claim: 1. A process of printing cellulosic textile ina2 0 terials in 'resist styles to produce patterns on a colore d ground which comprises applying to the cellulo sic textile material a resist printing paste which contains as the active resistagent an aliphatic -isocyanate having the general formula, 25, R-NCO, where R is an aliphatic hydrocarbon radical containing 12 or more carbon atoms, drying the material, steaming the material, and then dyeing it to produce a ground shade. 2. A process as claimed in claim I wherein the 30 printing paste also contains ati ice color preparation capable of being developed by acid. 3. A process as claimed in claim 1 wherein the dyestuff which is used to produce the grour@d shade is applied by padding. 35 4. A process as claimed in claim I wherein the dyestuff used to provide the ground shade is s(,lected from the group consisting of vat dyestuff., azoic colors, and mordant dyestuffs. 5. A process of coloring celliilosic fabric iii pre- 40 deterinined designs, which comprises printing upon the same in predetermined designs a resist paste comprising as active resist an alkyl isocyanate wherein the alkyl group contains not less than 12 carbon atoms; drying the printed fabi-ic, steaming the dried fabric to develop a temporary water-repellent effect in the printed areas, then padding the fabric with a developable ground color, and further treating the same to develop the ground color. 6. A process as set forth in claim 5 wherein heptadecyl isocyanate is used as the active resist agent in the resist printing paste. DENYS PERCIVAL MILBURN.

Patented Oct. 15, 1940 2@217,805 UNITED STATES PATENT OFFICE 2,217,805 PRDffMG CELLULOSIC TEXT]ILE MATERL4LS Denys Percival Milburn, Blackley, Manchester, England ' assignor to Lnperial Chemical Industries lamited, -a corporation of Great Britain No Drawing, AppUcation March 8, 1938, Serial No. 194,703. ]In Great Britain March 10, 1937 6 Claims. The present invention relates to the printing of cellulosic textile fabrics in resist styles so that there are produced white patterns on a coloured ground or, altematively, coloured patterns on a di:fferently coloured ground. . According to the inventio-Ti cellulosic textile materials are printed with a printing paste cGntaining, besides other usual Ingredients, a compound of the general formula 10 P-NCO where R is an aliphatic hydrocarbon radical having iiot less than 12 carbon atoms. The so-printed material is then dried and 15 heated as by steaming for a shgrt time and is then dyed, conveniently by padding; finally, the ground colour having been developed if necessary, the material is washed, soaped and dried in the usual way. 20 It will be understoc>d that when the printing paste contains only the resisting agent, together with the usual thickeners, for example, gum senegal, gum tragacanth or British gum, and assistants, for example,- emulsifying agents, such 25 as sulphated fatty alcohols, there are produced, finally, white patterns on a coIGured ground. Alternatively the pri3iting paste may contain, in addition to the resist agent and other ingre-dients, an ice colour preparation which is capable 30 of being developed by treatment with acid. In this case, the stearning operation tG which, after printing and drying, -the fabric is subjected, is modified in that it is carried out in the presence of the vapour of a suitable acid, for example, 35 formic acid or acetic acid. In this way there are finally produced coloured pattems on a differently coloured ground. As dyestuffs for Providing the ground colour, which is preferably applied by padding I may use 40 vat dyestuffs (applied either as such from reduction medium or in the soluble leuco ester form) ' azoic coIGurs (applied, for instance, as ready-forprinting preparations of e. g., diazoamino compound and cguplingcomponent) or mordant dye45 stuffs. In carrying the invention into practical effect it is preferable to work as far as possible at low temperatures (e. g., ioom tem@erature), as by using cold padding liquors and drying the fabric 50 after padding by means of hot air rather than by passing it over heated cylinders. It is believed that the success of the process depends upon the production, during the steaming operation, of temporarily water-repellent areas on the 55 fabric where the printing paste has been applied. Such water-repellency would be impaired or destroyed by working at elevated temperatures. Padding is preferably done through the nip so (CL 8-65) as to minimise the time of contact of the fabric with the padding liquor. Where the resist agent is an isocyanate it is convenientl y employed in the form of an aqueous emulsion or suspension which niay be produced, r, if desired, with the aid of an emulisfying agent such, jor example, as a sulphated fatty alcohol. As compounds of formula R-NCO suitable to be used in tiie process of the invention there may be mentioned, for example, dodecyl, tridecyl, 10 tetradecyl, pentadecyl, cetyl, heptadecyl, octadecyl, eikosyl and octadeci@nyl isocyanates, likewise mixtures of isocyanates such as may be obtained frgm. the mixed amines derived from the mixed acids olatained from coconut oil or stearin. 