US2430430A - Prevention of thinning of carbohydrate printing pastes containing diazonium salts with olefin carboxylic acid amides - Google Patents

Description

Patented Nov. 4, 1947 UNITED STATES PATENT OFFICE PREVENTION OF THINNING OF CARBOHY- DRATE PRINTING PASTES CONTAINING DIAZONIUM SALTS WITH OLEFIN CAR- BOXYLIC ACID AMIDES Roy H. Kienle and Frederic Brook, N. J., assignors to Company, New York, N. Y

Maine No Drawing. Application H. Adams, Bound American Cyanamid a corporation of June 19, 1945,

Serial N0. 600,417

11 Claims.

This invention relates to new compositions containing certain ice color forming components specifically, it relates to compositions containing acid amides.

An important method of producing prints of azoic colors on vegetable fibers consists in padding the goods with an salt derived from an ice color diazo component. The diazonium salt is either prepared in solution before use by diazotizing the corresponding amine base, or it According to the present invention, an ice color forming component included in the group consisting of compositions containing water-soluble diazonium salts and intermediates therefor consisting of amines diazotizable to produce compositions containing water-soluble diazonium salts are associated with a water-soluble olefin carboxylic acid amide, represented by the formula:

wherein R is an alkenyl radical containing not more than four carbon atoms; R and R" are radicals selected from the group consisting of hydrogen, alkyl, omega-hydroxyalkyl and alkenyl radicals containing not more than four carbon atoms.

When an aromatic amine is diazotized in acid solution, a diazonium salt is formed which is generally assumed to have the following formula:

where Ar stands for the aromatic radical of the diazo stabilized ey comprise such compounds ing referred to as Th diazonium salts.

Itshould be borne in min that also these stabilized diazonium salts including the abovementioned double salts are true diazonium salts,

diazonium salts described above exert the same thinning action. Presumably in aqueous solution, the stabilized diazonium salts are ionized to give the same diazonium cation. The pH of theprinting paste is not critical so long as it is on the acid side and the present invention does not deal with any other types of paste. Alkaline media, as is well the diazonium salts to diazo compounds of different structure which are referred to as diazotates or nitrosamines.

known, cause rearrangementof Further evidence appears to indicate that the thinning action is a colloidal than a chemical reaction. was made: A diazonium salt derived from 2-nitrO4=-meth0xy aniline was added to a printing paste made up with a starch thickener; after 20 hours, the then water-thin solutionwas coupled with an alkaline solution of beta naphthol and the azo dye formed was removed by filtration. The quantity of azo dyestuil obtained indicated that the bulk of the diazoniumsalt was-undecomposed while the filtrate still showed the reaction of'starch and not the reaction of reducing sugars. The degree of thinning action differs widely and depends upon the structure of the diazo component from which the diazonium salt is derived. We have found that those diazonium salts that are known to be very active couplers in the production of azo dyestuffs are also the worst thinners, while those that are slow in coupling power generally thin to a much lesser degree. Although there is certainly some parallelism in the coupling power and thinning action, these two properties are not strictly proportionate. The diazonium salts that are derived from nitranilines are the phenomenon rather worst thinners; particularly those derived from 2,4 dinitro 6 chloroaniline, from 2 nitro 4- chloroaniline, from 2-nitro-4-methoxy aniline, from 2-nitro-4-methylanilin thin the vegetable The following test gums very badly. The diazonium-salts derived from ortho-nitranilines thin more than those derived from the meta and para compounds. On the other hand, the diazonium salts derived from the 2-methyl-4-chloroaniline and from orthoanisidine have only little thinning action. Obviously, the rate of thinning depends upon'the concentration of the diazonium ions present in the printing paste.

The thinning action has been observed with all thickeners prepared from materials of vegetable origin, such as starches, gums, alkylcelluloses, etc. Wheat starch, corn starch, rice starch, sweet potato starch, tapioca starch, and chlorinated starch may be mentioned as examples of starches. Carob bean gum and gum mentioned as examples of gums, and methyl or ethyl cellulose as examples of alkyl celluloses. Ob-- viously, also mixtures of these materials are quite often used as thickeners and their viscosity is equally influenced by diazonium salts; It will be noted that all these thickeners are carbohydrates or carbohydrate derivatives.

expression fcarbohydrate,thickeneri; is used in a tragacanth may be 7 In, the claims, the

broad sense to cover pure carbohydrates and derivatives.

