US2375132A - Textile printing composition - Google Patents

Description

Patented May 1, 1945 TEXTILE PRINTING COMPOSITION v Roy A. Pizzarello, Mount Vernon, N. Y., asslgnor to Interchemical Corporation, New York, N. Y., a corporation of Ohio.

No Drawing. Application May 22, 1941, Serial No. 394,624

1 Claim.

nated with a compound capable of coupling with a diazo compound, and the printing paste is made up withthe diazo compound. In another method, the printing paste contains both the coupling compound and the diazo compound, which is stabilized against coupling by'the conversion of the diazo compound into a compound which is stable in alkali, but which reforms the active diazo compound on exposure to acid.

Coupling with substituted amines containing water-solubilizing groups is a preferred method of forming such coupling stabilized compounds; the resultant water-soluble triazenes (diazoamino and diazoimino compounds) are compounded with alkali acid coupling components,-

and' made up into printing pastes'in conventional fashion.

Such water-soluble triazenes are of rather recent origin, having been evolved within the last twenty years to meet the need of the trade for a means of printing ingrain azo colors without the necessity for pre-impregnating'the fabric. The older corresponding water-insoluble triazenes, made from amines not containing watersolubilizing groups, were never used because they could not be 'iispersedin water to make satisfactory printing pastes with the conventional water-dispersible thickeners.

In the copending application ,of Albert E. Gessler and myself-Serial No; 337,490, filed May 27, 1940, which issued on Feb. 2, 1943, as Patent No. 2,309,946there is described a type of printing paste which, for the first time, successfully employs water-insoluble triazenes.

These composition comprise essentially water-- insoluble tria'zenes of the group consisting of diazoamino and diazoimino compounds which can bereconverted into diazo compounds by aqueous acid uniformly dispersed through a hydrophobic liquid capable of forming stable water-in-organic liquid emulsions, most preferably water immiscible lacquers. Prior to printing, these composition are converted to waterin-organic liquid emulsions.

In the preferred form of that invention, the emulsion is formed with an aqueous solution of a compound capable of coupling with the diazo compound formed from the triazene, so that the final printing paste contains one dyestufl component in solution in-the water phase of the emulsion, and the other uniformly dispersed through the organic phase. On printing, the coupling component in aqueous solution is absorbed into, the cellulose fibers forming the yarns of the fabric, and the triazene is deposited on the outside of the fibers and yarns. When exposed to steam and acid fumes in an acid ager, the triazene is converted to the soluble diazo salt, which then couples with the coupling component. Since the coupling component is already fixed in the fibers in sharp outlines, the color is formed in these sharp outlines, and the resultant print is extremely sharp.

In another form of that invention, the emulsion is treated before printing with an aqueous acid solution added directly or preferably in the form of another emulsion. This aqueous acid solution converts the triazene to the water-soluble diazo salt which transfers from the organic into the aqueous phase; the resultant printing paste is a standard dyestufi solution-in-organic liquid emulsion paste, and may be printed on grounds prepared by impregnation with the coupling component. The principal advantage in this type of paste is that the water-insoluble triazenes are perfectly stable over extended periods in all hydrophobe organic solvents whether they are soluble or insoluble in them. Furthermore, these compounds, after conversion to the water-soluble diazo state, in the emulsion, are stable for several times as long as the same compound in conventional printing pastes.

The degree of dispersion of the triazene in the organic medium has a pronounced effect on the color of the prints. The dispersed compound should be at least microscopically dispersed-4. e. as particles which-are not individually visible to the naked eye, and should most preferably be in solution in the solvent to obtain optimum color value.

azine bis-diazoimino compounds; and that these compounds may also be employed in conventional water-pastes provided they are distributed microscopically, or smaller. This effect may be obtained by dissolving them in a water-miscible solvent, and adding the solution to the paste.

While water-soluble triazenes made from piperazine acetic acid have been used in printing pastes (see British Patent No. 423,587), these products are distinctly less advantageous than mine, since only, one molar equivalent of diazo compound is stabilized per mol of their piper'a- Y zine derivative. With piperazine itself the molar combining ratio is two to one.

