DE2511537C3 - Process for printing with developing dyes - Google Patents

Description

The invention relates to a process for producing prints with developing dyes on cellulosic! or textile material consisting exclusively of cellulose by printing the Fabric with a printing paste that

a) the alkaline solution of one or more coupling components that can be used for developing dye printing,

b) one or more such amines suitable for the production of developing dyes, vt

c) sodium nitrite and

d) contains a print thickening,

and developing the print with an acid,
which is characterized in that the amine is present as a dispersion having a mean grain size of high-η least 0.002 mm and d;> ß one dye formation on the fiber by application of dilute aqueous solutions of organic acids with a minimum water of 30 g per 100 g water, a pK value of 4.0 to 2.5 at 20 ° C and a bo boiling point above 175 ° C at normal pressure, and an air passage of 40 to 90 seconds or steaming with neutral steam or rapid drying with the addition of heat .

The coupling components used for the implementation b '> tion of the process according to the invention preferably low- or medium-noun arylamides of acetoacetic acid, of 2-oxynaphthalene-3-carboxylic acid or heterocyclic o-oxycarboxylic acids. Be mentioned for example

S-CMor ^ -aceto-acetylamino-l. ^ Diethoxy-

benzene,
4,4'-bis (acetoacetyl-amino) -33'-dimethyl-

diphenylund

2-aceto-acetylamino-6-ethoxy-benzothiazole,
Further

2-Oxy-naphthalene-3-carboxylic acid-phenylamide and
its in the phenylamide residue
Alkyl or alkoxy radicals or chlorine
substituted derivatives such as
2-oxynaphthalene-3-carboxylic acid (2'-methyI-phenyl-1 ') amide,

2-oxy-naphthalene-3-carboxylic acid (2'-methoxyphenyl-l'j-amide,

2-Oxy-naphthalene-3-carboxylic acid (3'-chloro-6'-methoxyphenyl-1 ') amide and
2-Oxy-carbazole-3-carboxylic acid (4'-chlorophenyl-1 ') amide.

Can be used as amines
Nitraniline, like
2-nitroaniline,
3-nitroaniline,
4-nitro-2-amino-anisole,
5-nitro-2-amino-anisole,
5-nitro-2-aminotoluene or
S-nitro ^ -amino-anisole,
Aminocarboxamides, such as

5-Amino-4-methoxybenzoes ^: acid amide,
Aminosulfonic acid amides, such as
2-Amino-anisole-4-sulfonic acid diethylamide
or

2-amino-anisole-4-sulfonic acid-n-butylamide,
Amino-nitrile, such as

l-Am''no-2,5-dimethoxy-4-benzonitrile,
Benzoyl-phenylenediamines, such as

l-Amino ^ -benzoyl-amino ^ .S-dimethoxy-benzene,

l-Amino ^ -benzoylamino ^ S-diethoxy-benzene
or

2-amino-4-methyl-5-benzoylamino-anisole,
Diamino-diphenyls, such as
Di-o-toluidine or dianisidine as well
others in the ice trap technique
common amines.

The dispersions of the amines required for the new process can be based on various known ones Ways to be prepared:

Suitable dispersions are thus obtained, for example, by grinding the amine in an aqueous solution Slurry, expediently in the presence of a dispersant, to prevent agglomerations from forming to avoid. This operation can be carried out in a roller or vibrating mill filled with balls; Agitator ball mills filled with glass beads or natural sand are particularly suitable. Fine distribution using a so-called dissolver also often leads to useful results.

Another possibility consists in introducing a solid preparation in water, which was prepared containing base dispersion by spray drying a dispersant, a solid or, prepared by milling a mixture of a solid dispersant and the amine,? .. as in a pin mill. Suitable dispersions can also be prepared by introducing a solution of an amine and a suitable dispersant in a water-soluble

Solvent in water or in the printing paste can be obtained. Is the dispersant liquid and if it has sufficient dissolving power for the amine, a separate solvent can be dispensed with will.

