to this solution at 0-3o. The reaction solution is then stirred into a mixture of 100 g of ice water and 65 ml of 2N soda solution, the pyridine is distilled off in vacuo at 400, the residue is taken up in water and the dye is salted out of this solution, filtered off with suction and dried.

2 g of this dye are dissolved in 100 ml of water with the addition of 3.2 ml of sodium hydroxide, 0.5 g of Turkish red oil and 10 g of urea. The solution is padded on cotton and the soaked fabric is heated to 140o for 10 minutes. Then it is rinsed and soaped at the boil. A very wet-fast yellow coloration is obtained. Example.- 3: 12.4 g of the sulfuric acid ester of 3-amine-benzyl-B-hydroxyethyl-methylamine are dissolved in 50 ml of 1N sodium hydroxide solution, 31 ml of a 10% sodium nitrite solution are added and solution 3 is added to 80 ° C. at 0 ° C ml of 2N hydrochloric acid stirred in. An almost arbless diazonium salt solution is obtained, which is added to a suspension of 15.8 g of the reaction product of nickel phthalocyanine (3) tetrasulfonyl chloride with four times the molar amount of l- (3'-aminophenyl) -3-methyl -pyrazolon- (5) in 500 ml of water and 20 g of soda at 0-3o, -stirred. After the coupling has ended, the dye is salted out, filtered off with suction and dried at 50 ° in vacuo. 2 g of the isolated dye are dissolved in 100 ml of water with the addition of 3.2 g of sodium hydroxide, 0.2 g of Turkish red oil and 10 g of urea. The solution is padded on cotton and the soaked fabric is heated to 140o for 10 minutes. Then it is rinsed and soaped at the boil. A very wetfast green dyeing of good lightfastness is obtained.

Example 4: 18.2 g of the sulfuric acid ester of 3-aminobenzyl-B-hydroxyethyl-methylamine are dissolved in 75 ml of 1N sodium hydroxide solution, 46.5 ml of a 10% sodium nitrite solution are added and the solution is stirred into 120 ml-2N hydrochloric acid at 0-30C . The diazonium salt solution obtained is stirred into a solution of 18 g of 1,8-dihydroxynaphthalene-3,6-disulfonic acid sodium in 100 ml of water and a pH of 9-10 is maintained by adding soda. After the coupling has ended, the dye is salted out, filtered off with suction and dried. 2 g of this dye are * dissolved in 100 ml of water and 3 g of sodium hydroxide and 5 g of urea are added. The solution is padded on cotton nettle and the soaked fabric is heated to 3.40 ° for 10 minutes. Then it is rinsed and soaped at the boil. A very wet-fast, navy blue dyeing is obtained.

Example 5 # 5.5 gw - (ß-Hydroxyethyl-methylamino) -4-aminoacetophenone are diazotized in 80 ml of 2N hydrochloric acid at 0-5o by adding 18.5 ml of a 10% sodium nitrite solution and with 4.6 g 1- Phenyl-3-methyl-pyrazolone- (5), dissolved in 27 ml of 1N sodium hydroxide solution and 50 ml of water, coupled. A pH of 10 is maintained by adding 10 g of soda. The dye is suctioned off and dried sharply at 70o. 9.5 g of the dye are dissolved in 120 ml of pyridine and 2.9 g of chlorosulfonic acid at 0-3C. dripped in. The mixture is stirred into ice water, neutralized with soda, the pyridine is distilled off in vacuo at 40 °, the residue is taken up in water, the dye is salted out, filtered off with suction and dried.

2 g of the dye are added to 100 ml of water with the addition of 4 g of sodium hydroxide, 0.2 g of Turkish red oil and 10 g of urea. The solution is padded on cotton nettle and the soaked fabric is heated to 100o for 10 minutes. After rinsing and boiling soaps, a very wet-fast yellow color is obtained. . Example 6: 18.3 g of 4-aminobenzyl-β-4-hydroxyethyl thioether are dissolved in 300 ml of 2N hydrochloric acid and added diazotized by -69 ml of 10 O sodium nitrite solution at 0-5o. The diazonium salt solution is stirred into a solution of 17.4 g of 1-phenyl-3-methyl-pyrazolone- (5) in 100 ml of 1N sodium lye and 100 ml of water and holds by adding 40 g Soda a pH before. 9-10 a. After the coupling is completed the Parbsto: f salted out, suctioned off and sharp at 700 dried. 18.4 g of the dye are in 300 ml Pyridine dissolved and at 0-3o with 6 g of chlorosulfonic acid esterified. The mixture is then stirred in ice water which Solution neutralized with soda and the pyridine in vacuo distilled off at 400. The residue is dissolved in water taken, the dye salted out, vacuumed and dried. 2 g of the dye thus obtained are dissolved in 100 ml of water dissolved with the addition of 4g sodium hydroxide and 10 g urea. The solution is padded on cottonness egg and that soaked tissue is heated to 140o for 10 minutes. Afterward is rinsed and soaped at the boil. You get a very true-to-size yellow color. Example?: A solution of 2 g of the dye prepared according to Example 4 in 33 ml of water and 5 g of sodium hydroxide solution (38oBe) is stirred into 50 g of alginate thickener, which contains 30 g of dry substance per 1 kg, after adding 10 g of urea.

