Патент USA US2024975код для вставки
Patented!’ Dec'. 17,1935 2,024,915 * I UNITED} STAT‘Esp PATENT OFFICE VATAPPLICATION DYE CODIPOSITIONS THEREOF Herbert A. Lubs and John Elton Cole, Wilming ton, Del., assig'nors to E. I. du Pont de Nemours & Company, Wilmington, DeL, a corporation of Delaware No Drawing. Continuation of application Serial No. 504,274, December 23, 1930. This applica ,tion December 19, 1933, Serial No. 703,156. ‘23 Claims. (Cl. 8-6) ( This invention relates to the art ofv applying vat dyes to textiles, and more particularlylto the art of textile printing. It also" relates to new vat dye compositions. _ This application is a continuation ofour co pending application, Serial No, 504,274 ?led De cember 23, 1930. It‘ also contains subject matter disclosed in our co-pending application Serial No. 703,155.1i1ed December 19, 1933.~ 10 Except for indigo, vat dyes (which are unlike all other types" of dyes both in properties and mode of application to the ?ber) were not known prior to the beginning of the present century. “By the term vat dye is meant a colouring mat ter insoluble in water, but which can be converted ' on reduction ‘into a so-called Ileuco compound, which is soluble in alkalis, and in such a solution, termed a vat, the actual dyeing process is ef fected; on removing the material from the bath "20 and exposing to the air oxidation‘ takes place, the dye being precipitated on the ?bre in insoluble form; . . .” From page 423 of “A Textbook of Dye Chem istry” by Georgievics and Grandmougin (1920). In the application of vat dyes to textile ?bers, a distinction is to be made between dyeing (that is, coloring of the entire fabric) and printing, in‘ which only a portion of the fabric is colored. The mode of applying the dye in each case is 30 different. ' The process of dyeing comprises suspending the insoluble vat dye in an alkaline solution and thereafter adding a reducing agent to change tive, penetrate the ?ber and, upon removal from the solution followed by oxidationyare regen erated, resulting in a dyeing taking place as in the general process ?rst described. ' As will be obvious‘, some of the dye‘is lost from the ?ber by reason of going into solution in the vat. If this process is continued long enough, su?lcient dye ‘ would be removed from the ?ber to render the reducing solution a dye vat of ordinary concen tration. Inasmuch as a reduction to the hydro 10 derivative is necessary‘both in dyeing from a solution and by the padding method, the so1u-> tion-dyeing process is the one most widely used where space and equipment permit. s While various reducing agents may be used 15 in the dyeing (as differentiated from printing) of vat dyes, the one most commonly utilized is a hydrosiil?te. “For some years past solid 'hydrosulphite‘of soda, containing amounts of Nazsaoi varying 20' from 60 to 95 per cent., has been in the -market in the form of a dry,‘almost white, powder“ It is largely used in the dyeing“ of indigo and other vat dyes, but, owing to the rapidity with which its solutions oxidize in contact with the air, it 25’ is not suitable for textile printing.” From page 250 of the “Principles and Practice _ of Textile Printing” by Knecht 8: Fothergill (1924) . As indicated in the above quotatio , the ordinary reducing agent utilized in the dyeing 01.30‘ vat dyes cannot be used practically in the print ing of vat dyes on textile. This is a serious dis advantage because vat dye printing is, for other the vat dye to its hydro derivative (the reducing ‘ reasons, much more complicated than vat dyeing. I This particular difficulty has been partially over- 35 come by the discovery and commercial produc tion ofthe compound sodium formaldehyde sul foxylate which only exerts its reducing in?uence at elevated temperatures. By use of this and soon as a su?icient amount of ' the leuco body solution has been ‘absorbed. Exposing the equivalent compounds the vat dye can be im soaked fabric to an oxidizing in?uence, usually printed on a fabric in the desired design and the oxygen oft/the atmosphere, regenerates the thereafter reduced and ?xed to the ?ber. At the present time, the most extensive textile vat dye on the ?ber producing a dyed material. There is an alternative process known _' as printing is done with cylinder or roll printing ma chines. The fundamental principles in this proc- 45 y ' “padding” which is used to some extent at pres ess are simple and. comprise passing the cloth ent. According to this process the ?ber is im mersed in a suspension of a‘ vat dye until a to be printed under some tension and pressure . "1 ' over an intaglio metal roll, the engraving of which sumcient quantity of the dye has adhered me‘ is ?lled with a printing paste. After leaving the chanically to the ?ber (this adherence is analo printing machine, the printed cloth is quickly ‘0 gous to wet sand clinging to stick used for stir ring a sand and water mixture). Thereafter the passed into a drier. This dries the printing paste ?ber, with the dye particles mechanically held on the cloth in its proper place and prevents the dye from spreading to other portions of the fabric thereon, is immersed in an alkaline solution con taining a reducing agent whereby the dye pare‘ with consequent ruination of the design (in dyeing agent may also be added before or simultaneously with the dye). The ?ber is then steeped in the solution of the. hydro derivative (referred to above as leuco compound) and is removed as :1,$1" ticles are reduced to the soluble deriva with vat dyes, spreading of the colorsolution over?