DE1061739B - Process for printing textile goods with Kuepen and / or sulfur dyes - Google Patents

Description

GERMAN

There are known methods for printing textiles with vat and sulfur dyes those of the dye together with certain coagulable thickeners, e.g. with alkyl cellulose ether, locust bean gum ether, polyvinyl alcohol, Ether of guar gum, alginates or simple carob gum thickenings, printed on will. The printing pastes themselves do not contain any reducing agents, but occasionally alkaline ones Agents such as potassium or sodium carbonate or sodium hydroxide, depending on the tolerance of the Thickenings with these alkaline agents. After printing and drying, the goods are finished with if necessary alkaline agents containing reducing agent solutions treated, which mostly still the Additives which cause or promote coagulation of the abovementioned thickeners, such as sodium borate or sodium aluminate, in some cases also sodium sulfate. These are also reducing agent solutions now and then thickened with non-coagulable thickeners such as tragacanth mucilage.

The textiles are z. B. by means of a padder or engraved rollers, that is, while still moist, subjected to a heat treatment with the exclusion of air. Achieved thereby reducing and fixing the dyes. Here, the heat transfer agent air-free saturated or superheated steam from 1 to 3 at abs. be at a temperature of 100 to 200 ° C. It will but also hot metal baths or hot oil baths are used, as well as hot water, if necessary is enriched with electrolytic agents. After all, the heat can also act on that Moist textile goods are transferred through hot metallic surfaces, with access to atmospheric oxygen to the textile material is prevented by a preheated rubber blanket.

In all of these processes, which are known as indirect printing with vat dyes, Vat pigment printing processes and two-phase printing processes are known as reducing agents mainly sodium formaldehyde sulfoxylate, less commonly sodium dithionite.

The advantage of sodium formaldehyde sulfoxylate solutions lies in the stability of these solutions at 20 ° C and in the fact that these solutions at 20 ° C do not yet have a reducing effect on vat dyes. It also occurs when the printed fabric webs are padded in the foulard chassis neither a vat of the printed dyes (and thus no bleeding on the unprinted areas) soiling or a toning of the padding liquor. if with the development of the printed dyes

Method of printing

of textile goods with vat

and / or sulfur dyes

Applicant:

Aniline & Soda Factory in Baden

Corporation,

Ludwigshafen / Rhine

Dr. Johannes Conrad, Adolf Blum,

Ludwigshafen / Rhine,

and Wilhelm Küppers, Frankenthal (Pfalz),
have been named as inventors

at the same time a coloring of the unprinted areas in light tones is to be achieved, so can small amounts of vat and / or sulfur dyes are added to the sodium formaldehyde sulfoxylate solution to add.

A disadvantage, however, is that when using sodium formaldehyde sulfoxylate as a reducing agent Treatment times in the usual dampers depending on the square meter weight of the textile webs 3 to 5 minutes are required to completely set the printed dyes. Used if sodium dithionite is used as the reducing agent, the steaming times are shorter of about 30 seconds Duration possible, but it is disadvantageous that sodium dithionite solutions already have vat dyes at 20 ° C reduce in the presence of alkali hydroxides and / or alkali carbonates. This leads to, that the printed vat dyes vat already during preparation in the foulard chassis, in the bleed in unprinted ground and also the padding liquor or the thickened sodium dithionite solution in undesirable Tint or color wise.

The instability of cold sodium dithionite solutions, even in the presence, is just as disadvantageous of alkaline agents. Therefore, when using sodium dithionite fixation, the padding liquors must be used to treat the tissue in a shorter time

909 578/387

vacate, d. H. at intervals of 30 to 90 minutes, respectively prepare fresh.

In this state of the art, processes had to be sought which had the advantages of reduction Combine sodium dilhionite and the advantages of reduction with sodium hydroxide sulfoxylate, without having the disadvantages caused by the use of these reducing agents.

