GB1568172A

GB1568172A - Process for dyeing or printing cellulose textiles with azo dyestuffs produced on the fibre

Info

Publication number: GB1568172A
Application number: GB389677A
Authority: GB
Original assignee: Hoechst AG
Current assignee: Hoechst AG
Priority date: 1976-01-30
Filing date: 1977-01-31
Publication date: 1980-05-29
Also published as: DE2603445B2; DE2603445C3; BE850920A; DE2603445A1; FR2339699A1; FR2339699B1; IT1075270B

Description

(54) PROCESS FOR DYEING OR PRINTING CELLULOSE TEXTILES WITH AZO DYESTUFFS PRODUCED ON THE FIBRE (71) We, HOECHST AKTIENGESELLSCHAFT, a body corporate organised according to the laws of the Federal Republic of Germany, of 6230 Frankfurt/Main 80, Postfach 80 03 20, Federal Republic of Germany, do hereby declare the invention for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement:- From German Patent Specification No. 965,902, a process is known according to which coupling components containing fibre-reactive groups may be applied onto textile substrates from neutral or acidic baths by an exhaust process with a high goods-to-liquor ratio.In a second step the coupling component is reacted with the fibres by treatment in an alkaline bath also at a high goods-to-liquor ratio. The dyestuff is developed only subsequently in a third operation in a third bath, again at a high goods-to-liquor ratio. The printing of textiles is also carried out in three steps according to this scheme.

This process is, however, unsuitable for dyeing cellulose fibres because the reaction of the coupling component and the fibres proceeds only very slowly, and there is a risk that the coupling component applied onto the fibre in the first process step, and which is adhering to it by adsorptive power only, may come off before its reactive fixation. Therefore, only those reactive coupling components which have a high affinity for the fibre can be used.

The present invention provides a process for pad-dyeing or printing a textile material made of or containing cellulosic fibres, which comprises padding or printing the material with a padding liquor or printing paste which comprises a water-soluble coupling component containing a group which is fibre-reactive under alkaline conditions, but not containing the grouping

-N=C-halogen fixing the coupling component on the fibres, for example by allowing the material to dwell at room temperature, by drying the material, or by subjecting the material to a dry heat or steam treatment, and subsequently completing formation of an azo dyestuff on the fibres, the padding liquor or printing paste also comprising a compound that renders the medium alkaline at least during the fixation process, such as an alkaline agent or a compound yielding an alkaline agent under fixation conditions. The formation of the dyestuff is preferably completed by applying a diazonium compound to the material.

Compared to the process of German Patent Specification No. 965,902 the process of the invention has the advantage that the affinity of the coupling component for the fibres is not at all important; on the contrary, high affinity may be undesirable since it may cause uneven fibre end dyeings during the padding step.

Therefore, the reactive coupling components which are preferably used in the process of the invention are those whose water-solubility is not only due to a solubilizing effect of the reactive group, but also to the presence of further hydrosolubilising groups in the molecule, for example sulfo or carboxy groups. This increased water-solubility is furthermore advantageous because padding liquors require considerably higher concentrations than exhaust baths.

The process of the invention generally requires only a small volume of liquor, and generally does not require a further bath for fixation, since this may be carried out continuously or semi-continuously by simply allowing the material to dwell at room temperature.

Preferably the formation of the complete dyestuff is carried out in a continuous operation, which saves water and time to a considerable extent.

Compared to impregnation with conventional coupling components, the water-solubility properties of the reactive coupling components used according to the invention have the following advantages: An impregnation obtained with conventional coupling components is sensitive to water, because these components dissolve in water. Moreover, they can be dissolved according to the hot dissolving process at boiling temperature only, according to the cold dissolving process with the use of large amounts of ethanol only. Because of the permanent affinity and the relatively high dyeing speed in the case of pad-dyeing, the batch must be thinned in order to obtain uniform fibre end dyeings, that is, the first charge of the pad trough has to be diluted, or the subsequent impregnation bath has to be concentrated (feed concentration).