“ ' 2 the entire cloth is earnestly sought for, but in the printing of vat dyes, the slightest spreading of the color destroys the value of the printed cloth to such an ‘extent that the same is ‘not salable). The printing paste applied to the cloth from theroller is a material thickened to such an ex tent that it does not run readily. It varies with different fabrics and manufacturers, but usually consists of a ‘mixture of unreduced vat dye, a 10 strong reducing agent such as sodium formalde hyde sulfoxylate, an alkali and a thickening agent. The thickening agent is usually a gum (for instance, British gum) , starch, or both. The printing paste is usually prepared .by mixing a 15 dye paste or pastes with the other ingredients enumerated, said other ingredients being in the form of a gummy mixture hereinafter called '“printing gum”. The dye pastes are essentially ?nely divided suspensions of dye with or without 20 a dispersing, agent. These dye pastes (herein after referred to as “dye pastes”, “dyestu? pastes” or “color pastes”) usually have the dye sus pended in water. . In order to complete the printing, the cloth, 25 after leaving the drier, is passed into an ager (usually a steam ager) for a period of a few min utes, during which time the vat color undergoes reduction ‘(the sodium formaldehyde sulfoxylate in the printing paste producing its reducing action 30 r 2,024,975 because of the elevated temperature in the ager) and passes to the ‘?ber. The fabric is then sub jected to oxidizing conditions which may include passing it into a steeping bath, usually of water or water containing an oxidizing agent. Any ex erty enables them themselves to exert a reducing action upon the vat-dyestuif used; this enhance- ‘ ment of the reducing power of the vats is also favourable for the setting and working of the vats, because on the one hand the dyestuff is re duced more quickly and on the other hand the oxidation of the vats is better checked. . . .”I This patent indicates that substances such as anthraquinone act as assistants in reducing the dye and in checking oxidation, thereby effecting 10 a better utilization of the dye, but it does not indicate that better dyeings are obtained. Simi larly, Remlein, U. S. Patent No. 1,750,942, dis closes a padding process (de?ned above) in which , anthraquinone is used, although its use is not I i.) claimed nor is its function given. The following tests indicate that anthra quinone does not in fact give stronger dyeings: A cotton skein was introduced into a vat whose volume in cubic centimeters was approximately 2 0 twenty times the weight of the skein in grams. The vat was maintained at a temperature of about 160° F. and contained 5% of a color paste comprising approximately 12% 6:6’-diethoxy thioindigo, about 4% caustic soda and about 1: 7.5% sodium hydrosul?te (all percentages based on the weight of the skein). The reduction > took place at about 180° F. The skein was then oxidized and soaped in the well known manner. A similar dyeing, except that the vat contained a one gram of anthraquinone per liter of solution, was judged to be only about 33% as strong as the dyeing made from the vat in which no anthra quinone was present. ’ ' . cess color is washed off in a soap solution with On account of the greater complexities, it is 3 which the textile‘ material is treated‘ following much more dif?cult to obtainv suitable assistants the steeping. ' for printing than for dyeing. However, a num~ j Vat dyes at the time of printing are not in true ber of such assistants have been proposed. One solution. For this reason,_ the effecting of com such compound is tri-ethanolamine (U. S. Patent 40 plete reduction of the dye and the transfer of the ’ No. 1,790,950) and with it markedly improved re- 4 color to the fabric‘ in the brief time which the sults have been produced. Another compound goods are steamed is a process accompanied by which has been proposed for this use is ‘ great difficulties, as previously stated. In‘ order to make sure that satisfactory resultsare ob 45" tained, it is important’ that the dye paste be of special ?neness, but even then a great deal of ' color is lost because of its failure to dye the cotton. This excess color is washed oif during the soap ing which follows the steaming. In both dyeing and printing it has been pro posed to assist the process by the addition of various substances, for convenience called “as sistants”. The purpose for‘which such assistants are added and the functions which. they perform - may vary widely. _ Thus, in dyeing, some assist ants are added to speed up reduction of the dye, others to retard oxidation of the vat. ’ It does not follow, however, that more brilliant and brighter 6 dyeings are obtained. 0v in 8. Y - The same is true of print-,. . . 0 illustrate this distinction, attention is called to British Patent No. 3241 of 1911, in which it is stated that: “. . . the preparation and the work ing of vats of indigoid dyestuifs (that is to say dyestuffs, except indigo, which, like indigo, ‘contain the chromophorous group —CO—-C= C—CO-—) can be greatly facilitated by adding anthraquinone or a derivative thereof, such, for example, as (alpha-): or .(beta) -oxyanthraquin - one, a dioxyanthraquinone or a sulphonic acid 1 of one of these, to the stock-vats and to the dye vats. The action of the anthraquinone-and its derivatives in the vat is due to the ease with which they are reduced and to their power of Y 75 acting as hydrogen carriers. This latter prop U beta:beta'—dihydroxy-diethyl ether (British Pat ent No. 368,910). Further examples might be given without adding anything to the discussion 4; of the prior art. _ Practical experience has shown those skilled in the art the utter futility of attempting to predict what substances will or will not be good assistants in dyeing and/or printing; or that assistants in - dyeing produce stronger and brighter printings; or that assistants in printing produce stronger and brighter dyeings. It is well recognized by those skilled in the art, and is therefore worthy of note, that assistants in dyeing and printing other types of dyes cannot be expected to be assistants in dyeing and printing vat dyes because the mechanisms of the reactions involved are different. ' ' It is an object of this invention to produce new (I; and improved “dye compositions of the indigoid type. A further object is to provide new and improved dye compositions of the indigoid type which are suitable for