Typical examples of my invention are as follows:

A. PREPARATION OF PIPERAZINE DIAZO- NIUM COMPLEXES EXAMPLE A1 Stabilization of -nltro-2-amino anisol .azine hexahydrate and 25 grams of sodium carbonate at 0 C. A yellow fiocculent precipitate was immediately formed. This mixture was stirred until there was no more free diazo present. The precipitate was then filtered, washed and dried. The yellow powder obtained weighed 24.2 grams (76.2%).

EXAMPLE A2 Stabilization of 4-chlor0-2-amino anisol One tenth mol (19.4 grams) of 4-chloro-2- amino anisol hydrochloride was pasted with 50 cc. of hot water. To this paste 250 cc. of cold water and ice was added. When the temperature reached 10 C., 15 cc. of MN hydrochloric acid were added. Diazotization was brou ht about by the addition of 7.0 grams of sodium nitrite in 2500. of water. After keeping the mixture at 10l2 C. for one-half hour, the solution was clarified andfiltered. The clear yellow colored filtrate was slowly added to a solution of 9.7 grams (.05 M) of piperazine hexahydrate and 25 grams sodium carbonate. held at 0 C. until coupling'was complete. The

.colored precipitate was filtered, washed and dried.

The tan powder weighed 20.4 grams (70%),

' EXAMPLE A3 Stabilizati n of dianisidine One tenth mol (24.4 grams) of dianisidine was dissolved in 20 cc. of 1ON hydrochloric acid. To effect dissolution heat was required. When solution was completed the mixture was cooled to 0-5 C. by the addition of ice and water. To the cold solution 30 co. more of 10N hydrochloric acid were added, followed by the addition of 14.0 grams of sodium nitrite in 50 cc. of water. Tetrazotization was continued for 30 minutes, when the solution was clarified and filtered. The light brown tetrazo solution was then coupled at 0 C. in the presence of sodium carbonate with 19.4 grams (one tenth mol) of piperazine hexahydrate. The precipitate was filtered, washed and dried. 29.1 grams (84.1%) of a tan powder was obtained.

EXAMPLE A4 Stabilization of ortho chlor aniline One tenth mol (12.7 grams) of O-chlor aniline are suspended in 250 cc. of water and 25 cc. of 10N hydrochloric acid added. The mixture is cooled to 10 C. by the addition of ice. A- solution of 7.0 grams sodium nitrite in 25 cc. of water The temperature was to a solution of 9.7 grams (.05 mol) of piperazine hexahydrate and 25 grams of sodium carbonate in water. Coupling takes place at 0 C. The resulting precipitate is filtered, washed and dried.

.The light cream colored powder weighed 27.5

grams (76%).

EXAMPLE A5 Stabilization of4-nit1'O-2-amino anisol 16.8 grams (0.1 mol) of 4-nitro-2-amino anisol are suspended in 250 cc. of water and25 cc. of 10N hydrochloric acid added. Ice is added to cool to 10-15 C. 7.0 grams of sodium nitrite dissolved in 50 cc. of water is added rapidly and the mix allowed to stir for 45 minutes, when it is clarified and filtered. The clear yellow colored diazo solution is slowly added at 0 C. to a solution of 9.7 grams of piperazine hexahydrate and 25 grams of sodium carbonate. A yellow precipitate formed immediately. This material was isolated, and the resulting yellow powder weighed 23.8 grams (75% yield) EXAMPLE A6 Stabilization of 4-chloro-2-amino toluene One tenth mol (14.2 grams) of 4-chloro-2- amino toluene were added to cc. of hot water. Then 25 cc. of 10N hydrochloric acid were added and the solution diluted with ice and water to .500 cc. so that the temperature was lowered to 10-12 C. During the course of 5 minutes, 7.0 grams of soduim nitrite in 25 cc. of water were added. Diazotization was continued for ari additional 25 minutes, when the solution was clarilied and filtered. The clear yellow filtrate was added to a water solution of 9.7 grams (.05 mol) of piperazine hexahydrate and 25 grams of sodium carbonate at 0 C. The temperature was maintained at 0 C. until coupling was complete. The faintly yellow precipitate was filtered, washed and dried. The resulting faintly yellow powder weighed 26.5 grams (68.0%).