According to the present invention the thinning action of the diazonium salts on the carbohydrate printing pastes is inhibited or greatly reduced by using water soluble olefin carboxylic acid amides. While not critical the eflective concentration of the thinning inhibitors of the presentinvention will vary to'a considerable degree with the particular diazonium compound present in the paste and with the particular thinning inhibitors. In general, from 20 to 50% of thinning inhibitor based on thetotal-weight of the particular amine from'which the diazonium compound is produced give optimum results. With certain exceptional diazonium compounds amounts of thinning inhibitor be1ow-.20%- are effective, and in certain other-casesam unts,above 50% may be used with advantage! The olefin carboxylic acid amides must contain at, least one double bond. They may contain more than .one and the nitrogen of the amide may carry one or two alkenyl groups.

Some typical examples of olefin carboxylic acid amides useful in the present invention are: propenoic acidgamide (acrylamide), propenoic acid- N -(omega -hydroxy.=-methyl) amide (methylol acrylamide), 2-methyl propenoic acid amide (methyl acrylamide or methacrylamide) A -butenoic acid; amide (crotonamide), A -butenoic acid- N-allylamide .(N-allyl crotonamide), n -butenoic acid-N,N-diallyl amide (-N,N-diallyl crotonamide) N-butenoic N ethylamide (N-ethyl crotonamide), 3-methy1-A -butenoic acid amide (dimethyl-acrylamide), A -butenoic acid amide (vinyl acetamide), n -pentenoic acid amide (betaethyl acrylamide), M-pentenoic acid amide (allyl acetamide), 2-rnethyl-A -butenoic acid amide (tiglic-acid amide), and the like.

Preparation of; these new thinning inhibitors in most casesis accomplished by the customary procedure ofreacting' the olefin carboxylic acid halide with ammonia or an amine, though in some specific casespreparation is best accomplished through dehalogenation of the corresponding dibromo; or dichloroderivative or by dehydrohalogenation of the corresponding mono-bromo or mono-chloro derivative of the saturatedamide.

Thepresent invention includesall the diazonium salts derived from ice'color diazo compo-.

monofiuoroanilines, 2,5-difluoroaniline, z-fiuoro- 5-chloroaniline,- 2,51 dichloroaniline; m-aminobenzotrifluoride, p-amino-benzotrifiuoride, 3- amino-4-chlorobenzotrifluoride, 2 methyl 3 chloroaniline, 2-methyl l-chloroaniline, Z-methyl-5-chloroaniline, 3-methy1-4-chloroaniline, 5- methyl-Z-chloroaniline, Z-methyl 4 chloro-5 bromoaniline,v 2-methyl-4,5-dichloroaniline, 4-