use in printing pastes and when printed on the textile ?ber yield .prints of (. unusual strength and brilliancy. A more spe ci?c object is to provide new and improved thio indigoid dye compositions. Other objects are to produce improved printing pastes, improved printing gums, improved dye pas‘es and to pro- 7; vide new and improved results in textile printing. Still further objects will appear hereinafter. These objects are accomplished by the-produc tlon of dye compositions comprising an indigoid dye, or mixture of indigoid dyes, containing as an 7 2,024,975 the silver salt was omitted, was prepared and prints made from the two pastes under similar conditions. The prints obtained from the print ing paste containing silver salt were v10 to 25% stronger than those obtained fromrthe other 5 assistant an alkali metal or ammonium salt of anthraquinone-Z-sulfonic acid, or a mixture of said salts, and by the application of such com positions to textile ?bers and fabrics. The new printing assistants may be used alone or in con junction with other assistants. They may be in corporated into the dye paste, printing/gum, or printing paste either as such or in the form of the free sulfonic acid. It will be recognized that the 10 free sulfonic acid may be converted to the alkali metal salt by reaction with alkalis such as are present in the printing gum or printing paste. printing paste. <. and made into a printing‘ gum having the follow' 1 __ 67.5, Potassium carbonate...v _____ __‘ __________ __ 8 SulfoxiteC _______________ ___T _________ __ 4 . . Percent ' following composition: . 5 15.5 , ' p Percent 25 i. Printing gum __________ __., __________ __'_'__ 79.5 Sulfoxite C (sodium formaldehyde-sulfoxy ‘ 15 A dye paste-containing 12% of ~6:6'-dimethoxy- 20 thioindigo and the sodium salt of .anthraquinone 2-sulfonic acid were incorporated into the print ing gum to produce a printing paste having the Thickener _____________________________ __ 57.5 Potassium carbona‘te ___________________ __ 16.0 Dye paste ______ __'_____ "a _______________ __ 20 __ 11. Glycerine; ______________ ....d.__‘ __________ __ 5 ' ____ __ Water ______ __'_ ______________ __,________ __ From this thickener a printing gum consisting of : Water- , Percent _ Glycerine ___________________ _, _____ __-____ A thickener was prepared containing 10% late) ' Thickener wheat starch, 30% British gum and 60% water. r ‘ ing composition: Ezrdmple I ‘ . A'thickener consisting‘ of 10% wheatstarch, is not limited, by the following examples. 20. '_ 30% British gum and 60% water was prepared 10 The invention will be further understoo’dfbut 15 , Example III Strong alkalis also tend to replace weak alkalis such as ammonia. 3 , ___ ' Anthraquinone-2-sodium sulfonate______ __ .5 10.5 Example IV 30 was prepared. This printing gum was made into a printing paste by incorporating therein a dye \_ I’ 30 A thickener containing 10% wheat starch, 60% " paste of 4:4’-dimethy1-6:6'-dichloro-thioindigo. water and 30% British gum was prepared and and anthraquinone-2-sodium sulfona‘e._ The made into a. printing paste having the following 35 percentage composition: percentage. composition of the printing paste was as follows: ' . - - '. ' Thickener____. __________________________ __ 67.5 Percent Potassium carbonate _________ __‘ _________ __ Sulfoxite C_'_ ________ __‘.. _________________ __ Printing-gum __‘ ________________________ __ 79.9 Dye paste (12.5% dye) __________________ __ 20 40 'AnthraQuinone-Z-sodium sulfonate ______ __ Water __ - v ‘- . _ - 1 _ Percent Dye paste - Sil er I “"1 2o t _____ __' ______________________ __ ~ P°ta53ium_carb°mte ___________________ __ 16_ , was printed on cotton, dried, aged and developed sulfoxite c ____________________________ __v 11 Glycerin? _____ 5 _ in the usual way. The prints obtained were more ,, - ‘than 10% stronger than those .obtainedTrom a "d The thickener consisted of: , I I ' 10.5 > . J .v ‘0.5 Thickener___-_ _________________________ __. 57.5 Water ____________________ "Q ____ _; _____ ._ 60 15.5 4° Prmtmg gum --------------------------- -- 79-5 59 Percent .- _ mixture. the printing paste, / which was com A printing gum was prepared comprising: ‘ ' paste by stirring the same with a 20%. dye paste of 5:5’:7:7’-tetra-brom-indigo (C; I. No. 1184, brominationinnitrobenzene) and anthraquinone- 45 2-sodium su1fonate.- After producing a uniform posed of:. J I ___ This printing gum was made into a‘ printing Example II v 8_ 4 Glycerine ______________________________ __ \ 5 0.1 This product was printed on textile material which was then aged and developed in the usual‘ and well known way. .'The prints obtained were from 10 to 25% stronger than those obtained from a similar composition which differed only in the omission of the anthraq'uinone-Z-sodium sul fonate'. I ' Percent 35 - . ‘ paste printed under similar conditions which was similar in every respect except that the anthra - quinone-Z-sodium sulfonate had been omitted. Percent Example V . Wheat-starch"; _______________________ __ 10 60 Britishgum ________ -, __________________ __‘_ 30 WBWL. __ _ _ _ _ _ _ _ _:_ 6O 1 A thickener was prepared including 10% wheat starch, 30% British gum and 60% water. From This printing gum was made into a printing paste by mixing it with a 6_:6'-diethoxy-thioindigo (C. I. No. 1218) dye paste containing 11.5% solids. To this mixture there was added silver salt (the Thickener--.‘ ______ -7 ______ .._' ____ -Q _____ __ 57.5 sodium salt of anthraquinone-Z-sulfonic acid) . Potassium carbonate}, ___________________ __ 16 this thickener a printing gum consisting of: ‘ Percent The percentage composition‘ ot_ the resulting , Sodium formaldehydelsulfoxylate ____ __,____ >11 printing paste was as follows: Glycerine; ________ _'7__' _________________ __ 5 ~ Percent Printing gum __________ __' _____ -; __________ _. '79 Dye paste--- Silver salt 75 ' I’ -_~ 1 ...