US2386646A - Stabilization of coloring compositions containing diazonium salts - Google Patents

Description

Patented'Oct. 9, 1945' Frederic B. Adams, Bound Brook, Hans Z. Lccher, Plainlield, and William B. Hardy, Bound Brook, N. J assignors to American Cyanamid Com-' pany, New York, N. Y., a corporation of Maine No Drawing. Application July 5, 1943, a 1 6 Serial NQ.'Q93,592

, This invention relates to compositions contain-- ing diazonium salts derived from ice color diazo components and to methods of preventing the thinning of printing pastes containing such diazo compounds.

An important method of producing prints of azoic colors on vegetable fibers consists in padding the goods with an alkaline solution of an azoic coupling component and printing these goods with a printing paste containing a diam-- nium salt derived from an ice color diazo coni- Claims. '(01. 8-44)] double bonds,-borofluorides, particularly salts of .complexacids sometimes referred to as double -salts, the most important of them being the double ponent. The diazonium salt is either prepared by the printer, himself by diazotijzing the corresponding base orit is applied in the form-of a stable diazonium salt. This'simple and wellknown cheap process is open to a very seriousdisadvantage.

- the diazonium salts and a carbohydrate thickener The printing pastes containing tend to thin out rapidly losing their desired printing consistency. It is with this thinning action that the present invention is concerned.

According to the present invention the diazoenous base soluble in aqueous mineral acids and containing at least one olefinic double bond or one acetylenic triple bond for each 12 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:

Others are not so soluble and can be easily isolated. Some are difiicult to handle after isolation because oftheir explosiveness, others are rather stable and do not present an explosive hazard.

' It is also known that if the anion of the acid X- is properly chosen, in almost all cases diazonium salts of lower solubility may be produced and thereforeisolated, audit is also known thatmany of these diazonium salts have lost their explosive character and can be stored and handled in the dry state without danger; this kind of diazonium salts is sometimes referred to as stabilized diazonium salts. They comprise such compounds as certain aromatic sultonates, without olefliiic l v I mm salt is associated with an organic nitrogsaltsof diazonium chlorides and zinc which correspond to the iormula:

(4 11)" (zno1.)= 1 1 l K I It should be borne in mind that also these stachloride bilized diazoniuin salts including the above mentioned double salts are true 'azonium salts, i. e. the aqueous solution contains the same diazonium cations asthe solution of 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 diazota'tes, also known as nitrosamines, or diazo amino and diazo imino coma pounds which are only} stable and applied in 611- kaline medium, while on the other hand the diazonium salts are only stable and applied in acid medium. The present invention deals with inhibiting the thinning action of diazonium salts only and not with any similar actionthat might be observed with other types of diazo compounds. Whenever stabilized diazo compounds are referred to in this application this term shall be interpreted to include exclusively stabilized diazonium salts and not to include diazotates or diazo amino or diazo imino compounds.

While it is not intended to limit the present invention to any theory of action, we believe that nitrosamines.

it is highly probable that lowering of viscosity of printing gums is essentially caused by the diazonium cation because the same kind of thing results regardless of the anion of the diazonium salt and even the double salts of the stabilized diazoniumsalts described above exert a similar thinning action. Presumably in aqueous solution the stabilized diazonium salts are ionized to give the same diazonium cation. The pH of the printing paste'is not critical so long as it is on the acid side for the present invention does not deal with any other types of pastes. \Alkaline media, as is well known, cause rearrangement of the diazonium salts to diazo compounds of different structure which are referred to as diazotates or While not desiring to to, we believe that the evidence strongly indicates that the thinning action is a colloidal phenomenon rather than a chemical reaction.- The fol-.

lowing test was made:

oxy aniline was addedto a, printing paste made limit the invention there- .up with a starch thickener; after hours the then water thin solution was coupled with an alkaline solution of beta-naphthol and the azo dye formed was removed by filtration. The amount.