The decisive advantages of the coupling components used in accordance with this invention are the following: 1) Their water-solubility, which does not affect the alkali-solubilizing groups.

Moreover, even those coupling components may be used which do not contain OH groups but, for example, amino groups, thus reducing the amount of alkali required for the process.

2) The coupling components soluble in this manner do not yet have any affinity to the fibre in aqueous cold or hot liquors. Therefore, a precise calculation of the batch can be renounced, which simplifies the dyeing process.

3) The water-solubility facilitates handling of the compounds required for the dyeings.

4) Because of the homoeopolar linkage of the coupling component to the fibre, the dyestuff formed by coupling is linked to the fibre in a homoeopolar bond too, which results in excellent fastness properties, especially to solvents in drycleaning. Known insoluble azo dyestuffs produced on the fibre hitherto had drawbacks in this respect because of their solubility in these solvents.

The water-solubility of the coupling components used according to the invention facilitates handling of the compounds, and generally does not affect the alkali-solubilizing groups. Coupling components which do not contain hydroxy groups but contain one or more amino groups may be used, which reduces the amount of alkali required for the process. The coupling components used form a homopolar linkage to the fibres, which means that the completed dyestuff is likewise linked to the fibre by a homopolar bond, which results in excellent fastness properties, especially to solvents generally used in dry-cleaning.

Suitable coupling components which may be used in the process of the invention contain as fibre-reactive groups: vinylsulfone, 5-hydroxyethylsulfone ester, methylsulfonyl-benzothiazole, fluorobenzothiazole, phydroxyethyl sulfonamide ester, p-hydroxyethylsulfone-alkylamino ester, -bromo-acryloyl, A- chloropropionyl, -chloroacetyl, -phenylsulfonylpropionyl, halogeno-pyridazonealkyl, 2-chlorobenzothiazole-sulfonyl, alkyl-sulfonyl-pyrimidine, ammonium triazine or acryloyl groups or a radical which is converted to one of these groups under alkaline conditions.

Suitable compounds having an alkaline action are, advantageously, inorganic compounds such as sodium carbonate, sodium bicarbonate, trisodium phosphate, sodium hydroxide, sodium silicates, the corresponding potassium compounds, or mixtures of two or more of these compounds. Sodium hydroxide solution, sodium carbonate, trisodium phosphate or water glass are preferred.

Suitable alkali donors, i.e. compounds yielding an alkaline agent under fixation conditions, are, especially for printing pastes which are subsequently fixed by steaming, alkali metal salts of trihalogen-monocarboxylic acids, preferably sodium trichloroacetate. In the case of high temperature fixation processes, sodium formate or sodium acetate are preferably used.

The process of the invention is especially advantageous for dyeing fabrics containing a mixture of polyester fibres and cellulose fibres. The disperse dyestuff necessary for dyeing the polyester portion may be applied and fixed simultaneously with the coupling component. Thus in the case of large webs it is possible to predye the polyester fibre portion and to fix the cqupling component onto the cellulose fibre portion. A web which has been predyed in this manner may then be divided into different development parcels, so that varied colour shades may be obtained.

Depending on the diazo component used for the dyestuff development, shades in the range of from orange to bordeaux may be obtained on the cellulose fibre portion.

Advantageously, the combination dyeing is carried out as follows: The disperse dyestuff is dispersed in water having a temperature of from 40 to 60"C in the usual manner. The coupling component is dissolved in hot water and the solution combined with the dispersion of the disperse dyestuff to give the padding liquor having a temperature of from 40 to 600 C. A soda/borax mixture or a compound which splits off an alkaline agent at an elevated temperature, such as sodium formate, sodium trichloroacetate or sodium acetate, is then added to this padding liquor. The mixed polyester/cellulose fibre fabric is padded, dried and subjected to dry heat of from 180 to 2200 C for a period of from 30 to 60 seconds for fixation.For developing the azo dyeing, the fabric is subsequently passed through a solution of a diazonium compound, whereby coupling to form the dyestuff occurs.

