DE2511537B2 - 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 for the Developing dye printing usable coupling components,

b) one 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, which is characterized in that the amine is present as a dispersion with a minimum grain size of not more than 0.002 mm and that the formation of carbon on the fiber by the application of diluted aqueous solutions of organic acids with a minimum water solubility of 50 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 a Air passage from 40 to 90 seconds oiicr steaming with Brings about neutral steam or rapid drying with the addition of heat.

The coupling components used for carrying out the method according to the invention are preferably used low- or miltelsubstanlive arylamicles of acetoacetic acid, 2-oxy-nnphthalin-J-carboxylic acid or heterocyclic a-oxycarponic acids, may be mentioned for example

S-chloro-Z-aceto-acetylarrono-l ^ diethoxy-

benzoj, 4,4'-bis (aeetaacetyl-amino) -3,3'-dimethyl-

diphenyl and

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

2-Oxynaphthalene-3-carboxylic acid phenylamide and its derivatives substituted in the phenylamide radical by alkyl or alkoxy radicals or chlorine, such as 2-oxynaphthalene-3-carboxylic acid (2'-methylphenyl-1 ') amide _t

2-oxy-naphthalene-3-carboxylic acid (2'-methoxyphenyl-1 ') amide,

2-oxy-naphthalene-3-carboxylic acid (3'-chloro-6'-methoxy-phenyl-r) -amide and 2-Oxy-carbazole-3-carboxylic acid (4'-chlorophenyl-1 ') amide.

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

S-Amino ^ -methoxybenzoic acid amide, Aminosulfonic acid amides, such as 2-Amino-anisole-4-sulfonic acid diethylamide or

2-Amino-anisole-4-sulfonsäuΓe-n-butylaιr.id. Amino-nitrile, such as

l-amino ^^ - dimethoxy ^ -benzonitrile, Benzoyl-phenylenediamines, such as

I -amino- - -benzoyl-amino ^ .S-dimethoxy-benzene.

1-Amino-4-benzoylamino-2,5-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 color technique common amines.

The dispersions required for the new process the amines can be prepared in various known ways:

Suitable dispersions are thus obtained, for example, by grinding the amine in an aqueous solution Slurry, expediently in the presence of a dispersant, in order to avoid the formation of agglomerations. This operation can be done in one with Ball-filled roller or vibrating mills are carried out: agitator ball mills are particularly suitable are filled with glass beads or natural sand. The fine distribution by means of a so-called Dissolvers often lead to useful results.

Another possibility is to put a solid preparation in water, which through Spray-dry a base dispersion containing a solid dispersant or prepare the through Grinding a mixture of a solid dispersant and the amine, / .. I). in a pin mill, was produced. Suitable dispersions can also 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 it has sufficient solvent power for the amine, a separate solvent can be dispensed with,

The dispersants used can be anionic or nonionic in nature and, for example belong to the following substance classes:

Alkyl sulfonates, alkyl aryl sulfonates, Arylsulfonate, Ligninsulfonate, in

sulfonated cresol-formaldehyde resins,

Formaldehyde-naphthalenesulfonic acid condensates, Carbacylamino sulfonic acids, Alkyl polyglycol ethers, Alkylaryl polyglycol ether, Aryl polyglycol ether, Acyl polyglycol ester.

The dispersions consist of about 25 to 60% base and about 4 to 15% of the dispersant. In addition, you can use an agent such as glycol or> o Glycerine contains, to prevent freezing or drying out, or a fungicide such as pentachlorophenol to suppress any mold growth during prolonged storage.

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

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

The printing pastes can also contain customary printing auxiliaries such as glycerol, diglycol or diethyl sulfide contain.

In addition to the components for the developing dyes, the printing pastes can also be soluble Leukocup sulfuric acid ester color names contain η whereby the coloring possibilities are still let it multiply further.

This possibility opens up completely new perspectives for the so-called Africa printing, because, for example, the use of Sol. Vat Blue 1, C.I.No. 73002 the indigo, which is so popular in the African printing and batik industry, in a simple way can be imitated in a 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 from 4.0 to 2.5 at 20 ⁰ C and a boiling point above 175 ° C under normal pressure, such as vi 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, paddling, spraying or overpressure -, -, ken with a completely engraved, so-called thousand-point roller or a full-print stencil the previously printed and dried textile material transferred.

The diazotization and coupling to the finished ho Dye sets in spontaneously and practically at the same time, so that in the simplest case there is a continuous rise from 40 to 90 seconds is sufficient for the dye development to be complete. By adding heat the dye development can be significantly accelerated gene, for example by treatment 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 JOO to 15O ⁰ C,

This process delivers level and brilliant prints and is characterized as a result of the one-step, common Application of coupling component and amine in the printing ink is characterized by great simplicity compared to the usual printing processes with developing dyes. 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. So in the ancestor according to DE-PS 6 38 878 the development takes place 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, mineral acids, preferably hydrochloric acid, are mainly proposed in all of the patents.