The dispersants used can be anionic or nonionic in nature and belong, for example, to the following classes of substances:
Alkyl sulfonates, alkyl aryl sulfonates,
Aryl sulfonates, lignosulfonates,

sulfonated cresol-formaldehyde resins,
Formaldehyde-naphthalenesulfonic acid condensates, carbacylamino-sulfonic acids,
Alkyl polyglycol ethers,

Alkylaryl polyglycol ethers, aryl polyglycol ethers,
Acyl polyglycol ester.

The dispersions consist of about 25 to 60% base and about 4 to 15% of the dispersant. They can also contain an agent such as glycol or glycerine to freeze or dry out Avoid using a fungicide, such as pentachlorophenol, to prevent any mold growth during an extended period of time Suppress storage.

The said mean grain size of at most 0.002 mm is determined according to Ramler-Rosin.

All alkali-resistant, low-body thickenings can be used as printing thickenings, e.g. B. Corn meal ether thickenings.

• The printing pastes can also use conventional printing auxiliaries such as glycerine, diglycol, diethyl sulfide.

In addition to the components for the developing dyes, the printing pastes can also be soluble Contain leukocup sulfuric acid ester dyes, which means that the coloring options are still available let it multiply further.

This possibility opens up completely new perspectives for so-called Africa printing, since, for example, by using Sol. Vat Blue 1, GI.Nr. 73002 in Africa Print and Batik industry allows the popular indigo to be imitated in a simple and deceptively similar manner

Suitable acids for dye development on the fiber are all organic mono-oxy-mono-carboxylic acids, dioxy-dicarboxylic acids, mono-oxy-tricarboxylic acids or halocarboxylic acids with a water solubility of at least 30 g in 100 g water, a pK value of 4, 0 to 2.5 at 20 ° C and a boiling point above 175 ⁰ C under atmospheric pressure, such as lactic acid, glycolic acid, tartaric acid, citric acid or monochloroacetic acid.

These acids are used in amounts of 50 g / l to 300 g / l water, preferably 100 to 200 g / l water Padding, Pflatsciien, spraying or overprinting with a completely engraved, so-called A thousand-point roller or a full printing stencil on the previously printed and dried textile material transfer.

The diazotization and coupling to the finished w) Dye sets in spontaneously and practically at the same time, so that in the simplest case there is a continuous passage of air from 40 to 90 seconds is sufficient for the dye development to be complete. By adding heat the dye development can be significantly accelerated, for example by treating with hot air from 130 to 160 ° C for 20 to 60 seconds in the Attic or by neutral steaming with saturated steam or superheated steam for 10 to 20 seconds at 100 to 150 ° C

This process delivers level and brilliant prints and is characterized as a result of the one-step, common Use of coupling component and amine in the printing ink compared to the usual printing processes with developing dyes characterized by great simplicity. It also offers the option of simultaneous use of two or more coupling components or amines multiplied Coloring options.

Processes have already been described in the literature in which mixtures of azo components and Amines are printed. Thus, in the process according to DE-PS 6 38 878, the development is carried out to Dye through an acid passage with subsequent neutralization by passing through an alkali bath. In the DE-PS 6 61 226 is this alkali passage by gradually drying, hanging in the air or replaced by thorough rinsing; in DE-PS 6 63 496 there is a treatment with basic vapors instead described. For the acid passage in all patents mainly mineral acids are preferred Hydrochloric acid, suggested.

Compared with the method according to DE-PS 6 38 878 and DE-PS 6 63 496, the method according to the invention is much easier, since no alkaline aftertreatment is required for dye development. The essential thing The advantage over DE-PS 6 61 225 is the significantly higher color yield, quite apart from that, that process steps such as "hanging" or "slow drying" are not continuous Production process.

The most significant difference compared to the cited prior art, however, lies in the Use of dispersed bases of the grain size mentioned, with which is practically unlimited Can produce durable printing pastes, and in the possible simultaneous use of several coupling components or amines in the printing ink, which gives additional coloring options are.