Other known diazotized amines which can be 7 stabilized by-the same technique include the diazo derivatives of the following:

6-benzoyl amino-4-amino-meta-xylene 2 nitro-para-anisidlne Alpha-naphthylamine Beta-naphthylamine Benzidine 3:3 dichlor-benzidine Tolidine 4-amino-diphenyl-amine 4-amino-4' methoxy-diphenyl amine 4-amino-3 methoxy-diphenyl amine l-amino-anthraquinone EXAMPLE B1 A quantity of complex containing 1 gram of active diazo compound was dissolved in water to make 40 cc. This was emulsified into a. waterin-lacquer emulsion comprising- 150 grams Solvesso #2 (hydrogenated petroleum naphtha-B. R. 135 to 177 C.)

X parts by weight coupling component (see table) in the aqueousphase I X parts by weight 40% NaOI-I (see table) in the aqueous phase.

5 made to 100 parts by weight, with water.-

- 51.8 grams toluene P1 1 2 5? N hth 1 t Wit 80%!!! erazine com ex or a ano com on or p p ink p m ink hydroxide 5-nitro-2amino anisole 2. 44 Naphthol AS (anilide of beta-oxyuaphthoic 1. 56 2.

ac: 4-chlor-2-amino anisole 2. 40 Naphthol AS-OL (ortho-anisidide oi beta-oxy 1. 60 2.0

I naphthoic acid).

1. 63 Naphthol AS 2. 37 2. 2.35 1.65 2.0 2. 44 do l. 56 2. 0 4 chlor-2-aminotoluene 2 30 Naphthol AS-D (ortho-toluidid oi beta-oxy l. 70 2. 0

naphthoic acid).

5.0 grams concentrated emulsion consisting of 31.0 parts by weight alkyd resin (glycerol phthalate modified with 35% soya oil) 27.0 parts by weight of a solution of milled rubberv in Solvesso #2.

3.0 parts by weight linseed oil 8.0 parts by weight Solvesso #2 25.0 parts by weight aqueous NaCl solution 4.0 parts by weight sulfonated tannin 2.0 parts byweight 80% aqueous acetic acid Suflicient sulfuric acid to hydrolize the triazene (1.3 grams for monoamines, 2.5 for diamines) was then emulsified into the lacquer, as 20 cc. of an aqueous solution. Hydrolysis took about 15 above paste, gave satisfactory prints of good color value.

EXAMPLE B2 Emulsion pastes for printing on 'unpz'gment'ed cloth Printing emulsions were also made from each of these complexes according to the following formulation:

2.8 grams butanol 41.4 grams water parts by weight Solvesso #2 X parts by weight trlazene (see table) in the ganic phase EXAMPLE B3 Water pastes The equivalent amounts (see above) of the pigment components for each of the colors were mixed into the following paste:

minutes. A 20% sodium acetate solution made 25% sodium hydroxide 4.5 p to 20 W then added to buffer the acid; 35 'Cellosolve (ethylene glycol monoethyl ether) 10.0 the resultant paste was grams of a watertr l staroh-tragacanth thickening 70.0 in-lacquer emulsion containing the active diazo Pigment components 4.0 compound in the interior phase, ready to print w t 11.5

on cloth impregnated with coupling components.

Each of Examples A1 to A6 made up into the 40 The triazene is dissolved in the cellosolve before Obviously, the examples may be multiplied indefinitely without departing from the scope of my invention, which is defined in the claim.

I claim:

A textile printing paste comprising an emulsion, the inner phase of which is an aqueous alkaline solution of a diazo coupling component, and the outer phase of which is a microscopic dispersion of a piperazIne-bis-diazoimino com- 7 pound in which both heterocyclic nitrogens of the piperazineare attached to a diazo group in a hydrophobic liquid capable of forming stable water-in-organic liquid emulsions.

- nova. mam-Lo.