US2378305A - Stabilization of coloring compositions containing diazonium salts - Google Patents

Description

memes June 12, 1945 UNITED-1 STATE s- Partition-ice STABILIZATION F COLORING COMPOSI- TION S CONTAINING'DIAZONIUM SALTS Hans Z. Lecher, Plainfleld, and William B. Hardy and Frederic B. Adams, Bound Brook, N. J., assignors'to American Cyanamid Company, New York, N. Y., a corporation of Maine No Drawing. Application July 5, I943, I Serial No. 493,594

13 Claims.

An important method of producing prints of azoic colors on vegetable fibers consists in pad ding the goods with an alkaline solution of an 'azoic coupling component and printing these goods with sprinting paste containing a dimnium salt derived from an ice color diazocom I ponent. The diazoniuin salt is either prepared by the printer himself by diazotizing the corresponding base or it is applied in the form of a stable diazonium salt. This simple and well-known cheap process is open to a very serious disadvantage. The printing pastes containing the diazonium salts and a carbohydrate thickener tend to thin out rapidly losing their desired printin consistency. It is with this thinning action that Y the present invention is concerned. According to thepresent invention the diazonium salt is associated with a water soluble suli'on'ic acid containing at least one oleflnic double bond or acetylenic triple bond for each '10 carbon atoms.

When an aromatic amine .solution, a diazonium salt is formed which is generallyassumed to have the iollowing formula:

. mi-xwhere Ar stands for the aromatic radical or the diazo component and X stands'for the anion of the acid. These diazonium'salts are salts of the very strong diazonium bases and the aqueous solutions contain essentially the diazonium cations and the anions oi the acid used, as indicated by the formula. Some or thesediazoniu'm salts are diflicult to isolate because of their great solu-' bility. Others are not so soluble and can be easily isolated. Someare diflicult to handle after rather stable and do not represent an explosive hazard. It is also known that if the anion of the is-d'a'ot' ed in id I z m or diazoamino and diazoimino compounds which acid X- is properly chosen, in almost all cases diazonium salts of lower solubility may be produced and therefore isolated, and it is also known that many of these diazonium salts have lost their explosive character andcan be storedand handled in the dry statewithout' danger; this kind of diazonium salts is sometimes referred to .as stabilized diazonium salts. They comprise such compounds as certain aromatic sul-' fonates, without olefinic double bonds, Iborofluorides;- and particularly salts of complex acids sometimes referred to as double salts, the mostimportant of them being the double salts of diazonium chlorides and zinc chloride' which correspond to the i'ormula:

ArN V a m) -'(zncm= v V v .N a I It should be borne-in mind that alsothese stabilized diazonium salts including the above mentioned double salts are true diazonium salts,

i. 'e., the aqueous solution contains the same diazonium cations as the solution or any other diazonium salt derived from the same base. The stabilized diazonium salts should not be confused with other kinds of stabilized diazo compounds such as dia'zotates, also known as nitrosamines,

' are only stable and applied in alkaline medium,

' diafzo compounds are referred to in this applicawhile on the other hand the diazoniuni salts are only stable applied in acid medium. The present types-oi diazo compounds. Whenever stabilized tion this term shall be interpreted to includeex- -isolation because oi. their explosivity, others are clusively stabilized diazonium salts and not to 7 include diazotates or diazoamino or diazoimino compounds; 1

While it is not-intended to limit the present invention to any theory of action, we believe that I, it is highly probable that lowering of viscosity of printing gums is essentially caused by the diazonium' cation because the same kind of thing rsults regardlessoitheanionotthediamium saltandeventhedoublesalboffliestablliaed 'diasoniumsaltsdescribedaboveexertaslmilar -printingpasteisnot criticai'so longasitis on the acid side, for the present invention does not dealwithanyother typeset pastes. Alkaline media, as is well-known, cause rearrangement or thediaaoniumsaltstodiaso emnpoundsoidifl'ermtstructurewhicharereferredto asdiaaotates or nitrosamines.