The cotton nettle printed with this printing paste is dried at 800 and the. Pressure developed by subsequent steaming at 105o in 10 minutes. After rinsing and boiling soaps, a very good wetfast, navy blue print is obtained. Example 8: By pressing cotton nettle with a printing paste which is produced by stirring in a solution of 2 g of the dye shown in Example 3 and 10 g of urea in 25 g of water and 5 g of 38oBb sodium hydroxide solution in 58 g of alginate thickening, drying the print 80o and fixation at 140o in 10 minutes on the calender roller you get a very good wetfast, green print of good lightfastness after the boiling soap. Example 9: 82.5 g of Cu phthalocyanine trisulfochloride are dissolved in a solution of 35 g of N, N-dimethyl-propylenediamine added to ice water, made alkaline with sodium hydroxide solution after the reaction is complete, vacuumed, washed and dried. The color thus obtained The substance is dissolved in approx. 1000 g of tri (, t -ohloroethyl) amine at 140 - 150o entered slowly, stirred for about 5-10 minutes, the fallen dye sucked off after cooling, with something Washed petroleum ether and dried. 2 g of the dye are dissolved in 100 ml of water. These Solution is padded on cotton, dried, with a Solution of 4 g sodium hydroxide solution, 0.2 g Turkish red oil and 10 g Urea soaked in 100 ml of water and 10 minutes to 40o warmed up. After rinsing, you get a very good wetfast and lightfast turquoise-blue coloring, which is also process no shooting in the clay and no fading of the light shows authenticity. An equally good pizza can also be made with soda instead of sodium hydroxide solution can also be obtained at 40c . According to Example 9, add: The dyes given in the table below are prepared analogously to the embodiments of this example by reacting the dye sulfochloride with N, N-dimetrsylspropylenediamine and subsequent quaternization in tri-chloroethyl) amine. When fixed on cotton according to the above information, they give very good wet-fast dyeings in the shades given below. to example 9 Example 10: As in Example 9, the trisulfonyl chloride of the Cu Phthalocyanine with 40 g of N, N-dioxäthyl-propylenediamine to, heated the dye thus obtained with 1000 g of butane sultone approx. 10-15 minutes to 100 - 12009 gives after cooling approx. 2000 g of toluene are added, the dye is suctioned off and heated about 30 minutes in thionyl chloride, sucks off and dries. 2 g of the paraffin thus obtained are dissolved in 100 ml of water with the addition of 4 g sodium hydroxide solution or soda, 0.5 g turquoise red oil and 10 g of urea dissolved. The solution is on tree wool padded and the soaked fabric 10 minutes at 40o heated, then rinsed and soaped at the boil. Man acquires a very wet-fast turquoise-blue color. Example 11: Is used in the same way as in Example 10 that Monosulfonyl chloride of co-phtaooyanine and di- ( 4064-dioaethyl- aminoethyl) amine, a dye is obtained which is in Colored in the same way, a very washfast greenish color turns blue. Example 12: a) 0.15 mol of copper phthalocyanine (3) tetrasulfochloride are introduced into a solution of 150 g of ethanolamine in 1350 ml of water with ice cooling and thorough stirring. Man. removes the external cooling, stirred for a few hours at room temperature and then heated to 50-550 for two hours to complete the reaction. Then. The reaction product, which is insoluble in salt-containing water, is filtered off with suction while hot, washed with water to remove excess amine, and the blue copper-phthalocyanine- (3) -tetrasulfonic acid-oxyethylamine obtained is dried in vacuo at 65-70 °.

b) 127 g of copper phthalocyanine (3) tetrasulfonic acid oxyethyl amide are refluxed for five hours in 500 ml of thionyl chloride. After cooling, the reaction solution is poured onto ice, the completely insoluble precipitate is filtered off with suction, washed acid-free with water and the copper-phthalocyanine- (3) -tetrasulfonic acid-chloroethylamide obtained is dried in vacuo. c) You can also proceed in such a way that the excess thionyl chloride is distilled off and the residue is poured into ice water, filtered off with suction and washed with methanol.

d) - 0.025 mol of copper phthalocyanine- (3) -tetrasulfonsäureohloräthylamid five levels are heated to 110 - 120o in 100 g of ethanolamine. Then you pour the reaction solution in 500 ml of water, add some potassium chloride and suck it off obtained copper phthalocyanine- (3) - (SO2 N'rIC2H4NHC2H40H) 4 from.

e) 15 g of copper phthalocyanine- (3) -r (SO2NHC2H4NHC2H40H) 4 are introduced into a solution of 15 g of chlorosulfonic acid in 70 ml of pyridine at room temperature. Mix for two hours; then the reaction mixture is poured into 220 ml of a 10% aqueous soda solution. After the pyridine has been distilled off in vacuo at 30 - 40o, the dye copper phthalocyanine (3) - (SO2 NHC2 "4NHC2" 40s03Na) 4 is salted out, f) 0.2 g of this dye is dissolved in 10 ml of a solution which 25 ml of concentrated Natzo nlauge containing 100 g of urea and 5 g Türkischrotül in 1000 ml of water and applied to cotton or regenerated cellulose applied. After squeezing, it is dried for a few minutes at 100 - 140 ° and then soaped at the boil. This gives a very good wetfast blue coloration with good fastness properties.