The following examples are intended to explain the procedure according to the invention in more detail. The ones in the examples for the color index numbers used were the 3rd edition in 1971 taken. The amounts and percentages are parts by weight or percentages by weight.

example 1

20 parts of 2-oxy-naphthalene-3-carboxylic acid (2'-methylphenyl-1 ') amide (C.I.Nr. 37 520) with a mixture of 25 parts of ethanol, 30 parts / 3, j3'-Dioxydiethylsulfid and 20 parts of 33% sodium hydroxide solution and stirred by adding 100 parts of water 60 ° C dissolved. Then 20 parts of a 40% strength aqueous dispersion of 4,4'-diamino-3,3'-dimethoxydiphenyl (C.I.Nr. 37 235), which contains 15% of a lignosulfonate as a dispersant, with 80 parts of water diluted.

In 400 parts of a 5% aqueous thickening one Kernel flour ether diluted with 250 parts of water becomes the naphthol solution first, then the dilute amine dispersion and finally a solution of 20 parts of sodium nitrite in 40 parts of water 0 stirred.

On a Rouleaux printing machine, bleached and mercerized cotton fabric is printed with this

paste, printed and dried. Immediately before steaming, this product is then impregnated on a two-roll foulard with an aqueous, cold 10% solution of monochloroacetic acid at a liquor pick-up of 75% and ^{treated with neutral saturated steam at 102 °} C. for 2 minutes in the steamer

Then, as usual, it is rinsed cold and hot, washed hot, rinsed hot and cold and finally dried A print is obtained in a deep dark blue with the values for the combination CLNr. 37 52GrOLNr. 37 235 usual fastness properties.

Example 2

20 parts of 2-oxy-naphthalene-3-carboxylic acid (2'-methoxyphenyl-1 ') amide (CL No. 37 530) are mixed with a mixture of 40 parts of ethanol, 30 parts of /?, /? '- Dioxydiethylsulfid and 13 parts of 33% sodium hydroxide solution and stirred by adding 50 parts of 70 ° C warm water Then 20 parts of a 40% aqueous dispersion of S-amino ^ -methoxy-benzoic acid amide, which contains 12.5% glycol and 10% castor oil fatty acid polyglycol ether as a dispersant, with 80 parts Water diluted

In 400 parts of a 6% aqueous thickener of a gum meal ether, which is diluted with 300 parts of water first the naphthol solution, then the diluted amine dispersion and finally a solution stirred by 20 parts of sodium nitrite in 40 parts of water. jo

This printing paste is used to produce a bleached and mercerized cotton fabric on a film printing machine printed in any pattern. After the subsequent drying, the goods are placed on a Zwickelfoulard with a cold aqueous 20% solution of monochloroacetic acid (liquor absorption 80%) impregnated and the dye during an immediately subsequent air passage of 80 seconds continuously developed. After the usual aftertreatment, a print sample is obtained in one bright red with the known good fastness properties.

Example 3

A solution of 20 parts of 5-chloro-2-acetoacetylamino-1,4-dimethoxy-benzene (C.I.Nr. 37 613) in 32 parts of ethanol, 40 parts of water and 20 parts of 33% strength Sodium hydroxide solution is in 400 parts of an 8% aqueous thickener of a nonionic gum meal and 300 parts of water are stirred in. Then 20 parts of a 45% strength dispersion of 4-nitro-2-amino-toluo! (CL No. 37 105) in water / ethylene glycol with 14% of a lignin sulfonate as a dispersant, diluted with 100 Parts of water are added and 20 parts of sodium nitrite dissolved in 30 parts of water are topped up

This printing paste is used on a rotary film printing machine to print a bleached and causticized cellulose fabric with a round stencil engraved as desired and, after drying, again overprinted with a slightly thickened 25% aqueous solution of tartaric acid using a full printing stencil and then directly in the dryer downstream of the printing machine with hot air for 60 seconds dried from 130 ^{0 C.}

Then it is rinsed, soaped, rinsed again and dried as usual. You get a yellow one Print sample with the combination C.I.Nr. 37 613 / C.I.Nr. 37 105 usual fastness properties.