While not desiring to limit the invention thereto, we believe that the evidence strongly indicates thatthethinningactionisacolioidalphenmnenon rather than a chemical reaction. The following test was made: A diazonium salt derived from z-nitro-i-methoxy aniline was added to a printing paste made up with a starch thickener; aiterzohoursthethenwaterthinsolutionwas coupled with an alkaline solution of betanap'nthol and. the sac dye formed was removed by filtration. 'Ihe amount of am dyestuii obtained indicated that the bulk of the diazonium salt was lmdeeomposed and had acted while the filtrate still showed the reaction of starch and not the reactions of reducing sugars.

The thinning action diiiers widely and depends upon the structure' of the diam component the diasonium salt derives from. We have found thatthosediazoniumsaltsthatareknowntobe very active couplers are also the worst thinners, while those that are slow in coupling generally thin to a much lesser degree. Though there is certainly some parallelism in the coupling power and thinning action these two properties are not strictly proportionate. The diaaonimn salts that derive from nitroanilines are the worst thinners. Particularly those deriving from 2,4-dinitro-6- chloroaniline, from 2-nitro-4-chloroaniline, from 2-nitro-4-methoxy aniline, from 2-nitro-4- methylaniline thin the vegetable gums very badla'The diamnium salts deriving from o-nitraniline thin more than those deriving from the meta and para compounds. On the other hand the diazonium salts deriving from the 2-methyl-4-chloroaniline and iron:- o-anisidine have only little thinning action. Obviously, the rate of the thinning depends upon the concentration oithe diasonium 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, alkyl celluloses. etc.

Wheat starch, corn starch, rice starch, sweet P- tato starch, tapioca starch, chlorinated starch,

maybe mentioned as examples of starches. Carob bean mm and gum tragacanth may be mentioned as examples or gums and methylor ethylceilulose as examples of allwl celluloses. Obviously, also mixtures of these materials are quite often used in thickeners and their viscosity is e? influenced by dianonilmi salts. It will be no all of these thickeners are carbohydrates or carbohydrate derivatives. In the claim the expremon carbohydrate thickener is used in a broad sense to cover pure carbohydrates and derivatives. j

The water soluble suiionic acids containing at least one olefinic double bond or acetylenic triple bond for each 10 carbon atoms have the general 'il operty of preventing or reducing the thinning action of diazonium salts cm printing pastes. The

deereasestheamnityofthediazonimncafionand inhibitsitsacflmupunthethickener. Whemthe thickenerlaflrstaddedtothediamhnnsaltmlutioniollowedbyaddiiionotthethinninginhihitor, thinning is prewnted to ,a much lesse degree. Apparentlyinsuchacasethediamium salt has already commenced its thinning action onthethickenerandtheactionisnotreversihle sothattheadditionofthethinninginhibitordoes not remedythedamagealreadydone.

The present invention includes all the dissoniuni salts derived fmm ice eolor'diam nmtathatistosamnomalldiazotizable aromatic aminesfreefrom solubilizinggroupsuseiulin makingiceeolorsoramicpigments. Typicalare theiollowing:

Aniline and its homologues, as e. g. the toluidines, 2,4-dimethylaniline; halogen derivatives of aniline andof its homologues'.ase. g. the momfluomanilines, the monochloranilines, Zn-dimmroaniline, Z-fluoro-S-chloroanilhre, 25 4mmroanillne, m aminobenzois'ifluoride, p-aminobensotrifluoride, 3 amino-4 chlorobenzotrifiucide, 2-methyl-3-chloroaniline, 2-methyl-4-chlo- 4a roaniline, 2-methyl-5-chlornaniline, S-methwL i- 2-methoxy 5 bromoanillne, 3-bro1no-6-ethoxyaniline, 4-ch1oro-2-amino-diphenylether, 4-amino 2 chloro-diphenylether, i-amino-f-chlorodiphenylether, 4',4 '-dichloro 2 amino diphene yletber, 2,2,5'-trichloro-4-amino-diphenylether; ether derivatives of aniline and its homol es containing 'nitro groups as e. g. 2-methoxy-4- nitroaniline, 2-methoxy-5-nitroaniline, 2-nitro- 4-methoxyaniline, 2-methoxy-4-nitro-'-5-methyl.- aniline; monoacyl derivatives of aromatic diamines, as e. g. N-hexahydrobenzol-p-pheny1-. ene diamine; N-hexahydrobenzoyl-p-toluyh enediamine, N-benzoyl p phenylene diamine; monoacyl derivatives of diaminophenol ethers, as e. g. 2-benzoy1aminof-4- amino-aniaole, 2