Compared with the processes according to DE-PS 6 38 878 and DE-PS 6 63 496, the process according to the invention is much simpler, since there are none for dye development alkaline aftertreatment is required. The main advantage over DE-PS 6 61 225 lies in the significantly higher color yield, quite apart from the fact that there are procedural steps such as "impose" or "Slow drying" is not suitable for a continuous production process.

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

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.

Bet game I

20 parts of 2-oxy-naphthalene-3-carboxylic acid (2'-methylphenyl-1 ') amide (CI % sodium hydroxide solution is stirred and dissolved by addition of 100 parts of water at 6O ⁰ C. Then 20 parts of a 40% strength aqueous dispersion of 4,4'-diamino-3,3'-dimethoxydiphenyl (CINr. 37 235), which contains 15% of a lignin sulfonate as a dispersant, are diluted with 80 parts of water.

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 stirred in.

What is bleached is on a Rouleaux printing machine and mercerized cotton fabrics with this print

25 Π

paste printed and dried. After that, this goods will immediately before steaming on a two-roll pad with an aqueous cold 10% jgen solution of Monochloroacetic acid impregnated with a rot absorption of 75% and in the steamer for 2 minutes treated with neutral saturated steam of 102 "C.

Then, as usual, rinsing cold and hot, hot washed, rinsed hot and cold and finally dried. A full print is obtained Dark blue with the combination CLNr. ι ο 37 520 / CL No. 37 235 usual fastness properties.

Example 2

20 parts of 2-oxy-naphthalene-3-carboxylic acid (2'-methoxy-phenyl-l ') - amide (CLNr. 37 530) are mixed with a mixture of 40 parts of ethanol, 30 parts of jS, /?' - Dioxydiethylsulfid and 13 parts of 33 ° / cent sodium hydroxide solution and stirred by adding 50 parts of 70 ⁰ C warm water dissolved. 20 parts of a 40% strength aqueous dispersion of S-amino ^ -methoxy-benzoic acid amide, which contains 124% glycol and 10% castor oil fatty acid polyglycol ether as a dispersant, are then diluted with 80 parts of water

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 printed on a Gusset foulard 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-aeetoacetylamino-1,4-dimethoxy-benzene (CLNr, 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. 20 parts of a 45% strength dispersion of 4-nitro-2-aminotoluene are then added (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 aqueous 25% solution of wine iure using a full printing stencil and directly in the dryer 60 downstream of the printing machine Seconds dried with hot air of 130 ^{0 C.}

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

Example 4

A solution of 20 parts of 5-chloro-2-acetoacetylamino-1,4-dimethoxy-benzene (CL No. 37 613) in 32 parts of ethanol, 40 parts of water and 20 parts of 33% strength sodium hydroxide solution is dissolved in 400 parts of a 5% strength 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-anisoI (CI.Nr. 37 125) in water / ethylene glycol with 10% of the following polyglycol ethers as a dispersant

, —CH ₂ -O) ₁₈ -CH ₂ -CHj-O-CH.,

diluted with 100 parts of water, added and 20 parts Sodium nitrite, dissolved in 30 parts of water, added.

This printing paste is used on a film printing machine to bleach and mercerize cotton fabric 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 CI.No. 37 613 / CI.Nr. 37 125 usual fastness properties.

Example 5

20 parts of 2-oxy-naphthalene-3-carboxylic acid (2'-ethoxyphenyl-1 ') - arnid (CiNf. 37 558) are in a mixture of 16 parts of ethanol, 30 parts of β, β'-O \ o \ y diäthylsulfid, 16 parts of 33% sodium hydroxide solution and 40 parts of water dissolved from 40 ⁰ C and diluted with a further 200 parts of water.

In 400 parts of an 8% thickening of a non-ionic germ meal ether, only this naphthol solution, then 20 parts of a 1: 5 with

4) water-diluted dispersion of 4-nitro-2-aminoanisole, CI No. 37 130 (composition as given in Example 2) and finally a solution of 20 parts Sodium nitrite entered in 40 parts of water.

A bleached and causticized cotton poplin is printed with this printing paste on one of the customary Rouleaux printing machines and dried. This zwischeiigetrocknete product is again supplied to the same printing machine and by means of Üner so-called thousand point roller having a slightly thickened aqueous 25% solution of lactic acid / glycolic acid is 1: overprinted 1 and directly in the printing machine downstream dryer by treatment with hot air at 13O ⁰ C for 90 Seconds dried. It is aftertreated as in Example 1, and a scarlet pattern is obtained with the same characteristics as in the combination CI.No. 37 558 / CINr. 37 130 usual fastness properties.