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 diazonium salts that derive from nitroanilines are the worst thinners. Particularly those deriving from 2,4-dinitro-6- chloroaniline, from -2-nitro-4-chioroaniline, from 2-nitro-i-methoxy aniline, from 2-nitro-4- methylaniline thin the vegetable gums very badly. The diazoniuni 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 from o-anisidine have only little thinning action. Qbviouslmthe rate of the thinning depends upon the concentration of the diasonium ions present in the printing paste.

The thinning action has heenobserved with all thiclreners prepared from materials of vegetable origin such as starches, gums, alkyl celluloses, etc. Wheat starch, corn starch, rice starch, sweet potato starch, tapioca starch and chlorinated.

starch may be mentioned as esples of starches. Carob bean gum and gum tr-agacanth may be mentioned as examples of game, and methylor ethyl-cellulose as examples of alkyl celluloses.

Obviously, also mixture of these materials are quite often used in thiclseners and their viscosity is equally iniiuencedhy diasoniuni salts. It will he noted that all of these thiclteners are carbohydrates or carbohydrate derivatives. In the claims the expression carbohydrate thickener is used in a broad sense to cover pure carbohydrates and derivatives.

We have found that organic nitrogenous bases that are soluble in aqueous mineral acids and that contain at least one clefinic double bond or one acetylenic triple bond for each 12 carbon atoms or their water soluble salts delay the thinning to such an extent thatit becomes harmless from the practical point of view.

We believe that the diazonium cations which are the active thinning agents are unsaturated and have a marked tendency to combine. This unsatmaterl character i probably responsible for the ease with which they combine with coupling components to form one dyestufis. When an unsaturated thinning inhiliitor such as an unsaturated nitrogenous base is added to the diazoniurn salt solution before the printing thickener is added, it is probable that the diaaonlum cation forms a loose complex with the thinning inhibitor which decreases the aflinity of the diazonium c ation and inhibits its action upon the thickener. When the thickener is first added to the diazcnium salt solution followed by addition of the thinning inhibitor, thinning is prevented to a much lesser degree. Apparently in such a case the diazonium salt has already commenced its thinning action on the thickener and the actitm aseaeac aromatic amines free from solubilizing groups useful in making ice colors or azoic pigments Typical are the following:

Aniline and its homologues, as e.- g. the toluidines, 2,4-dimethy1aniline; halogen derivatives of aniline and of its homologues, as e. g. the mono-fluoroanilines; the monochloranilines, 2,5- difluoroaniline, 2 fluoro-E-chloroaniline, 2,5-dichloroaniline, m-aminobenzotrifiuoride, p-amino-benzotrifiuoride, Zi-amino 4 chlorobenzotrifluoride, 2-methy1-3-chloroaniline, 2-methy1-4- chloroaniline, 2-methyl-5-chloroaniline, 3-methyl-4-chloroaniline, 5-methyl-2-chloroaniline, 2- methyl 4-chloro 5-bromoaniline, 2 methyl-4,5- dichloroanlline, 4 methyl 2,5 dichloroaniline; nitro derivatives of aniline and of its homologues and their halogen derivatives, as e. g. the nitroanilines, 2 -methyl-l-nitroaniline, 2-methyl-5- nitroaniline, i-methyl-Z-nitroaniline, 2-nitr0-4- fiuoroaniiine, 2-nitro-4-chloroaniline, B-nitro-lchloroaniline, 4-nitro-2-chloroaniline; ether derivatives of primary aromatic amines and their halogen derivatives, as e. g. o-anisldine, Z -methoxy-S-methylaniline, 2,5 dimethoxy-aniline, 2-

