DE2826173C2 - Process for preventing reduction phenomena in printing and inking - Google Patents

Description

The subject of the main patent 27 30 313 is a method / to protection more sensitive to reduction Disperse dyes before reduction when pad dyeing or printing materials made of synthetic fibers or their mixtures with cellulose or regenerated cellulose fibers by adding oxidizing agents, which is characterized in that the 0.05% aqueous solutions of the oxidizing agents used an oxidation potential between + 20OmV and + 300 mV.

Reduction phenomena in the form of reduced color yield, which mostly result from prolonged exposure to in a small amount of reducing steam - both steam and superheated steam - can be attributed, but are also often based on the nature of the substrate, also occur often when using cellulose-affine dyes on cellulose substrates such as cotton or rayon on. For example, some reactive dyes are exceptionally sensitive in this regard, what particularly evident in light shades. Against reductive influences in textile finishing in general The alkali metal used is the m-nitrobenzenesulfonic acid not always able to cope with this occasional malady. The other in dyeing and Oxidizing agents commonly used in textile printing such as chloral and chromate divorce to combat the Reduction appearance off. because the former in the alkaline Milieu flour is effective and the latter / ur clouding of the shade leads.

In a further development of the inventive concept of the main patent application it has now been found that the im Process according to the main patent used oxidizing agent due to the comparison with nitrobenzenesulfonate stronger oxidation potential are able to cause the false failures shown above impede.

The subject matter of the invention is thus a process for shedding / reduction-sensitive dyes a reduction when dyeing or printing fiber materials by adding oxidizing agents, their 0.05% aqueous solutions form an oxidation pole between + 20OmV and + 30OmV, according to patent 27 30 313, which is characterized is that the fiber material consists of cellulose or contains cellulose and the dye is cellulose affine.

The amounts of oxidizing agent added to the printing pastes or padlocks correspond those of the main patent application,

Cellulose substrates are all materials made from native or regenerated cellulose and theirs To understand mixtures with one another or with synthetic fibers.

In the case of the dyes to be protected against reductive influences on cellulose substrates according to the invention On the one hand, there are reactive dyes, in particular based on azo, anthraquinone or phthalocyanine, soft with at least one of the known reactive substituents like the

ß-Hydroxyäthylsulfonschwefeisäure-

ester group,
Vinylsulfonyl group,
Monochlorotriazine group,
Dichlorotriazine group,
2,2,3,3-tetrafluorocyclobutane-l-acrylamino-

group,

Vinylsulfonylamino group,
jJ-Hydroxyäthylsulfonylaminosulfuric acid

ester group,
/ J-phenylsulfonylpropionylamino group

or have a dichloroquinoxaline residue or are capable of reacting with a colorless compound, which contains at least two reactive groups, and with both the fiber and the nucleophile Dye containing groups can react.

As compounds with at least two reactive groups that carry the nucleophilic groups Linking dye to the fiber as a bridge link, for example:

13,5-tris (acryloyl) hexahydro-s-triazine.
Ethylenebisacrylamide or
2,4,6-triethylenimino-s-triazine.

As dyes that have these bifunctional compounds react with the fiber are preferably those dyes of the azo and anthraquinone series suitable as nucleophilic groups, for example sulfonamides N-mono-substituted sulfonic acid amides Hydroxy. Mercapto and / or acetoacetyl groups and / or heterocyclic ring systems containing imino groups contain.

The reactive dyes described above can be fixed in that the printing ink or Padding liquor the required amounts of alkali, z. B. sodium hydrogen carbonate or anhydrous soda added and the prints or dyeings steamed in saturated steam or superheated steam or the action of Exposed to dry hits. But you can also prepare the rare substances without the addition of alkali and fixation by one of the so-called two-phase processes, with the alkali in a second Process step /. B. by padding, paddling or dipping, is applied to the goods, the then subjected to a short steaming process or to prolonged storage without supply of heat can be.

On the other hand, non-reactive dyes such as, for example, are substantive dyes in the inventive method ¹ dei efficient Reduklionsverhinderung included ',

Suitable thickeners for the printing pastes are, for. B, neutral, weakly alkaline or weakly acidic reactive alginates, gums, alkyl celluloses or hydroxyethyl celluloses. as well as their mixtures and emulsions or half-emulsions produced therefrom with the aid of suitable emulsifiers.

In the examples for the dyes used The color index numbers given were taken from its 2nd edition in 1956 and from the supplementary volume in 1963.

Percentages relate to weight
The specified oxidation potential (abbreviated »OP«) applies to the 0.05% aqueous solution.

Example 1 ίο

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

5 g of the dye of C I. No. 20 505 are with

20 g of urea mixed and in
200 g of hot water dissolved The dye solution is dissolved in

500 g of a 5% aqueous solution of a low-viscosity sodium alginate as a thickener are stirred into the mixture
10 g of sodium hydrogen carbonate were added. With
265 g of water or the aforementioned thickening

will be on
H) OOg filled up.

The printed fabric is steamed in a Mather-Platt steamer in saturated steam at 102 ^° C. for 5 minutes. Then, the pressure with 0.5 g / I of the sodium salt of a Fettsäuresarkosids is washed for 10 minutes at 80 ⁰ C, and gespflt ι .trocknet

The result is a bluish-gray shade with good Fastnesses.