Example 6

hi 15 parts of 2-oxy-carbazole-3-carboxylic acid (4'-chlorophenyl-1 ') amide (CINr. 37 600) were with 25 parts of ethanol, 30 parts of j3./?'- dioxyethyl sulfide and 20 parts 33% sodium hydroxide solution and stirred by adding

100 parts of 4O ⁰ C warm water dissolved. Then 30 parts of a 45% strength dispersion of 4-nitro-2-aminotoluene (Cl.Nr. 37 105) in water / ethylene glycol (with 14% of a lignin sulfonate as dispersant) were diluted with 100 parts of water.

In 400 parts of a 5% aqueous thickener Kernmehläthers is first the solution of the coupling component, then the diluted amine dispersion and finally registered a solution of 20 parts of sodium nitrite in 40 parts of water. u>

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 r> aqueous solution of 150 g / l of monochloroacetic acid and steamed for 30 seconds with superheated steam of 130 ⁰ C.

After tier üüueuen NuLii'uenuiiuiuiig ethäii mim cm brown print sample with the fastness properties usual for the combination: o C.I.Nr.37 600 / C.I.Nr.37 105.

Example 7

20 parts of nickel phthalocyanine-tetra- [sulfonic acid- (3 '- (3 "-methyl-pyrazolonyl-1") -phenyl-r) -amide] were r> with 25 parts of ethanol. , J3'-Dioxäthyl sulfide and 20 parts of 33% strength sodium hydroxide solution and stirred by adding 100 parts 4O ⁰ C warm water dissolved 30 parts /. 9 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 diluted amine dispersion and r. finally a solution of 20 parts of sodium nitrite in 40 Share water entered.

This printing ink is printed on a bleached and mercerized cotton twill according to the pattern on a printing device customary in practice and dried -m net. After spraying on a damper electrostatic spraying device upstream with a cold aqueous solution of 300 g / l of monochloroacetic acid to a liquor ratio of 20% is immediately 4> steamed 20 seconds with superheated steam at 150 ⁰ C in the damper.

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-oxynaphthalene-3-carboxylic acid naphthylamide (CIN No. 37 560) and 5 parts of 5-chloro-2-ciceto-acetylaniino-1.4-dimethoxybenzene
(CINr. 37 613) with 25 parts of ethanol. 30 parts of butyl diglycol and 2} parts of 33% sodium hydroxide solution are stirred up and dissolved by adding 100 parts of water at 60 ° C. This solution is stirred into 400 parts of a 5% aqueous thickener of a gruel, which is then 20 parts of that in Example I. The dianisidine dispersion described, diluted with 70 parts of water and 20 parts of sodium nitrite dissolved in 40 parts of water, can be added, and ¹ in 250 parts of water is added to set the required viscosity.

A bleached cotton tricot is printed with this printing ink on a planographic printing machine and dried. After that, the printed and dried Goods on a two-roll foulard with a 20 ° oigen aqueous solution of monochloroacetic acid and immediately in a hot flue with hot air son 140 C. wäni'enu 80 seconds geii "üCkilei.

After the usual rinsing and soaking, you get a printed pattern 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, are under Addition of 25 parts of butyl diglycol and 25 parts of Urnstor by pouring 150 parts of hot water over them Dissolved water and in 400 parts of an 8% aqueous thickening of a nonionic gum meal and Stir in 220 parts of water. Sodai: n becomes a solution of 10 parts of S-chloro ^ -acetoacetylamino-l ^ -dimethoxy-benzene (C.I.Nr. 37 613) in 15 parts of ethanol. 20 parts of water and 20 parts of 33% sodium hydroxide solution added with stirring. Then 10 parts of a 45% strength dispersion of 4-nitro-2-aminotoluene are added (CL no. 37 105) in water / ethylene glycol with 14% of one 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 onto a bleached and mercerized cotton fabric according to the pattern on a printing device customary in practice and dried. The printed and dried goods are then impregnated with a 25% strength aqueous solution of monochloroacetic acid in the gusset of a fiber (four-roll padder) (liquor uptake 70%) and immediately steamed with superheated steam at 150 ^° C. for 20 seconds. After the usual aftertreatment, a print sample is obtained in a strong lime green with excellent brewing fastness.

Claims (2)

Claims; 1, Method of making 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 which can be used for developing dye printing, b) one or more amine suitable for the preparation of developing dyes 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 grain 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 water, a pK value of 4.0 to 2.5 at 20 ⁰ C and a boiling point above 175 ° C 2> 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 brings about. 2. The method according to claim 1, characterized in that the fabric is used with printing pastes printed which, in addition to the components for the development dyes, contain soluble leukocupesulfuric acid ester dyes.