Example 13s 25 g of copper phthalocyanine (3) -tetrasailfonsäure-chloräthylamids prepared according to Example 12 b) in 150 N.Methyl ethanolamine g six hours at 120 0 heated. The reaction solution is then poured into water, the dye is salted out, filtered off with suction and washed with ethanol. Man holds copper phthalocyanine- (3) - (SO2 NHC2H4-02E4OH) 4. 6 3 30 g copper phthalocyanine- (3) - (S02NHC2H4NC2H40H) 4 CH 3 are dissolved in pyridine and 9 ml at room temperature Chlorosulfonic acid in 150 μl of pyridine was added dropwise. Included there is a slight self-heating. The mixture is stirred for 30 minutes ten after, whereby the paraffin ester precipitates oily. After this dbdekanßUeren des pyridine one gives the residue to 220 ml a 10% soda solution and salt the blue dye with Potassium chloride. For cleaning you dissolve again in water and precipitates with methanol. 33 g of copper phthalocyanine are obtained 3- (S02NHC2H4Y-02H40S03Na) ,. The dye can be after CH 3 Procedure of Example 12 in the presence of acid-binding agents Dye medium on cotton or viscose. The turquoise blue one The color is characterized by very good NaB and solvent realities. According to those given in Examples 12 and 13 Procedure can use the components of the table below Dyes are implemented according to the regulations the previous examples on cotton and regenerated Cellulose dyeings and prints in those given below Deliver shades with very good wet fastness properties. Hue of Starting dye 1. Amine 2. Amine Sulfur-LsäA, - halfway through Cotton Copper Phthalocyanine- HN (02H40H) 2 HN- 02 840H blue 3- (S0201) 4 1 uH 3 H2 N028408 HN (C2H40H) 2 blue H2N02H40H H2 NO 3H608 blue r H2NC3H60H HN-02H4OH blue 0H3 n H2NC4H8OH HN-02H40H blue @ H3 ~ HN-02H4OH H2NC2H40H blue 6H3 HN-02H40H. HN-02E40H blue I. CH 3 OH 3 HN-02H40H HN (C2H40H) L blue 0H3 Example -4: 0.05 mole copper phthalocy: -:?; .- (4) -tetrasuifocbia-z = id are cooled in a ne.tä: = - cj @ akalische -solution voi 0.4 mol of H2NC3H6N-C2H40S03H added to 1000 ml of water. CH 3 The p "value is maintained by adding dilute sodium hydroxide solution between 9 and 10. After about 30 minutes there is condensation completed. The mixture is stirred for one hour at room temperature and sucks the precipitate obtained in quantitative yield away. For cleaning, the dye ester is slurried in water bring it in by carefully adding caustic soda Solution and falls by blunting it with dilute salt acid again. Instead of caustic soda, others can also be used acid binding agents such as sodium carbonate, potassium carbonate, , Sodium bicarbonate, galium bicarbonate, primary or secondary dear sodium and potassium phosphate, sodium acetate, pyridine, Use triethylamine, etc. 2 g copper phthalocyanine-4- (S02NHC3H6NC2H40s03H) 4 6H3 are in 100 ml of the solution described in Example 12 dissolves and padded on a tree roll or regenerated cellulose. After intermediate drying at 50-600, the Were a few minutes with dry steam from. 102 - 1100 and holds such a reddish blue coloration of good NaB-, rubbing- and lightfastness. Example 15 s- 28 g copper phthalocyanine (3) tetrasulfochloride are in a neutralized solution of 33 g NH202H4NHC2H40s03H added to 300 ml of water. By access If a 10% soda solution is added, the p. Value constant. To. For 30 minutes, remove the external cooling and stir two , t Hours at 25 - 30o after. One sucks off and one receives one blue dye obtained according to the method described in Examples 121 # and 14 can be fixed on vegetable fibers. According to the procedure given in Example 14 can also valuable dyes from the following components are made based on materials containing hydroxyl groups Fixations in the specified color tones result in = Starting dye aminoalkyl hue mf sulfuric acid ester cotton fer-phthaloeyanine-- H @ NC @ H @ N-02H40S03H turquoise blue (S201) 4 - CH 3 Copper phthalocyanine- H2 N03 H6 N- (02H40s03H) 2 blue W (S02C1) 4 Example 84 g of copper phthalocyanine (3) tetrasulfochloride are introduced into a solution of 150 g of N-oxethylethylenediamine in 600 ml of water while cooling with ice. When the entry is complete, the external cooling is removed and the reaction solution is stirred overnight at tree temperature. The mixture is then heated to 60o for one hour, the condensation product is salted out with potassium chloride and filtered off with suction.

35 g of the dye prepared in this way are dissolved in pyridine and added at room temperature to a solution of 20 ml of chlorosulfonic acid in 80 ml of pyridine. Self-heating occurs to 30o. The mixture is then stirred for an hour and decanted the pyridine and dissolve the residue in iglasser. Then neutralize with sodium carbonate and sucks off the dye ester.

Example 17: 25 g of copper phthalocyanine (3) trisulfochloride are introduced into a solution of 40 g of trioxethyl diethylene triamine in 330 ml of water, with thorough stirring. The mixture is stirred overnight, then heated to the boil for 30 minutes and the condensation product is filtered off with suction while hot. To remove excess amine, it is washed with water and dried in vacuo. 23 g of the dye are poured into 69 ml at 15 - 20o Sulfuric acid monohydrate entered. After stirring for three hours the reaction solution is poured onto Bis and the differentiated dye - est; r from. One washes to remove of mineral acid with salty, Passes, Ä id se Ilämnt the residue ixt water. Then you neutralize with dilute sodium hydroxide solution and sucks off again. Example 1g s - Those obtained according to Examples 16 and 17, as well as those in the following table according to the same rule produced dyes, can also be found on tree wool or regenerated cellulose in the presence of an acidic stain binding fixative. Off: A sMaterial m_inoalkohol -Far BToN d. Dyeing, Copper-phthalocyanine- dioxäthyl- blue. (3) - (S0201) 4 ethylenediamine Copper - phthalocyanine- triozäthyl- (3 @ (S02o1) 4 diethylene turquoise blue triamine Example 19: In a solution. of 123 g of N-methyl-N-oxethyl-propylene- diamine / # Kp3) 82o / 1 Torr) in 750 ml of water is carried under ice cool 112 g copper phthalocyanine (3) tetrasulfochloride. The mixture is stirred over fold at room temperature, the condensation product is filtered off with suction and washed with water. after: The received Dye copper = Phthaloeya.nin-f- (S02NHC3H6NC2H4OH) 4 is un- soluble in methanol. . CH3 100 g copper phthalocyanine 7 @ (S02NHC3H6NC2H40H) 4 Cg3 (0.08 mol) are dissolved in 1000 ml of pyridine and added at 200 to a solution of 76 g of chlorosulfonic acid (0.64 mol) in 1000 ml of pyridine. The dyestuff ester precipitates out immediately. To complete the reaction, the mixture is stirred for a few hours and the solvent is decanted. The residue is slurried in 1000 ml of water, adjusted to pg 7 with dilute sodium hydroxide solution and the blue dye is removed. To remove any pyridine still adhering, it is washed with methanol and dried in vacuo at 500.