~ a ' i 20 1 Water ____ ' 70 __ ‘10.5 was prepared. This printing gum was made into a printing paste by incorporating therein a dye . paste of 5:5’z'lzT-tetra-brohr-indigo containing Another paste, similar in all respects except that‘ 20%‘ solids (C. 1.. No. 1184), anthraquinone—2- 75' 2,024,975 ‘ ~ ' sodiumwulfonate. The percentage composition wheat starch, 30% British gum and 60% water. of the printing paste was asfollows: From this thickener a printing gum consisting of: vPercent 79.9 Printing gum- . Percent Thickener Dye paste ‘(20% dye) ___________________ .... 20 I - 57.5 ' Potassium carbonate ____________________ __ 16 Anthraquinone-2~sodium sulfonate________- 0.1 5 Sodium formaldehyde-sulfoxylate (Ronga This product was printed on textile material which was then aged and developed in the usual way. The prints obtained were from 10 to 25% lite) 11 i 'Glycerine _ 5 _ Water _________________________________ ___. 10.5 10 stronger than those obtained from a similar com was prepared. This printi‘hg gum was made into 10 position whichidi?ered only in the omission of v a printing paste by incorporating therein, anthra the anthraquinone-2-sodium sulfonate. Example v1 15 quinorie-Z-sodium sulfonate and a dye paste of the dye resulting from condensing 5:7-dibrom ' isatin chloride with 3-hydroxy-4-methyl-6 chloro-thionaphthene. The percentage compo 15v [A thickener was prepared consisting of 10% wheat starch, 30% British gum and the remainder water. sition of the printing paste was as follows: Percent This thickener was incorporated in a printing gum having the following composition: 20 Printing gum ‘ . Percent Thickenen- Anthraquinone-Z-sodium sulfonate _______ __ “V 56.5 Potassium carbon ate 1 \ Commercial glucose ______________ __“ ______ __ 15 Glycerine _____ __'_ ______________________ __ Water- _____ __ ' ____ __ 5 12.5 anthraquinone-Z-sodium sulfonate. This printing gum was mixed with a 16% (solids) Example IX The printing paste having the following com- 30 dye paste of bis-beta-naphthio-naphthene indigo 30 and the sodium salt of anthraquinone-beta sulfonic acid to produce a printing paste. Thi printing paste, being composed of: position: > » Per cent 5:5 '-dichloro-7 :7 '-dimethyl-thioindigo (20 % ‘ dye paste) (C. I. No. 1209) ______________ __ 20 20 AnthraquinoneJ-sodium sulfonate _______ .. i _ , Percent Printing gum ___________________________ ___ 79 35 Dye paste 20 0.1 This product was vprinted on textile material which was then aged and developed in the usual way. The prints obtained were from 10 to 25% stronger than those obtained from a similar com- 25 position which differed only in the omission of the 10 Sodium hydroxide ______________________ __ 25 79.9 Dye paste (10% dye) ___________________ __ 20 "Thickener"- 1 > was printed on- cotton textile material in the well known way.- Comparison of these prints with prints obtained under similar conditions from a _____ 55 35 i Glycerine _______________ __; ______________ __' Sodium hydrosul?te ______ _b ______________ __ 5 5 Sodium hydroxide (36% strength); _______ ___ 5 Sulfoxite C __________________________ __-____ -5 40 similar printing paste which omitted the anthra quinone-2-sodium sulfonate showed them to be about 15% stronger. Water_______________________ ___V_____ ______ ___ 3 4O Anthraquinone-betaisodium sulfonate _____ __ 1 was prepared. In the preparation of this com position all of the ingredients except the last three mentioned (namely, the sulfoxite C, water and silver salt, were brought together, ‘uniformly 45 Example VII A thickener was prepared consisting of 10% wheat starch, 30% British gum and the remainder _ mixed and heated until reduction was complete, water. This'thickener was incorporated in a whereupon the remaining ingredients were added and the product stirred to uniformity. printing gum having the following composition: 50 thickener in this case consisted of: Percent 56.5 Thickener 80% of a thickener consisting of :_ 10%; ______________________ __wheat starch Potassium carbonate ____________________ __ 10 Sodium hydroxide _____ ___ _______________ -_‘ 1 Commercial glucose _____________________ _.. 15, 55 Glycerine v Water __ 30% ____________ __~_ _________ __British gum 60% ' 5 - dye paste of 6:6’-di?uoro-thioindig6 and sodium salt of anthraquinone-beta-st?fonic acid to pro duce a printing paste. This printing paste, being w‘ “ V. ‘ - Percent‘ Printing gum ___________________________ __ 79.1 65 Dye paste____ ' 20 Anthraquinone-Z-sodium sulfonate"; ____ __ 0.9 was. printed on cotton textile material in the well known way. Comparison with prints obtained‘F under similar condition from a similar printing 70 paste which omitted the anthraquinone-Z-sodium sulfonate showed that the (silver salt) paste gave prints about 15% stronger. Example VIII 75 , _ _water 5% __________ __, _____________________ __water 15% ____________________ __potassium carbonate 55 This product was printed on textile material which was then aged and developed in the usual way. The prints obtained were stronger than those obtained from a similar composition which _60 differed only in the omission of the anthraquiné 12.5 This printing gum was mixed with a 16% solids composed of : The q ' one-2-sodium sulfonate. . _ ' Example X A printing paste was made from the following ingredients: ' ' 6:6'-dichloro-thioindigo solids)___.. ' dye __ ___ ' paste (55 Per cent (10% _ 20 Thickener ________________________________ __ 55 Glycerine _______________________________ __' 5 70 NazSzOr __________________________________ _.. 5 NaOH (36% strength) ____________ -._ ______ __ x 5 Sodium formaldehyde-sulfoxylate (Rongalite) 6 Water ______________________________ __'____ > 3 v A thickener was prepared containing 10% _Anthraquinone-Z-sodium sulfonate__=_' ____ __ 1 75 _ 2,024,975 5 . - The method of preparation was as follows:. The composition adding 5% water and 15% potassium dye _ paste, thickener, glycerine, NazSaO. ' and NaOI-I wereuniformly mixed and heated until re carbonate. When the product was printed on‘ a textile material, aged and developed, the prints ' duction'was complete.