claim: 1. The process for the application of sulfuric ester salts of leuco vat dyestuffs to textiles, which 25 comprises the @ addition to the ester salts of a compound of the general formula 8 0 3 R The. cotton is then rinsed thoroughly, boiled - -water at 65' C., washed' C C 8 5 where @R stands for an atom-or radical conferring solubility. In water, said compound being free of the corresponding salt of mono-benzyl-sulfanilic acid. 2. The process as claimed In - claiin I which 40 comprises the application of the said compounds in solution 4h a polyhydrig alcohol. @ 3. The proce@a of colorijig textfle fiber which comprises spplying thereto- the sulfuric acid ester of a leuco vat dyestuff In the presence of a water- 4r3 soluble salt of dib6nalsulfanflic acid substan. tially fiee of salts of mono-benzylswfanilic acid, and diethylene-glycol. 4. The process of coloring textile fiber which comprim applying_ thereto the sulfuric acid ester r)O of a leuco vat dyestuff in the presence of a waterfuric acid 160',TW., per 100 gal. of water at-50, C. soluble salt of'dibenzylsulfanilic acid, the amount The coit;@ Is worked In this bath for 3 min- of the said salt being at least equal in -weight to utes, removed, rinsed thproughly, boiled ln- 1% that of the leuco-ester. . 55 soap soluti(m, rimed and dried., ALEC WOP.BL4LD. 55

Patented Feb. 4, 1936 2 1 0 2 9 2 3 5 1 UNITED STATES PATENT GFFICE 21029,351 DYEING PROCESS, Alec Wormald, BIackley, England, assignor to linperial ChemicaI Industries Lbuited, a corporation of Great Britain No Drawing. Application June 20, 19t4, Serial No. 731,571. In Great Britain June 26, 1933 4 Claims. (CL Mtherto it has been proposed to use solution 'with hot water. The sodium salt is formed by salt as an assistant in applying sulfuric ester salts of leuco vat dyestuffs to textiles. Solution salt B consists essentiary of the so(iium salt of ,5 monobenzylsulfanilic acid, but as technically pre-. pared, it.sometimes'contains a @mall proportion 6f dibenzylsulfanilic acid. I have now found dibenzylsulfanilic acid is a better -assistant than monobenzyLsWfanilic acid in the application of the said sulfuric ester salts. Her6after in this specification when I speak of dib enzylsulfanilic acid I do not include the dibenzylsulfanilic acid which is ordinarily present in monobenzylsulfanilic acid. The present invention consists in a r-,rocess for the application of s ulfuric ester salts of leuco vat dyestuffs to textiles, whieh comprises the addition to the ester salts of a. compound of th.e generai formula B OsR 20 25 C where R stands for hydrogen, sodiitm, potassium, ammonium or other substituent confe:rring solu30 bility in water. It also comprises the appucation of the said compounds in solution in a polyhy&ic alcoliol. Application may be by any of the usual methods, Including printing, dyeing, padding and stenculing. 35. Generally the use of dibenzyLmHanfflc acid improves the solubuity of the sulfuric ester salt: it gives printing pastes with better working properties, and enables prints and dyibings to be obtained in deeper shades. These advantages show 40 most with those su.1furic est6r salts of, low solubirty, particularly with Indigosol brown nMD, (Schultz, Parbstqfftabellen, 7th edit., vol 1, page 139) pink IIR extra (Supplement to, the Colour index, page 43) and red violet@ IRH, (Schultz iiii 45 page 133), and Soledom br!Mant -purple, (Supplement, page 52). DibenzylsulfaniUc acid is prepated as follows:173 parts of sulfanire acid, 1000 parts of. water, -480 parts of aqueous caustic soda Hquor (33%) 50 and -317 parts of benzyl chloride are itirred at C. for 48 hours. The e7xcess caustic soda is neutralized with concentrated hydrochloric acid and then, a further 80 parts@ of hydrochloric acid added; the precipitated -dibenzylsulfanire ae.id Is ffltered off and washed free from benzyl chloride dissolving the acid in water containing the the"oretical amount of sodium hydroxide - and then either allowing to crystalhze out or evaporating to dryness. The following examples in which parts are by weight irustrate but do not limit the invention. -Example l.-The forowing printing paste is made up:- Parts 10 Indigosol brown IRRD -------------------- 4 S6dium salt of dibenzylsulfanilic acid ------- 5 Hot. water ----------------------------- --- 31 Neutral starch tragacanth thickening ------ 60 100 dr White cotton cloth is printed with this paste, ied, aged for 5 miniites in a rapid agek if desired, and developed by passing at 35, C. through a bath containing 20-30 parts of sodium bichro- 20 mate and 60-80 parts sulfuric acid (1681 Tlw.) per 1000 parts of water, washed and soa@-boiled. Example 2.