EP0021432B1 - Two-phase printing process for the manufacture of conversion style and discharge resist articles - Google Patents

Description

The invention relates to two-phase printing processes for the production of conversion articles with reactive and vat dyes and of etching reserve articles with reactive and optionally vat dyes on cellulosic fiber materials, the reactive dye or a mixture of reactive and vat dye being printed or padded with in a weakly acidic medium a neutral paste containing a stable reducing agent based on a sulfinic acid and optionally a vat dye is overprinted, after an intermediate drying the pressure is brought into contact with an aqueous, strongly alkaline liquor and dampened.

In textile printing practice - in contrast to the autotype screening technique prevailing in paper printing - the production of high-color articles is extremely cost-intensive because a separate roller or stencil is required for each individual color nuance, apart from overprinting points. It is therefore of great advantage if the number of color tones contained in a print pattern can be increased in another way, for example by conversion printing.

For this purpose, the fiber materials to be dyed are printed with mixtures of reactive and vat dyes set to be slightly acidic, and these prints after intermediate drying or advantageously in the same operation, overprinted wet in wet with printing inks, which are stable reducing agents in the neutral medium even under customary drying conditions, e.g. B. sodium formaldehyde sulfoxylate, in amounts of 100 to 200 g per kg of printing paste. After drying, the printed fabric is up to 200 g through a strongly alkaline padding liquor with approximately 100 32.5 ⁰ / cent sodium hydroxide solution per liter of liquor out or equivalent amounts of sodium or potassium carbonate or water glass, and then about 5 to 30 seconds, preferably 10 to 20 seconds, treated with saturated steam or superheated steam.

The dyes can also be used in other ways, e.g. B. by padding or splashing. Likewise, the alkali by other methods, e.g. B. by splashing or spraying, are brought into contact with the coloring.

In this process, only the reactive dye is fixed at the places that were printed with the dye mixture and not overprinted with the reducing agent, whereas where the reducing agent was found, the reactive dye is etched and the vat dye is developed.

These processes, which are known per se, are of particular importance because, on the one hand, a drying-stable reducing agent must be used, which on the other hand should react so quickly that the vat dyes in the short steaming time, which must not be exceeded without damage due to the reactive dyes - the high one The amount of alkali in the pad bath would cause the dyes to bind to the fibers if the steaming time was longer - fixed.

Suitable reducing agents are primarily alkali metal or alkaline earth metal salts of sulfinic acids which have arisen from a reaction with aldehydes or amines and have thereby been stabilized, in particular sodium formaldehyde sulfoxylate. Formamidine sulfinic acid (thiourea dioxide) is also particularly advantageous.

In this context, it is noteworthy that the breakdown of stable reducing agents, such as. B. the sodium formaldehyde sulfoxylate, can be forced through high amounts of alkali. A further increase in the rate of decay is achieved with the aid of catalysts as described in DE-PS 1220825 and in Melliand Textile Reports, 1967, 1341-1345, as an additive to printing pastes with vat dyes. These are cyano- or diacetyldioxime complexes of the heavy metals Fe, Cu, Cr, Mn, Co or Ni, whereby the co-complex of the diacetyldioxime has proven itself best. 0.1 to 10 g of these metal complexes are preferably added to the alkaline pad baths per liter of liquor.

If formamidine sulfinic acid serves as a reducing agent, it is not necessary to add these metal complexes.

Mixtures of alginates and starch derivatives are advantageously used as the thickener; locust bean gum ether or cellulose ether may also be used.

Because of the weakly acidic reaction of formamidine sulfinic acid (pH approx. 3), it is advisable to use locust bean gum derivatives instead of the alginates usually used in combination with starch ethers when adding the printing inks, or to cause the pH to shift towards the neutral point by adding alkali.