It has now been found that textile goods, especially those made from native or regenerated cellulose, Can print natural silk or polyamides with vat and / or sulfur dyes, if the material is printed in the first stage with dyes with the addition of coagulant thickeners and after drying the prints in a second step by treating them with an alkaline agent Solution of an alkali or ammonium salt of a straight-chain or branched hydroxyalkylsulfinic acid fixed with 2 to 4 carbon atoms and subsequent brief heat treatment or if in the first stage the material is dyed with the addition of alkaline agents and coagulants Thickener)! and after drying, the prints are treated in a second stage with a solution of an alkali or ammonium salt of a straight or branched one T-hydroxyalkylsulphic acid having 2 to 4 carbon atoms and subsequent short heat treatment or if you have the good in the first stage with ! • "Open with the addition of non-coagulable thickeners printed and after drying the prints in a second stage by spraying a alkaline agent-containing solution of an alkali or ammonium salt of a hydroxyalkylsulfinic acid with 2 to 4 carbon atoms and subsequent brief heat treatment or if you have that Good in the first stage with dyes with the addition of alkaline agents and non-coagulants A ^ crdickenmittcln printed and the prints in one second stage by spraying on a solution of an alkali or ammonium salt of a hydroxyalkylsulfinic acid fixed with 2 to 4 carbon atoms and subsequent brief heat treatment.

As the alkali salt of hydroxyalkylsulfinic acids with 2 to 4 carbon atoms are, for example, the sodium or potassium salts of Hydroxyäthansulfinsäurc, the hydroxy-n-propanesulfinic acid, the Hydroxyjso-propanesulfinic acid c or the hydroxy-n-butanesulfinsiiurc and as alkaline agents are z. B. Sodium Hydroxide, Potassium hydroxide, sodium carbonate or potassium carbonate and / or mixtures thereof are called. As koagulicrbarc thickeners are z. B. alkyl chloride, cornbread flour ether, polyvinyl alcohol, Ether of guar gum, alginates or simple carob gum thickenings and as a not koagulicrbarc thickener z. B. Tragantschlcim mentioned.

An advantage of the new process is that the alkali used as reducing agent or Ammonium salts of straight or branched hydroxyalkylsulfinic acids with 2 to 4 carbon atoms, those at normal temperature even in the presence of strongly alkaline agents, such as Do not reduce sodium or potassium hydroxide, vat dyes and therefore none in the padding liquor Dye detachment when preparing the printed fabric cause such a high rate of disintegration Have at temperatures above 50 ° C that you can with the same short heat treatment as in the use of sodium dithionite as a reducing agent can fix the dyes on the fabric. The new quick fixation process also allows to use a far larger number of vat dyes than before, because when using Sodium dithionite only those vat dyes are useful which, because of their high Lcuco dye potential not reduced by cold hydrosulphite solutioncii will. The resistance of aqueous solutions of the alkali salts of straight-chain or branched ones

ίο Hydroxyalkylsulfinsäuren having 2 to 4 carbon atoms is even so large at 2O ⁰ C against oxygen and carbon dioxide content of the air, that one can spray the aqueous solutions onto the printed textile material without having substantial losses suffered of reducing agents. If, on the other hand, aqueous sodium dithionite solutions are sprayed, usually only between 5 and 30% of the reducing agent originally present can be detected in the collected solution after spraying. Although aqueous solutions of sodium formaldehyde sulfoxylate can also be sprayed without a significant decrease in the reduction value, it is known that the use of this reducing agent requires a much longer heat treatment to fix the dyes. If, on the other hand, the printed fabric is sprayed, as described, with aqueous solutions of alkali or ammonium salts of straight-chain or branched hydroxyalkylsulfinic acids with 2 to 4 carbon atoms, one is able on the one hand to use short heat treatment times and on the other hand to use coagulable thickenings in the printing paste no longer bound.

The parts mentioned in the examples are parts by weight.

example 1

A cotton fabric is printed with the following printing paste:

100 parts of a yellow vat dye, e.g. B. Vat Yellow 1 / CI 70 600 (Color Index, 1956, Vol. 2, p. 2427), in the form of a 20% aqueous dough,
100 parts of water,

600 parts of a 3% boiling of locust bean gum,

200 parts of a 10% wheat starch paste,

1000 pieces,
so

After printing and drying, the fabric is also prepared

800 parts of water,

200 parts of a 30% aqueous solution of the potassium salt of hydroxyethanesulfinic acid,
50 parts sodium hydroxide,
5 parts of sodium tetraborate.