B) The pressure produced under A) is instead of 5 minutes 15 minutes under the same conditions steamed as under A) and then post-treated as there The gray one created under A) The hue is significantly weaker after longer steaming and subsequent washing violet-tinged shade turned over.

C) To the printing ink described under A), an additional 10 g of potassium iodate (OP at pH 10: + 285 mV) was added. Then proceed as under B). The same color is obtained in the same strength as under A).

Example 2

A) A rayon knitted fabric is padded with a padding liquor with the following composition:

3 g of the C.I. No. dye. 18 097 are with

20 g of urea mixed and in
Dissolve 200 g of hot water. The dye solution is with

100 g of a 5% strength aqueous solution of a highly viscous sodium alginate are added. Then will
8 g of sodium hydroxide solution (32.5%) are added, with water being added

1 1 filled up

The padded knitted fabric is steamed in a hanging loop steamer at 102 ° C. for 5 minutes. then is washed, rinsed and dried with the addition of 1 g / l of a nonionic surfactant

A light violet dyeing with good fastness properties is obtained.

B) The dyeing produced under A) is steamed for 15 minutes instead of 5 minutes and the same further treatment as under A) exposed

The resulting color is compared to that under A) heavily lightened or the color is only still vaguely recognizable.

C) In addition to the padding liquor described under A)

10 g / I 2-chloro-4-nitrobenzoic acid (OP at pH 10: + 20OmV)

added, then the procedure as under B) is repeated

The result is the same color as under A).

Example 3

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

3 g of the C.I. No. dye. 17 757 will be

with

20 g of urea mixed and in
200 g of hot water dissolved the dye solution

is in

500 g of a 5% aqueous solution of a medium viscosity sodium alginate were incorporated as a thickener. Become the mix
6 g trisodium phosphate were added. With
271 g of water or the aforementioned thickening

will be on
1000 g completed.

The printed fabric is steamed for 3 minutes in a continuous steamer at 102 ° C. Then it will be the pressure treated as in Example 1 to the end. A light orange-colored print with good marks is obtained Fastnesses.

B) The fabric printed as in A) is 10 minutes instead of 3 minutes under the same conditions steamed as under A) and then treated as there. The unier A) resulting color has almost disappeared.

C) To the printing ink described under A, 10g / kg of the sodium salt of m-nitro-benzene sulf fonsäure added, the procedure is repeated as under B). This results in a more than that half the color strength weaker shade than under A).

D) The printing ink described under A) is additionally 10 g / kg of the potassium salt of 2-chloro-1 J-dinitrobenzene-5-sulfonic acid (OP at pH 10: + 24OmV) added. The printing · and fusing process is carried out as under B). The result is the Orahge color shade with the same color strength as under A).

Example 4

A) A fabric made of highly moisture-resistant CelluloSegeneratfa ' It is then printed with a printing ink of the following composition;

5 g of the dye of the 73% compound of the formula

HO ₃ S

HO NH ₂

SO ₃ H
and 27% of the compound of the formula

SO, CH ₃

SO ₃ H

N = N-

N-

-NH-

SO ₂ CH ₃
N
CH ₃

SO ₃ H

contains are with

20 g urea mixed and ^poured into r '

Dissolve 200 g of hot water. The dye solution is in

500 g of a 6% aqueous solution of a highly viscous hydroxyethyl cellulose mixed in as a thickener. Become this mixture ³ⁿ

10 g of sodium carbonate were added. With
265 g of water or the aforementioned thickening is applied

1000 g filled up ³ⁱ

The printed fabric is steamed in an HT steamer at 130 ° C. for 5 minutes. The print is then treated further as in Example 1. The result is a gray print with good fastness properties. _w

B) To better illustrate a reducing atmosphere, 1 g / kg of glucose is added to the printing ink described under A) and the printing carried out with it is subjected to the same fixing operation as under A). ^VI A hue that is strongly shifted towards violet is obtained.

C) In addition to the printing ink shown under B), 10 g / kg of sodium meta-vanadate (OP at -, n pH 10: + 29OmV) and the procedure repeated as there.

The result is the same color as under A).

Example 5 "

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

5 g of the C.I. No. dye. 20 505 are dissolved in 200 g of hot water, and the dye solution is in

500 g of a 5% aqueous solution of a medium viscosity sodium alginate as thickening stirred in. With

295 g of water or the aforementioned thickening is applied

1000 g completed.

The printed fabric is passed through a liquor on a padder, the 600 cnVl water glass (NaX): SiO2 = 1: 1.6; spec. Density 1.42 at 20 "C) and contains 90 g / l sodium carbonate, and immediately afterwards in a special steamer Steamed for 40 seconds at 102 ° C. The printed matter is then washed as usual. The result is a bluish gray print with good fastness properties.

B) The pressure produced under A) is stored for 24 hours after padding and steaming and then washed. This creates a hue that is strongly shifted towards red-violet.

C) The printing ink described under A) is additionally 10 g / kg of the sodium salt of 4-chloro-nitrobenzene-5-sulfonic acid (OP at pH 10: +215 mV) added. Then proceed as under B).

In this way the same pressure loss is obtained as under A.

Claims (1)

Claim: Process for the protection of reduction-sensitive Dyes before reduction in pad dyeing or printing of fiber materials by addition of oxidizing agents whose 0.05% aqueous solutions have an oxidation potential between Show + 20OmV and + 30OmV according to patent 27 30 313, characterized in that that the fiber material consists of cellulose or contains cellulose and the dye is cellulose affine.