- methoxy 1 naphthylamine, 2-aniino-diphenyino-Z-chloro-diphenylether, e amino-4'-chl0rocliphenyl ether, 4,4 dichlcr-Q-amino-diphenylii ether, 2,2, trichloro i-arnino-diphenylether;

ether derivatives of aniline and its homologues containing nitro groups as e. g. 2-methoxy-4-nitroaniline, 2-n1ethoxy-5-riitroaniline, Z-nitro-imethoxyaniline, Z-methoxy-d-nitro 5 methylaniline; monoacyl derivatives of aromatic diarnines; as e. g, N-hexahydrobemoyl-p-phenylene diamine, N- hexahydrobenzoyl-p-toluylene diamine, N-benzoybp-phenylene diainine; monoacyl derivatives or diamino-phenol ethers as e. g. 2 henzoylainino-l-aminoanisole, 2 hexahydrobenzoylamino 5 aminoanisole, 2-arnino-5-benzoylamine-hydroquinone dimethylether and di--' ethylether, 2 amino-5-hexahydrobenzoyleminohydroquinone dimethylether and diethylether, 2-amino-5-butyrylamino hydroquinone dimethylether and diethylether, Z-amino-E-phenoxyacetylarnino-hydroquinone diethylether, the monomethyl and the monobenzyl and the monophonyl-urethane of 2,5-diamino-hydroquinone dimethylether and diethylether, 1-amino-3-benzoyla nino 4,6 dimethoxy-benzene; analogous monoacyl derivatives of 2,5-diaminoi-allroxytoluenes and of 2,5-diamino-4-alkoxy-chlorcbentones and of 2,5-diamino-i-alkoXy-benzene sulfodialkylamides; analogous monoacyl derivatives of 1,3-diamino-i,5-dimethylbenzene; the diethylamide of 2-amino-i(i'-chlorophenory)-benzoic acid; monoacyl derivatives of diamino-p-chlorophenyl others as e. g. 2-amino-4-chloro-5-acetylaminodiphenylether, 2-benzoylaminoi-chlorofi-aminoanisole amino derivatives of aromatic sulfones as e. g. 3-amino-4-rnethyl-diphenyl sulione, 2-amino-4'-methyl-diphenyl sulfone, 2- amino-4-acetyl-diphenyl sulfone,'the ethyl ester of 3-amino-4- (p-toluene-sulfony1) -benz'oic acid,

7 v 2,aso,c4'e I '3 4-methoxy 3 amino phenyl-ethylsulfone, (4'- metho'xy 3 amino-phenyl) -benzyl' 'sulfone, 4-

ethoxy 3 amino-diphenyl' sulfone. 2-amino-4-v (trifluoromethyll-phe'nyl ethyl sulfone;' amino derivatives of aromatic" dialkylsulfonamides as e. g. 3-amino-4-methyl benzenedimethylsulfonamide and diethylsulfonamide, 3 amino-4-methoxy-benzene diethylsulfonamidef xenylamine;

- alpha. and beta naphthylamine; ,alpha amino anthraquinone; 2 amino-3-nitro-fluorene and 2.-

amino-3-nitro-fluorenone; amino diarylamines and their ether derivatives and their nitro. de-

' rivatives as e. g. 2-methoxy-5-aminodiphenylamine, 4 methoxyi'-amino-diphenylamine, 4-

ethoxy-4'-amino-diphenylamine, 3,4 dimtI'O-4- amino-diphenylamine; amino-azo compounds, as e. 'g. 3,2'-dimethyl-4-amino-azobenzene, Z-methyl 4 amino-5-methoxy-4-chloroazobenzene, 4-

. amino-4'-nitro 3-methoxy-6#methyl-azobenzene,

' onto alpha naphthylamine.

4 amino-4'-nitro-2,5 dimethoxy-azobenzene, 4- amino-4-chloro-3-methoxy-61- methyl azobenzene, the azo dye: diazotized o-anisidine coupled There are also diazonium salts deriving from aromatic diamines in which only ,one of the amino groups is diazotized and they also fall within the scope of the presentinvention. An example of this type of amine is 2,6-dichlro'-l,4-phenylene diamine. "Diazonium salts deriving from diamines in which both amino groups are'diazo tized to form tetrazo compounds fall within its scope. Typical amines of this class are p-phen- Y ylene diamine, benzidine, o-tolidine, o-dianisidine, 4,4'-diamino stilbene, 4,4'-diamino diphenj yl-amine, 2,2 dimethyl-4,4'-diamino diphenylamine and 1,5-diamino naphthalene.