“ The Rongalite, water and were found to be 10 to 25% stronger than those made without. any anthraquinone-2-sodium 5111- 5' anthraquinone-2-sodium sulfonate were there: after added. The product _was stirred to uni 'fonate. - ) 80% of a composition comprising: . A thickener was ' prepared containing 10% ' .wheat starch, 30% British gum and the re mainder water. This thickener was incorporated 1° 10% ______________________ "wheat starch 10 \ 30% , British gum 60% ' in a printing gum having the following composi tion: Per cent __water I 5% ___water . 15% K2003‘ Thickener Y Potassium carbonate "15 The product was printed on‘ textile material. This was aged and developed in the usual way. The prints were 10 to,25% stronger than those _ made with a similar composition from which the ' anthraquinone-2-sodium sulfon'ate had beerromit ted. ~ I ' - v Example XI _ - Water ‘ Gly'cerine \ / ~ ' ___ (7.5 > 5 . This fprinting gumwas mixed with a 12.5% color-g2o . paste of -4:fi'-dimethyl-6:6'-dichloro-thioindigo ‘_ ‘and sodium salt of anthraquinone-beta-sulfonic The following ingredients were incorporate into a printing paste: . 56.5 \ 10 15 ‘Sodium hydroxide ‘ 1 Preserver’s syrup___-___.,_ _______________ ___.. 20 . I v I’ ' Example XIII formity. \ The thickener used was: I ' acid to produce a printing paste. This printing , . Per' cent . paste, being composed of: 5:5’-di?uoro-thioindigo dye paste (10%so1ids) . V20 Thickener Glycerine , ~' , ‘ NazSiO: ' ‘ _ L 55 ' . Printing gum - '- . a Per cent J Dye paste .2 25 ' '79 ‘ - 20 Anthraquinone-2-sodium sulfonate _______ __ NaQH (36% strength) __________ __g__'_ ____ __ '1 was printed on cotton textile material in the well 30 Sodium formaldehydel-sulfoxylate (Rongalite) 6 known way. ~ Water ‘' Comparison with prints obtained under similar conditions’ from a similar'printing paste which omitted the silver salt showed about 20% greater strength in the print from the print a _ Anthraquinonee2-sodium sulfonate____.-._____ The dye, thickener, glycerine, Nazszdi andNaOH were brought together and uniformly mixed. ing paste of this invention. Heat was applied until reduction wasfycomplete. Ezample‘XIV ,Then' the Rongalite, water and anthraquinone-2- ’ , 9 35 ' A thickener was prepared containing 10% sodium sulfonate were added. The product was stirred to uniformity. ~ wheat starch, 30%_ British gum and-the re . The thickener used was prepared as follows: 1‘ mainder water. This thickener was-incorporated 40 , In a composition consisting of 10% wheat starch, in a printing gum having-the following composi 40 30% British ,gum and 60% water, ‘there were tion: ' I " Per cent stirred K300: 'and water until" the resultant ma terial was as follows: as u ' ' Thickener 56.5 Potassium carbonate__g_-_ _________ __'_____ __ 10 ' 45 -_Per cent ~ ' . J . Composition‘ ’~ Water ' ~ ' ' ' v > KaCOa ' ~ ' ” Sodium hydroxide _______ __' _______ -__ ____ _- 80 - ‘ - ' ‘ '1 , I Commercial glucose _____ _1 __________ _r_____ 15 5 Glycerine 15 ‘ Water The printing paste obtained was printed on 5 " - 12.5 This printing gum was mixed‘ with a 20% solids 60 50 a textile material and aged and developed as usual. These prints were from 10 to 25% stronger than ‘dye paste of 5:5'-dibrom-7:'l'-dimethyl-thioin- . _digo and anthraquinone-betaesulfonic acid ,to a corresponding paste without the silver salt. produce a printing paste. This printing paste, “T ‘ Example XII being composed of: m ,. ~ ‘ >‘ - Printing gum I Glycerinev - 65 _ / ~ > g '__ _ i 75 ‘British gum’and 60%‘water and to 80% or such - ‘ Example‘ XV ‘ 3 was. stirred to uniformity. The thickener used was made by mixing 10% wheat starch, 30% > '79‘ 20 were about 15% weaker. Sodium 'formaldehyde-sulfoxylates-nr _____ -1 6 ‘ ' 1 omitted the anthraquinone-2-sodium sultonate' ' NazSzQa . i ', ' v f ' NaOH-_"(36% strength) ...a _______________ __ I 5 Water I ' known way. The prints-obtained under similar 60‘ conditions from a similar printing paste which‘ ‘5 - Anthraquinone-2-sodiu1n sulfonate_‘___.._'____ 1 The method used in preparation was this: The dye paste, thickener, glycerine, N82S2O4 and 70 NaOH were uniformly mixed and heated to com plete reduction. The sulfoxylate,‘ water and an thraquinone sulfonate were added. This product ' was printed on cotton textile material in the'weil 55. y" ' Anthraquinone-2-sulfonic acid__- _____ __'____.. 1189) (20% solid dye paste) ____________ .._ 20 Thickener ' > Dye paste Percent 4:4'-dichloro-5;5'-dibromo-indigo (C. I. No. 60 ' cent 56 J Agprinting paste of the following composition was prepared:- ’ . - _ The printing paste having <the following com position: . .- ' - . . Per cent 4;4'-dimethyl-thioindigo (10% dye) _______ __ 20 Thickener ' - » 55 70 Glycerine 5' Sodium hydrosul?te ______ n. ______________ __ ‘5 Sodium hydroxide (36% strength) _v__..______ 5 Commercial glucose_-_-__‘ __________________ __ 9 Silver salt 1 76 - -' G 2,024,975 ‘ and the product stirred to uniformity. The was prepared. In the preparation of this compo ' sition all of the ingredients except the commer thickenerlin this case consisted of: cial glucose, water and silver salt were added, Water complete, whereupon the remaining ingredients Wheat starch listed were added and the product stirred to uni formity. The thickener in this case consisted of : Potassium carbonate ____________________ __- 15 British gum 24 , >Water ' Per cent uniformly mixed and heated until reduction was 8 5 _‘ which was then aged and developed inthe usual. way. The prints obtained were from 10 to 25% m 8 stronger than those obtained from a similar ' composition which differed only in the omission . of the silver salt. ' Potassium carbonate___'_ _________________ __ 15 ' British gum ________________________ ___'.