methyl-2,5- dichloroaniline; nitro ,derivatives of aniline andof-itshomologuesand their halogen derivatives, ,as e. g.,. the nitroranilines, Z-methyl- 4-nitroaniline, 2-methyl-5-nitroaniline, l-met-hyl-2-nitroanil-ine,- Z-nitrol-fiuoroaniline, 2-nitrol-chloroaniline, ,3-nitro-4-chloroaniline,- 4- nitro-2-chloroani1ine; ether derivatives of primary aromatic amines and their halogen derivatives, as e. g., o-anisidine, 2-methoxy-5-methyl aniline, 2,5-dimethoxy-aniline, Z-methoxy-lnaphthylamine, 2-amino-diphenylether, 2-amino-4-acetyl-diphenylether, benzyl-2-aminophenylether, 3-fluoro-4-methoxyani1ine, 2-methoxy- 5-chloroaniline, 2,5-dimethoxyl-chloroaniline, 2-methoxy-4-chloro-5-methylaniline, 2 methoxy-5-bromoaniline, 3-bromo-6-ethoxy-aniline, 4-chloro 2 amino diphenylether, l-amino-EZ- chloro diphenylether, 4-amino-e-chloro di phenylether, 4,4'-clichloro 2 amino diphenylether, 2,2',5-trichloro 4. amino-diphenylether; ether derivatives of aniline and its homologues containing nitro groups as e. g., 2-methoxy-4-nitroaniline, 2-methoxy-5mitroaniline, 2-nitro-4- methoxyaniline, 2-methoxy-4-nitro 5 methylaniline; monoacyl derivatives of aromatic diamines, as e. g., N-hexahydrobenzoyl-p-phenylene diamine, N-hexahydrobenzoyl-p-toluylenediamine, N-benzoyl-p-phenylene diamine; monoacyl derivatives of diamino-phenol ethers, as e. g., 2-benzoyl-amino-4-aminoanisole, Z-hexahydrobenzoyl-amino-5-aminoanisole, 2-amino-5-benzoyl-amino-hydroquinone dimethyl ether and diethylether, 2-amino-5-hexahydrobenzoyl-aminohydroquinone dimethylether and diethylether, 2- amino-5-butyrylamino hydroquinone dimethylether and diethylether, 2-amino-5-phenoxyacetylamino-hydroquinone diethylether, the monomethyl and the monobenzyl and the monophenylurethane of 2,5-dia-mino-hydroquinone dimethylether and diethylether, 1-amino-3-benzoy1amino- 4,6-dimethoxy-benzene; analogous monoacyl derivatives of 2,5-diamino-4-alkoXy-to1uenes and of 2,5-diamino-4-alkoxy chlorobenzenes and of 2,5- diamino-e-alkoxy-benzene sulfodialkylamides; analogous monoacyl derivatives of 1,3-diamino- 4,6-dimethylbenzene; the diethylamide of 2-amino-lMJ-chlorophenoxy) -benzoic acid; monoacyl derivatives of diaminop-chloropheny1 ethers as e. g., 2-amino-4-chloro-5-acetylamino-diphenylether, 2-benzoylamino-4-chloro-5-aminoanisole; amino derivatives of aromatic sulfcnes as e. g., 3- aminol-methyl-diphenyl sulfone, 2-amino-4- methyl-diphenyl sulfone, 2-amino-4-acetyl-diphenyl sulfone, the ethyl ester of 3-amino-4-(ptoluene-sulfonyl)-benzoic acid, 4-methoxy-3- amino-phenyl-ethyl sulfone, (4-methoxy-3- amino phenyl) benzyl sulfone, 4 ethoxy 3 amino-diphenyl sulfone, 2-amino-4-(trifluoromethyl) -phenyl-ethyl sulfone; amino derivatives of aromatic dialkylsulfonamides as e. g., B-amino- 4-methyl-benzene dimethyl-sulfonamide and diethylsulfonamide, Q aminol-methoxy-benzene diethylsulfonamide; xenylamine; alpha and beta naphthylamine; alpha aminoanthraquinone; 2- amino-3-nitro-fluorene and 2-amino-3-nitrofluorenone; amino-diarylamines and their ether derivatives and their nitro derivatives as e. g., 2- methoxy-5-aminodiphenylamine, 4-methoxy-4'- amino diphenylamine, 4 ethoxy 4'-amino-diphenylamine, 3,4-dinitro 4 amino diphenylamine; amino-azo compounds, as e. g., 3,2'-dimethyll-amino-azobenzene, 2-methyl-4-amino- 5 methoxy 4- chloroazobenzene, 4 amino-4- nitro-3-methoxy-B-methyl-azobenzene, 4-amino- 4'-nitro-2,5-dimethoxy-azobenzene, 4-amino-4- chloro-3-methoxy-6-methyl-azobenzene, the azo dye: diazotized o-anisidine coupled onto alpha naphthylamine.

There are also diazonium salts derived from aromatic diamines in which only one of the amino groups is diazotized and they also fall Within the scope of the present invention. An example of this type of amine is 2,6-dichloro-1,4-phenylene diamine. Diazonium salts deriving from diamines in which both amino groups are diazotized The method of addition of the thinning inhibitor is not critical. In general it may be added in various stages in the production of the diazonium printing paste. Thus, the aromatic amines used in forming ice color diazo compounds may be blended with the inhibitor and the blends then diazotized in the customary manner and incorporated into a printing paste. Another meth- 1 0d is to blend diazotizable amine salts with the hibitor and the inhibitor, which gives the same result on diazotization. A further variant is to dissolve the inbase separately before diazotization. A second general procedure is to blend the inhibitor with diazonium salts which are very stable per se, or which may have been stabilized by conventional means. The blend forms a solid composition which can be incorporated into a printing paste. A variant of the second procedure is to add the inhibitor to a prepared diazo solution before the printing paste is made up.