The esterification of the dye can also be carried out according to Example 17 with sulfuric acid monohydrate. Example 20: 0.1 mol of nickel phthalocyanine (3) trisulfochloride will be - according to the procedure given in Example 19 with 60 g N-methyl-N-oxäthyl-propylenediamine @ d; @@ mol) in 600 ml Water condenses. 100 g of this condensation product are in 300 ml Dissolved sulfuric acid monohydrate and heated to 600 for one hour. warms. The reaction mixture is allowed to cool and it is poured then on ice. The dye ester Icridallin precipitates out. After pressing, you wash. acid-free with water, schläylnt the residue in water and sets up with Nato alaiige p $?. By again sucking off urrl drying in vacuo at 400 1'i2 g of a dye is obtained which is characterized by a? kGJ_isches '' Fixing on cotton or regenerated cellulose a green-- gives a pungent blue coloration with good wash fastness. ; Example 21 0.2 moles of copper phthalocyanine (4) tetrasulfochloride are in 1 ¢ 2 g of N, N-dioxäthyl-propylenedia with ice cooling. i. (0.88 mol) added to 1400 ml of water. The condensation product precipitates as a gelatinous mass. By adding galium chloride and heating to 80 - 90 °, crystallization suddenly occurs: One sucks off hot and receives in good yield copper phthaloeyanine - @> (S02NHC H6NIC2H40H12) 4, which can be obtained by one of the above methods with chlorosulfonic acid / pyridine or Sulfuric acid monohydrate can be quantitatively converted into the corresponding dye ester.

At 22 162 g of N, N-dioxäthylpropylenediamine are dissolved in 1200 ml of water and adjusted to p. 10 with dilute acetic acid. 217 g of copper phthaloeyanine (3) tetrasulfochloride are added to the cooled solution and held the pH value is kept constant by means of dilute sodium hydroxide solution After the condensation has ended, the dye is salted out, filtered off with suction and dried in vacuo.

30 g of copper phthaloeyanin4> (SO2NHC3H6N [C2H40H @ 2) are esterified in 90 ml of sulfuric acid monohydrate. The dyestuff precipitated by means of Eiswassex is filtered off with suction and washed acid-free with a proprietary potassium chloride solution. The press cake is slurried in 1000 ml of water and adjusted to pH 7 with 0.2 ml of 1N sodium hydroxide layer. The dyestuff ester dissolves. After viewing 185 g of galium chloride 0, it is again suctioned off and dried in vacuo at 50. 2 g of the dye obtained are dissolved in 100 ml of an aqueous solution containing 40 g of potassium carbonate or sodium carbonate, 100 g of urea and 5 g of Turkish odor oil per liter , ge solves and in de Iden Examples 12 f) or 14 described Manner applied to hydroxyl group-containing materials. The turquoise blue dyeings obtained show excellent fade, boil, light and rub fastnesses.

Is used at. the fixation on cotton or regenerated Cellulose instead of potassium carbonate sodium bicarbonate or potassium bicarbonate, this also results in a quantitative color yield that is level, solvent-resistant Colorations.

In a similar way, other acid-binding agents, such as tertiary or secondary sodium or potassium phosphate or sodium acetate to fix the Use the dye described above.

Example 23:.

a) 0.029 mol of cobalt phthalocyanine- (3) -disulfochloz-id are introduced into a solution of 13.5 g of N, N-dioxäthyl-propylenediamine- (1,3) in 60 ml of water. After the addition is complete, the cooling is removed and the pH is kept at 9-9.5 with potassium carbonate. Then it is heated to the boil for a short time. and separates from the colorless mother liquor. b) .52 g of moist copper phthalocyanine- (3) -trisulfoehlorid (corresponding to 12.5g dry substance) are in a cooled Solution of 1.8 g of N-methyl-N-oxäthylpropylenediamine An'100 ml (Added methanol. The mixture is stirred overnight and then filtered off with suction. C) 0.1 mol of copper phthalocyanine (3) tetrasulfochloride is dissolved in a solution of 106 g of N-methyl-N- , oxäthylpropylenediamine / f @; 8) mol) - entered in 1000 ml of water. Before the addition of the sulfochloride, the amine solution was buffered to pH 10 with 10% sulfuric acid. After warming to room temperature, the pH is kept at 9.5-10 with 250 ml of 10% sodium hydroxide solution. The condensation is over after four hours. It is heated to 60o, suctioned off warm and washed with 2000 ml of water. You get Copper Phthalocyanine- (3) - (S02nC3H6NC2H40H) 4. 206 g moist copper phthalocyanine- (3) - (S02NHC3H @ N- . j H3 C2H40H) 4 (corresponding to 78 g dry matter) are included in 10 - 200 entered into 240 ml of sulfuric acid monobydrate within one hour. 877 g of 65% strength oleum are then added dropwise at the same temperature over 90 minutes. The esterification is complete after a further 30 minutes. It is poured onto ice and the dye is isolated in the usual way. The quantitative yield results from the observation that all of the filtrates and wash water are uncolored. The products obtained under a) and b) can be used in be esterified in the same way. Example 24 0.1 mol ferrite Irupfer-Phthalocyanir _- (3) -tetrasulfo- chloride are cooled in 80 g of N-methyl-N-oxä'thyl- propylenediamineAin.c1 000 m1 ethylene chloride entered. bian stirs for five hours at room temperature and then distills off the water azeotropically. The condensation product is insoluble in the solvent. After cooling, 400 ml of sulfuric acid monohydrate are added dropwise and allowed to act for a few hours. The sulfuric acid solution of the dye is then separated off from the ethylene chloride and poured onto ice. The dye ester is worked up in the customary manner.