Example 4

A solution of 20 parts of 5-chloro-2-acetoacetylamino-1,4-dimethoxy-benzoi (C.I.Nr. 37 613) in 32 parts of ethanol, 40 parts of water and 20 parts of 33% sodium hydroxide solution is converted into 400 parts of a 5% aqueous solution Thickening of a gruel and 300 parts of water are stirred in. Then 20 parts of a 45% strength Dispersion of 5-nitro-2-amino-anisole (C.I.Nr. 37 125) in water / ethylene glycol with 10% of the following polyglycol ethers as a dispersant

₂ - CH ₂ -O) _1x -CH ₂ -CH., - O — CH.,

diluted with 100 parts of water, added and 20 parts of sodium nitrite, dissolved in 30 parts of water, topped up.

This printing paste is used to bleach and mercerized cotton fabric on a film printing machine printed. After drying in the drying box downstream of the printing machine, the fabric on an electrostatic spray device upstream of the damper with a cold aqueous spray device 30% solution of monochloroacetic acid sprayed up to a liquor application of 20% and immediately im Steam treated with superheated steam at 150 ° C for 20 seconds. After the usual rinsing and soaps you get a print sample in a gold tone with the combination of C.I.No. 37 613 / C.I.Nr. 37 125 usual fastness properties.

Example 5

20 parts of 2-oxy-naphih. ^ n-3-carboxylic acid (2'-ethoxyphenyl-l ') - amide (Ciisi. 01 558) are in a mixture of 16 parts of ethanol, 30 parts of j3, j3'-dioxydiethyl sulfide, 16 parts of 33% sodium hydroxide solution and 40 Parts of water at 40 ° C dissolved and diluted with a further 200 parts of water.

In 400 parts of an 8% thickening of a non-ionic core steel, this naphthol solution is first then 20 parts of a dispersion of 4-nitro-2-aminoanisole diluted with water in a ratio of 1: 5, C.I.No. 37 130 (composition as given in Example 2) and finally a solution of 20 parts Sodium nitrite entered in 40 parts of water.

On one of the usual Rouleaux printing machines

> o With this printing paste a bleached and Leached cotton poplin, printed and dried. This intermediate dried product is again fed to the same printing machine and by means of a so-called thousand-point roller with a light

v> thickened aqueous 25% solution of lactic acid / glycolic acid 1: 1 overprinted and dried directly in the dryer downstream of the printing machine by treatment with hot air at 130 ° C. for 90 seconds. It is aftertreated as in Example 1, and

bo you get a scarlet pattern with the Combination C.I.Nr. 37 558 / C.I.Nr. 37 130 usual fastness properties.

Example 6

b5 15 parts of 2-oxy-carbazole-3-carboxylic acid (4'-chlorophenyl-1 ') amide (C.I.Nr. 37 600) were mixed with 25 parts of ethanol, 30 parts of j9, ß'-dioxyethyl sulfide and 20 parts 33% sodium hydroxide solution and stirred by adding

25th

Dissolved 100 parts of warm water at 40 ° C. Then 30 parts of a 45% dispersion of 4-nitro-2-aminotoluene (C.I.Nr. 37 105) in water / ethylene glycol (with 14% of a lignin sulfonate as a dispersant) diluted with 100 parts of water. ■>

In 400 parts of a 5% aqueous thickening of a gum flour ether, only the solution of the coupling component, then the dilute amine dispersion and finally a solution of 20 parts of sodium nitrite in 40 Share water entered.

This printing ink is transferred to a bleached and mercerized cotton twill using a conventional flat stencil. After drying, the fabric is slop on a conventional two-phase dampers upstream block device with a cold aqueous solution of 150 g / l of monochloroacetic acid and steamed for 30 seconds with superheated steam of 130 ⁰ C.

After the usual aftertreatment, a brown print pattern is obtained with the combination C.l.Nr.37 600 / C.I.Nr.37 105 usual fastness properties.

Example 7

20 parts of nickel phthalocyanine tetra- [sulfonic acid- (3 '- (3 "-methyl-pyrazolonyl-l") - phenyl-r) -amide] were mixed with 25 parts of ethanol, 30 parts of j?, JS'-dioxäthyI sulfide and Stirring 20 parts of 33% strength sodium hydroxide solution and dissolving it by adding 100 parts of warm water at ^{40 ° C.} Then 30 parts of a 45% strength dispersion of 4-nitro-2-aminotoluene (CINr. 37 105) in water / ethylene glycol (with 14% of a lignin sulfonate as a dispersant) were diluted with 100 parts of water.