hexahydrob'enaoylamino 5 aminoanisole, 2 amino 5 benzoylamino hydroquinone dimethyl ether and diethylether, z-amino-d-hexahydroami tion. Typ cal heterocyclicamines are 2-aminoycarbazole, 3,6 diaminocarbazole, 2-nitro-3'-a-'- mino-carbazole, 2 nitro 3'-aminodibenzofuran, Z-amino 3-nitrobenzothiophene, 1 amino-5-fludiethylether, '2 amino 5 butyrylamino-hydroquinone dimethylether and diethylether, 2-amino- 5 phenoxyacetylamino -"hydroquinone diethylether, the ,monomethyl and the monobenzyl and the monophenyl-urethane of 2,5-diamino- 1 I benzoylamino-hydroquinone dimethylether andhydroquinone dimethylether and diethylether, 1-

amino-3-benzoylamino-4,6-dimethoxy benzene;

' analogous monoacyl derivatives of 2,5-diamino-4- alkoxy-toluenes and of 2,5-diamino 4-alkoxy chlorobenzene and of 2,5-diamino-4-alkoxy-benzene sulfodialkylamides; analogous monoacyl derivatives of 1,3-diamine-4,6-dimethylbenzene; the diethylamide f 2-amino-4(4'-chlorophenoxy) -benzoic acid; monoacyl derivatives of diamino-p-chlorophenyl ethers as e. g. 2-amino-4- 'chloro-fi-acetylamino diphenylether, 2-benzoylamino-4-chloro-5-aminoanisole; amino derivatives of aromatic sulfones as e. g. 3-amino-4- methy-diphenyl sulfone, 2-amino-4'-methyl-diphenyl sulfone, 2-amino.-4-acetyl-diphenyl sul- -fone, the ethyl ester of 3-amino-4-(p-toluene-- sulfonyl) -ben'zoic acid, 4 methoxy 3 aminophenyl ethyl sulfone, (4 methoxy. 3 aminophenyD-benzyl sulfone, 4-ethoxy-3-amino-diphenyl sulfone, 2 amino 4 (trifluoromethyl) phenyl-ethyl sulfone; amino derivatives of aromethyl-benzene. dimethylsulfonamide and diethylsulfonamide, 3.-'amino '4 methoxy-benzene diethylsulfonamide; xenylamine; alpha and beta naphthylamine; alpha aminoanthraquinone; 2-

'amino-3-nitro-efluorene and 2-amino 3 nitro- .fluorenone; amino-diarylamines and their ether derivatives and their nitro derivatives as e. g- 2- methoxy-S-amino-diphenylamine, 4-methoxy-4- amino'diphenylamine, 4 ethoxy 4'-'a-mino-diphenylamine, 3,4'-dinitro 4 amino-diphenylamine; aminp-azd' compounds, as e. g. 3,2'-dimethyl-4-amino-azobenzene, 2-methyl-4-amino- 5 methoxy-4'-chloroazobenzene, 4-amino-4'-nitr0-3-methoxy-6-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.

include the water soluble sulfonic acids that contain at least one oleflnicdouble bond or acetylenic triple bond. The inhibitors of the present invention may contain one or more oleflnic double bonds or acetylenic triple bonds in the same molecule, or they may contain both double bonds and triple bonds, We have found that the anti-thinning action appears to depend mainly on the presence of the double or triple bond. In, order to be practically efl'ective, we have found that there must be a certain minimum number of the unsaturated bonds in a molecule of given size.