According to the invention, the technique described can now be transferred to the etched article by breaking down the original dye application into two steps, i. That is, the cellulosic fiber structure is printed with a printing paste containing the reactive dyes or the liquor is padded (or splashed), then dried and then, as described for the conversion article, printed with a printing paste containing a stable reducing agent and, if appropriate, one or more Vat dye (s) were incorporated. The process then continues as shown above. Background and possibly colored etching colors are fixed after the alkali passage during the short steaming operation.

Since the described procedure is an etching reserve, the reactive dyeing is no longer required, which contributes to making the process cheaper.

While the previously used etching printing pastes such as the classic sulfoxylate process in sufficient quantities hygroscopic substances, such as. As glycerin, had to be added, can be dispensed with in the process according to the invention because of the sufficient moisture absorption in the course of the alkaline block passage before steaming on such products. What is also noteworthy in the method according to the invention is the fact that the etching prints do not need to be stored after steaming and, if appropriate, need to be cooled, which cannot be avoided in the traditional single-stage etching printing method for safety reasons, but can be further processed continuously.

Last but not least, the durability of the printing inks and the prints before steaming is significantly better with a number of vat dyes than with the old etching printing processes with printing inks containing alkali and reducing agents.

• 1. Die Ätzreservetechnik,
• 2. die Aktivierung eines trocknungsstabilen Reduktionsmittels und
• 3. diedadurchermöglichteAnwendungderZweiphasentechnikmitKurzzeitdämpfung.

The new method of producing the etched article is thus shaped by three factors:

• 1. The etching reserve technology,
• 2. the activation of a drying-stable reducing agent and
• 3. This enables the use of two-phase technology with short-term damping.

DE-OS 1 929 231 and DE-OS 2 003 363 already describe processes which aim to apply reactive and vat dyes in padding liquors or printing inks together to textile substrates made of cellulose fibers and the action by different handling of the process steps to design the fixing aid in such a way that the two representatives of different dyestuff classes, in the course of two-phase processes, are undamaged and produce colorful pattern effects. The interaction of reducing and oxidizing agents, the latter for protecting the reactive dyes, which is not easy to control even with the aid of different amounts of use, is of major importance. The difficulties associated with this have not given the methods described any access to practical implementation.

In contrast to this, in the process according to the invention, in which reactive and vat dyes are optionally applied together to the textile material, the aim is not to fix the reactive dye at the points where the vat dye is intended to fix. It is therefore not necessary to protect the reactive dye by adding more oxidizing agent; the relatively small addition serves only as a precaution against the coating of printing rollers due to the etching effect of the reducing agent. The new process is therefore not in competition with the design methods according to the aforementioned DE-OS, but rather represents a significant improvement in the process technology previously used for the production of conversion and etching reserve articles.

The reactive dyes which can be used in the process according to the invention both in the case of the conversion article and the etching article can be obtained from various organic base bodies, such as, for. B. azo, anthraquinone or phthalocyanine compounds, and should have at least one β-hydroxyethylsulfonic sulfuric ester group, vinylsulfonyl group, monochlorotriazine group, dichlorotriazine group, 2,2,3,3-tetrafluorocyclobutane-1-acryloylamino group, vinylsulfonylonylamino group, vinylsulfonylonylamino group, Phenylsulfonylpropionylamino group or a 2,3-dichloroquinoxaline, monofluorotriazine, 2,4-dichloroquinazoline, 1,4-dichlorophthalazine, alkylsulfonylpyrimidine, tri- or tetrachloropyrimidine, 2,4-difluoro-5-chloropyrimidine or a 1- Aryl-4,5-dichloropyridazone residue. Dyes are preferred which contain a vinyl sulfone group or a corresponding precursor.

Suitable vat dyes include representatives with anthraquinone, indigoider and naphthoquinoid structure as well as naphthalene tetracarboxylic acid derivatives.

All substrates of cellulosic origin are suitable for the process according to the invention, that is to say both native products such as cotton or linen and regenerated cellulose such as cellulose or viscose and their highly wet-strength variants.