One can also proceed in such a way that, after the condensation and azeotropic distillation, the solvent is first decanted and then the esterification is carried out. If, in this example, chloroform, benzene or toluene is used as the solvent instead of ethylene chloride, the results are equally good. - According to the information in Examples .1g-24, the starting components specified in the table below can also be converted and the dyes obtained can finally be esterified; the dyestuff esters yield cotton or regenerated cellulose according to the methods described or after minor modifications to the pixing conditions, such as temperature, type of acid-binding agent or dwell time at elevated temperature, "dyeings and prints which are characterized by particularly good fastness properties, especially very good ones Distinguish wet fastness properties. Hue of sweat Starting component% ^ i.noalkohol felsäurehz-Ubestem on cotton Copper Phthaloc; "" anine-N-Methyl-No xäthyl- rotstichi g (4) -tetrasulfochloride propylenedi amir- (1,3) blue Nickel-Phthalocyani.n- n Turquoise - (3) - tetrasulfochloride Cobalt phthalocyanine @@ ged fites (3) -tri sulfo chloride blue Cobalt Phthalocyanine "Masked" (3) -tetrasulfochloride blue sulfochlorinated green Tetraphenyl copper Phthalocyanine sulfochlorinated azo _ dye o-anien red - din> 2, 3-oxynaph- tnoic acid-o-anisidide Hue of sweat Starting component amino alcohol _ fel acid half-ester - on B aunYvolle Ku f er-Phthalocyanin- N, N-Dioxäthyl- Türkisb7a u (33-trisulfochloride propylenediamine- (1,3.) Nickel Phthalocyanine " Turquoise (3) trisulfochloride Nickel Phthalocyanine " Turquoise (3) tetrasulfochloride Cobalt Phthalocyanine "Masked" (3) -trisulfochloride blue Cobalt Phthalocyanine " Masked (3) -tetrasulfochloride blue sulfochlorinated " lightfast Tetraphenyl copper green Phthalocyanine sulfochlorinated Azc- Farbotoff. o-anisi- @@ red din ---- i 2, 3-Oxynaph-- thoic acid-o-anisidide Copper Phthalocyanine- HN @ CH2CH2, N- C2H40H Blue (3 @ -tetrasulfochloride OH 20H2 Copper-Phthalocyanine- H2N - CH2-QH2-S-CH2-CH2-OH Blue (3) tetrasulfochloride Example 25: 50 g of chloromethylated copper phthalocyanine are used in excess N, N-dioxäthyl-propylenediamine / Äclig) hours heated to 950 , allowed to cool and poured into 1000 ml of water. After the addition of potassium chloride, it is suctioned off and the dye copper phthalocyanine (CH 2NHC3H6NCC2H40H12) n (n = 1.75) is washed with ethanol to remove any amine that is still adhering. 30 g of the dye thus represented. Esterified at 20-22o in 90 ml of sulfuric acid monohydrate. After four hours you put on ice and work up as usual.

0.2 g of dye are dissolved in 10 ml of the solution given in Example 12 f) and padded onto cotton. Drying the goods at 60 - 80o results in a very extensive blue print with very good wet fastness properties. Example. ?, 6; 30 g of 1-amino-4-bromantttaclinone 2-sulfonsälzre are heated in excess N, N dioxätliyl-propylenediamine- (1,3) in the presence of some -copper-e) chloride for a few hours to 60o, then to 100o and afterwards the replacement of the halogen poured into five times the amount of water. It is salted out with potassium chloride, filtered off with suction and redissolved again from salty water. This gives 31.5 g of a blue dye which, after esterification with chlorosulfonic acid / pyridine or. Sulfur acids monohydrate can be dyed on cotton or viscose according to the instructions given in the previous examples. Example 27 1 19.2 g of cyanuric chloride are dissolved in 200 ml of acetone and poured into 600 ml of ice water. To 0 - 5 0 cooled suspension a liösung of 0.1 mol of the azo dye obtained from diazotised 2-aminonaphthalene-4,8-disulfonic acid and m-toluidine is added dropwise in 500 ml of water. One holds the p. Value with. dilute sodium hydroxide solution to 5.5 - 6 until no more amine can be detected, adjusts to pH 6.5 and gives 65 g of N, N-dioxäthyl-propylenediamine @ to @ 3 @ after the initial ] Stirring at -200 warms up to swap the two remaining chlorine atoms of the cyanuric chloride finally three Hours to 400, then eight hours to 950, it is allowed to cool and the dye precipitates with acetone. The hydroxyl-containing dye can be lost. the methods described in the previous examples to esterify. 0.4 g of dye ester are dissolved in 10 ml of a solution the 40 g sodium carbonate and 100 g urea in 1000 ml Contains water; solved. By padding and then e Fixing at 100 - 140o leads to clear yellow Coloring with very good wash and soda boiling fastness . Example 2R : A printing paste consisting of 20 g of the rare substance obtained according to Example 19, 100 g of urea, 150 ml of water, 10 g of sodium hydroxide solution (38o 8e), 400 g of alginate thickening (120-1000) and 320 ml of water is used applied in the usual way to cotton and viscose. 1) The dried prints are steamed neutral for 7 minutes at 100-104 ° and washed on the wide washing machine. A print of good levelness is obtained.

Example 29 40 g moist copper phthalocyanine- (3) - (SO 2NHC3H61% Tu2H40H) 4 (corresponding to 20 g of dry substance) are introduced at 10-20 ° irr 100 ml and stirred for two hours. Then the sulfuric acid half-ester of the dye is worked up as usual.

When printing cotton according to the method given in Example 28 colorings with excellent fastness properties are obtained.

Example 30: 15.7 g of the sulfuric acid half ester of 1-methyl-2- (N-methyl-N-Ahydroxyethyl-aminomethyl) -5-aminobenzimidazole are dissolved in 75 ml of 2N hydrochloric acid and added as usual by adding 35 ml of 10% sodium nitrite solution diazotized. The diazonium salt solution obtained is stirred into a solution of 12.7 g of 1- (3'-stilfopheny 1) -3-methyl-pyrazolone- (5) in 2N soda solution. After the coupling is complete, the dye is through. Acidification with hydrochloric acid and salting out isolated. 2 g of the dye thus obtained are dissolved in 100 ml of water with the addition of 3 g of soda and 10 g of urea. The solution is padded onto cotton and the soaked fabric is heated to 140 ° for 10 minutes. Then it is rinsed and soaped at the boil. A yellow dyeing which is very fast to wet is obtained. Example 31 .: In a solution of 50 g of the sulfuric acid half-ester of 3-aminobenzyl-hydroxyethyl-methylamine in 300 ml of water. 43 g of copper phthalocyanine (3) tetrasulfochloride are entered at 30o and a p. of 10 complied with. If no more alkali consumption can be observed, hydrochloric acid is added to -p. 7.5 and the dye salted out, suction filtered and dried. 2 g of this dye are dissolved in 100 ml of water with the addition of 3.2 g of sodium hydroxide, 0.5 g of Turkish red oil and 10 g of urea. The solution is padded on cotton and the soaked fabric is heated to 140o for 10 minutes. Then it is rinsed and soaped at the boil. A very wetfast blue dyeing of good lightfastness is obtained.