____ 24 This product ;was printed on textile material 151 which was then aged and developed in the usual Example xvm way. The prints obtained were from 10 to 25% stronger than those obtained from a similar com position whi'ch'di?ered only in the omission of - . . - ‘Example XVI Per cent 20 6:6'-diethoxy-thioindigo (C. I. No. 1218) (11.5% solids dye paste) ______________ -The printing paste having the following com- ' position: Thickener 25 ‘e Glycerine Dye paste of the thionindigo dye prepared by well known methods. from 2-thio glycol naphthalene (14% solids) ______ _K___ 20 II'hickener ‘ 55 Glycerine » 5 Sodium hydroxides (36% strength) ________ .._ Commercial‘gluco ______________ __\___-___.._ 5 9 Anthraquinone-beta-sodium sulfonate _____ __ 1 55 , 5 25 Sodium hydroxide (36% strength) _i..____-_.. 5 Commercial glucose _____ __' ______________ .._ 9 Silver salt 1 '~ complete, whereupon the remaining ingredients mercial glucose, water and anthraquinone-beta Per cent sodium sulfonate were added, uniformly mixed Water ' and heated until reduction was complete, where the product stirred to uniformity. The thickener '53 _ British gum the anthraquinone-2-sodium. sulfonate. Example XVII _ Per cent droxy - 4 - methyl-?-chloro-thionaphthene Thickene'r 20 ' 55 ' 5 ,. Sodium hydrosul?te _______ -_'_ ______ _-v..___ 5 70. Sodium hydroxide. (36% strength) _______ __ 5 Commercial glucose____;___, ____________ __ 9 Anthraquinone-2-sodium sulfonate _______ __ 1 1 was prepared. c > I " ’ the silver salt. ’ \ . Example XIX 60 The, printing paste having the following com position: ' ~ ' , Per cent 4:-i'-dichlor-5:5'-dibrom-indigo.(20% solids ,5 dye paste) 20 Dye paste of the dye resulting from condens ing 5:7-dibrom-isatin chloride with 3-hy Glycerine 24 . The printing paste having the following com position: 65 British gum_ position which differed only in the omission of ___.. 24 (10% solids‘) - 15 40 stronger than those obtained from a similar. com- 45 This product was printed on textile material , which was then aged and developed in the usual 50 way. The prints obtained were from 10 to 25% stronger than those obtained from a similar com position which di?ered only in the omission of 60/ 8v Potassium carbonate ___________________ ...:.. way. ‘The prints obtained were from 10 to 25% 8 Potassium carbonate____.. ________________ __ 15 - 53 This product was printed on textile material which was then aged and developed in the usual Per cent ‘ 45 Wheat starch i - ; I . "as 1 Wheat starch 40 upon the remaining ingredients were added and Water‘ 5 ' were added and the product stirred to uniformity. The thickener in this case consisted of: 35 35 was prepared. In the preparation ’of this ‘com position all of the ingredients except ‘the com in this case consisted of: . 20 was prepared. In the preparation of this com position all of the ingredients except the com- 80 mercial glucose, water and silver salt were added, uniformly mixed and heated until reduction was 5 . Sodium hydrosul?te _..___- _______________ __ , Sodium hydrosumte Per cent 30 )1‘ The printing paste having the following com position: a the silver salt. 20 53 This product was printed on textile material ' Per cent _ 53 Wheat starch ____________________ __> ______ __ ' Thickener ' Glycerine 55 _ 5 - Sodium hydrosul?te ____ -_._-_'_' ____ _.>._..;_'__ ' 5 Sodium hydroxide (35% strength) _____ -_.._l_ 5 60 Commercial glucoseuii. ____________ .._'_____ Anthraquinone-beta-sodiuni sulfonate____ ..- 9 1 ' was prepared. ‘ In the preparation ‘of this com- ‘ position all of the ingredients except the glucose, vwater and anthraquinone-beta-sodium sulfonate 66 V were added, uniformly mixed and heated until reduction was complete, whereupon the remain- _ ing ingredients were added and. the product stirred to uniformity. The thickener in this case consisted of: In the preparation of this-com- ' “ ‘ . ‘l0 Per cent ' position ‘all of'the ingredients except the glucose, water and silver salt were added, uniformly mixed and heated until reduction was complete, Water 53‘ Wheat starch ‘ Potassium carbonate 8 15 whereupon thelremaining ingredients were added British gum ____________ __' ________ ..-........_.. 24 76 - 3r ' 7 2,024,975 Example XXII This product was printed on textile material which was then aged and developedin the usual way. The prints obtained were from 10 to 25% stronger than those obtained from a similar com position which differed only in) the omission of Thickener the anthraquinone-beta-sodium' sulfonate. K2003 _______________ _Q ________________ .. 10 A printing gum was made from: . ' _. Per cent ___ 56.5 NaOH ___- tose) _________ __‘___ _______________ __‘___ Glycerine_ A printing gum was prepared from: ' , Thickener ___. ________________________ _,__ 57.5’ E0031. 16 15 ___ Sultoxite C-.. - 11 iGlycerine ___ . Water 5 10 I e The thickenercontained 10% wheat starch, 30% British gum and 60% water. A printing paste was .made from the printing gum by adding 6:6’ diethoxy-thioindigo (C'. I. No. 1218) dye paste containing 11.5% solids. To this ‘mixture was added milled silver salt (sodium. salt of anthra; quinone-Z-suli'onic acid). The resulting print - - Per cent gum_ ____________ _1 ______ ________ 79.9 Dye paste _ 20 Milled silver salt ________ ____'__________ _..__ 0.1 Two other pastes were prepared, similar vin all respects except that in one the ‘silver salt was not milled and in the other the silver salt was omitted. Prints were‘ made from the’ three pastes under similar conditions. The prints made from the two printing pastes containing the silver salt were 10 to 25% stronger than those made from the paste from which silver salt was omitted. But it is also worthy of notice that those prints made from the paste containing the milled silver salt were noticeablystronger than those printed with the paste containing silver salt which had not been milled. . Per cent KaCOa __________ __'________ _'__. _________ __ 8 Sulfoxite C :3. ____________ __, ___________ __ 4 . Glycerine___; ' ' \ 5 ____ __ wasJused to make a printing paste by mixing uni 60 Iormly with a dye paste containing 12.5% of 4:4’ Jdimethyl-6:6'-dichloro-thioindigo and, a small amount of milled silver salt. The following pro portions were present in the ?nished composi tion: . ~ )Dye paste. Per cent __ 79.9 1 ' 20 Milled silver salt--. ____________________ __ 0.1 70 