The still moist fabric is then exposed to an air-free steam atmosphere without excess pressure for 30 seconds exposed at 108 ° C.

To finish, the fabric is treated for 2 minutes in running water at 20 ° C, for 2 minutes in a 95 ° C warm aqueous solution containing 2 g of sodium perborate per liter, oxidized, soaped, rinsed and dried. A bright yellow print is obtained on a white background.

One arrives at the same result if one starts with the 30 second steaming process

the prepared, still moist tissue is applied to a ^{metallic surface heated to HO 0} C and covered with a rubber blanket preheated to about 80 ° C., this heat treatment being allowed to last 25 seconds.

Example 2

A viscose rayon staple fiber fabric is printed with the following printing paste:

100 parts of a blue vat dye, e.g. B. VatBluel4 / CI 69 810 (Color Index, 1956, Vol. 2, p. 2501), in the form of a 15% aqueous dough, 50 parts of water,
600 parts of a 4.5% carob bean gum

ether boiling in water, 200 parts of a 10% corn starch paste, 30 parts of potassium carbonate,
20 parts sodium hydroxide,

Instead of the solution of the sodium salt of hydroxyethanesulfinic acid, one can also use the solution of the ammonium salt of hydroxyethanesulfinic acid under otherwise identical conditions.

Example 4

A copper-gray fabric is printed with the following paste:

30 parts of a purple vat dye, e.g. B. Vat Violet 1 / CI 60 010 (Color index, 1956, Vol. 2, p. 2479), in the form of a 15% aqueous dough,
220 parts of water,
500 parts tragacanth slime (6%),
200 parts of a 10% wheat starch paste, 50 parts of a 30% British gum thickening (starch degraded by roasting),

1000 parts.

After printing and drying, it is treated with a solution

850 parts of water,

150 parts of a 40% aqueous solution of the

Potassium salt of hydroxypropane

sulfinic acid,
15 parts of sodium tetraborate.

The still moist material is immersed in an oil bath at 98 ° C and left in it for 45 seconds. the Finishing, consisting of oxidizing, soaking and rinsing, takes place as indicated in Example 1.

A rich, blue print is obtained on a white background.

Instead of the oil bath, a liquid metal bath of the same temperature can be used and reduce the treatment time to about 12 seconds.

Example 3

A cotton fabric is printed with the following printing paste:

100 parts of a yellow vat dye, e.g. B. Vat Yellow 1 / C. I. 70 600 (Color Index, 1956, Vol. 2, p. 2427), in the form of a 20% aqueous dough,

150 parts of water,

500 parts tragacanth gruel (6%), 250 parts of a 10% wheat starch paste,

1000 parts.

The printed and dried fabric is sprayed with the following solution in such a way that the fabric absorbs at least 50% of its own weight in solution:

800 parts of water,

200 parts of a 40% aqueous solution of the sodium salt of hydroxyethanesulfinic acid,
50 parts of sodium hydroxide.

The still moist tissue is continuously fed to a steamer and ^{treated there for 30 seconds at about 110 °} C. in air-free steam without excess pressure. The fabric is finished according to Example 1.

A bright yellow print is obtained on a white background.

1000 parts.

After printing and drying, the following solution is sprayed in such a way that the fabric as absorbs at least 50% of its own weight in solution:

800 parts of water,

200 parts of a 35% aqueous solution of the sodium salt of hydroxybutanesulfinic acid,

50 parts of sodium hydroxide.

The still moist goods are continuously fed to a steamer and ^{treated there for 30 seconds at HO 0} C with air-free steam. The fabric is finished in the same way as indicated in Example 1.

The result is a bright red-purple print on a white print.

Instead of the sodium salt of hydroxybutanesulfinic acid, the sodium, potassium or Ammonium salts of hydroxyisopropanesulfinic acid or their aqueous solutions can be used.

Example 5

A natural silk fabric is printed according to the following instructions:

40 parts of a green vat dye, e.g. B. Vat Green 1 / C.I. 59 855 (Color Index, 1956, Vol. 2, p. 2519), in the form of a 10% aqueous dough,

210 parts of water,

500 parts of a 5% alkyl cellulose ether thickener,

1000 parts.

