DE2049154C3 - Process for achieving multicolored prints on cellulose fiber material that appear to be exactly in register, if necessary without repeat - Google Patents

Description

It is known that reactive dyes can only be properly fixed on cellulose fibers in the presence of alkali can. Dyes of this class which do not result in homopolar dyes in the course of dyeing or printing operations Binding with the cellulose, on the other hand, can then be removed again completely and without major Wash out trouble when the hydrolysis product of the reactive dye with the hydroxyl ions of the Cleaning liquor has no substantivity to the fiber.

It is also known that by preprinting acidic reserves in the form of small motifs, preferably also in the form of lines that separate individual colored areas from one another or through several Pulling colored areas through, can achieve attractive effects.

It has now been found that apparently precisely fitting, if necessary, multicolored prints without repeats on textile fabrics made from native or regenerated materials Cellulose fiber material can be achieved if the textile material in any order

a) with a printing paste containing non-volatile, organic or inorganic acids or acid salts contains as a reservation agent, preprints a planar motif and uses this pattern several different reactive dyes or mixtures thereof and alkaline dyes Substances containing printing pastes overprinted in a different design, the composed of several adjoining, relatively smaller areas compared to the form is, or if one

b) by means of several, each containing different reactive dyes or mixtures thereof neutral to slightly acidic printing pastes one of several adjoining, small ones A pattern composed of areas is preprinted as well as this pattern with an alkaline-looking one Printing paste containing substances in one

relatively larger area than the individual areas of the form, different motif overprinted,

Buu then the fixation of the reactive dyes according to a method known for this; performs.

pie fixation of the prints produced in this way takes place Bach expediently drying the goods by a steaming process, e.g. B. in a Continuous Damper, for 3 to 10 minutes at temperatures between 98 and 115 ° C, depending on the one used Textile material. The one to be used in this context The relationship between temperature and treatment time is inversely related. Of course other types of fixation can also be used, for example drying in the attic with a feeder of warmth.

In the course of the measures of the invention Procedure, novel patterning effects are obtained, which are achieved through other methods, above all by direct printing, can not be produced or only with great technical difficulties.

Pas the feasibility of this reserve technique The underlying principle is that at those points of the in the above-mentioned manner treated substrate, where no alkaline fixative is printed or this by the action of the acidic reserving agent neutralized, the reactive dyes are not fixed. You can washed out again after steaming. and you are on green. * This valley thing is capable of for creating multicolored designs on a white background.

If, in order to illustrate the procedure 'b) by way of an example, neutral printing pastes containing reactive dye are printed on the cellulose fiber material a fully occupied five-color pattern, which is composed of relatively small areas, and this pattern is overprinted wet-on-wet with a liquid alkali water glass of 48 to 52 "Be, preferably soda waterglass, in the form of relatively larger patterns, e.g. egg-shaped motifs and also others of roughly the same size, the said ί fixation of the within this area shows

. Reactive dyes overall have a sharp

fen edge and is composed of several to many differently colored zones that add up to this egg shape. If one wanted to try to imitate such egg-shaped structures by direct printing, then passport difficulties are to be expected; _{5 (} in this case the figure would have a jagged, unsightly edge, the nmr at very low

wedge, because the figure recurring in the Rupport and created by the overprinting is now on the Material line shifted and now continues to breathe together from differently colored small zones. As is customary in the industry, this is viewed as an increase in value.

Pattern effects similar to those with water glass can be achieved by overprinting with a 3 to 10 / o Aqueous soda solution, containing paste, with other alkaline instead of soda Active substances, in particular sodium or potassium bicarbonate, or substances that split off alkali, e.g. the alkali salts of trichloroacetic acid can kick. However, in these cases it must be used for fixation steamed and, moreover, care must be taken that the alkali printing paste does not remove the dye from the printed matter Tissue takes over and becomes apparent in the process, which would diminish the effect. If necessary, this can be done by adding 200g / kg Glauber's salt to e.g. impede.

If in the example of the egg-shaped figure with the same roller or stencil - instead of using soda in the last hand on neutral reactive printing inks as in procedure (b) - a large-area pattern on the cellulose fiber material according to procedure (a) with an acid reserve, ™ ^{r / M} Z ^s:, tartaric acid, and also citric acid or pnmäre alkali metal phosphates, g in quantities of 50 to 2UU / Kg paste printed in the first hand under alkaline reactive ink so are achieved in AnscMuu to a steaming process, a pattern which comprises Nega ^{tiv of} * ^eMASS procedure If one chooses in the course of a variant according to procedure (a) the amount of acid in the pre-pressure reserve sufficiently high, one can get the same negative without changing the originally used, namely neutral printing inks by padding, patting or Spraying an electrolyte-like alkali liquor fix the prints according to the usual two-phase steam process is made. The alkali-free printing inks are coated with traces of pnmarem, sodium phosphate or Ess _Ig acid against by the Fixierungsa.kali on the ™ £ ™ £ Ste, | en ^ schut ^ ^ «Jf ^

also by overprinting alkali with the negative form corresponding to the roller (large motif)

^ _{S e} nding ffi11 acreage lend its strict loan regularly repeat.