Alternatively, for development sodium nitrite and a non-diazotized aromatic amine, for example in disperse form, may be added to the padding liquor or printing paste, and the dyestuff may be formed after fixation of the coupling component by treating the material with an acidic agent, for example by repadding with an acid or acidic salt, or by an acidic steaming process.

The following Examples illustrate the invention, the percentages being by weight unless otherwise stated.

Example 1.

22 g of the compound of the formula

were dissolved in warm water, and the resulting acidic solution was adjusted to a pH 7 by means of sodium carbonate. 12 ml of 32.5% sodium hydroxide solution (380 Be) were then added, and the solution was made up to a total volume of 1 litre with cold, soft water. A cotton fabric (plain weave) was padded with the above liquor with a liquor uptake of 90%, so that the naphthol compound was applied to the goods in an amount of 20 g per kg of fabric. The padded fabric was then allowed to dwell for a period of from 14 to 16 hours in a state where it was batched up and prevented from draining.

Subsequently the fabric was passed through a solution of 35 g/l of the diazonium compound of C.I. No 37000 (Azoic Diazo Comp. 44) using a roller vat. A full scarlet dyeing was obtained. Alternatively development on a Jig is possible.

Example 2.

A material padded according to Example 1, but with a padding liquor containing 16 g/l of soda (anhydrous) instead of the indicated amount of sodium hydroxide solution, was dried after the padding for 2 minutes at 140"C.

Subsequently, the material was passed through a solution of 43 g/l of diazotized C.I.

No 37 090 (Azoic Diazo Comp. 32) and 13 ml/l of 60% acetic acid using a roller vat.

A scarlet dyeing having great tinctorial strength was obtained.

Under the same conditions, and using 60 g/l of C.I. No. 37 245 (Azoic Diazo Comp. 109) and the same amount of acetic acid, a deep, neutral black dyeing was obtained.

Examples 3 to 7.

In the following Table of Examples the Azoic Diazo Components were used in the form of the commercial, stabilized diazonium salts.

When operating according to the method described in Example 1 or Example 2, dyeings having good fastness properties were obtained with the indicated amounts of coupling and diazo components:

Example g/l| Coupling Component /1 Diaeo Shade No. Coupling Component . . . ~~ /1 Domiponent 3 18 3FCH3 45 Azoic Yellow H0 Diazo Comma 44 C. I. AND so,,c,.cH,.oso3H 37000 S02.OH2.CH2.0S03H 37000 HO H-CO.HH i 4 20 $OI;THOONHO2.OH2. OH2. Cl 32 Azoic Bordeaux fW S 2- CR2 . CAS12 . C1 Diazo HOZS S C. I.ND. 37125 5 16 SO2. CAII2 . CH2C1 S02.OH2.OH2Ol 27 Azoic Red HO KH. cho NH.CO Diazo Comp. 37 C 11035 .SO II 37035 ~~~~~~ ~~~ .~~~~~~~,~~,~~,~,,~~,~,,~,,,~~,,,~ ~~~ Azoic orange 6 25 HO , Azoic orange X Y Y ~ n p D aX p ,o 2 H0.5S NIA, CO. CH=}S-CHCH C}lD, C. 1. 37035

Example g/l Coupling Component g/l Diazo Shade No. component

7 15 J;c; CE3 HO 36 H0 < CE3 36 Az6ic Diazo yellow Comp. 14 L ! C.I.No. 37000 SO2NH Ooh2. Ooh2. 3 Example 8 22 g of the compound of the formula

were dissolved in warm water, and the acidic solution was adjusted to a pH of approximately 7 by means of soda; 12 ml of 32.5% sodium hydroxide solution were added, and then cold water was added until a total volume of I litre was obtained.

A cotton fabric (plain weave) was padded with this solution with a liquor uptake of 90%, so that 20 g/kg of the above compound were on the fabric. The padded material was allowed to dwell for 14 hours at room temperature in a state where it was batched up and prevented from draining.