In the following examples, the percentages relate to the weight. The specified Color Index numbers were taken from its 2nd edition (1956) and the supplementary volume (1963).

example 1

A cotton fabric is printed in a specific design with a printing ink of the following composition:

The printed fabric is overprinted wet in wet in a different design with a printing ink containing 200 g / kg sodium formaldehyde sulfoxylate in the same thickening. The subsequently dried goods subsequently pass through an immersion bath with 100 g / l of 32.5% sodium hydroxide solution and 100 g / l of sodium carbonate and are then steamed in saturated steam for 20 seconds. After the steaming process, the pressure is thoroughly rinsed with cold water, treated at 40-50 ° C with 2 g / l hydrogen peroxide and 5 ml / l acetic acid, rinsed again and finally with 0.5 g / l sodium-oleic acid. N-methyl taurides washed at 90 ° C, rinsed and dried.

A print sample in red and golden yellow color with good fastness properties is obtained.

Example 2

A cellulose knitted fabric is printed as in Example 1 with a printing ink of the same other composition, which contains the following dyes:

The printed goods are processed and finished as in Example 1.

A print sample in blue and orange tone with good fastness properties is obtained.

Example 3

A fabric made of highly wet-strength regenerated cellulose fibers is printed as in Example 1 with a printing ink which contains the following dyes in the same composition as there:

The printed goods are processed and finished as in Example 1.

A violet and green patterned print with good fastness properties is obtained.

Example 4

A cotton fabric is padded on a foulard with a dye liquor with a squeezing effect of 100%, that per liter

The padded and dried fabric is printed with a printing ink of the following composition:

enthält und gleich anschließend 20 Sekunden im Sattdampf gedämpft. Dann wird die Ware gründlich mit kaltem Wasser gespült, bei 40-50°C mit 2 g/I Wasserstoffperxoid und 5 ml/I Essigsäure behandelt, erneut gespült und zuletzt mit 0,5 g/I eines Natrium-Ölsäure-N-methyltaurids bei 90°C gewaschen, gespült und getrocknet.The printed and dried fabric is padded with a liquor absorption of 100% with an alkaline liquor, per liter

contains and then steamed in saturated steam for 20 seconds. Then the goods are rinsed thoroughly with cold water, treated at 40-50 ° C with 2 g / l hydrogen peroid and 5 ml / l acetic acid, rinsed again and finally with 0.5 g / l sodium-oleic acid-N-methyl tauride Washed, rinsed and dried at 90 ° C.

The result is a scarlet-colored print on a brilliant blue background with good fastness properties.

Example 5

im übrigen die gleichen Ingredienzen wie in Beispiel 4 enthält.A cellular wool fabric which had been leached without tension with 4.5% sodium hydroxide solution is, as in Example 4, with a liquor per liter

otherwise contains the same ingredients as in Example 4.

The further treatment is carried out as in Example 4.

You get a deep blue print on a brilliant red background with good fastness properties.

Example 6

• 60 g der handelsüblichen Einstellung des Farbstoffes C.I. 20 505

wie in Beispiel 4 angesetzt worden war.A knitted cotton fabric is splashed with a dye liquor, which is washed with

• 60 g of the commercial setting of the dye CI 20 505

as set out in Example 4.

• 120 g der handelsüblichen Teigform des Farbstoffes C.I, 68 420 enthält,

und nach dem Trocknen mit einer alkalischen Flotte geklotzt (Flottenaufnahme 100%), der pro Liter

The dried goods are printed with a printing ink per kg

• Contains 120 g of the commercial dough form of the dye CI, 68 420,

and after drying padded with an alkaline liquor (liquor absorption 100%), that per liter

After padding, the goods are steamed for 15 seconds in saturated steam and then treated and finished as in Example 4.

The result is a yellow print on a black background with good fastness properties.