By changing the one with the one that affects the pH value Ink-fed preprint or overprint roller or stencil can be turned in and out create almost any number of other motifs of the same basic design,

The washing baths to complete the invention With all methods, reserve items must be designed in such a way that they do not stain areas of the tissue supplied with fixative are avoided Wash liquors ensure a neutral or weakly acidic reaction of the bathroom and the goods. This is in Case of using soda easier than if you use water glass to fix the reactive dyes has used 4

Of course, in the context of procedure (b), the fixing agent does not necessarily have to be wet-on-wet can be printed on in the same operation, but the alkali application can be used at any later time Point in time. As a result, one is able to take advantage of the disposition options of the design to be hooked open for a long time.

For the production of the multicolor effects according to the present invention are used as reactive dyes all dyes of this category are suitable, the substantivity of which is so low that there is no risk of tinting the reserved areas and show sufficient stability in the form of neutral printing inks. Such reactive dyes can be found in the commercial dye assortments of the dye manufacturers, and it does not matter for the feasibility of the claimed method whether this is now as fiber-affine constituent, for example a / i-sulfatoether sulfone group, / f-thiosulfatoethy & sulfone group, Dialkylaminoethylsulphone group, vinylsulphone group, monochlorotriazine group, dichlorotriazine group, trichloropyrimidine group, Dichloroquinoxaline group, 2,2 ^, 3-tetranuorcyclobutane-1-acryloylamino group, Vinylsulfonylamino group, dichlorophthalazine group, / J-sulfatoethylaminosulfone group, ethionylamino group or a ß-sulfatoethylcarbonylamino group, or optionally contain several of these reactive radicals. As a basic body of this organic Dyes are those from the series of anthraquinone, azo and phthalocyanine dyes, it being possible for the azo and phthalocyanine dyes to be both metal-containing and metal-free. the The amount of reactive dyes used in the printing pastes used depends on the desired color depth.

Another very valuable addition to the design options according to the method of the invention consists in, for the various, dye printing pastes containing reactive dyes of different fixability or, in particular, hybrids to use thereof by quick-fixing dyes, e.g. B. of the sulfatoethyl sulfone type, which can be obtained by the two-phase cold pad process or by a two-phase rapid fixation process for reactive dyes can be fixed, combined with those whose fixation according to the aforementioned Fixing processes cannot be carried out or can only be carried out with a very low yield because they are too slow to react for this are. The latter applies e.g. B. for the Dialkylaminoäthylsulfonfarbstoffr to. The fixation of the dyes is in these cases by steaming in combination made with one of the two-phase fixation methods mentioned above. If you mix z. B. a fast-fixing yellow dye with an inert blue mark and applied this dye mixture on the cellulose fiber material, both types of Fix reactive dyes through a steaming process. If you now, instead of washing immediately to remove unfixed dye components, close beforehand still a two-phase wet fixation of a known type, this is done at the previously neutral points only the fast-fixing yellow dye, but not the slow-fixing blue dye, fixes the agent Strongly colored patterns generated by excess alkali pressure, for example the egg figure already quoted, is no longer there surrounded by white, but by lighter shades, namely those of the fast-setting dyes, im above case of yellow. It is obvious that this modification of the method according to the invention can also be transferred to dyes with reactive systems other than those mentioned above, provided in their selection of the requirement for correspondingly faster and slower fixing speed Is taken into account, prak'-sch is achieved through this variant of the method according to the invention doubling the number of shades from which z. B. five-color basic pattern therefore 10 shades. This means over other methods, for example direct printing, a considerable saving in engraving coasts and other technical effort.