The development was carried out in a winch-vat at a goods-to-liquor ratio of 1:25 with a cold liquor containing 1.6 g/l of the diazonium compound of Azoic Diazo Component 44 (C.I. No. 37 000) and within 20 minutes. Subsequently the material was rinsed, soaped as usual and dried.

A full scarlet dyeing was obtained.

Example 9.

A material, padded and dried according to the method of Example 2, was developed in a winch-vat at a gdods-to-liquor ratio of 1:18. The cold, aqueous developing bath contained 2.5 g/l of the stabilized commercial diazonium compound of Azoic Diazo Component 32 (C.I. no. 37 090) and 1 ml/l of 60% acetic acid. The dyestuff was developed within 20 minutes, and after rinsing, soaping and drying, a scarlet dyeing of great tinctorial strength was obtained.

Examples 10 to 14.

When operating according to Example 8 or Example 9, using the indicated amounts of the coupling and diazo components given in the Table, fast dyeings were obtained. In these Examples the commercial stabilized diazonium salts of the Azoic Diazo Components were used. The numbers in brackets are the amounts for the development according to Example 9 (goods-to-liquor ratio 1:18).

Example g/l Coupling Component g/l Diazo Shade No. Component

10 18 | 1l CH3 2 Azoic Diazo yellow 1 (3) Comp. 44 HO | C.I. ANO.

9 37000 S02 CH2.CH2.OS03E 11 20 2 Azoic Diazo bordeaux (2) Coinp. 5 HO lH-CONHt C 0.1. No.

r 'SH I 37125 w S02CH2CH2C1 HO38 H SO3H 3 3 12 16 SO2CH2CK2C1 HO NEI.CO 1.5 Azoic Diazo red 9 (2) Comp. 37 HO38 3E C . 0.1. No.

37035 13 25 HO 2.5 Azoic Diazo orange (3) Cp,-e (g) Comp. 2 00. CH=CE-CCHE%H C.I. No.

HO38 . CO. CH=CH~CH - CH~CH3 37005 Example g/l Coupling component g/l Diazo Shade No. Component

14 15 CH3 1.5 Azoic Diazo yellow / (2) Comp. 44 Hd | C.I. No.

1) 37000 S02-NH-CH2. CE2.OsO3H Examples 15 to 21.

Examples 1 to 7 were repeated with the variation that the padded material was developed on a jig, at a goods-to-liquor ratio of 1:5, using amounts of the Azoic Diazo Components calculated by dividing the amounts used in Examples 1 to 13 by 5 and approximating to the next integer. For example, Example 17 was based on Example 3 (which used 45 g/l of Azoic Diazo Component 44 -- C.I. No. 37 000) and used 9 g/l (45 + 5) of the Azoic Diazo Component.

Example 22.

40 g of the red disperse dyestuff C.I. No. 60756 was dispersed in water at 600 C, and 20 g of the compound of the formula

were dissolved in hot water (800 C).

The dispersion of the disperse dyestuff and the solution of the coupling component were combined, and water having a temperature of 60"C was added to form 1 litre of padding liquor. 20 g of sodium acetate and 40 g of polyglycol having an average molecular weight of 400 were added to the padding liquor.

A mercerized, bleached fabric made of 70% of polyester fibres and 30% of cotton was padded with a liquor uptake of 70% and then dried at 110 C.

Subsequently, the fabric was subjected to a thermosol treatment for 60 seconds at 210"C. The fabric was then cooled in an air flow, and padded on a foulard with a solution of the stabilized diazonium compound of 46 g/l of Azoic Diazo Component 37 (C.I. No. 37035) at a liquor uptake of 80%. After an air passage of 30 seconds, the material was rinsed and soaped at boiling temperature in usual manner.

Example 23.

When, in Example 22, instead of the Azoic Diazo Component 37, the same amount of Azoic Diazo Component 2 (C.I. No. 37 005) was used for the development, an orange dyeing was obtained on the cellulose fibre portion, while the polyester portion was dyed in a red shade.