.Practically useful anti-thinning action is obtained when there is at least one double bond or triple bond per 10 carbon atoms of the molecule. of the sulfonic acid. The unsaturated bond may be located almost anywhere in the molecule. Thus, it

. may be linked directly to the carbon to which the sulfonic acid group is connected or it may be located elsewhere in a carbon chain, which may be interrupted by other elements such as oxygen,

' matic dialkylsulfonamides as e. g. 3-amino-4- nitrogen, sulfur and the like.

The sulionic acid compounds used in the present invention are true sulfonic acids or sulfonates, that is to say organic compounds containing the group EC-SO3H, and it is necessary that the inhibitor be free from groups which are capable of azoic coupling with the diazo compound or condensation to form a diazoamino or diazoimino compound in acid medium.- Itis also necessary that the cation of the inhibitor shall not becapa- There are also diazonium salts derivin from aromatic diamines in which only one of theamino groups is diazotized-and they also fall within the 1 scope of the present inventionz 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 -to form tetrazo compounds fall within-its scope. Typical amines of this class arep-phenylene diamine, benzedine, vo-tolidine, o-dianisidine, 4,4- diamino stilbene, 4,4-diamino diphenylamine,

- '2,2'.-dimethyl-4,4'-diamino diphenylamineand 7 1,5-diaminonaphthalene.

Also di nium alts deriving from heterocyclic nmofiamines fall under the presentinvenorobenzothiazole:

of difierent diazonium ble of coupling with the diazo compound, condensing therewith to form a diazoalnino or diazoimino body or of catalytically decomposing it. as is the case with certain copper compounds.

The present invention is not limited to using a single inhibitor and mixtures are equally efiective.

Since the sulfonicacid compounds stabilize in an aqueous composition the acid itself or its water soluble salts may be used. I

Examples of aliphatic sulfonic acids containing one double bond are: ethylene sulfonicacid, 2- propene-l-sulfonlc acid, 2-methyl-2-propene 1- sulfonic acid, Z-butene-l-sulfonic acid, lgl-dimethyl-Z-propene-l-sulfonic acid, 3,3-diethyl-2- propene l-sulfonic acid. Examples ofaliphatic sulfonic acids containing two double bonds are:

1,6-heptadiene-4-sulfonic acid, 3,7-dimethyl 2,6-.

octadiene-l-sulfonic acid. As an example of an aliphatic sulfonic acid with a triple bond there 7 1 may be mentioned 2-propine-l-sulfonic acid.

With the exception of ethylene sulfonic acid these aliphatic sulfonic 'acids are most conveniently prepared by reactingthe corresponding chloride with sodium sulfite in the well-known manner.

The unsaturated grouping does not necessarily have to be connected to. the sulfonic group by a carbon chain. On. the contrary this chain may be interrupted by other atoms. Typical examples are N -a'llyl taurine, diallyl suffosuccinate, and dimethallyl sulfosuccinate, a compound containing 12 carbon atoms and two olefinic double bonds. tainedfrom the'corresponding maleic acid esters by reaction with sodium bisulilte.

The sulfonic acids of the present invention need not belong to the aliphatic series. On the contrary. they may contain ring systems, so long as there is at least one olefinic double-bond or a. triple bond. It should be noted that the double bond must be oleflnic in nature, thus for example the double bonds in the benzene ring are not olefinic in nature and accordingly benzene sulfonic acid does not behave as an inhibitor and is not included in the present invention. How- The latter two compounds may be 'ob- 4 ever, alicyclic compounds which do contain double bonds of oleilnic character are active inhibitors. Typical examples are cyclohexene 3 sulionic acid, l-p-menthene-ii-sulfonic acid and 1-pmenthene-4-sulfonic acid which are obtainable in the molecule does not affect its inhibiting,

action provided that the molecule also contains olefinic double bonds or acetylenic triple bonds outside of the aromatic ring. Typical examples of such compounds as styrene-beta-sulfonic acid, alpha metlmlstyrene p sulfonic acid, phenyl acetylene-p-sulfonic acid, and the like.

As with the purely aliphatic compounds referred to above, the sulionic group does not, have to be connected to the unsaturated group through a carbon chain onlv. Thus for example the allyl ether of phenol p-suli'onic acid acts as inhibitor.