It has already been proposed, using an acid reserve technique, e.g. B. when using of tartaric acid, with reactive dyes according to the previously defined different Degree of fixability, for example with sulfate ethyl sulfone dyes among dislkylamino ethyl sulfone dyes, produce very effective multi-color effects on cellulose fiber materials in the form of a web, if you fix the alkali-containing print pattern with the inert dye Steam, and at the overflow points that of the acidic colored reserves with the reactive dye carries out according to a two-phase fixing process for reactive dyes. However, after this lies State of the art as well as other methods using acidic reserves or separation of colored areas, but not the achievement according to the invention of apparently precisely fitting, possibly non-repeat, multicolored designs by using reactive dyes and fixing agent or acidic reservation agent in a separate operation and only in places under Overlap are applied. In addition, in the known process of acidic reserve paint to protect the sulfatoethyl sulfone dyes from the dialkylaminoethyl sulfone dyes during the steaming process dialkylamine released and accumulated in the acidic printing ink is a larger one Amount of suitable alkylating agents, e.g. B. Disulfatdiäthylsulfon, are added to prevent that in the subsequent treatment the pressure "with the alkaline padding liquor in the course of the two phase fixing process of the sulfatoethyl sulfone dye is quickly converted into a corresponding inert dialkylaminoethylsulfone dye which would result in lower color yields for the quick fixation of the dye.

In the context of the measures for carrying out the method according to the invention, on the other hand, an Do not worry about enrichment of dialkylamine when using neutral printing inks, but rather leaves there

volatile dialkylamine immediately puts the damper on. No protective additives are therefore required, which means a simplified way of working is given.

The printing inks can be applied to the textile material by any known method, preferably this is done by roller printing or film printing.

The following examples are intended to illustrate the invention Explain working methods in more detail, but without restricting them in any way.

example 1

To produce a five-color print sample with 100% surface coverage, five neutral « Prepare printing pastes by pouring over the following dyes in the amounts given below dissolves with 300 parts by weight of hot water, in 500 Ge parts by weight of a 4 percent by weight, aqueous Algi Stir in natural thickening and adjust to 1000 parts by weight with water:

A. 30 parts by weight of the dye of the formula

SO ₃ H

N = N - CC - CH ₃

CN

HO N

B. 25 parts by weight of the dye of the formula

HO ₃ S

SO ₃ H

SO ₂ - CH ₂ - CH ₂ - O - SO ₃ H

SO ₃ H

-n = n

SO ₃ H

SO ₂ - CH ₃

C. 30 parts by weight of the dye of the formula

HO ₃ S - O - H ₂ C - H ₂ C - O ₂ S

O - CH ₃ HO NH - CO - CH ₃

HO ₃ S

SO ₃ H

D. A mixture of 20 parts by weight of the dye indicated under C and 20 parts by weight d Dye of the formula

SO ₃ H

O NH -C V-SO ₂ -CH ₂ -Ch ₂ -O-SO ₃ H

E. A mixture of 20 parts by weight each of the dyes of the following formulas

O NH ₂

Cl

NH

SO ₁ H

SO ₃ H

and

Cl

Cl

SO ₃ H

The printing pastes prepared in this way are then printed one after the other on a mercerized cotton fabric with the help of a Mchrfarben-Roulcaux printing machine and this design is then imprinted on same process with the last roll of soda water glass at 48 ° Be, thickened if necessary Addition of silica gel or an alkali-resistant alginate or starch ether thickening, in any pattern and with one opposite the Form differing report overprinted. After the reactive dyes have been fixed by drying the prints in the attic at a temperature between 120 and 140 ° C will be the goods in a aqueous liquor with the addition of acetic acid thoroughly rinsed cold and neutralized, then with a 1% aqueous solution of a synthetic detergent (e.g. sodium salt of the condensation product of oleic acid and N-methyl-taurine) soaped at the boil and finished as usual

In this way of working, you get a mark on the fabric at the points where the waterglass print is Sharp, five-color, repeatless pattern, while the preprinted flustering is completely washed out in the alkali-free areas, so that there appear pure white effects.

Example 2

On a fabric made of mercerized cotton, the five neutral printing pastes produced according to the recipes in Example 1 are applied one after the other by means of a planographic printing machine faithfully reproduced. This pattern is then applied without drying the goods beforehand, with another stencil of another corrected pattern, the repeat of which with that of the form Corresponds, an alkali solution overprints the out 50 parts by weight of calcined soda, 200 parts by weight of I-adened Glauber's salt, 250 parts by volume of water and 500 parts by weight of an aqueous, 4% by weight jo percent, electrolyte-resistant alginate thickening or a corresponding thickening based on Hydroxyethyl cellulose consists.

After the alkaline agent has been overprinted and dried, the goods are used for dye fixation Steamed for 3 minutes in a continuous steamer of the Mether-Platt type at 102 ° C and the pressure then finished as in Example 1.

In this way, a sharp, five-

colored, precisely fitting pattern, while the dyes on the alkali-free areas of the pre-thickened design are washed out and only white effects occur there.