, also diazonium salts deriving from heterocyclic amines or diamines fall under the present invention. Typical heterocyclic amines'are 2-aminocarbazole, 3,6 diaminocarbazole, 2 nitro 3 [Obviously also mixtures of different diazonium. salts may be used.

The inhibitors claimed in the present invention salts regardless of the form in which they are in- 'troduced. It is also necessary that the bases and their salts be .free from constituents capable-of bonds or acetylenic triple bonds.

- azoic coupling with the diazonium salt, condensation therewith to form diazoamino or diazoimino compounds in acid medium, or'catalytic decom'-' position thereof at room temperatures. The sec- .ond limitation is not 'a serious one as it isdiflicult to form a diazoamino or diazoimino compound under the acid conditions which obtainin the compositions of the present invention. Examples of compounds whichcatalytically decompose the diazonium salts are iodides of the inhibiting bases. I or more basic nitrogenous groups and, of course, they may contain one or more olefinic double The same molecule may also contain both kinds of bonds. Theportion ofthe molecule containing the unsaturated bonds may be connected to the basic nitrogenous groups through a carbon chain or a carbon chain interrupted by other elements such as oxygen, nitrogen, sulfur, and the like. The invention is not limited tothe use of any single inhibitor and mixtures may be employed where desired.

The organic nitrogenous bases may be divided into two main groups- In the first group the basic portion of the molecule contains only one nitrogen atom connected with the same carbon atom and this group comprises the primary, secondary and tertiary amines and the quaternary bases. It also comprises compounds which contain two or more such groups which, however, are not connected f with the same carbon atom. In thesecond group the basic part of the molecule contains two or three nitrogen atoms connected with the same carbon, atom and this group comprises amidines and the closely related isoureas, isothioureas,

guanidines, ureas, etc.

. tene-l, 5-amino-hexene-l, 4-allyl-5-amino pencomprise' all organic nitrogenous basesthat are- I soluble in aqueous mineral acids and that contain at least one olefinic double bond or at least one .acetylenic triple bond. .We have found that the olefinic double bond or acetylenic triple bond appears to. be mainly responsible for the anti-thinning action of the nitrogenous bases'of the. present invention. However, we have found that there there is at least one olefinic double bond or acetylenic triple bond for each 12 carbon atoms of the nitrogenous base. In addition to the above limitation on the nitrogenous base. it is necessary that the base be soluble inmineral acids since the printing pastes containing the diazonium salts are always acid. The bases may be used as such if there is sufiicient acid in the printing paste to both neutralize and dissolve them, or they may be-used in the form of any of their water soluble salts.

.doubtedly exist in the form of their water soluble In factin the printing paste they untetra-allylethylene diamine.

tene-l, 2,6 dimethyl 8 amino .0ctadiene-2,6,

(beta-amino ethyD-allyl ether and thioether,

N,N,Nf,N'-

2-propynylamine (proparglyamine),

As examples of aliphatic bases belonging to the second group there may be mentioned N-allylurea. N-ethyl N allylurea, N,N'-diallylurea, O-allyl isourea, S-allyl isothiourea, S-beta-methyl-allyl isothiourea, allyl guanidine, omega-allyl-biguanide.

It is not necessary that the bases of the present invention belong to the aliphatic series. and bases having ring systems are also included, provided they contain at least one double bond of olefinic character or at least one triple bond. It should be noted that double bonds occurring in aromatic r ngs are-not of olefinic nature. Thus N-phenyl- N,N,N-trimethyl ammonium hydroxide is not an inhibitor covered by the present invention because the benzene ring does not contain olefinic double bonds. However, unsaturated alicyclic bases are active inhibitors such as, for, example, 4-a'mino cyclohexene-i, 3-N,N-dimethylamino cyclohexene-l and the corresponding quaternary ammo- The inhibitors may contain one' nium base containing one methyl ,more on the nitrogen, 5-amino cyclo-octene-l, S-amino-paramenthene-l, 2-amino-para-menthene-8.

