DE2237572A1 - PROCESS FOR COLORING AND PRINTING FIBER MATERIAL CONTAINING CELLULOSE WITH KUEPEN AND / OR SULFUR DYES - Google Patents

Description

Badische Anilin- & Soda-Fabrik AG 2237572

Our mark O.Z. 29 518 Noe / LG 67OO Ludwigshafen, July 28, 1972

Process for dyeing and printing cellulose containing Fiber material with vat and / or sulfur dyes

The invention relates to a method for dyeing and printing of cellulose-containing fiber materials with vat and / or sulfur dyes using reducing agents, obtained by reacting aliphatic and / or cycloaliphatic ketones with sodium dithionite.

For dyeing and printing cellulose or fiber material of cellulose-containing fiber material with vat and / or sulfur dyes are generally sodium dithionite and / or oC-hydroxyalkylsulfinic acids unbranched in the oL position or their alkali salts or their nitrogenous ones

Derivatives used as reducing agents. The selection of the The reducing agent is primarily based on the requirements that are met by the various dyeing or printing processes Reducing agents are provided. Above all, the air sensitivity of the reducing agent plays a role in the alkaline one Solution and its reactivity; towards the dyes used those used in the dyeing or fixing machines Temperatures play a major role.

Sodium dithionite has high reducing power even at low temperature, but it is very strong in the alkaline solution sensitive to oxygen. When impregnating sheets padded with dye, oxidation occurs very quickly, with a considerable amount even before the dye is vetted Part of the reducing agent is consumed. Therefore, only one is obtained without a large excess of the reducing agent poor color yield.

06-Hydroxyalkylsulfinic acids or their alkali metal salts or their nitrogen-containing derivatives are much more stable towards oxygen. But these funds are only at temperatures

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100 ° C and above sufficiently effective as a reducing agent against vat dyes. The reactivity can be varied within certain limits by the allyl radical. By incorporating longer alkyl residues, the reactivity is increased somewhat, but the solubility in water and the durability in substance are reduced. All bekannten'd-Hydroxyalkylsulfinsäuren, which are derived from aldehydes, however, are not reactive enough to allow a sufficient vatting at temperatures below 100 ⁰ C.

Dye baths are used to stabilize the sodium dithionite Additions of ketones or aldehydes are recommended, but in practice no satisfactory results are achieved.

DT-AS 1 920 428 discloses mixtures of sodium dithionite and to use bisulfite compounds of aldehydes or ketones as reducing agents. The ones for dyeing and printing The solutions used are similar in their reducing effect to the aforementioned oC-hydroxyalkylsulfinic acids.

Furthermore, in DT-PS 162 875 and 165 808 reducing agents described that of hydrosulfite and acetone or methyl ethyl ketone arise in strongly alkaline solutions. The reaction products can be isolated in solid form and should also be storable according to the information in the patent specifications. A technical application is up for these products not known today.

According to this, no reducing agents are known for vat dyeing which have good air resistance when used and which also at Tempe:
Success can be used.

have and which also at temperatures below 100 ⁰ C with

The object of the present invention was to find a process which makes it possible to produce ^{dyeings and prints with vat dyes at temperatures between 20 and 120 ° C. using a reducing agent that is sufficiently air-resistant and reactive.}

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It has now been found that cellulose-containing fiber material can dye or print with vat and / or sulfur dyes in the presence of reducing agents and alkali, if reaction products are used as the reducing agent used, the reaction of aliphatic and / or cycloaliphatic ketones with 4 to 8 carbon atoms and sodium dithionite can be obtained in the presence of basic nitrogen-containing compounds.

According to the process of the invention, strong and strong colors are obtained level dyeings or prints, with a high yield of dye and - because of the higher stability of the Reducing agent versus oxygen - a much smaller excess of the reducing agent must be used than with the use of sodium dithionite.

Reaction products of aliphatic or cycloaliphatic are used as reducing agents for the process according to the invention Ketones with 4 to 8, preferably 5 to 8 carbon atoms or of Mixtures of these ketones with sodium dithionite are possible.

The reaction products can be obtained if a Mixture of ketone, sodium dithionite and the basic nitrogen-containing compound allowed to stand in water. The relationship from ketone to dithionite appropriately 2 to 1 mole. An excess of ketone does not harm, but also brings no advantages. On the other hand, if you apply the ketone in an amount of less than 2 moles per mole of dithionite, a A mixture of reducing agents that still contains dithionite. Such mixtures can be advantageous for some dyeing processes.