The fact that the introduction of the thinner can be effected in so many ways imparts a desirable flexibility to the present invention, which is a practical working advantage.

The above methods of introducing the thinning inhibitor are preferred. However, the invention is not limited thereto. In a number of cases it is possible to mix the diazonium salt with the printing gum and add the inhibitor afterwards. This procedure, however, is not universally applicable with full effectiveness because in the case of very active diazo compounds a certain amount of thinning may take place before the inhibitor is added. This somewhat restricts the scope of this modification, which should normally be used only with diazo compounds which do not thin carbohydrates at an excessive rate. With many printing pastes containing diazonium compounds, however, this procedure is efiective and is included within the broad scope of the present invention.

The invention will be illustrated in the specific examples which describe typical embodiments of the present invention. The parts are by weight.

Example 1 329 parts of the dry mixture of the zinc chloride double salt of the diazonium chloride derived from 4-methyl-2-nitroaniline and a suflicient quantity of partially dehydrated aluminum sulfate and anhydrous magnesium sulfate to reduce the strength to 23.1% on an amine basis are intimately mixed with 21.6 parts of acrylamide and 81.4 parts of partially dehydrated aluminum sulfate. This mixture is then dissolved in 2500 parts of water, and the resulting solution is in- 288 parts of a dry mixture of the Zinc chloride pastes have the outstanding advantage over similar pastes which do not contain acrylamide in that'their relative viscosities and hence their utility for textile. printing are maintained much longer than the relative viscosities of similar pastes which donot contain this amide. This advantage of the pastes containing the acrylamide over those which do not is shown in the following table. In this table the relative viscosities shown are the times in seconds for copper plated steel shot weighing 0.358 gram apiece to fall through 130. mm. of the printing paste in a glass .tube of mm. diameter.

Relative Relative .Relative Base Used for Diazonium g g Viscosity Viscosity fig g ggf i gggfgg u ed Salt After ,1 Hr. After .3 Hrs. After Na hthoic Acid S Mixing Mixing Mixing P Acrylamidc 4-methyl-2-nitro aniline- 20. 5 26. 5 21.0 Bluish red. one 23. 5 2. 5 Less than 0.5.. 0. Acrylamide 29. 8 27. 0 Yellowish red. None 0 24. 5 2.0 Less than 0 o. Acrylamide." 2-methoxy-5enitro aniline. 48. 0 45. 0 44.0. Reddish scarlet. None 0 42. 5 12. 5 6.0 Do. Aerylamide. 2,5-dich1oro aniline 48. 5 38.0 40.0 Yellowish scarlct.

do. 34. 5 1. 5 Less than 0.5.. Do. Ortho dian 26.0 22. 5 16.0 Navy blue. ..do 25. 5 3. 5 Less than 0.5.. Do.

4-methoxy-2-nitro aniline 28.0 23. 5 16.5. Bordeaux. do 25. 5 0.5 Less than 0.5.. Do.

double salt of the diazonium chloride derived from 2--methoxy-5-nitroaniline and suificient anhydrous magnesium sulfate and partially dehydrated aluminum sulfate to reduce the strength to 29.1% on an amine basis, are intimately mixed with'32.8 parts of acrylamide and 116.2 parts of anhydrous magnesium sulfate. The resulting dry powder is dissolved in 2500 parts of water, and. the solution so obtained is intimately mixed with 7500 parts of 2.5% aqueous carob bean gum.

394 parts of the dry mixture of: the zinc chloride double salt of the diazonium chloride derived from 2,5-dichloro aniline and suificient partially dehydrated aluminum sulfate to reduce the strength to 20.55% on an amine basis arethoroughly mixed with 20.9 parts of acrylamide. The resulting dry powder is then dissolved in 2500 parts of water. and the solution thus prepared is intimately mixed with 7500 parts of 2.5% aqueous carob bean gum.