15 If desired, the said isocyanat ' es may be used in egniunction with other known resist agents, for example gelatine, glue size, or other proteins or albumengids. As thickening agents there may be used, for 20 example, British gum, starch-British gum, gum Senegal or gum arabic. The invention is illustrated but not limited b@ the following examples in which the parts are by weight. 25 E=mple I Cotton fabric is printed with a paste I made by incorporating together Parts Heptadecy l lsocyanate --------------- ----- 4 so Sodium cetyl sulphate - - --------- -------- 0.2 Starch-tragacanth thickening 1:1 --------- 50 Water --------------------- 45.8 loo . 35 The printed fabric is dried, steamed for 15 minutes and then grounded by padding in one of the following sqlutions: 40 A B Soledon Jade Green XS paste (the sulphuric ester Parts Part8 of leuco dimethoyydibenzanthrone) ------ 3 ------- Soledon Orange R powder (Schultz Farbsio--ff-t-a--- I i.5 45 bellen, 7th edtn. No. 1349) ---------------------- -------- Tragacanth thickening 1:1 --------- --------------- 5 5 BodiLLm nitrite 30% aqueous solution --------------- - 3 3 Water --------------- ------------------------------ 89 90.5 100 100, It is then dried, developed by passing through a 50 2 % solution of sulphuric acid (1680 Tw.) at 70' C., washed, soaped and dried. There is thus obtained a clear-cut white pattem on either a green or an orange ground. 55 Example 2 Cotton fabric is printed and steamed as in

2 2,217,805 Example 1. It is then grounded by padding in one of the following solutions: A B 5 Parta Parts Caledon lade Green paste (Colour Index No. 1101) 3-------- Caledon Blue 3G paste (Colour Index No. 1109) --- -------- 2 ,Tragamuth thickening 1:1 ------------------------- 5 5 Sodium formaldehyde sulphoxylate --------------- 6 6 Potg@ssium carbonate ------------------------------- 12 .12 10 Water ------------------------------------ ------- 74 75 1001 100 The grounded print is dried, steamed for 10 min-' utes, oxidised in the usual manner to develop the 15 ground colour, soaped at the, boil and again &ied. There is thus obtained a clear-cut white pattem on either a green or a -blue ground. Example 3 20 Cotton f ab@ric is printed and@ steamed as in Example 1 and then padded with the following: Parts A blue dyestuff which is the sodium salt of 1- 25 sulphohydroxydimethylfuchson dicarboxylic acid (Colour Index No. 722) ------------I Acetate of chrome liquor 281 Tw ------------7 Tragacanth twckening 1: 1 ------------------ 5 water ----------------- - ----------------- 87 30 100 The grounded print is steamed for 1/2-1 hour washed, soaped and dried. A clear-cut whit@ pattern'on a blue ground is thus obtained. 35 ExamPle 4 Cotton fabric is printed and steamed as in Example 1 and is theri padded with one of the 40 following solutions: A B An azole dyestuff printing preparation as com- Parts Parts erciauy supplied, comprising a rnixture of a 45 d'iazoimino compound of diazotised 4-chloro-otoluidine and the o-toluidide of 2:3- hydroxynaphthoic acid ---------------------------------- 0. 7 -------An azoic dyestuff printing Preparation as commercially supplied, comprising a diazoimino compound from diazotised 4-benzoylamino-2:5diethoxyaniline mixed with the anilide of 2:3r)o hydroxy-naphthoic acid -------------------------- --------- Caustic soda aqueous solution 761 Tw ------------- 1 2 Tragacanth thickening 1:1 ------------------------- 5 5 Water --------------------------------------------- 93.3 92 - 100 100 -- 55 It is then dried, steamed--for 15- minutes in the presence of acetic and formic acid vapgurs, wa,shed, soaped at the boil and dried. There is thus obtained a clear-cut white pattern on either 60 a red or a blue ground. Example 5 Cotton fabric is printed and steamed as In Example 1 and is padded in the following liquor: 65 A Parts Caledon Jade Green X 200 paste flne (Colour Index No. 1101) ------------------------- 2 Caustic soda aqueous solution 76' Tw -------- 1 2 70 Sodium hydrosulphite ----------------------2 Water ------------------------- ----------- 30 B Water ------------------------------------ 64 100 -A is heated until the dyestuff is completely vatted; it is then cooled and B is added to it. After padding, the material is exposed to the air for 1/2 minute to develop the dyestuit, then washed, chromed, soaped at the boil and dried. 