After printing and drying, the following solution is padded on the padder:

850 parts of water,
150 parts of a 30% aqueous solution of the sodium salt of hydroxyethanesulfinic acid,

15 parts sodium hydroxide,
25 parts of potassium carbonate.

The still moist material is heated with air-free steam for 60 seconds at 0.3 atmospheres overpressure treated. The further finishing of the fabric takes place according to Example 1.

7 8

The result is a bright green print on. You get gray prints on a white background,

white ground. -r,. . , _R

One can also use the alkyl chloride thickening

by the same amount of a 17% polyvinyl A cotton fabric is printed with the following

replace alcohol thickening. 5 paste:

ω ■ ■ \ μ. 70 parts of a yellow vat dye, e.g. B.

¹¹⁰¹⁸ P ¹⁰¹ ° Vat Yellow 2 / CJ 67 300 (Color In-

The following paste is used to print a fabric dex, 1956, vol. 2, p. 2428),

from polycaprolactam filter material: 30 parts of water,

40 parts of a green vat dye, e.g. ¹⁰ 600 parts of a 4.5% carob bean gum

Vzt Green 1 / Cl 59 855 (Color In- ether thickening,

dex, 1956, vol. 2, p. 2519), in the form of 300 parts of a 10% wheat starch paste,

of a LO% aqueous dough, 1000 parts 1 LO part of water,

600 parts of a 5% sodium alginate thickener. After printing and drying, it is

kung, a roller engraved on the entire surface

250 parts of cincs'iO% wcizen starch paste, the following thickened reducing agent solution.

- TTT-. -: prints:

1000 lcilc.

70 parts of water

After printing and drying is _Tei with folic 20 _{1QQ) e eineg 6 M} i Tragantschleimes,

padded on the two-roll pad: _{200 Tdle of a 40 % solution of the} sodium

800 parts of water, hydroxyethane sulfinic acid salt,

15 parts anhydrous aluminum sulfate, 60 parts sodium hydroxide.

45 parts of sodium hydroxide, -, -. . ·, _,, -. , ", - r. ,,. ,,,.

40 parts of sodium carbonate, calcined, ^a5 _ ^Dan _ ^ach ^ ¹ JJ * ^G , ^cwcb ? ³⁵ seconds in air free

200 parts of a 40% solution of potassium vapor at 105 ° C without the application of excess pressure

salt of hydroxyethanesulfinic acid c. ^^ ^{Finished position} ' ^U " ^{g the DmCke erf} °' ^{gt ge} "

The moist tissue is continuously fed into a bright, grim-tinged yellow print

Damper closed and treated in 50 seconds with 30 received on a white background.

air-free steam of 105 ° C. The thickened reducing agent solution is provided

muted prints according to the example! done and receives coagulation of the locust bean gum ether thickening

a full bluish green print on white, 1 to 3% sodium tetraborate can be added. Reason.

You can also use an excess pressure of 1.5 atmo- 35 Example 9 Mute spheres for 40 seconds.

A viscose cyan staple fiber fabric is made with the following

Example 7 gender printing paste printed:

100 parts of a red vat dye, e.g. B.

A cotton fabric is printed with the following 40 Vat Red 10 / C.I. 67 000 (Color Index,

Printing paste: I956, Vol. 2, p. 2460), in the form of a

20 parts of a gray vat dye, e.g. B. 15% aqueous dough,

Vat Black 25 / C. [. 69 525 (Color In- 50 parts AVasscr,

dcx, 1956, vol. 2, p. 2560), in the form of 600 parts of a 4.5% carob bean

cincs 20% aqueous dough, ⁴⁵ ether thickening,

130 parts of water, 250 parts of a 10% wheat starch paste,

600 parts of a 4.5 per cent guar gum ether 1000 parts

Boiling in water,

250 parts of a 10% wheat starch paste. The printed and dried fabric is mixed with

—-—-—-—— So the following reducing agent solvent on the Zwciwalzen-

^{1000 lciIc} foulard prepared:

After printing and drying, the following 75g of water is added

gender solution padded on the double-roll foulard: _{5 Tcjle cin} ' _{es g} ' _e , _ben vat dye, z. B.