320 parts of the dry mixture of the zinc chloridedouble salt of the tetrazonium chloride derived from ortho-dianisidine and sufficient anhydrous'magnesium sulfate to reduce the strength to 19.1% on an amine basis are intimately mixed with 19.3 parts of acrylamide' and 3!? parts of anhydrous sodium sulfate. The resulting mixture isthen dissolved in 2500 parts of water, and the solution so made is thoroughly and intimately mixed with 7500 parts of 2.5% aqueous carob gum.

343 parts of a'mixtureof'the 'zinc chloride double salt of the-diazonium chloride derived from 4-methoxy-2-nitroaniline' and sufficient anhydrous magnesium sulfate to reduce the strength to 24.5% on an amine basis are mixed with 34 parts of acrylamide and 77 parts of anhydrous sodium sulfate. The resulting: dry -mixt-ure is then'dissolved in 2500 parts of water, and the solution so obtained is thoroughly mixed with 3500-parts of 2.5% aqueous carobbean: gum.

. The six printing pastes described above are useful for the preparation offast color prints on cloth impregnated with ice color coupling components, 'suchas the anilide .of 2,3-hydroxynaphthoic acid. 'Furthermore, theseprinting Example 2 2000 parts of a mixture of the zinc chloride doublesalt of the diazonium chloride derived from 4-methyl-2-nitroaniline and sufficient anhydrous magnesium sulfate and partially dehydrated aluminum sulfate to reduce the strength to 17.6% on an amine basis are intimately mixed with 102.5v parts of methacrylamide (melting point 111-.112 C.). 363 parts of this mixture, which contains 4.7% by weight of methacrylamide, are dissolved in 2500 parts of water, and the resulting solution is then intimately mixed with 7.500 parts of 2.5% aqueous carob bean gum.

343 parts of mixture of the zinc chloride double salt of. the diazonium chloride derived from 4- methoxy-2-nitroaniline and sufficient anhydrous magnesium sulfate to reduce the strength to 24.5% on an amine basis are mixed with 34 parts of methacrylamide and '17 parts of anhydrous sodium sulfate. The resulting mixture is then dissolved in 2500 parts of water and the resulting solution is then intimately mixed with 7500 parts of 2.5% aqueous carob bean gum.

381 parts of a mixture of the zinc chloride double salt of the diazonium chloride derived from 4-chloro-2-nitroaniline and sufficient partially dehydrated aluminum sulfate to reduce the strength to 22.6% onan amine basis are intimately mixed with 23.2 parts of methaorylamide, and the resulting mixture is dissolved in 2500 parts of water. The solution thus made is then intimately mixed with 7500 parts of 2.5% aqueous carob beangum.