Example - 3 Batun wool fabrics are soaked with 1% sodium hydroxide solution, Squeezed well and dried at 1000. Au = the fabric treated in this way then becomes a solution of 3 g of dye (reaction product of 1 mol gupfer - phthalocyanine (3) trisulfochloride with 5 moles of N, N-dihydroxyethyl-propylenediamine- (1,3) and subsequent esterification with sulfuric acid) and 6 g of urea in 250 ml of water and the tissue Heated to 140o for 10 minutes. Then it is rinsed and soaped at the boil. Man acquires a very wet-fast blue color.

You also get a wet-fast blue coloration if you the paraffin solution mentioned in the above example padded on cotton fabric, the one previously impregnated with a 1% aqueous galium / drug carbonate solution and [ has dried at 100o.

The dye can also be fixed by steaming. -, example 33s.

. 41.8 g (0.1 mol) of 1,4-di-p-toluido-anthraquinone are introduced into 100 ml of chlorosulfonic acid with cooling and then heated at 800 for one hour, after which the evolution of hydrochloric acid has essentially ended. The reaction mixture is then cooled to 600 and a total of 35 ml of thionyl chloride are added dropwise, the temperature being slowly increased to 900 at the same time. After stirring for about half an hour at this temperature, the reaction mixture is cooled, applied to bis and the sulfochloride, which is soluble in water, is washed acid-free on the suction filter.

The filter cake is introduced into a mixture of 265 g of N-methyl-N-ogäthyl-propylenediamine- (1,3) and 500 ml of water and stirred overnight. The next: n morning stirs. it is then cooled for about two hours at 50 °, the reaction mixture is neutralized by the addition of half-concentrated hydrochloric acid, the intermediate product is isolated and it is dried.

The dried sulfonamide is introduced into 250 ml of Schwzf-α-acid conohydrate with external cooling until. Room temperature is kept stirred and then poured into a mixture of 20% potassium chloride solution and ice. The precipitated dyestuff bis-sulfuric acid half ester is filtered off with suction, washed largely acid-free with dilute potassium chloride solution, then adjusted to pH 7 with the aid of a pH meter, isolated again and added in a vacuum drying cabinet. 40 - 50o dried. The resulting dye corresponds to the likely formula It can be fixed to fiber materials by the methods described above and produces a somewhat dull blue-green with good wet fastness. In an analogous manner, the following. The starting components given in the table by sulfochlorination, condensation and esterification produce dye esters which, when fixed on cotton and regenerated cellulose by the working methods indicated, provide wet-fast dyeings and prints in the shades indicated below. Hue of Anthraquinone component -amine component sulfuric acid- half of the best cotton 1,4-di-p-toluido- N, N-dioxyethyl-. 'blunt anthraquinone propylenediamine (1,3) blue green 1,4-di- (21,61-dimethyl- N-methyl-N-oxäthyl- clear red- ania.ido) -anthraquinone propylendiamine- (1,3) blue 1,4-di- (2 ', 6'-dimethyl- N, N-dioxäthyl- clear red- anilido) anthraquinone propylenediamine (1,3) blue 1, 4-di- (2 '-methyl - 6' - N-methyl-N-oxäthyl- clear red- ethylanilido) - anthraquinone propylenediamine- (1,3) blue 1,4-di- (2'-methyl-6'- N, N-dioxäthyl- clear red- äthylariilido) anthraquinone propylenediamine (1,3) blue 1,4-di- (2 ', 6'"diethyl- N, N-diox-ethyl- clear red- anilido) -anthrachi.non propylenediamine- (1,3) blue 1,4-di- (2 ', 6'-diethyl- N-methyl-N-oxäthyl- clear red- anilido) anthraquinone propylenediamine (1,3) solid blue 1,4-di- (2 ', 4', 6'-trimethyl-N-mathyl-N-oxethyl clear anilido) anthraquinone propylene diamine (1,3) blue 1,4-di- (2 ', 4', 6'-trimdhyl- N, N-dioxäthyl- clear anilido) anthraquinone propylenediamine (1,3) blue 4-p-toluido-N-methyl-N-methyl-N-oxäthyl bluish tint anthrapyridone pz-opylenediamine- (1, 3) red 4-p-toluido-N-methyl-N, N-dioxäthyl bluish tint anthrapyridon propylene diamine- (1,3) red 4-anilido-IV-methyl-N, N-dioxäthyl- yellowish anthrapyridon propylenediamine- (1,3) red 4-anilido-ii-methyi- N-methyl-N-oxäthyl- yellowish anthrapyridone propylenediamine- (1,3) red 4 - (3'-chloroanilido) -N- N-methyl-N-oxäthyl- strong yellow- methyl-anthrapyridon propylenediamine- (1,3) tinged red 4- (3'-Chioranilido) -N- N, N-dioxäthyl- strong yellow- methyl-anthrapyridone, propylenediamine- (1,3) tinged red 4- (4'-Benzylanilido) -N- N, N-dioxäthyl- bluish tinge methyl-anthrapyridone propylenediamine- (1, 3) * red 4- (4'-Benzylanilido) -N- N-methyl-N-oxäthyl- bluish tinge methyl-anthrapyridon propylenediamine- (1,3) red Example 34 23.9 g of the dye obtained by coupling diazotized 3-aminobenzyl / 3-hydroxyethyl ether with 1-phenyl-3-methyl-pyrazolone- (5) are dissolved in 150 ml of pyridine. 23.7 g of chlorosulfonic acid are added dropwise to this solution at 00 in the course of 30 minutes, the mixture is then stirred for two hours at 0 ° and the reaction mixture is then added to a solution of 28.8 g of soda in 250 ml of ice water. The dye is salted out, filtered off with suction and dried.

0.1 g of the dye obtained in this way and 1 g of urea are dissolved in 10 ml of 8% sodium hydroxide solution. The solution is padded onto cotton and the soaked fabric is heated to 1600 for 30 minutes. Then it is rinsed and soaped at the boil. A yellow coloration which is very fast to wet is obtained.