As aliphatic and / or cycloaliphatic ketones with 4- to 8 carbon atoms come, for example, methyl ethyl ketone, diethyl ketone, 4-hydroxy-4-methyl-pentanone-2 (diacetone alcohol), cyclohexanone, Cyclopentanone, methyl cyclohexanone into consideration. Particularly preferred mainly the reaction products with cyclohexanone or diethyl ketone are used for economic reasons.

Put aqueous mixtures of ketones and sodium dithionite

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just turn around very slowly. The reaction often only begins after an induction period of several hours. Be against it Reaction products that are excellent for dyeing and / or printing with vat dyes are obtained if you carry out the reaction in the presence of basic nitrogen containing Performs compounds as catalysts.

The basic compounds used for this purpose are e.g. morpholine, piperidine, piperazine, ethylenediamine, propylenediamine 1,3 * ethanolamine, triethanolamine, diethanolate, Propanolamine, tripropanolamine, ethylenedlamine tetraacetic acid, Nitrilotriacetic acid, ammonia and / or ammonium salts of weak carboxylic acids into consideration.

The acceleration of the reaction of the ketone with the dithionite depends not only on the amount of the basic compound added also depends on the connection itself. The reaction takes place in the presence of morpholine, piperidine, piperazine, ethylenediamine, Propylenediamine-1,3, ethanolamine and ammonia particularly quickly, which is why these are preferred as additives.

The amount of the basic compounds added is generally 4 to 50, preferably 10 to 20 percent by weight, based on the ketone.

In the presence of the compounds with basic nitrogen, the reaction takes place immediately and is generally at room temperature after 30 to 120 minutes, in most cases already after Finished in 30 to 60 minutes. At 40 ° C., the reaction is complete after 10 to 30 minutes.

The concentration of the reactants should be as high as possible, but not too high after the implementation a clear solution is obtained. Small amounts of soda or potassium carbonate can also be added to the reaction mixture so that the solution does not become acidic due to decomposition products of the dithionite.

The reaction of ketone with dithionite in the presence of

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solutions of the reaction products obtained from basic "compounds are not very sensitive to oxygen and even without it Can be kept for a few weeks if air is excluded. These. Solutions are expediently prepared in such concentrations that these can be used as stock batches, so that by mixing together with the other agents, such as alkali, leveling aids, Ready-to-use thickeners, optionally vat dye or sulfur dye and other auxiliaries Dye baths or printing pastes can be obtained.

According to the invention to use reaction products are suitable as reducing agents for all dyeing and printing processes with vat dyes and may be in the machine dyeing at Tempeisburen zwtehen 20 and 120 ⁰ C in the cold pad-batch, in dyeing on the jigger and on the winch and for the pad-steam process and used for two-phase printing.

The method according to the invention has the advantage that, despite the relatively good stability of the reducing agent towards oxygen at room temperature to 115 ° C complete vatting of the dye takes place and that at a high application concentration, e.g. in the block process, practically the same reducing effect as can be achieved with the unstable dithionite »

Because of the much higher stability of the invention Reduction oils to be used against oxygen are found when working on the jigger, on the reel skid and in the block process with significantly smaller amounts of reducing agents than were previously used. For the same Reason can be dyed on the above-mentioned machines at higher temperatures than before, which results in very level dyeings can be obtained.

In the pad steam process, because of its stability against oxygen, there is a saving of more than 50 % in reducing agent compared to the dithionite previously used for this process.

The same applies to the cold pad process, in which a

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Fabric padded with vat or sulfur dye is soaked in the reducing agent liquor, the fabric is wound up and is stored for a few hours at room temperature, the fixation of the dye takes place. Here, too, becomes clear less reducing agent is required than on the dithionite previously used.

In the case of two-phase pressure, the method according to the invention also gives poor to moderate steaming conditions (Fixing conditions) still high color yields. The color yield is at least as high, in many cases even significantly better than when using the reducing agents previously used in these processes, such as the salts of OL-Hydroxyäthansulfinsäure.

The process of the invention can also be used for single-bath pad dyeings possible with vat dyes. A mixture of dye, alkali, reducing agent and a retarder is used padded onto the fabric and the color developed and fixed either by steaming or by the cold bake process.

The examples are intended to explain the process of the invention in more detail. The parts and percentages given below relate to weight.

example 1

Viscose yarn on packages is made on a commercially available yarn dyeing machine with a liquor ratio of 1:15 in treated in a bath of the following composition:

1.5 parts of the dye CI Vat-Red 10, C.I. No. 67000

(50 percent merchandise)
13 parts of sodium hydroxide solution (38 ⁰ Be),
40 parts of sodium sulfate, anhydrous,

50 parts of the reducing agent solution described below and 895.5 parts of water

1,000 parts

The temperature increases from 24 to 45 ° C. within 15 minutes

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increased and stained at this temperature for 50 minutes. Then it is finished as usual. You get a very Uniformly dyed yarn, which in terms of color yield and fastness properties is compared to conventional dyeings with sodium dithionite as a reducing agent not inferior.