850 parts of water, Vat Yellow 1 / C.L 70 600 (Color In-

150 parts of a 30% aqueous solution of ⁵⁵ dex, 1956, vol. 2, p. 2427), in the form

Potassium salts of hydroxyethane sulfine of a 20% aqueous dough,

acid, 200 parts of a 40% solution of sodium

20 parts of sodium tetraborate, salt of hydroxyethanesulfinic acid,

50 parts of sodium hydroxide. _g 50 parts sodium hydroxide,

", _R , _. ,. ,, ...., 1 j 15 parts of sodium tetraborate. The still moist fabric is passed through the following 95 ° C warm solution for heat treatment: The fabric is then treated for 30 seconds in 730 parts of air-free water, steam at 110 ° C without excess pressure. The 200 parts of sodium sulfate, anhydrous, _c completion of the attenuated tissue, ^{6s Be} f / ^iel 1 made parts of sodium tetraborate as in the twentieth _,., ._, 20 parts sodium hydroxide. JJan gets a red print on a yellow background

One can also contain the copper dye

The working time in this solution takes 40% of a solvent solution with 100 parts of a 6% strength

announce. The completion of the prints, like oxy-tragacanth slime, omitting the same water

Dicrcn, soaping and rinsing, is done as in Example 1. 70 thicken the amount and add this thickened solution

with a roller engraved on the entire surface.

Example 10

A white cotton fabric is printed according to the following rule:

50 parts of a yellow sulfur dye, e.g. B. C.I. Sulfur Yellow 5 (Color Index, 1956, B. 2, p. 2365),

15 parts sodium sulphide, crystallized,

135 parts of water,
600 parts tragacanth slime (6%), 200 parts wheat starch paste (10%),

1000 parts.

After printing and drying, the fabric is sprayed with a solution

900 parts of water,

100 parts of a 40% aqueous solution of the

Sodium salt of hydroxyethane sulfate

fic acid,
50 parts of sodium hydroxide.

The still moist fabric is continuously fed to a steamer and treated ^{there in air-free steam at 110 ° C. for 45 seconds.} The completion of the print, such as oxidation, soaping and rinsing, is carried out as in Example 1.

A yellow print is obtained on a white background.

Instead of the aforementioned yellow sulfur dye, you can also use a brown sulfur dye, z. B. C. I. Sulfur Brown 16 / C. I. 53 285 (Color Index, 1956, B. 2).

In this you get a deep brown print on a white background.

Claims (4)

Patent claims: 1. A method for printing textile goods with vat and / or sulfur dyes, thereby characterized in that the material is coagulated in the first stage with dyes with the addition of coagulants Thickener printed and after drying the prints in a second stage by treatment with a solution of an alkali or ammonium salt containing alkaline agents a straight-chain or branched hydroxyalkylsulfinic acid having 2 to 4 carbon atoms and subsequent brief heat treatment. 2. Process for printing textile goods with vat and / or sulfur dyes, thereby characterized in that the good in the first stage with dyes with the addition of alkaline agents and printed by coagulable thickeners and after drying the prints in a second stage by treatment with a solution of an alkali or ammonium salt a straight-chain or branched hydroxyalkylsulfinic acid having 2 to 4 carbon atoms and subsequent brief heat treatment. 3. Process for printing textile goods with vat and / or sulfur dyes, thereby characterized in that one does not add dyes to the material in the first stage coagulable thickener and after drying the prints in a second Step by spraying on an alkaline agent-containing solution of an alkali or ammonium salt a hydroxyalkylsulfinic acid having 2 to 4 carbon atoms and a subsequent brief heat treatment. 4. Process for printing textile goods with vat and / or sulfur dyes, thereby characterized in that the good in the first stage with dyes with the addition of alkaline agents and non-coagulable thickeners and the prints in a second stage by spraying on a solution of an alkali or ammonium salt Hydroxyalkylsulfinic acid with 2 to 4 carbon atoms and subsequent brief heat treatment fixed. © 909 878/387 7.