WHAT WE CLAIM IS: 1. A process for pad-dyeing or printing a textile material made of or containing cellulosic fibres, which comprises padding or printing the material with a padding liquor or printing paste which comprises a water-soluble azo coupling component containing a group which is fibre-reactive under alkaline conditions, but not containing the grouping

-N=C-halogen fixing the coupling component on the fibres, and subsequently completing formation of an azo dyestuff on the fibres, the padding liquor or printing paste also comprising a compound that renders the medium alkaline at least during the fixation process.

t. A process as claimed in claim 1, wherein the compound that renders the medium alkaline is an alkaline agent.

3. A process as claimed in claim 2, wherein the alkaline agent is sodium carbonate, sodium bicarbonate, trisodium phosphate, sodium hydroxide, or a sodium silicate, or a corresponding potassium compound, or a mixture of two or more thereof.

4. A process as claimed in claim 3, wherein the alkaline agent is sodium hydroxide, sodium carbonate, trisodium phosphate or water glass.

5. A process as claimed in any one of claims 2 to 4, wherein fixation of the coupling component is carried out by allowing the material to dwell at room temperature or by drying the material.

6. A process as claimed in claim 1, wherein the compound that renders the medium alkaline is a compound that yields an alkaline agent under fixation conditions.

7. A process as claimed in claim 6, wherein a compound is used that yields an alkaline agent under steaming conditions, and the coupling component is fixed by subjecting the material to a steam treatment.

8. A process as claimed in claim 7, wherein an alkali metal salt of a trihalogen monocarboxylic acid is used as the compound yielding an alkaline agent.

9. A process as claimed in claim 8, wherein the alkali metal salt is sodium trichloroacetate.

10. A process as claimed in claim 6, wherein a compound is used that yields an alkaline agent under high temperature fixation conditions.

11. A process as claimed in claim 10, wherein sodium formate or sodium acetate is used as the compound yielding an alkaline agent.

12. A process as claimed in claim 10 or claim 11, wherein the coupling component is fixed by subjecting the material to a dry-heat treatment.

13. A process as claimed in any one of claims 1 to 12, wherein the dyestuff is completed by applying a diazonium compound to the material.

14. A process as claimed in any one of claims 1 to 12, wherein the padding liquor or printing paste containing the coupling component also contains a nondiazotized aromatic amine and sodium nitrite, and the dyestuff is completed by treating the material with an acidic agent.

15. A process as claimed in claim 14, wherein the dyestuff is completed by padding the material with an acid or an acidic salt, or by an acidic steaming process.

16. A process as claimed in any one of claims 1 to 15, wherein the coupling component has a water-solubilizing fibre-reactive group and one or more sulfo and/or carboxy groups.

17. A process as claimed in any one of claims 1 to 16, wherein a textile material made of a polyester fibre/cellulosic fibre mixture is dyed or printed, which comprises applying a disperse dyestuff with the coupling component and fixing the disperse dyestuff on the polyester portion of the material prior to the azo dyestuff development.

18. A process as claimed in claim 17, wherein the disperse dyestuff and the coupling component are fixed simultaneously.

19. A process as claimed in claim 18, wherein fixation is carried out by subjecting the material to dry heat at a temperature of from 180 to 2200C for a period of from 30 to 60 seconds.

20. A process as claimed in claim 1, conducted substantially as described he rein.

**WARNING** end of DESC field may overlap start of CLMS **.

Claims

**WARNING** start of CLMS field may overlap end of DESC **. WHAT WE CLAIM IS:

1. A process for pad-dyeing or printing a textile material made of or containing cellulosic fibres, which comprises padding or printing the material with a padding liquor or printing paste which comprises a water-soluble azo coupling component containing a group which is fibre-reactive under alkaline conditions, but not containing the grouping

21. A process as claimed in claim 1, conducted substantially as described in

any one of Examples 1 to 42.

22. A textile material made of or containing cellulosic fibres, whenever dyed or printed by a process as claimed in any one of claims 1 to 21.