The reducing agent solution is prepared as follows:

55 parts of cyclohexanone,
9 parts of morpholine and
50 parts of sodium dithionite

are dissolved with water to 1000 parts and at room temperature left to stand until vat paper is no longer immediately dyed blue,

- Example 2

3 parts of the dye CI Vat Blue 43 (CI. No. 53.630) are with
27 parts of an aqueous sodium hydroxide solution (38 ⁰ Be) - made into a paste and after 15 minutes into a 7O ⁰ C warm solution

120 parts of the reducing agent solution described below and 850 parts of water given »·

1000 parts.

After 5 minutes, the dyebath is filled in a commercially available yarn dyeing machine and dyed on cross-wound bobbins with a liquor ratio of 1 i 10 at 70 ⁰ C cotton yarn. After a dyeing time of 60 minutes, it is finished as usual. The typical blue coloration of this dye with good fastness properties is obtained.

The reducing agent solution is prepared as follows;

50 parts of diethyl ketone,

9 parts of concentrated ammonia water and 50 parts of sodium dithionite are dissolved in water to 1000 parts and at 24 ⁰ C allowed to stand until the immersion of Küpenpapier occurs no immediate blue coloration.

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Example 3

Rohbaumwollgarn is on a commercially available high temperature dyeing machine at a liquor ratio of 1: 15 treated at 20 ⁰ C with a bath of the following composition:

0.5 part of CI Vat Black 25 dye, C.I. No. 69

(40 percent commercial product) 27 parts of aqueous sodium hydroxide solution (38 ⁰ Be)

3 parts of the sodium salt of ethylenediaminotetracetic acid, 60 parts of the reducing agent solution described below and 909.5 parts of water

1000 parts

The liquor is placed in the dyeing machine and heated to 115 ° C. within 30 minutes. Dyeing is 30 minutes at 115 ° C, cooled to 70 ⁰ C and the dyeing as usual done. A uniformly dyed textile material with very good dyeing and very good fastness properties is obtained.

The reducing agent solution is prepared as follows:

55 parts of cyclohexanone,

9 parts of monoethanolamine,
100 parts sodium dithionite,

3 parts of sodium carbonate and
833 parts of water
are dissolved and stirred at 25 ° C for 60 minutes.

Example 4

Cotton yarn is on packages on a usual Dyeing apparatus dyed with a liquor of the following composition at a liquor ratio of 1 s 10:

0.5 part of the dye CI Vat Blue 7, C.I. No. 70 305

(5 ^ percent commercial goods) 13 parts sodium hydroxide solution (38 ⁰ Be)
20 parts of the reducing agent solution described below

1000 parts fleet.

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The dye liquor is added to the dyeing machine and pumped with alternating direction through the material and DABD heated within 4θ minutes at 80 ° C .. After 10 minutes at 80 ° C is cooled within 30 minutes to 40 to 50 ⁰ C and the cheese finished as usual. A uniformly dyed textile material with more very good dyeing is obtained.

The reducing agent solution is prepared as follows 110 parts of cyclohexanone ^

10 parts of monoethanolamine and
100 parts of sodium dithionite

are dissolved with water to 1000 parts and left to stand at 24 ° C, until after about 30 to 40 minutes vat paper not more immediately turns blue. Then the reducing agent solution can be used »

Example 5

Precleaned and bleached cotton twill is at 25 ° C in a conventional two-roll pad with 25 parts of the dye CIo Vat Blue 4, C.I. No. 69 800 (43 percent merchandise) and 975 parts of water

1000 parts

padded «The liquor pick-up is 85 % _s based on the unpadded fabric _{or the like}

This is followed by intermediate drying and the dyeing on a jigger with a liquor ratio of 1; 5 developed with the following bath at 70 ^° C

40 parts of sodium hydroxide solution (38 ⁰ Be),
100 parts of the reducing agent solution described below,

20 parts of anhydrous sodium sulfate and 840 parts of water

1000 parts fleet.

After a dyeing time of 45 minutes, the fabric will be as usual oxidized and soaped <■ The result is a level and deep blue

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dyeing with good fastness properties.

The reducing agent solution is prepared as follows:

90 parts of cyclohexanone,

10 parts of morpholine,
100 parts of sodium dithionite and
800 parts of water

1000 parts are left to stand for 60 minutes at 24 ° C and then used for the reduction bath »

Example 6

Precleaned and bleached cotton poplin is placed in a two-roll foulard at 25 ° C
50 parts of the dye CI Vat Green 1, CI No. 59 825 (22-

(percent merchandise) in 950 parts of water

1000 parts of the fleet padded.