Heterocyclic sulfonic acids are also useable as long as they contain double bonds or triple bonds of oleilnic or acetylenic character respectively. These bonds may be inside or outside of the heterocyclic ngs.

Inhibitors of the present invention may have other substituent groups, thus for example allyl ethers of Z-sulfo-i-nitrophenol, 2-sulio-4-chlorophenol, or 2-sulfo-4-aminophenol are useful inhibitors.

It should be noted however, that the inhibiting effectiveness is not imaifected by the presence of azotization. If the inhibitors are used in this manner they obviously should not contain diazotizable amino groups. In the second place diazonium salts .either stable per se or stabilized in a customary way, may be blended with the inhibitor to form solid compositions suitable for incorporation into printing pastes. The obvious equivalent is to add the inhibitor to a separately prepared diazo solution before the printing paste is made up. It does not make any difference what procedure is used in every case the thinning of All substituents. The so-called negative substituents when attached directly to a carbon of the double bond group lower the inhibiting action. Thus ethylene sulfonic acid is by no means as powerim an inhibitor as 2 propene 1 sulfonic acid where the negative group is separated from the double bond by a methylene group. This be havior appears to be general with the sulfonic acids of flue present invention and is further evidence that the double or triple bond is the portion of the molecule which apparently exerts the primary inhibiting Since the sullonic acids of the present invention behave as they do by reason of their anion and their effectiveness is not greatly influenced y the nature of the cation except where it interferes as in the case of copper, it is preferable'in many cases to use a salt of the. sulfonic acid instead of the sulfonic acid itself as these salts may be very readily handled.

The sodium and potassium salts of the sulfonic the printing gum is greatly delayed.

If the diazonium salt is first mixed with the printing gum and the inhibitor is added afterwards, then in a great many cases of very active I diazo compounds a certain amount of thinning has already taken place before the inhibitor is added. This procedure, therefore, should be used only where the thinning action is slow, but it is included in the broad scope of the invention.

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

Example 1 Four parts of a mixture of the zinc chloride .double salt of the diazonium chloride obtained cH2='cH cHiso3Na are dissolved in 21 parts of water and the resulting solution is thoroughly mixed with '75 parts of a 2 /2% carob bean" gum. The resulting paste is suitable for use in the production of fast color prints on textile material, especially cotton cloth,

acids oi the present invention are the cheapest nes and in general the most convenient to prepare. The invention, however, is not in any sense limited to the use of these preferred salts and on the contrary other salts such as zinc or calcium salts may be used. Ammonium salts and salts of organic bases such as amines, amidines. guanidines and the likemaybeused.

The inhibitors of the present invention may be added intwo stages. either before or after the dimotization. In the first place the aromatic bases known as ice color diazo components may be blended with the inhibitor and such blends maybe subsequently diaaotired in the customary manner and incorporated into a printing paste.

, The equivalent of this procedure is to dissolve the impregnated with ice color coupling components such as the anilide of 2 -hydroxy-3-naphthoic acid, bis-acetoacetic-o# t0lidide, etc. The advantage of a printing paste such as this over one made in a similar manner, but without the-sulfonate is shown in the following table:

The relative viscosity is expressed by the times in seconds taken for copper plated steel shot weighing approximately 0.107 gram each to fall through millimeters of the printing paste.

Example 2 In a manner similar to that described in Example 1 printing pastes are made containing the zinc chloride double salts of the diazonium chlorides of the following ice color bases, sodium-2- methyl-2-propene sulfonate of the following formula:

', cu,=c--on,-soma and suitable thickening gums. In every case the sulfonate inhibits the thinning of the printing paste as is shown in the following table:

. a 5 ice color coupling components. The superiority .oi a printing paste thus made over one similarly Stabilized Parts real I I v Viscosity Time of Method oi Base used for the Diluent of SW i f Water Kind and percent measuresecond g g ig measurepreparation of ,bmzed sponds to propene used, oi gum used (75 ment 2 reading measure}: ment of disco puts real Sultanate parts parts) 7 min. alter alter went relative mm 1 mixing mixing viscosity Hours 3-nitro-4-amino. Magnesium 0. 74 0.106 21 Carob bean 2.5%-. 79.6v 2 34.3 A1 nfiia'r'aaira' o 3'52 8106 2-2 3 3 ii o 0. s4 0 46.0 s 15. 4 A1 0. 81 I 0. 106 56. 6 3 37. 7 A1 0 0.81 0 21 -....do 53.6 .3 6.0 A1 3-nitro-4-amino 0.84 0. 273 21 Methyl cellulose 40. 6 21 23. 4 1 A3 anisole. gi iethocel 4000) m o 0.84 o 21 .....?1'0 40.5 21 7.2 113 Dianisidin 0 0. 61 0. 106 21 Carob been 2 l9. 3 2 13. 6 A2 Dn o 0.61 0 21 --.-do 20.0 2 6.3 A2

1 Nora-0n viscosi y u e t Al Cu lp Steel shot weighing 8 g. dropped 130 mm., time in seconds. A2 Cu plated steel shot weighing .107 g. dropped 130 mm., time in sccon' s. A3 glass spherical beads .097 g. dropped 130 mm.,- time in seconds.

Example 3 An intimate mixture is made of 100 parts of 3- nitro-4-amino anisole, 25 parts of sodium-2- methyl-2-propenevl-sulionate of approximately 73% purity, and 75 grams of sodium chloride. This mixture can be treated with mineral acid and sodium nitrite and the resulting diazo solution can then be bufiered .with sodium acetate and mixed with thickening gum for the production of fast color prints on textile materials'impregnated with ice color coupling components such as arylides of 2-hydroxy-3-naphthoic acid, etc.

Printing pastes made from such mixtures have "the advantage over thosepastes made from the prepared but without the sulfonate is shown by the following figures:

The viscosity measurements indicated above are the times in seconds for lead shot weighing advantage can best be seen by consulting the fol- 3 lowing table. In this table the change of viscosity 0.069 gram each to fall 130 millimeters.

Example 5' 5.03 parts of the zinc chloride double salt obtained from diazotized 3-nitro-4-amino anisole corresponding to 16.7% real base are mixed with 0.408'part or the allyl ether of sodium p-phenol sulfonate. This mixture is dissolved in 21 partsof water and the resulting solution is intimately. mixed with 75 parts of 2.5% carolo bean gum. inc superiority of a printing paste thus made chloride double salt obtained from tetrazotized o-dianisidine corresponding to 48.8% of real base and 0.215. part of potassium 2-methyl-2-pro-' pene-1.-sulfonate of 70% purity are intimately mixed and dissolved in 23 parts of water and v the resulting solution is thoroughly mixed with 75 parts of 2% carob bean gum. This viscous paste I. 1 V J 158g parts of a product containing the zinc is useful fort e preparation of deep blue patterns upon ce lulosic material impregnated with I) arylides of 2-hydroxy-3-naphthoic acid, or other 76 weighing 0 10? gram each to fall 130 millimeters.

P8118 0f 73 Tim f I Ziggy Part5 z cjf i' i l g if Second Inert diluent and real parts) gum v cos yviscosit v cos y 3- diam'iud f' ggi'g parts per part base base in used and strengt jgfgff reading f ggz mixing f I Hours 5-nit c-2-amino anisole 8.5 Sodium chloride 0.3 OargEBean 2.5%-. 2 12.3

o------ l 4-chloro2nitro-aniline. 0. 0 0, 9 .do 27.0 4 13.5 A2; Do 9 o 0.69 -do 24.1 4 0.8 A2

*' Emmple 4 over one similarly prepared, but without inhibitor is shown in the following -table:.

Relative Relative viscosity viscosity Printing paste used measurement measurement after 5 alter 4 minutes hours Paste containing inhibitor..- 60. 2 29. 8 Paste without inhibitor- 47. 0 0. 7

These relative viscosity measurements are the times in seconds for copper plated steel shot 6* moans 1 Brande?- with '15 ports of 25% carol! gum. The actw sulfonicacidcompmmdbcingmcimttosoblhniiam' inhibit thinning of the carbohydrate 3. lcompositionaccordingtoclann linwhich the diazonium salt is a diazonium chloride-zinc chloride double salt.