Also aromatic amines are useful provided they contain an unsaturated olefinic or acetylenic bond outside the aromatic ring and provided they are not capable of azoic coupling; as examples.

of such compounds there may be mentioned N- allyl N ,N dimethyl N phenyl ammonium hydroxide, N,N-diallyl-para-chloroaniline, N,'N,N- triallyl N para-tolyl ammonium hydroxide, (which compound, it will be noted, contains 16 carbon atoms and 3 olefinic double bonds), N- propargyl N,N-dimethyl-N-phenyl ammonium hydroxide.

Also heterocyclic bases are useful provided they contain double bonds of olefinic character either in the ring or outside the ring, r provided they contain outside the ring acetylenic triple bonds and also provided they do not couple. As exam-' ples of such compounds there may be mentioned N,N-diallyl furfurylamine, N,N-diallyl-6amino- 1,4-benzodioxane, tropidine, N-allyl pyridinium hydroxide.

The inhibitors of the present invention may be added either before or after the diazotization. However, not all of the inhibitors claimed in this invention can be added before the diazotization because a great many or them would react with nitrous acid. Thus all primary and secondary amines cannot be added before the diazotization. If the inhibitor is to be added before the diazotizatlon we therefore prefer to use aliphatic tertiary or quaternary compounds. aromatic bases known as ice color diazo components may be blended with the inhibitor'and such blends may be subsequently diazotized in the customary manner and incorporated into a printing paste. The obvious equivalent of this procedure is to dissolve the inhibitor and the ice color diazo component separately before the diazotization is carried out.

When the inhibitor is added after diazotization also a primary or secondary. amine may be used. Since printing pastes containing diazonium salts are acid, no formation of diazo-amino or diazoimino compounds or of analogous condensation products with amidines or guanidines takes place. Diazonium salts either stable per Se or stabilized in a customary manner may be blended with the inhibitor. The obvious equivalent is to add the inhibitor to a separately prepared diazo solution beiore the printing paste is made up.

It does not make any different what procedure is used, in every case the thinning of the printing gum is greatly delayed.

In this case the whenever a dry blend with either the ice color diazo component or with the diazonium salt is to be made. Obviously the salts'must be Water soluble, .but it'is not necessary that the corresponding base is water solublesince the free base would be liberated only after the diazonium salt has been printed on the naphthol prepared goods and after the inhibitor had already accomplished its task of keeping the printing paste stable.

The invention will be further illustrated with the specific examples which describe typical ombodiments of the present invention. The pacts are by weight.

Example 1 2.56 parts of the zinc chloride double salt of the tetrazonium chloride derived from o-dianisi- 'dine, diluted with partially dehydrated magnevantage over a. paste not containing the ailyl triethyl ammonium chloride that the former retains its viscosity better than the latter, as is shown by the following'figures:

Relative Relative viscosity viscosity ,Printing paste used measurement measurement after half an after 4.7 hours hour Printing paste as described above 33.0 17.0 Same but without inhibitor 26. 5 3. 5

In this experiment the relative viscosities are measured by noting the time for lead shot weighing .071 gram each to fall 130 millimeters through the paste.