5 There isdbtained a clear-cut white pattern on a green ground. Example 6 The following mixtures P and Q are made up 10 separately by warming the Ingredients together until all is dissolved: A B 15 Parts Parts An azole dyestuff printing preparation, as cominerciary supplied, comprising a 3n!xture of a diazoimino compound of diazotised 4-chlorootoluidine and the o-phonetidide of 2:3- hydroxynaphthole acid -------------------------- 7 -------- An azoic dyestuff printing preparation, as com20 p mercially supplied, comprising a mixture of a diazoimino compound of diazotised 4-chloroo-toluidine and the 0-toluidide of 2:3-hydroxynaphthoic acid ------------------------------- - -------- 7 Methylated spirit ------------------------------ 3 3 Aqueous sodium hydroxide 761 Tw ------------- - 3 3 Starch-tragacanth thickening (1:1) -------------- 50 50 ater ---------------------------- ------------- 15 15 25 (Hoptadecyl isocyanate ---------------------- 4 4 QjSodium cetyl sulphate -------------------------- 0. 2 0. 2 (Water ------------------------------------------ ig. 8 100 100 1 P and Q are then cooled and mixed together to 3U form a printing paste. Cotton fabric is printed with one of the printing pastes A and B. It is then dried and steaxned for 15 minutes in the presence of acetic and formic acid vapours. The printed fabric is then grounded by padding in one of the followitig lirluors, solution A being used 35 on niaterial printed @-vith paste A and solution B on material printed with paste B: 40 A B Soledon lade Green XS paste (the sulphuric Parts Parts ester of leuco dimethoxy dibenzanthrone) ------- 3 -------- A blue dyestuff whieb is the sulphuric ester of leuco 16:17-diethylene ether of dihydroxydibc-nzanthrone in the form of a 20% aqueous paste-- -------- 3 45 Tragacanth thickening (1:1) ----------------------- 5 5 Sodium nitri6e 30% aqueous solution -------------- 3 4 Water. -------------------------------------------- 89 88 1(0 100 50 It is then dried, preferably by hot air, and developed by passage through a 2% aqueous solution of sulphuric acid (1681 Tw.) at 70' C. It is finally washed, soaped at the boil and dried. There is'@ thus obtained a clear-cut scarlet Pat- 55 tern on a green ground and a clear-cut red pattern an a blue ground. Example 7 Cotton fa;bric is printed and steamed as in Go Example 6. It is then grounded by padding with the following liquor: Parts An azoic dyestuff printing prepsration as commercially supplied, comprising a mixture of 65 a diazoimino compound of diazotised 4- benzoylamino-2:5-diethoxyaniline and the anilide of 2:3-hydroxynphthoic acid ------- 2 Aqueous sodium hydroxide 76' Tw ---------- 3 Tragacanth thickening (1: 1) ---------------- 5 70 Water ------------------------------------ 90- 100 It is then dried and steained in the presence of ilcetid and fornite acid vapours for 1/4 to V2 hour. 'I@

2,217,805 3 7he material is finally soaped at the boil and dried. 7here is thus obtained a clear-cut warlet or red pattern an a blue ground. 5 Example 8 Cotton fabric is printed and steamed as in Example 6. It Is then grounded by padding in the .fohowing liquor: Parts 10 A blue dyestuff which. is the sodium salt of 1- sulphohydroxydimethylfuchson dicarboxylic acid --------------------------- -------- Aqueous acetate of chrome solution 28' Tw-- 7 Tragacanth thickening (1:1) --------- ------ 5 15. Water ------------------ I------------------ 87 100 The printed and grounded fabric is then steamed for 1/2to 1 hour, soaped and dried. There is tlius 20 obtained a clear-cut scarlet or red pattern on a blue grourid. Example 9 Cotton fabric is printed and steaaned as In Ex25 ample 6. It is then grounded by padding in the following liquor: Parts Flast Printing Green S (Colour Index No. 2) - - 2 Water ------------------------------------- 89 30 Tragacanth thickening (1: 1) ---------------- 5 Aqueous ferrous sulphate 21' Tw ------------ 4 100 The printed and grounded fabric is then dried 35 and passed through a boiling 1% aqueous solution of sodium carbonate (arlhyd.), washed, soaped at the boil and dried. 7bere is obtained a clear-cut scarlet or red pattern on a green ground. 40 Example 10 Cotton fabric is printed and steamed as in Example 6. It is then grounded by padding in the follgwing liquor: Parts 45 Caledon Jade Green X 200'paste fine ------- 2 Aqueous caustic sodw 76' Tv ---------------- 2 Sodium hydrosulphipe - --------------------- 2 Water -------------------- ---------------- 94 50 100 In making this @olution the first three ingredients are heated wi@h 30 parts of water until the dyestuff is completely vatted. The solution is then cooled and the remaining 64 parts of water are added. Aft er grounding the material is exposed to the air for 1/2 minute to develop the ground colour and is then washed, chromed soaped at the bo.U 5 and dried. There is obtained a clear-cut scarlet or red pattern on a green grou'nd. Tf in the above exajnples theheptadecyl isocyanate is replaced by an equal weight of hexadecyl isocya nate or octadecylisocyanate, similar excel- lo lent resists are obtained. The above examples deal only with the application of the process to cotton fabric, but it is to be understood that it can be applied also to other cellulosic material, e. g., viscose rayon and I also to fabrics constituted in part of other textile fibres, for example certain cotton-wool, viscosewool or visco se-pure silk unions. I