-The following printing paste is made up:- 25 Parts Indigosol pink IR, extra ------------------- 4 Sodium salt of dibenzylsulfanille acid ------- 5 Diethylene glycol --------------- ---------- 10 Hot water--- 15 30 ---------------------------- Neutral starch tragacanth thickening ------- 60 Sodium nitrite 30% solution --------------- 6 100 The paste Is printed on white, cotton elotli, 35 dried, developed by passing at 700 C. through p6 bath containing 35 parts of 'sulfiiric acid (168 Tw.) per 1000 parts of water, washed and soapbojjed. vxample 3-The following printing paste is 40 made up:- Parts Indigosol briuiant pink I3B ----------------- 6 Sodium salt of dibenzylsulfanire acid -------- 5 Diethylene glycol -------------------------- io 45 Hot water -------------------------------- 18 Neutral starch tragacanth thickening -------- 55 Bodium.nitrile 30% solution ---------------- 6 loo 50 The print is dried, aged 5 minutes and developed as in Example 2. Example 4@10 lb. of 3:,31-dichlorodianthrahydroquin oneazinetetrasulfurleacid ester potass!Um,rD5

sai@ (U. S. -application Serial No. 433,498), and 10 lb. of,the sodium salt of dibenzyLmffanWe acid are dissolved-in 9 gal. of hot.water containing I gal, of an 8% solution.of gum tragacanth. This 5 so lutioniscooledto2O'C.andIY2pintsofa2O% solution of sodium nitrite are added. Cotton cloth is passed through this solution --squeezed between rokers and dried. After dryIng, the cotton is treated for 3 minutes at 50o C. io In a bath containing I gal, of sulfuric acid 160, Tw. to 100 gal. of water. in 1% -soap s6lution, rinsed and dried. Example 5@A padding solution containing 6 15 lb. of Indigosol brown IRM powder, 6 lb. of the sodium salt of dibenzylsulfanilic acid, 8 gal., of hot water, 3/4 gal. of an 8% solutton of gum triigacanth and 2 gal. of a 7.5% solution of sodium nitrite is prepared as In Example 4 2o Cotton cloth is passed. through this solution,' squeezed betweeil rollers and drled After drying lt is treated -for 3 minutes at 501 C. In a bath cdntaining 20 lb. of sulfuric acid (160, Tw.) per 100 gal. of water. 25 The cotton is then rinsed thoroughiy, bofled in 1% soap solution, rlnsed and dried. Example 6.-;20 lb. of the sulfuric acid ester of,,. leuco dichloroisodibenzanthrone paste (Soledon brilhant purple RP.) and 20 lb. of the sodium so salt of dibenzylsulfanthe acid are dissolved in hot water and dfluted to 200.gal. with water containing 100 lb. of common st&lt and the temperature then adjusted- to 500 C. 100 lb. of'cotton cloth are entered into the dye35 bath at 500.C. and turned f6r 45 minutes, then removed, squeezed and entered fnto a develOPIng bath containing 7 lb. of sulfuric acid (160o Tw.) and Y2 lb.- of sodium.nitrite in 100 gal. of water. 40 The cotton is worked cold in this bath for 5 minutes, removed, rinsed thoroughly, boiled in a 1% soap solutioji, rinsed and dried. Example 7.-A dye bath is prepared by dissolving 10 lb. of Indigosolbrown IRRD powder, and 45 10 lb. of the sodium salt of dibenzylsulfanibe scid'in hot water ind diluting to 200 gal, with water contwning 60 lb. o@ sodiuit sulfate (anhydrous) and 10 lb., of sodium nitrite. The cottlon is worked in this dye bath at 70' C. 5.01 for half hour, lifted, squeezed, and trimsferred without rb2sing to a bath contammg 20 lb. of qulExample 8.-4% 00 of rndigosol i5ink M, extra I)Owder, -8 oz. of the sodium salt of dibenzylsulfanilic acid and 1 pint of diethylei2e glycol are disiolved ln'3 pints of hot water and 4 pints of thickening are added. After cooling a 1/@ pint of 5 a 30% aqueous solution of sodium nitrite Is added. Thts paste Is applied to the, cotton :fabric by brush stencbling: and the stencihe& and dried materlal is aged for 5 minutes in the ra@id ager If desired, -then passed through a bath containing 10 3Y2 lb. of sulfurle acid (168' Tw.) to 10 gal., of and boiled in 1% soiip. iwlution. Example 9.--8 oz. Indigosol brown n:tRD powder, 8 oz. of thesodium aWt of dibenzylsulfanflic .lb acid and 16 oz. of diethylene glycol are dissolved in 3 pints of'hot water and 3 pints of an 8% solution of gum tragacanth and % piht of a 30% aqueous solution i)f sodium nitrite are added. This solution is applied to the fabri6 by sPraY 20 stencilling, the: stencffled and dried material being aged aqd developed as in Example 8. I