Prints made from this printing paste were 10 to 25% stronger than those made from a‘ similar paste in which silver salt was absent, and vnotice ably stronger than those made from a similar paste which contained silversalt which had not 75 ' Per cent 20 Printing gum '79 ' Dye paste ____ 20 Milled anthraquinone-beta-sodium sulionate- 1 .Prints were made from this paste. These prints paste which lacked the presence of the milled assistant. The prints from the paste with the milled silver salt assistant were 10 to 25% strong er than the others. They were also noticeably ‘ stronger than prints made from 'a similar paste in which the silver salt assistant used was not milled. Example XXIII A printing gum was prepared containing: 1 I ' ‘ 35 Per cent Thickener _____________________________ __ » 56.5 Potassium carbonate _______________ _l______ 10 Sodium hydroxide ________________ ...' ____ ___ 1 40 Commercial‘ glucose ____________________ __ 15 Glycerine- __ water 5 ___- 12.5 undergone themilling process. This printing .vgum was made into a 'quinone-Z-sulfonic acid.. The composition of the 50 printing paste was: , Per cent Printing gum__ 79 Color paste (12.5% dye solids) ____________ __ 20 Anthraquinone-2-sulfonic acid. ________ _'.._-_ 1 55 15.5 The thickener contained 10% wheat'starch, 30% British gum and 60% water. This pririting gum Printing gum _ lowing proportions: printing paste with a 5:5'-dichloro-6:_6’-di methyl-thioindigo dye paste containing anthra: Thickener ______________________________ ___ 67.5 65 The thickener contained 10% wheat starch, 30% British gum and 60% water._ A printing paste was made from this gum by mixing uniformly 1 with a 16% solids dye paste of bis-beta-naph thio-naphthene indigo, and the milled sodium salt of anthraquinone-beta-sulfonic acid in the fol water. A printing gum was made from: Water__‘__ 7.5 The composition of the thickener herein utilized was 10% wheat starch, 30% British gum and 60% Example XXI 60 - 10 were compared with prints made from a similar .ing paste had the following composition: Printing 20 5 E20 ___________________________________ __ . ' _ p Per cent . _ 1 Preserver’s syrup (mainly glucose and truc Example XX 10 5 ‘ ' This paste gave prints several percent stronger than a similar paste not containing anthraquin one-2-suli'onic acid when printed, dried, aged and‘ developed in the usual way. 00 Example XXIV I A thickener whose composition was 10% wheat starch, 30% British gum and 60% water, was in corporated into a printing gum whose composi tion was: v . ' 1 > Per cent Thickener _____________________ _________ ___ 57.5 Sodium formaldehyde-sulfoxylate _______ __ 11 Glycerine ___________________ __~-_ ________ __ 5 ' 7o LThis printing gum was made into a printing paste by mixing the same ‘with appropriate quantities of a 20% dye paste 0! 5:5'-_dichloro-7:'l'-dibrom- 7§~ 8 2,024,975 indigo and a water suspension of anthraquinone the speci?c embodiments thereof except as de 2-sodium sulfonate which had been milled in ?ned in the following claiins. water. The composition of the resulting print'-' We claim: 1. A dye composition comprising a vat printing and a substance selected from the group consist $1 ing paste was as follows: Per cent 20 Anthraquinone-2-sodium sulfonate ______ __ - and alkali metal salts of anthraqulnone-Z-sul ‘0.1 ionic acid. It is to be understood that the invention is not 10 limited to the speci?c dyes listed in the above examples. Other indigoid dyes are well known - ing and a substance selected from the group con publications as: sisting of anthraquinone-Z-sulfonic acid; the am monium salt of anthraquinone-2-sulfonic acid and alkali metal salts of anthraquinone-2-sul-y - .1. Technologie Der Textilefasern- Kiinstliche ionic acid. 15 Organische Fabsto?e H. E. Fierz-David, 1926. 2. Color Index (1924) , Supplement (‘1928), So ciety of Dyers and Colourists. Friedlaender. ’ sisting oi'anthraquinpne-Z-sulfonic acid, the am monium salt of anthraquinone12-sulfonic acid ' and alkali metal’ salts of anthraquinone-2-sul- L 4. Farbstoiftabellen Gustav Schultz (1931). fonic acid. 5. Enzyklopadie der Kiipenfabstoffe Truttwin (1920). Speci?c mention may be made of such other * digo, indigo,‘ . in- thioindigo 2- (5:7-dibrom-indol) -2'-an ' methyl-bis-thionaphthene indigo,-bis-alphanaph- ' prepared by the condensation of reactive 2-isatin ' derivatives with naphthocarbazole bodies-(e. g., ortho-tolu-5 -hydroxy-alpha-naphthocarbazole) , 35 indolacenaphthene indigos, thionaphthene-indol indigos, and the like. The speci?c dyes of U. S. Patents Nos. 1,558,252 and 1,792,648 also merit. particular mention. Theamount of the assistant is ordinarily va 40 ried directly with the amount of solid dye andv the paste used, based on a 12.5% solids dye‘paste. In printing, ‘the preferred amounts are about} 1 to about 5%. Greater or smaller amounts than this may be used when desired. For example, the use of 0.5 to 10% of the assistant'in printing gives good results. Less than 0.5% maybe used if de sired, although the result is‘not as'noticeable as i that produced by using an amount falling within the preferred range. ‘Generally, more than 10% ing and the sodium salt of anthraquin'one-Z-sul 1 ' 5. A printing paste comprising an indigoid dye 2'51 1. and an alkali metal salt of anthraquinone-2-sul- thalene indigo 4:4'-diet_hyl-thioindigo, 5:5'-di indigo, dimethyl-indirubin, dibrom-indirubin, dyes . ionic acid. thracene indigo, 2- (5 : 7 -dibrom-ind'ol) -2'-naph 30 thindol indigo, 4:516:7z4':5’:6':7’-octo~chloro . 4. A dye paste comprising a thioindigoid prlnt- ‘ compounds as 2:3:2’ :3’-di-anthraquinone indigo, bromo-2~beta-naphthindol-2~indol 15. - 3. A dye paste comprising a thioindigoid print ing and a substance selected from the group con 3. Fortschritte der Teerfarben—Fabrikation 'P. 25 . 