Example 7

• 40 g der handelsüblichen Einstellung eines Farbstoffgemisches der Formel
  
  (CuPc=Kupferphthalocyanin, n=1 -3)

zugesetzt worden waren.A cotton fabric is padded as in Example 4 with a dyeing liquor per liter

• 40 g of the commercial setting of a dye mixture of the formula
  
  (CuPc = copper phthalocyanine, n = 1 -3)

had been added.

• 80 g der handelsüblichen Teigeinstellung des Farbstoffes C.I. 73 365 und den gleichen Zusätzen wie in Beispiel 4 zusammensetzt.

The padded and dried fabric is printed with a printing ink that comes out

• 80 g of the commercial dough setting of the dye CI 73 365 and the same additives as in Example 4 are composed.

und dann 20 Sekunden im Sattdampf gedämpft.After drying, the printed goods are passed through an alkaline liquor (squeezing effect 90%), which is per liter

and then steamed in saturated steam for 20 seconds.

The further treatment is carried out as in Example 4.

You get a bluish-red print on turquoise background with good fastness properties.

Example 8

• a) Known method (application of an alkaline, reactive dye-containing liquor): A fabric made of highly wet-strength regenerated cellulose fibers is padded, as in Example 4, with a dyeing liquor, per liter
  • 30 g of the commercial setting of the dye with the formula (in the acid form)
    
    further
  • 100 g urea,
  • 10 g sodium meta-nitrobenzenesulfonate,
  • 3 g of a wetting agent and
  • Contains 12 g sodium carbonate.
• a1) Part of the dried block is printed with a printing ink, which is composed as follows:
  • 120 g of the commercial dough form of the dye of the formula
    
    
    The printed fabric is steamed for 8 minutes in saturated steam and then rinsed, reoxidized and washed as described in Example 4.
  • The result is a color-deep gray print on a brilliant red background with good fastness properties.
• a2) A second part of the padded and dried fabric is printed with the same printing ink as before, which was kept for 3 days, and treated as described above. The gray print on the red background shows less than half the color strength of the first print.
• b) According to the invention: The same fabric as described above is padded with an analog dyeing liquor, but which only contains the dye and the ingredients shown in Example 4 (i.e. instead of urea, wetting agent and sodium carbonate, here sodium dihydrogen phosphate and alginate).
• b1) A part of the padded and dried fabric is printed with an ink with the same dye as described above, but only with the addition of thickening and sodium formaldehyde sulfoxylate, and then further processed and finished as shown in Example 4.
  As before, a color-deep gray print is created on a brilliant red background.
• b2) Repeating the printing process with the same printing ink that was stored for 3 days results in the same loss of printing without any noticeable drop in color strength.

Example 9

• 18 g der handelsüblichen Pulvereinstellung des Reaktivfarbstoffs der Formel
  
• 30 g der handelsüblichen Pulvereinstellung des Reaktivfarbstoffs der C. I. Nr. 17 757 und
• 12 g der handelsüblichen Pulvereinstellung des Reaktivfarbstoffs der Formel
  
  sowie
• 120 g der handelsüblichen Teigeinstellung des Küpenfarbstoffs der Formel
  
  werden in
  

A cotton fabric is printed with a printing ink of the following composition:

• 18 g of the commercially available powder formulation of the reactive dye of the formula
  
• 30 g of the commercially available powder formulation of the reactive dye of CI No. 17 757 and
• 12 g of the commercially available powder formulation of the reactive dye of the formula
  
  such as
• 120 g of the commercial dough setting of the vat dye of the formula
  
  are in
  

The printed fabric is overprinted wet in wet with a printing ink which contains 160 g of formamidine sulfinic acid in 600 g of a 5% aqueous solution of locust bean gum glycolate. The mildly dried product then passes through an immersion bath with 100 g / l of 32.5% sodium hydroxide solution and immediately afterwards a steamer in which it is steamed for 10 seconds in saturated steam. The pressure is then thoroughly rinsed with cold water, washed at 40-50 ° C with 2 g / I hydrogen peroxide and 5 cm ^3/1 acetic acid treated again and finally with 0.5 g / I of sodium oleic acid-N-methyl tauride at 90 ° C washed, rinsed and dried.