The three printing pastes described above are usefulfor the preparation of bright fast color prints on cloth impregnated with ice color components, such as, for example, th anilide of 2, 3-hydroxy-naphthoic acid. These pastes, containing methacrylamide, retain their viscosity, and hence their usefulness for printing, a much longer time than similar pastes prepared without the use of methacrylamide. This advantage is clearly shown in the following table. In this table, the relative viscosity figures are the times for .stainless steel spheres weighing 1.023 grams apiece or-lead spheres weighing 0.536 gram apiece to fall through 130 mm. of the paste in a tube 20 from 4-methoxy-2-nitroaniline and sufficient anmm. in diameter. hydrous magnesium sulfate to reduce the strength Kind of B d U at Di sl zihlerte for gg g, Relative xIfelatiifre Golgi of grinft use so or azonlum e a We lscosl y on hi i e Thmmng Inhlbltor Used Salt Viscosity &8? gi gtg 3 Hrs. After 2, 3-Hydroxy glziire- Mixing Mixing Mixing Naphtholc Acid 4-methyl-2-nitro ami1ine stainlesssteel 16 0 16.0 14.5 bluish red. o do 13 2.0 Less than 0.5 Do. 4-lnethoxy-2-nitroaniline- Lead 18 0 17. 5 16.0 Bordeaux. o d 16 0 0.5 Less than 0.5-. Do. 4-chloro-2-nitro aniline... d 14 0 14.0 12.5 yellowish red. do 12 5 2. 0 Less than 0.5 Do. Example 3 15 to 24.5% on an amine basis are mixed with 34 329 parts of a mixture of the zinc chloride parts of crotonamide and 77 parts of anhydrous double salt of the diazonium chloride derived from sodium sulfate- The resulting mixture is 4-methyl-2-nitroaniline and sufficient partially solved in 2500 parts o t d t solu ion dehydrated aluminum sulfate and anhydrous hus obtained is intimately mixed with 7500 parts magnesium sulfate to reduce the strength to of aqueous Carob bean 23.1% on an amine basis are mixed with 81.4 parts 381 P rts of a mixture of the zinc chloride of partially dehydrated aluminum sulfate and double salt of the diazonium chloride derived the resulting mixture is dissolved in 2450 parts from 4-oh1ero2-nitroani1ine and sufiioient p of water. To this solution is then added 60 parts tielly dehydrated a um n m su fate to reduce the of a 36% aqu o l ti of N-methylo] 1 25 strength to 22.6% on an amine basis are mixed amide and the resulting solution is then intiw h parts f crotonamide. The r su tin mately mixed with 7500 parts of 2.5% aqueous mixture is dissolved in 2500 parts of water, and carob bean gum. the solution so obtained is then intimately mixed 381 parts of a mixture of the zinc chloride w 7500 parts f aq u a b b n sum. double salt of the diazonium chloride derived v The two printing pastes described a v ar from 4-chloro-2-nitroaniline and suflicient paruseful for the preparation of fast color prints on tially dehydrated aluminum sulfate to reduce material impregnated with the usual ice color th strength to 22.6% on an amine basis are dismp n nts s as t a i f ,3- yd y solved in 2440 parts of water to which are then napht c acid. Th se print as s ta added 60 parts of a 36% aqueous solution of their body or viscosity much better than similar N-methylol acrylamide, The resulting solution pa t s ade in the Same manner but Without is then intimately mixed with 7500 parts of 2.5% crotonamide This is shown n he fo w n aqueous carob bean gum. table. In this table the relative viscosities are These printing pastes described above are used the times in seconds for lead spheres weighing for the production of fast color prints on fabrics 40 0.536 gram apiece to fall through 130 mm. of the impregnated with ice color coupling components paste in a tube 20 mm. in diameter.

B U at D l telatilze {Eftelative Sharia olfclirirt ase se or iazonium lscosi y lscosi y on n11 e0 Thm'nmg Inhlbltor salt 2:4 3 1 Hr xfter 3 Hrs. after 2,3-Hydroxy Mixing Mixing Mixing naphtholc acid Orotonamide 4-methoxy-2-nitroaniline 19.5 9.5 5.0 Bordeaux. None d0 16. 0 0.5 Less than 0.5.... Do. Orotonamide 4-chloro-2-nitro 13.5 8.0 3.0 yellowish red. None do 12. 5 2. 0 Less than 0.5.-.. Do. such as, for example, the anilide of 2,3-hydroxy- The crotonamide used in this example melted naphthoic acid. These printing pastes maintain at 159-160 C. and was prepared from crotonyl their viscosity, and hence are useful for the chloride and liquid ammonia according to the preparation of prints, for a much longer time method of Stoermer et al., Ber, 47, 1789 (1914). than pastes similarly made but without the N -methylol acrylamide. This is shown in thefol- Example 5 lowing table. 343 parts of a mixture of the zinc chloride dou- In this table, the figures for the relative visble salt of the diazonium chloride derived from coslties are the times in seconds for copper plated 4-methoxy-2-m'troaniline and sufficient anhysteel shot weighing 0.358 gram apiece to fall drous magnesium sulfate to reduce the strength to through 130 mm. of the paste in a tube 20 mm. 4.5% on an aminebasis are mixed with 77 parts in diameter. of anhydrous sodium sulfate and the resulting Relative Relative Relative Color of Print Viscosity Viscosity Thinning Inhibitor Base U 131m" 2 Ming, 1 hr. f mum Salt After After 3 Hrs. Aftcr N2, 3 Hfivdrozyd Mlxmg Mixmg Mixing apht 01c 01 N-meth lola r lamide 4-meth l-2-nitroani1ine 28.5 25.0 22.5 bluish red. Nonei luff 110. 23. 5 2. 5 Less than 0.5..-- Do N-methylolacrylamide. 4-chloro-2-ni oamlin 30.5 25.0 21.5 yellowish red. None do 24. 5 2.0 Less than 0.5 Do.