The impregnated fabric is then dried between then padded in a continuous process at 120 ⁰ C and at 25 C in a conventional two-roll with a chemical liquor, which was prepared as follows;

20 parts of diethyl ketone,
7 parts of 1,3-propylenediamine and

20 parts of sodium dithionite
are in water too

400 parts of solution dissolved. After 60 minutes this solution becomes with

40 parts of sodium hydroxide solution (38 ⁰ Be) and

50 parts of anhydrous sodium sulphate and made up to 1000 parts with water. The liquor uptake of the fabric is 80 %. Then it is steamed with saturated steam in a continuously operating steamer for 60 seconds at 100 to 103 ° C. and the fabric is finished as usual. The result is a perfect coloring with the same ends and sides «

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In contrast to a corresponding · log fleet, which only Contains sodium dithionite, the same color will also be obtained if you look at the development 24 hours after the preparation Chemical fleet carries out.

Example γ

A mixed fabric of 65 % polyester fibers and 35 % cellulose fibers is made with a dye dispersion

20 parts of Disperse Violet 8, CJ. No «62 030 and 10 parts C ₀ I ₀ Vat Violet 9, CI No. 6θ 005.

1000 parts of liquor impregnated. The liquor pickup is 100 ^ o After a drying process at 12O ⁰ C the fabric to a heat treatment of JO seconds at 20O ⁰ C is subjected. (Thermosoling). The fabric then runs through a chemical bath, which was set up as follows

22 parts of cyclohexanone,
4 parts of morpholine and
40 parts of sodium dithionite. .
are in water too

300 parts of solution dissolved. After 60 minutes, this solution is mixed with 54 parts of sodium hydroxide solution (38 ⁰ Be) and 50 parts of anhydrous sodium sulfate and made up to 1000 parts. The liquor pick-up is set to 100 % by squeezing off. The fabric web is then rolled up wide and evenly on an axle and. sealed airtight by wrapping with a plastic film. The roll is allowed to rotate for 4 hours and the dyed fabric is finished as usual by oxidizing and soaping = a uniformly purple-colored mixed fabric is obtained, its. Polyester portion of disperse dye and the cellulose portion of which contains the vat dye.

Example 8

A cellular wool structure fabric is printed with the following printing paste %

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150 parts of the vat dye C.I. Vat Blue 14, C.I. No. 69 (17 percent merchandise)

350 parts of an aqueous solution of locust bean gum ether (3.5 percent),

350 parts of an aqueous starch ether solution (jj, 5 percent) and 150 parts of water

1000 parts.

After printing and drying, the fabric is prepared with a chemical liquor that has been prepared as follows:

44 parts of cyclohexanone,
7 parts of morpholine and

40 parts of sodium dithionite are dissolved in water to make 400 parts of solution. After 60 minutes this solution becomes with

120 parts of sodium hydroxide solution (38 ⁰ Be) are added and the mixture is diluted to 1000 parts of liquor with water.

The still moist fabric is then exposed to 15 seconds of air-free saturated steam atmosphere at 100 to 1OJ ⁰ C. To complete, the fabric is treated for 2 minutes in running water at 2O ⁰ C, 2 minutes in a 95 ° C aqueous solution containing per liter of 2 g of sodium perborate, oxidized / soaped, rinsed and dried "to give a blue print on white ground, which is more deeply colored than a similarly treated print which was developed with a chemical liquor containing 40 parts of sodium dithionite, 50 parts of acetaldehyde bisulfite compound and 182 parts of sodium hydroxide solution (38 ⁰ Be) in 1000 parts.

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Claims (4)

- 13 - O.Z. 29 claims 1. A process for dyeing and printing cellulose-containing fiber material with vat and / or sulfur dyes in the presence of reducing agents and alkali, characterized in that the reducing agent used is reaction products obtained by reaction of aliphatic and / or cycloaliphatic ketones with - 4 to 8 carbon atoms and sodium dithionite in the presence of basic nitrogen-containing compounds are obtained. 2 ο Process according to Claim 1, characterized in that the reducing agent used is reaction products of 2 moles of ketone with 1 mole of sodium dithionite. 3 »Process according to claims 1 or 2, characterized in that the reaction product of cyclohexanone and sodium dithionite is used as the reducing agent. 4. The method according to claims 1 to. j5, characterized in that a mixture of sodium dithionite and the reaction product of ketone and sodium dithionite is used as the reducing agent. Badische Anilin- & Soda-Fabrik AG 409827/0859