In 400 parts of a 5% thickening of a flour ether, the coupling component is first dissolved, then the dilute amine dispersion and finally a solution of 20 parts of sodium nitrite in 40 Share water entered.

This Printing ink printed on a bleached and mercerized cotton twill according to the sample and dried. After spraying on an electrostatic spray device upstream of the damper with a cold aqueous solution of 300 g / l monochloroacetic acid up to a liquor application of 20% Immediately steamed in the steamer for 20 seconds with superheated steam at 150 ° C.

After the usual rinsing and soaping, a green print sample with good fastness properties is obtained.

Example 8

A mixture of 15 parts of 2-oxy-naphthalene-3-carbuiisäuie-iiaphihyiamid (CiNr. 37 560) and 5 parts S-Chlor ^ -aceto-acetyiamino-1,4-dimethoxy-benzene (CLNr. 37 613) are with 25 parts of ethanol, 30 parts of butyl diglycol and 23 parts of 33% sodium hydroxide solution is stirred and dissolved by addition of 100 parts of water at 6O ⁰ C. This solution is stirred into 400 parts of a 5% aqueous thickener of a gum meal ether, to which 20 parts of the dianisidine dispersion described in more detail in Example 1, diluted with 70 parts of water, and 20 parts of sodium nitrite, dissolved in 40 parts of water, are added. The required viscosity is set by adding 250 parts of water.

A bleached cotton tricot is printed with this printing ink on a planographic printing machine and dried. Thereafter, the printed and dried fabric is slop on a two-roll padder with a 20% aqueous solution of monochloroacetic acid and immediately dried in a hot flue with hot air at 14O ⁰ C for 80 seconds.

After the usual rinsing and soaping, a print pattern is obtained in a rich, highly lightfast black with the usual good fastness properties.

Example 9

25 parts Sol. Vat Green 1, C.I. No. 59 826, with the addition of 25 parts and 25 parts of butyl diglycol Dissolve urea by pouring 150 parts of hot water over it and add 400 parts of an 8% strength aqueous solution

Thickening of a non-ionic gruel and 220 parts of water are stirred in. Then there is a solution of 10 parts of 5-chloro-2-acetoacetylamino-1,4-dimethoxy-benzene (Cl.Nr. 37 613) in 15 parts of ethanol. 20th Parts of water and 20 parts of 33% strength sodium hydroxide solution are added with stirring. Then another 10 parts are added a 45% dispersion of 4-nitro-2-aminotoluene (Cl.Nr. 37 105) in water / ethylene glycol with 14% of a Lignosulfonate as a dispersant, diluted with 100 parts of water, added and 30 parts of sodium nitrite, dissolved in 50 parts of water, replenished.

The printing ink prepared in this way is printed in accordance with the pattern on a bleached and mercerized cotton fabric on a printing device customary in practice and dried. ) and immediately for 20 seconds steamed with superheated steam of 150 ⁰ C. After the usual aftertreatment to obtain a print pattern in a strong lime green with excellent Gebrauchsechiheiien.

Claims (2)

Patent claims: 1. Process for the production of prints with developing dyes on cellulose-containing! or Textile material consisting exclusively of cellulose by printing the fabric with a Printing paste that a) the alkaline solution of one or more which can be used for developing dye printing Clutch components, b) a for the production of developing dyes suitable amine or several such amines, c) sodium nitrite and d) contains a print thickening, and developing the print with an acid,
characterized in that the amine is present as a dispersion with an average particle size of at most 0.002 mm and that the dye formation on the fiber by applying dilute aqueous solutions of organic acids with a minimum water solubility of 30 g per 100 g of water, a pK value of 4.0 to 2.5 at 20 ° C and a boiling point above 175 ° C at normal pressure, and air passage of 40 to 90 seconds or steaming with neutral steam or rapid drying with the addition of heat brings about 2. The method according to claim 1, characterized in that the fabric with printing pastes printed, in addition to the components for the developing dyes, soluble leukocupesulphuric acid ester dyes contain. 35