Now, in a further experiment, a different rapport is used for overprinting with the alkali solution selected, which is shifted by about 7% compared to the uniform report of the form, then The same pattern is generally given on the goods - namely according to the overprint of the alkali but here have the individual filling out this design each have a different shape and a different color composition.

Example 3

Medium on a mercerized cotton fabric! a printing machine in any pattern a fore nod reserve of the following composition applied:

M »parts by weight of tartaric acid are in 300Ge

parts by weight of water are dissolved and this solution is added under stirring with 600 parts by weight of a 5 weight percent aqueous thickening of hydroxyethyl cellulose. yy ■>

After preprinting and drying, the se

^ fTT ^{1016 Ware 2} ^ Manufacture of a five-color

Print sample with 100% area coverage in Roulea impression one after the other with five printing paste

that are prepared as follows:

11th

A. 25 parts by weight of the dye of the formula

-C-N = N- / \

Cl

SO, H

are dissolved by pouring 300 parts by volume of hot water, this solution is 20 parts by weight Sodium bicarbonate added, in 500 parts by weight of a 4 weight percent aqueous alginate thickener stirred in and adjusted to 1000 parts by volume with water.

B. In the same way, a printing paste is made from 25 parts by weight of the dye of the following formula:

SO ₃ H OH

Cl

HOjS

C. Another printing paste is made from 30 parts by weight of the dye as described above of the following constitution:

SO ₃ H

D. Likewise, a printing paste with a mixture of 20 parts by weight of the dyes is as follows Formulas made:

O - CH ₁

H ₃ C - CO - HN OH

SO ₂ - CH ₂ - CH ₂ - O - SO ₃ H

O NH -Y \ - S

CH ₂ - CH ₂ - O - SO ₃ H

E. As described under A, another printing paste containing a mixture of 20 wt
share the dyes A and D from Example 1, set.

After the reserve overprint with these five print pastes and drying, the fabric is steamed for dye fixation in a Kontinuedampfer type Mather slab 3 minutes at 102 ⁰ C and the pressure then feitiggestellt as in Example. 1 In this way, a five-color print pattern is obtained in which the acid preprinted design is reserved in pure white.

Example 4 _{| 0}

On a fabric made of viscose rayon of any processing form, as described in Example 3, an acidic pre-pressure reserve, but with an increased amount of tartaric acid of 200 g / kg fast, in any Pattern is printed on and the goods are then dried.

The five printing inks of the are then applied to the material treated with the reservation agent Example 3, but here prepared without the addition of sodium bicarbonate and optionally with something Acetic acid or monosodium phosphate to protect against coating have been added by means of a Flat printing machine overprinted in the same order.

Now the goods treated in this way are padded with an alkali solution of the following composition:

30 parts by weight of 38 ° Bc sodium hydroxide solution

(32%),

200 parts by weight of calcined Glauber's salt,
770 parts by volume of water.

Finally, the pressure is attenuated as the dye-fixing during two-phase Dämpfvcrfahren in a Kontinuedampfer 2 minutes at 108 ⁰ C, washed as in Example 1 and completed

A five-color, Exactly fitting print pattern obtained, which, as a result of the acidic reservation, was permeated with pure white effects is.

Example 5

To achieve a twelve-color, fully occupied print pattern, six neutral print colors are used prepared, each obtained by mixing a fast and a sluggishly fixing reactive dye will.

In detail, the following dyes and quantities are poured over them with 300 parts by volume dissolved in hot water, this solution in 500 parts by weight a 4 percent aqueous alginate thickener stirred in and adjusted to 100 parts by volume with water:

nuance

I.
violet

Fast filing component

20 parts by weight of dye C
from example 1 (red)

II.
Light green

IH.
orange

25 parts by weight of the dye of the formula HOOC-C -C N = N -i,

Il Il \

NC OH ^x

False fixing component

20 parts of the dye of the formula
O NH ₂

- SO ₃ H

O NH - { ^N \ - SO ₂ - CH ₂ CH ₂ - N (C ₂ H,),

j (blue)

SO ₂ CH ₂ CH ₂ O —SOjH

(yellow)

10 parts by weight of the dye of the formula

Cl

(Red)

SO ₃ H

15 parts of the sluggishly fixing dye
from mixture I from example 5 (blue)

30 parts by weight of dye A from Example 3 (yellow)

continuation

nuance

Scarlet fever

V.
Dark green

Vl.
Red

Fast fixing components e

15 parts by weight of the dye of the formula
OH

(orange

Q-SO ₃ H

15 parts by weight of the dye of the formula

SO ₃ H

H ₁ C - C

Il Il

N C-OH

SO ₃ H

ΝΛ NH- ^ f N

(yellow)

15 parts by weight of the dye of the formula

CH ₃

jC - C C-N = N - <

(yellow)

These six neutral printing pastes are now printed in the order given by means of a multi-color roller blind printing machine printed on a mercerized cotton fabric with full surface coverage and this design is then imprinted in in the same operation with the last roller, any other pattern with an alkali solution, consisting from 50 parts by weight of calcined soda, 450 parts by volume of water and 500 parts by weight of one 5 weight percent, aqueous thickening based on hydroxyethyl cellulose overprinted.