Example 2 25 parts of a solution of diazotized 5-nitro-2- amino anisole, equivalent to 0.84 part or reai base, are mixed with a solution of 0.256 parts of N-allyl-N,N,N-triethyl ammonium chloride in 11.6 parts of water and the resulting solution is thoroughly mixed with parts Or 2.5% carcb been gum. This paste is used for the production of fast red prints on cotton cloth impregnated with the anilide of 2-hydroxy-3-naphthoic acid. The advantage of this paste over one similarly prepared but without the N-allylN,N,N-triethyl ammonium chloride is shown in the following I table:

Relative Relative viscosity viscosity Prmtmg paste used measurement measurement after three after three minutes hours Printing paste as described above. 19. 6 l4. 2 Same, but Without inhibitor 20.0 10.8

make any diiference whether the base is used as such or whether a water soluble salt is used. It is however, very difiicult to isolate quaternary bases and in most cases they can not be isolated These relative viscosity measurements are the times in seconds for copper plated steel shot Weighing 0.107 gram each to fall millimeters.

Instead of the N-allyl-N,N,N-triethyl ammonium chloride, other water soluble salts such as fthe sulfate, phosphate, nitrate, ethane sulfonate,

Example 3 the diazonium chloride obtained from 2,5-dichloraniline, corresponding to approximately 50% real base, and 0.331 part of N-beta-methylallyl-N,N,N-trie thyl ammonium chloride of the following formula:

- cHFc-cHr-m-m Ha (elm); are dissolved in 21 parts of water, and the resulting solution is intimately mixed with '75 parts of 2.5% oarob bean gum. The resulting printthe production of fast prints on fibers impregnated with the usual ice color coupling components in the usuaLmanner. In each case the relative viscosity of the printing paste so prepared decreased less rapidly than the relative viscosity' of similar printing pastes prepared without the addition of the quaternary salt used as inhibitor.

In the following table the relative viscosities made and after a certain length of time, are compared with the relative viscosities of. similar gums not containing the inhibitortaken at the same m p te 1s used for the preparation of fast ne S... g... e t e etr Parts of n o viscosi m g re a ve re ve Nature Punting water to Kind of thickening gum usedthickening reading 88001151 viscosity Mt! v powder dissolve gum after 2 .tive viscosity measuremeasure minutes measurement ment ment Percent Hours Contains inhibitor... 21 2. 5 56. 5 1 39. 4 ,A Without inhibitor- 21 -6 7- 8 I 1 2. 1 A With inh..bitor 21 3.0 39. 8 21 24. 4 A Without .nhibitor. 21 3. 0 40. 5 v 21 7. 2 A With inh..bitor 23 5.26 34.5 3 34.4 B Without .nhibitor.-- z; 5. 26 35. 0 3 28. 0 B With inhibitor 21 3.5 121.0 4 I 107.0 C Without inhihiton 21 3. 5 12L 0 4 57. 0 C

Norr.-Method iA" consists of the measurement of the time in seconds for beads weighing 0.097 gram to all 130 millimeters through taken on a Brookfield electn'c viscosimeter-speed 60, spindle No. 3.

scarlet prints upon cottonl cloth impregnated with the anilide of 2-hydr0xy-3-naphthoic acid and for the preparation of fast orang prints upon cotton cloth impregnated with the ortho.

phenetidide of 2-hydroxy-3-naphthoic acid in the well-known manner. The printing paste so prepared retains its relative viscosity, and hence its utility for printing much-better than a similar paste whichdoes not contain the N-betamethyl-allyl-N,N,N-triethyl ammonium chloride, as is shown by the followingfigures:

Printing pastes are made by dissolving in water the numberof parts of the zinc chloride double salt of the diazonium chloride obtained from of real base and 0.331 part of N-betamethyl allyl-N,N,N-tri ethyl ammonium chloride, and the resulting solutions are mixed with various aqueous printing gums. These gums can be used for the gum. Method B" consists in timing in seconds the flow of cc. of

Example 5 3.86 parts of a mixture of the zinc chloride-double salt of the diazonium chloride obtained from '3-nitro-4-amino anisole and partially dehydrated 40 bromide). The mixture is then dissolved in 21 3-nitro-4-amino anisole equivalent to 0.84 part 7 parts of water and the resulting solution is thon- 'ouglily mixed with parts of 2.5% carob bean gum. The resulting paste is used for the production of fast color prints upon fibers .im'-

pregnated with ice color couplin components in the usual manner.