The result is a print pattern with dark brown and yellow-green tones and good fastness properties.

Example 10

As in Example 9, a cellulose knitted fabric is printed with a printing ink of the same other composition which contains the following dyes:

The printed goods are processed and finished as in Example 9.

The result is a print pattern with red and blue colors and good fastness properties.

Example 11

A cotton cretonne is padded with a dye liquor at a squeezing effect of 100% on a foulard, which per liter

The padded and dried fabric is printed with a printing ink of the following composition, which has a pH of 6-7:

The printed and mildly dried goods are padded with a liquor containing 100% 32.5% sodium hydroxide solution per liter and then immediately steamed for 10 seconds in saturated steam.

The goods are then rinsed with cold water, rinsed again at 40-50 ° C with 2 g / I hydrogen peroxide and 5 cm ^3/1 acetic acid, and finally treated with 0.5 g / I of sodium oleic acid-N-methyl tauride at 90 ° C washed, rinsed and dried.

The result is a golden yellow print on a black background with good fastness properties.

Example 12

• 40 g der handelsüblichen Pulvereinstellung des Reaktivfarbstoffes der Formel
  
  neben den dort beschriebenen anderen Zutaten enthält, und nach der anschließenden Trocknung mit einer Druckfarbe nachstehender Zusammensetzung bedruckt:
  

A fabric of high-wet strength regenerated cellulose fibers is padded, as in Example 11, with a liquor which is per liter

• 40 g of the commercially available powder formulation of the reactive dye of the formula
  
  contains in addition to the other ingredients described there, and after the subsequent drying is printed with a printing ink of the following composition:
  

The fabric is further treated as in Example 11.

You get a pink print on a golden yellow background with good fastness properties.

Example 13

• 30 g der handelsüblichen Pulvereinstellung des Reaktivfarbstoffes der Formel
  
  neben den in Beispiel 11 beschriebenen sonstigen Ingredienzen enthält.

A cell wool fabric is, according to Example 11, splashed with a liquor per liter

• 30 g of the commercially available powder formulation of the reactive dye of the formula
  
  in addition to the other ingredients described in Example 11.

• 150g der handelsüblichen Teigform des Küpenfarbstoffes der C.I.-Nr. 68 420 enthält.

The dried fabric is printed with a printing ink which is constructed as in Example 11, but instead of the dye mentioned there

• 150g of the commercial dough form of the vat dye of CI no. 68 420 contains.

The printed and mildly dried cellulose fabric is padded with a liquor absorption of 90% with a liquor containing 100 g 32.5% sodium hydroxide solution and 150 g sodium carbonate per liter, and then steamed for 10 seconds in saturated steam.

The further treatment is carried out as in Example 11.

The result is a yellow print on a brilliant red background with good fastness properties.

Claims (5)

1. A two-phase printing process for the preparation of conversion articles with reactive and vat dyestuffs or of discharge resist prints with reactive and optionally vat dyestuffs on cellulosic fiber materials, which comprises printing or padding the material with a weakly acidic printing paste or padding liquor containing the reactive dyestuff or a mixture of reactive and vat dyestuffs, overprinting the material with a neutral printing paste containing a stable reducing agent based on a sulfinic acid and optionally a vat dyestuff, contacting the material, after intermediate drying, with an aqueous strongly alkaline liquor, and steaming the article.

2. A process as claimed in claim 1, wherein the reducing agent is sodium formaldehyde-sulfoxylate.

3. A process as claimed in claims 1 and 2, wherein the strongly alkaline liquor contains a cyano complex or a diacetyldioxime complex of iron, copper, chromium, manganese, cobalt or nickel.

4. A process as claimed in claim 1, wherein the reducing agent is formamidine sulfinic acid.

5. A process as claimed in claims 1 to 4, wherein steaming is performed for 5 to 30 seconds with saturated steam.