Example 35: 0.05 mol of the monoazo dye obtained by diazotizing 2-aminonaphthalene [, 8-disulfonic acid and coupling with m-toluidine, further diazotizing and coupling with 2-aminonaphthalene-1-sulfonic acid with subsequent oxidation of the o-aminoazo group for Triazine ring was produced, is converted into disulfochloride. The acid-free washed sulfochloride is well suspended in 50 ml of ice water and under Ice cooling into the solution. Of 26.4 g (0.2 mol) N-methyl-N- ozäthylpropylenediamine - (1.3) added to 100 ml of water. After 2 - 3 hours of stirring at 00 , it is slowly increased to 50o heats and the easily filterable dye after cooling sucked off. After drying, the dye thus obtained becomes under Ahlen in excess sulfuric acid monohydrate worn so that a good solution occurs, and three hours stirred at 20o. The solution is then added to the necessary amount Poured ice, the esterified dye by adding salt falls. To eliminate the excess that is difficult to wash out Acid it is recommended to add a little water to the dye suspend and neutralize with soda before re-isolating to deliver. The dye obtained corresponds to the true apparent formula Example 36.- 0.05 mol of the monoazo given in Example 35 dye disulfochloride are thoroughly dissolved in 50 ml of ice water suspended and with ice-cooling in the solution of 32.4 g (0.2 Nol) N, N-Dioxäthyl-propylenediamin- (1.3) in 100 ml Water entered. The reaction mixture is three hours at Stirred 0o, heated slowly, kept at 50o for one hour and after cooling, filtered and dried. To the rasterization of the oxethyl groups is the dye obtained in this way Cooling in excess sulfuric acid monohydrate contribute - three hours. 20 0 stirred and the sulfuric acid semicester, as indicated in Example 35, isolated acid-free. The dye that is the likely formula is very soluble in water. For isolation is a Addition of potassium chloride required until saturation: 2 g of that obtained according to this and according to Example 35 Dyes are dissolved in 100 ml of a solution of 10 g of urea, 4 g of soda and 0.2 g of Turkish red oil dissolved; with this par- fabric solution is treated according to the dom padding process made of natural or regenerated cellulose with or without prior drying for 10-15 minutes at 120 ° C. This gives clear yellow colors of excellent washing and chlorine fastness and good lightfastness. In the same way as given in Example 3 5 and 6, the following triazole monoazo compounds are theirs Sulfochlorides into the corresponding reactive. Sulfur- acid half-esters, which according to the. previous Examples of working methods dyed on cotton wool or printed yellow to red-embroidered yellow tones of outstanding excellent wash fastness and chlorine fastness and good light deliver real. 2-aminonaphthalene-4,8-disulfonic acid>1-amino-2-methoxy-5-methylbenzene.> 2-aminonaphthalene-1-sulfonic acid, triazolated, _2-aminoxiaphthalene-4,8-disulfonic acid> 1-aminonaphthalene - @ 2 -Aminonaphthalene-6-sulfonic acid, triazolated, 2-aminonaphthalene-6, 8-disulfonic acid) 1-amino-3-methylbenzene> 2-aminonaphthalene-1-sulfonic acid, triazolated, 2-aminonaphthalene-6, 8- disulfonic acid> 1-amino-2-methoxy-5-methylbenzene) 2-aminonaplithalin-1-sulfonic acid, ° triazolated, 2-aminonaphthalene-4,8-diaulfonic acid>1-amino-3-methylbenzene; condensed with cyanuric chloride and hydrolyzed residual chlorine atoms, -.

2-aminonaphthalene-4,8-disulfonic acid> 2-aminonaphthalene-5-sulfonic acid, triazolated, the nitro group reduced, 1-amino-3-methylbenzene ---> 2-aminonaphthalene-6-sulfonic acid, triazolized to the bis -triazole of the formula or Similar yellow dyes are obtained if the. 2-aminonaphthalene-5-sulfonic acids (last example by 2- Aminonaphthalene-6-sulfonic acid or the 2-aminonaphthalene-6- sulfonic acid replaced by 2-aminonaphthalene-5-sulfonic acid. Instead of m-toluidine you can get a similar result i aniline, xylidine, xresidine or naphthyl amine are also used will. Example cotton fabric is treated with an aqueous solution that Contains 3% galium carbonate and 1% alginate thickening, soaked, sucked off and dried. Then you print that fabric treated in this way with a printing paste 2 g of the dye mentioned in Example 32 10 g urea 25 ml of water 60 g alginate thickening The printed fabric is dried at 80o and - then heated to 140o for 10 minutes. Then it is rinsed and soaped at the boil. A very wet-fast blue is obtained Pressure. The dye can also be fixed by steaming. Suitable acid-binding agents with which the cotton fabric is previously treated are, for example, sodium hydroxide, sodium carbonate, sodium hydrogen carbonate, trinatrium phosphate.

Example 38: Cyanuric chloride is first condensed at low temperature with an equimolar amount of 2,4-diaminobenzenesulfonic acid, then at higher temperatures with twice the molar amount of 1-amino-3- (di-oxethylamino) propene. If this condensation product is diazotized and coupled with 1-oxy-8-benzoylaminonephthalin-3,6-diaulfonic acid and finally the coupling product is converted into the sulfuric acid half-ester by means of chlorosulfonic acid and pyridine, a dye is obtained which, according to the example 30 method described cotton is very washable and solvent-resistant, blue-tinged red in color.

Example # 9 The sulfochloride obtained by the action of chlorosulfonic acid on the condensation product of tetrachloro-p-benzoquinone and 3-amino-N-ethylcarbazole is reacted with 1-amino-3- (methyl - o.tbylamino) propane to form the corresponding sulfonamide . 30 g of the with. Sulfuric acid esterified dye is dissolved in 1000 ml of a * solution containing 15 g of sodium hydroxide, 1 g of Turkish red oil and 100 g of urea.

Cotton fabric impregnated with this solution is left on for 10 minutes 110o heated. After rinsing and boiling soaps, you get a very washable and Solvent-neutral blue-violet staining.

Example q f By reacting copper phthalocyanine (4) tetrasulfochloride with the fourfold polar amount of 1-amino-2-oxy-3-diethylamino-propane is obtained Sulphonamide obtained by the action of concentrated sulfuric acid with the addition of Oleum is converted into the sulfuric acid half ester. 20 g of this dye will be dissolved in 1000 ml of the solution described in Example j9, the solution on cotton poplin padded and the impregnated fabric treated at 1200 for 10 minutes. After rinsing and boiling soaps, a very wet-fast greenish blue coloration is obtained.