Example 4 dry powder is dissolved in 2500 parts of water.

34 parts of a mixture f t Zinc chloride There is then dissolved in this solution 34 parts double salt of the diazonium chloride derived of N-allyl crotonamide and the resulting solution same manner except that the N-allyl crotonamide is omitted.

The printing pastes prepared. as: described above are'used for the preparation: oirfastcolor prints on materialimpregnated with ice color coupling components such as theanilide of 2,3-hydroxy-, naphthoic acid- The;ormer printing paste, containing the N-allyl crotonamide, maintains its vis cosity,'and hence its utilityfor printing, much longer than the-latter paste'which does not contain this amide. Thisidifference is shown in the following table, in which the relative viscosity figures are the times. in seconds for lead shot weighing onv an average of 0.5365 gram apiece to fall through 130 mmyof the paste in a tube 20 mm. in diameter.

The N-allyl crotonamide is prepared by allowing one molecular proportion of crotonyl chloride to react in ether solution with approximately 3 molecular proportions of allyl-amine. The allylamine hydrochloride. formed during. the reaction is filtered off, and the excess allylamine and other are evaporated from the filtrate, leaving the desired N-allyl crotonamide'as a viscous oil.

Paste Con- Paste Containing tairing' No N--Allylv Thinning Crotonamide Inhibitor Relative viscosity:

3 mins. after mixing; 11. 10.0 mins. after mixing... 17. 5 5. 5 a hr. after mixing 17. 5 2. 0 1 hr. after mixing. 15. 5 0.5 2 hrs. after. mixing.-. 12.0 Less than 0.5

Example 6 381 parts of a mixture of thezinc chloride'double salt of the diazonium chloride. derived from 4-- chloro-2-nitroaniline and sufficient partially dehydrated aluminum sulfate to reduce the strength to 2 .6%on an amine basis are dissolved in 2500 parts of water and to the solution are then added containing. the Neethyl' croton'amide' maintains its. longer, and hence: can :be used by the.

viscosity. printer for a longertimeth'an the latter: which does not contain this N-ethyl crotonamide. This N-ethylcrotonamide. The resulting difference is shown by the figures in the foll'owing table, in which therelative viscosityfigures are the times in seconds for. spherical lead'shot weighing on an average .0.5365-.gram apiece to fall through 130 mm. of .the paste in. a tube. 20mm.

in diameter.

The N-ethyl crotonamide is prepared from crotonyl chloride and anhydrous ethylamine in ether solution by the same procedure as thatdescribed in Example 5 for the'prcparation' of N-allylcrotonamide. pared is a pale yellowish oil.

The ,N-ethyl crotonamide thus .pre-.

Paste Gon- Paste Containing taining No N-cthyl Thinning Crotonamide Inhibitor Relative Viscosity:

3 mins. after mixing V 13.0 12.5 15 mins. after mixing 12.5 6. 5 30 mins. after mixing 10. 5 4. 5 45 mins. after mixing 10. 0 3. 5 1 hr. after mixing 8.0 2.0 1.5 hrs. after mixing 6. 0 0. '1 P Example 7 200 parts of 4-methoxy-2-nitroaniline, 50 parts of acrylamide and 150 parts of sodium chloride are thoroughly ground together in a mortar to form a homogeneous orange powder. This mixture can be used for the preparation of a printing paste which retains its viscosity, and hence its utility for printing; a much longer time than a printing paste made from the same base but without the acrylamide. This is shown by the following illustration:

168 parts of the mixture of 4-methoXy-2-nitroaniline, acrylamide and salt described above is thoroughly mixed with 1000 parts of water and 325'parts of 5N hydrochloric acid and sufficient ice to lower the temperature to approximately 5 C. To the resulting slurry is then added over a period of two or three minutes 550 parts of 1N sodium nitrite solution and the resulting mixture is stirred until diazotization iscomplete, 15

or 20 minutes being sufficient. The resulting diaz'o solution is then filtered to remove small amounts of impurity and diluted with water until it occupies the same volume as 2500 parts of wa ter. This solution is then intimately mixed With 7500 parts of 2.5% aqueous carob bean gum.