2. A dye paste comprising an indigoid print- 10 to those skilled in the art and are disclosed in such 20 . ing of anthraquinone-Z-sulfonic acid, the am monium salt of’ anthraquinone-Z-sulfonic acid Printing gum _______ _1 __________________ __ 79.9 Coloripaste ______________ __' ____________ __ ’ fonic acid. ' J 6. A printing paste comprising a thioindigold dye and an alkali metal salt .of anthraquinone-2 sulfonic acid. ‘ 30 '7. A printing paste comprising 4:4'-dimethyl 6:6'-dichloro-thioindigo> and an alkali metal salt of anthraquinone-Z-sulfonic acid. 8. A printing paste comprising ?z?i-diethoxy thioindigo and an alkali metal salt of anthra quinone-2-sulf0nic acid. ‘ ' 9. An indigoid printing'gum comprising an al kali metal salt of anthraquinone-2-sulfonic acid. 10. A thionindigoid printing gum comprising an alkali metal salt of anthraquinone-2-sulionic 40 ‘acid. - 11. The ‘process of printing indigoid dyes which comprises applying to the ?ber a printing paste‘ comprising the indigoid dye, an alkali metal salt of anthraqulnone-Z-sulfonic acid, printing gum, 45 alkali and a reducing agent suitable for printing, and thereafter drying, aging and developing the print. ' v 12. In the process of printing indigoid‘v dyes on 50 may be used without detriment to'the printing _ textiles, the step'which comprises incorporating 50 a substance from the group consisting of anthra process. quinone-Z-sulfonic acid and an alkali metal salt‘ It will be recognized that the type of reduc _ ing agent is to be chosen according to the method to be used in applying the dye to the ?ber. 55 Sodium formaldehyde-sulfoxylate is a material well adapted for printing vat dyes, inasmuch as it is not oxidized at ordinary temperatures and ex ercises its reducing action at elevated tempera tures. ' This invention is of great technical and corn-7' mercial importance since it has been-found that the presence of assistants of the type described in indigoid printing pastes, and especially in the printing of thioindigoid dyes, makes possible the production of prints of superior strength and brightness to those obtained fromia similar print ing paste from which the assistant has been omit ted. The prints are also much stronger and brighter than printing‘ pastes in which the as 70 sistant is a substance such as anthraquinone.v As many apparently widely di?erent embodi ments of this invention may be made without de parting from the spirit and scope thereof, it is to N be understood that we do not limit ourselves to thereof into the printing paste. ' ’ 13. In the process of printing thionindigoid dyes on textiles, the step which comprises'incor- 55'. porating a substance from the group consisting of anthraquinone-2-sulfonic acid and an _ alkali metal salt thereof into the printing paste. .14. In the printing of textilematerial, the step of printing on the textile material with a printing 60 paste comprising an indigoid dye and an alkali metal salt of ‘anthraquinone-Z-sulfonic acid. 15. In the printing of textile material, the step of printing on the textile material with a printing paste comprising an indigoid dye and-milled so- 65 / dium anthraquinone-2-sulfonate. 16. The. process of printing thioindigoid dyes which comprises applying to the ?ber a printing ' paste comprising the thioindigoid dye, an alkali metal salt of anthraquinone-2-sulfonlc acid, 70v printing gum, alkali and a reducing agent suit? able for printing, and‘ thereafter drying, aging and developing the print. ~ 17. The process of printing thioindigoid dyes which comprises applying to the ?ber a printing ‘75" 9 2,024,975 paste comprising a thioindigoid dye, an alkali metal salt of anthraquinone-Z-sultnnic acid, printing gum, potash and sodium formaldehyde sisting of anthraquinone-2-sulfonic acid and al kali metal salts thereof. > _, ,- ' the indigoid type which comprises applying to the 21. The process of preparing printed textile materials which comprises printing on a textile material with a printing paste containing a water- 5 insoluble thioindigoid color, a. printing gum and from about 0.1 to about 1.0% of an alkali metal . goods a composition containing the indigoid dye, a reducing agent suitable for printing, an alkali 22. The process of preparing printed materials ‘ sulfoxylate, and thereafter drying, aging and de veloping the print. i ' 18. The method of printing with vat dyes of metal salt of anthraquinone-2-sulfonic acid and 10 an alkali ._ metal carbonate, aging the same in steam, and re-oxidizing in a developer. . ‘19. A vat dye-printing paste comprising a wa ter-spluble polyhydric alcohol and a substance from the group consisting of anthraquinone-2--v 15 sulfonic acid, the ammonium salt of. anthraquin one-2-sulfonic acid and alkali metal salts of an thraquinone-2_-.sulfonic acid. . 20. A printing, paste comprising a thioindigoid dye, glycerin and a substance from the group con salt of anthraquinone-2-sul1onic acid. ' which comprises printing on a textile ‘material low with '4:4'-dimethyl-6:'6'-dichloro thioindigo in the presence of an alkali metal salt of anthra- ’ , quinone-Z-sultonic acid. - 23. The process of preparingprinted materials which comprises printing on a textile material 15 with 6:6'-diethoxy thioindigo in the presence of an alkali metal salt of anthraquinone-2-sulfonic acid. HERBERT A. LUBS. JOHN ELTON COLE. 20 Certi?cate of Correction Patent No. 2,024,975 December 17, 1935 HERBERT A. LUBS ET AL. It is hereby certi?ed that errors appear in the printed speci?cation of the above numbered patent requiring correction as follows: Page 4, second column, line 39, for “Sulfoxite C___5” read Sulfowite C'___6; page 5, ?rst column, line 2, for “M2520” read Na2S2O4; page 8, second column, lines 4, 10, 16, and 22, claims 1, 2, 3, and 4, respectively, for “dye” read printing; and lines 4, 10—11, 16—17, and 22—23, claims 1, 2, 3, and 4, respectively, for “printing” read dye; same page and column, line 39, claim 10, for “thionindigoid” read thioindigoid; and that the said Letters Patent should be read With these corrections therein that the same may conform to the record of the case in the Patent Of?ce. Signed and sealed this 11th day of February, A. D. 1936. [sEAL] LESLIE FRAZER, Acting Commissioner of Patents.