Example 41: In, a mixture of 148 g (2 moles). N-methyl-N # -oxy- ethylamine and 5 ml of water are carried at 100o 0.1 mol of the Copper Phthalocyanine (3) Tetra Sulfuric Acid Half Ester sulfon713 - oxyäthylamids and heated for 3 1/2 hours 140o in an oil bath. After cooling, 250 ml are added Water and carries the contents of the flask in 500 ml of a 20% Potassium Chloride Solution. The reaction mixture is through addition of half-concentrated hydrochloric acid, neutralized, then filtered off and put on the filter with approx. 10 1 600 warm water washed. The dried product will with external cooling in 440 ml of sulfuric acid monohydrate entered and stirred for four hours at room temperature. The contents of the flask are then placed on a mixture of ice and 20% galium chloride solution, sucks off, washes with Potassium chloride solution, slurries the dye in water, makes it neutral by carefully adding sodium hydroxide basks it completely by adding potassium chloride, sucks and dries in the vacuum drying cabinet at 40 - 500.- The dye obtained can according to the previous examples given methods on fiber materials be fixed and provides a clear blue of good wet authenticity. ' Example j? % In a mixture of 168 g (1.6 mol) N, N -Di ß-oxy- ethylamine and 5.m1 tYasser one carries 0.1 mol des at 100o Sulfuric acid half-ester of copper phthalocyanine (3) tetra sulfo-P oxyäthylamids.ein, heated for 3 1/2 hours at 1600 and proceed as described in Example 41 for the rest. The dye obtained can, as indicated, - on Fixes fiber materials; grounds and provides a clear blue of good wet fastness. Example 43 A mixture of 74 g is placed in an autoclave (1 mol) £ X "methyl-N / 4oxyethylamine, 200 ml of water and 0.05 viol Copper Phthalocyanine (3) - Sulfuric Acid Hulbesfier trisulfo oxyäthylamiü.a and heats the reaction mixture 74- acnt hours at 150o. The work-up of the experiment takes place as in example 41. The obtained dye yields on cotton and regenerated cellulose fixed, a clear blue of good Wet fastness properties. Example 4 4s A mixture of 105 g is placed in an autoclave (1 M01) N, N - Di - / I-oxyäthylaain, -200-m1 water and 0.05 biol des Copper Phthalocyanine (3) @ -tri- sulfo - # oxyäthylamids and heated the reaction mixture eight Hours to 1500. The work-up of the experiment is carried out on the route outlined in Example 41. The dye supplies, fixed on fiber materials, a clear blue with good wet fastness properties. Example 45: 116 g of the sulfuric acid ester of the-l-amino-4- (3 'i-oxyethylsulfonamido-phenyl) -amino-anthraquinone-2- sulfonic acid. are in a mixture of 405 g of N, N -Di? oxyethyl amine and 405 ml of water and heated to 105o. Of the The progress of the reaction is monitored by chromatography. To Completion of the reaction (10-15 hours) one carries the re- action mixture in a 20 % galium chloride solution, sucks off and washes with potassium chloride solution. The dried dye is dissolved in 400 ml sulfuric acid Registered nonobydrate and stirred overnight. The next Tomorrow the reaction mixture is poured onto a mixture 20 % potassium chloride solution and ice, sucks off, washes den.:Nutschkuchen with methanol, slurries. the dye in Water on, adjust carefully by adding: sodium hydroxide solution neutral, salt out the product by adding potassium chloride and dries. The dye obtained can be fixed to fiber materials by the methods described in the preceding examples and provides a clear, somewhat reddish blue with good wet fastness properties.

Example 4 @@ 50 g of the dye of the presumed formula are introduced into a mixture of 250 g of N, N -Di - @ - oxyäthylamine and 250 ml of water and heated to 110. The progress of the reaction is monitored chromatographically; Response time approx. -15 - 20 hours. The experiment is worked up as in Example 41. The dye provides? Fixed to hydroxyl-containing materials, a somewhat dull blue-green of good wet fastness. Example 47z, -50 g of the dye of the likely formula become -in one. Mixture of 250 g N9 N -vi-% ox ;;. thylamine ur: ct 250 ml water and heated to 1100. The progress of the reaction is monitored by chromatography; Reaction time about 15-20 hours. The work-up of the experiment and the fixing of the dye on fiber materials are carried out as in Example 41. A clear reddish blue of good wet fastness is obtained: Example 48: 5 g of the dye which is obtained by coupling diazotized 4-aminobenzyl-iI-hydroxyethyl- thioether with 2-hydroxynaphthalene 5, 7-di-sulfonic acid and whose hydroxyethyl group has been converted into a 6-chloroethyl group by treatment with thionyl chloride, are dissolved in 100 ml of water with the addition of 40 ml of sodium hydroxide solution 38o Bb. The dye solution obtained is padded onto cotton nettle and the fabric treated in this way is heated to 140 ° for 10 minutes. Then it is rinsed and soaped at the boil. An orange-red, very wet-fast dyeing is obtained. The same color is obtained if soda is used as the acid-binding agent.

Claims (3)

Claims: Method for. dyeing and printing hydroxyl groups or. Materials containing amide groups, which is known as 'characterized' by the fact that one contains dyes which contain at least one of the following groupings: where R is an alkylene or cycloalkylene radical, R is an alkylene radical with two or three carbon atoms between the radicals R and Y, R is a nitrogen, oxygen or sulfur atom, Y in the event that 3 is an oxygen or sulfur atom; a pair of electrons and, in the event that H represents a nitrogen atom, hydrogen denotes an aliphatic or cycloaliphatic substituent which can be part of a heterocyclic ring, and Y stands for a substituent to be split off as a negative ion e is applied to the material to be colored and Aas treated material, in Gekenwart acid-binding agents subjected to the action of elevated temperature. 2) Method according to claim 1, characterized in that the FixierproseS is followed by a wash in neutral or alkaline liquor. 3) Method according to claim 1, characterized in that one sulfonic acid and / or carboxylic acid group-containing dyes are used.