Another printing paste is then made in exact-- ly the same manner except that 84 parts of 4- methoxy-2-nitroaniline are substituted for 168 parts of the mixture of base, acrylamide and salt. The superiority of the paste made from the base containing the acrylamide is shown in the following table, in which the relative viscosity figures are the times in seconds for spherical lead shot weighing on an average 0.5365 gram apiece to fall mm. through the paste in a tube 20 mm. in diameter.

Thinning Inhibitor in Printing Paste Acrylamide None Relative viscosity:

2 mins. after mixing 15.0 14. 0 0.5 hr. alter mixing 13. 5 6.5 1 hr. aitermixing 11.5 4.0 1.5 hr.after mixing 10.0 3.0 3 hrs. after mixing 9. 0 1.5

Example 8 A thorough mixture is made in a mortar of the following ingredients:

Parts 2-methoxy-4-nitroaniline 200 Methacrylamide (M. P. ill-112 C.) 50

Epsom sa then mixed with 7500 bean gum.

In an entirely similar manner another printing paste is prepared from 84 parts of Z-methoxy- 4-nitroaniline alone. These two printing pastes are used for the production of fast prints on the fiber impregnated with ice color coupling components, for example, for the production of fast bluish red prints on cloth padded with an alkaline solution of the anilide of 2,3-hydroxy-naphthoic acid. The former paste, however, which contains the methacrylamide, maintains its viscosity much longer than the other and hence is useful for printing for a longer period of time. This is illustrated by the following figures, in which the relative viscosities are the times in seconds for lead shot weighing on an average 0.5365 gram apiece to fall 130 mm. through the paste in a tube 20 mm. in diameter.

Thinning Inhibitor Used in Printing Paste Relative Viscosity:

2 mins. after mixing 0.5 hr. after mixing. 1 hr. after mixing 1.5 hrs. after mixing. 2 hrs. after mixing..." 3 hrs. after mixing parts of 2.5% aqueous carob Methacrylamide N one We claim:

1. A composition suitable for the preparation of printing pastes containing carbohydrate thickeners comprising an ice color-forming component included in the group consisting of compositions containing water-soluble diazonium salts and intermediates therefor consisting of amines diazotizable to produce compositions containing Water-soluble diazonium salts; the color-forming component having associated therewith an olefin carboxylic acid amide represented by the following formula:

wherein R is an alkenyl radical containing not more than four carbon atoms, R and R". are radicals selected from the group consisting of hydrogen, alkyl, omega-hydroxyalkyl and alkenyl radicals containing not more than four carbon atoms; the amount of organic olefin carboxylic acid amide being sufiicient to substantially inhibit thinning of a carbohydrate thickener.

2. A composition suitable for the preparation of printing pastes containing carbohydrate thickeners comprising an ice color-forming component included in the group of water-soluble diazonium salts; the color-forming component having associated therewith an olefin carboxylic acid amide represented by the following formula:

wherein R is an alkenyl radical containing not more than four carbon atoms, R and R" are radicals selected from the group consisting of hydrogen, alkyl, omega-hydroxyalkyl and alkenyl radicals containing not more than four carbon atoms, the amount of olefin carboxylic acid amide being sufficient to substantially inhibit thinning of the carbohydrate thickener.

4. A composition according to claim 1 in which the olefin carboxylic acid amide is propenoic acid amide.

5. A composition according to claim 2 in which the olefin carboxylic acid amide is propenoic acid amide.

6. A composition according to claim 3 in which the olefin carboxylic acid amide is propenoic acid amide.

7. A composition according to claim 1.in which the olefin carboxylic acid amide is 2-methyl propenoic acid amide.

8. A composition according to claim 2 in which the olefin carboxylic acid amide is Z-methyl propenoic acid amide.

9. A composition according to claim 3 in which the olefin carboxylic acid amide is Z-methyl propenoic acid amide.

10. A composition according to claim 2 in which the diazonium salt is a diazonium chloride-zinc chloride double salt.

11. A composition according to claim 3 in which the diazonium salt is a diazonium chloride-zinc chloride double salt.

ROY H. KIENLE. FREDERIC H. ADAMS.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 2,378,305 Lecher June 12, 1945 2,378,276 Adams June 12, 1945 2,319,265 Rossander May 18, 1943 2,386,646 Adams Oct. 9, 1945