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

A composition comprising a water solvanfiage: of'the printing paste thus prepared over me H mm salt derived from 34] I onemade but without the inhibitor is shown in the following: table:

g who Relative Printfiigposteused 1! m2 ms minutes: hum

Paste: confirming; inhihitor..- Pal 43.4 Pastewiihoutinhibitor..- 141.3; I

These relative. viscosity measurements are the times in seconds for spherical glass beads weighing 0.0% gram to: 1301 mm'irneiers;

can be seen styrene: beta-sulionaie' is a, less efl'ecti ve inhibitor because: of the proof-mil oi the double bond and of the group.

application is in part; a. oi

our; co-pending application, Serial No. 431,224,,

l1. Diazo compositions suitable for printing, containing e water soluble salt defroxn an ice color diam component and an organic compound not more than 11 carbon atoms: belonging to group consisting oi water soluble acids containing at East one oleflnicdouble bond for each lflcarbonatomo, water soluble acids containhlg at least one acetglenic bond. for 10 carbon atoms, and water soluble salts. or the above acids, the sultonic acid compounds being free from constituenis capable of uoic coupling with the disalt, catalytic decomposition thereof at room temperature or therewith to form diazoamino or diazoimino compounds in acidmediunu-theamouncotthesulionicacidl pound being suilicient 'to substantially inhibit thinning of a carbohydrate 2, A paste a carbohydrate thickener atleast one soluble dluonium 'salflderired-firomanicecolordiamcompcncnt andmorganiocompolmdhavingnotmorethan mcarbonaiomsbelonging-tothcgroupcmslsiingernmmmmemumwwumnmmu leastoueoleflnicdoublebondioc 10 carbonaboms,

ntersoluble sulfonic acids containing at least maceiylenictriplebmaifcreaohlllcarbcn mandwatcrsohxblesalisottheaboreacids.

ibcsulionicacidcmnpoundbeing'frccfromconsfimentscapoblcot amiccmlplingwiththe dicanpotmdr anisole and a suihcient amount of sodium 2- mefihwl-E-propene-i-sulfonate \to substantially inhibit of a. carbohydrate printing thickener by the diazonium salt.

6 A priniing paste containing a carbohydrate thickener and awater soluble diazonium salt derived from diazotized 3-nin'o-4-amino-aniso1c and & sufioiem"r amount of sodium 2-methyl-2- m a mopene-l-sulfonatc to substantially inhibit thinning of the paste.

T. A composition suitable for the preparation of printing pastes containing carbohydrate gum comprising an" ice color fonm'mg componenc included in the group consisting of compositions containing water soluble diazonium salts and intermediates therefor consisfing of amines diazotizablc to produce compositions containing water soluble diazonium salts, the color forming w component having associated therewith an organic compound with not more than 12 carbon atoms selected from the group consisting or water soluble sulfonic acids containing at least one olefinic double bond for each 10 carbon atoms,

a; water solublesulfonic at least one acetylenic triple bond for each 10 carbon atoms, unclv water soluble salts of the above acids, the sulfonic acid compounds being free from constituents capable of azoic coupling with the disalt, catalytic dccompodtion thereof at room temperamre, or condensation therewith to formdiazoaminoordiazoiminocompolmdsin acid medium, the amount. of sulfonic acid compound being surlficient to substantially inhibit 45 thinning of a carbohydrate thickener.

8. Acompodtion accordingtoclaim'l inwhich thethinninginhibitoristhesod umsaltof Z-methxl-Z-propene-l-sulfonic acid.

' 0. A composiiion according to'claim 1 in which SG-the thinning inhibitor is the sodium salt of 2-methu1l-2-propene-1-sulfonic acid.

ma composition according to claim 3 in which. the thinning inhibitor is 2-metbyl-2- m which the thinning inhibitor B,H-a.'fly1 taurine.

'mmsnmcnen.