After drying, one half of the fabric printed in this way is ^{steamed for 3 minutes in a Mather-Platt type continuous steamer at 102 °} C. for dye fixation and the printing is completed as in Example 1. A sharp, six-colored, precisely fitting print pattern in the tones of the color mixtures 1 to VI is obtained on the fabric at the points of the alkali overprint, while the inert fixing component

25 parts by weight of the dye of the formula
H ₃ C-CO-HN OH OCH ₃

HO ₃ S SO ₃ H SO ₂

(red) CH ₂ -CH ₂ -

25 parts by weight of the dye of the formula

O NH ₃

Cl

«Ι * .χ N

O NH - <f ■ / - NH -Λ _N. ^ - NH

(blue)

25 parts by weight of the sluggishly fixing dye
from mixture IV from example 5 (red)

the preprinted pattern is washed out on the alkali-free surfaces, so that white effects occur there.
After steaming - without washing the goods - the other half of the printed fabric is padded with a strongly alkaline, electrolyte-containing solution to fix the dye in accordance with the two-phase cold dwell process and packed airtight with a plastic film for about 8 hours on the dock or in a paneled state , left to linger at room temperature and then finished as usual.

In this last-mentioned procedure, the washed-out, white areas of the first tissue section are applied in addition, the fast-fixing dye * Fabric components of the six dye mixtures described above are fixed, so that a total of a print pattern is obtained from twelve shades of color.

Claims (9)

Patent claims: 1. Process for the achievement of apparently precisely fitting, possibly non-repeat, multicolored ) back on textile fabrics made of cellulose fiber material, gekennzeichi e t that one can on the textile material in any loan order a) with a printing paste that contains non-volatile, organic or inorganic acids or acidic salts as a reservation agent, preprints a planar motif and overprints this pattern using several printing pastes containing different reactive dyes or mixtures thereof and alkaline substances in a different design a plurality of adjacent, relatively smaller compared to the form surfaces composed ^ is, or in that b) by means of several neutral to weakly acidic printing pastes containing different reactive dyes or mixtures thereof, a pre-printing composed of several adjoining, small areas and this pattern with a printing paste containing alkaline substances in a relatively larger area than the individual areas of the pre-printed, 3 ° ^; different motif overprinted, »Nd then the fixation of the reactive dyes carries out according to a known method. 2. The method according to claim 1, characterized in that the fixation of the reactive dyes by steaming for 3 to 10 minutes in a continuous damper. 3. The method according to claim 1 and 2, characterized in that one for the different, Dyes containing printing pastes reactive dyes of different fixability or Mixtures thereof are used, one category of which is based on the two-phase cold pad process or can be fixed by a two-phase rapid fixation process for reactive dyes while not or only the fixation of the other category after the aforementioned fixation methods can be carried out with a very low yield and you fix the dyes in these cases by steaming in combination with one of the previously mentioned two-phase fixing process makes. 4. The method according to claim I a), characterized in that that neutral printing pastes, the each contain different reactive dyes or mixtures thereof, corresponding to those there Application methods mentioned and you can fix the reactive dyes after Padding, paddling or spraying on an alkali liquor containing electrolytes according to the two-phase steaming process undertakes 5. The method according to claim 1 a), characterized in that that tartaric acid is used as the acidic reservation agent in amounts of 50 to 200 g per 1 kg of printing paste. 6, method according to claim I b), characterized in that that the alkaline substance is a liquid alkali water glass from 47 to 52 ° Be used. 7, method according to claim I b), characterized in that that as an alkaline substance, 3 to 10% strength aqueous solutions of Sodium carbonate, sodium or potassium bicarbonate or under the fixing conditions alkali separating substances are used. 8. The method according to claim I, characterized in that that the overprint is carried out with a more or less different report, that compared to the uniform report of the preprinted sample not in the ratio of whole numbers stands. 9. The method according to claim I, cc characterized by, that in the same printing process a combination of the acid prepress method (a) and the overpressure alkali method (b).