In a similar manner a printing paste is made from 1.62 parts of the zinc chloride double salt of the diazonium chloride of 2,5-dich'loroaniline, 0.288 part of N-vinyl-N,N,N-trimethyl ammonium bromide, 21 parts of water, and 75 parts or 2.5% carob bean gum. This paste is used for the production of fast color prints in impregnated cloth in the manner described above.

The advantages which these printing pastes Time after m by I Time after mixing for re mg of Second re- Base used {or diazo mung first relative ag second relagg'i viscosity tive viscosity reading Monies Hbura with inhl'bitnl'- 2 58. 9 2 12.8 Without inhibitor- 2 55- 2 2 1. 2 with inhibitoruu 8 61. 8 3 ALB Without inhibitor. 8 52. 7 3 2L 3 The relative viscosi y readings to tall mm. through the gum.

arethetimesinseeondslorspheticelglessbeadsweighing 0.0976 gram the paste from a 10 cc. pipette. Method 0" consistsolreadings Example 6 2.54 parts of the mixture of the zinc chloride double salt of the tetrazonium chloride derived fromp-dianisidine and partially dehydrated magnesium sulfate, having a strength equivalent to 29.8% real base, are mixed with 0.3 part of N-allyl pyridinium sulfate of the following formula:

2 N )so.

2 and the mixture is dissolved in 22.1 parts of water. The'resulting solution is intimately mixed with '75 parts of 2.5% carolobean gum. In an entirely analogous manner, a printingpaste is made from the same ingredients except that.

Relattive iziis- Reliative gs cosi y re cos ty re Inhibitor used I mg 16 hour mg 4% hours after mixing after mixing N-allyl pyridinium sulfate- 29. 9 17. 1 N -allyl pyridinium chloride; 27. 6 13. 3 None 26. 6 3. 5

These viscosity measurements are the times in seconds for lead shot weighing 0.071 gram each to fall 130 millimeters.

Example 7 A mixture is made of 1.62 parts of the zinc chloride double salt of the diazonium chloride derived for example, for the production of fast bright scarlet prints on cloth impregnated with the anilide of 2-hydroxy-3-naphthoic acid; for the production' of bright reddish orange prints on cloth impregnated with the ortho phenetidide of 2-hydroxy-3-naphthoic acid; or for the production of bright yeliowprints on cloth impregnated with bis-acetoacetic acid o-tolidide. The beneficial effect of the allyl isothiourea hydrochloride on maintaun' 'n'g the relative viscosity of the printing paste is shown in the following table:

Relettive vs- Relative vscosi y res cosity rea Prmtmg paste used ing after ing after 2 minutes 4 hours Printing paste as described above. 41. 7 33. 8 Same but without allyl isothiourea...- 41. 3 17.9

These relative viscosity measurements are the times in seconds for special glass beads weighing 0.0975 gram each to fall 130 mm.

Example 8 Solutions are made by dissolving in 21 parts of water an amount of the zinc chloride double salt of the diazonium chloride derived from 3-nitro-4- amino anisole equivalent to 08d part of real base and 0.264 part of allyl isothioureahydrochloride of the following formula: v

Each solution is mixed with 75 parts of an aqueous gum thickener of vegetable origin. These printing pastes are suitable for the preparation of fast color prints on fiber impregnated with ice color coupling components in the usual manner.

They are distinguished for their ability to retain their relative viscosity, and hence their utility for printing a longer tme than simlar pastes prepared without the presence of the allylisothiourea hydrochloride. This is shown in the following table:

' Time of Time of first second Method of Water to i First Second Strength relative visrelative relative Netuix-Jeog'g'r nt g 3531K; Thickening gum used o1!)e gium itn ctgityaifgead- 3:38. viscgsity 2 x dvigcosity cen g rea mg 9 .rnnnapowder mixing reading an?! to ading ti on mixing Manta Hours with inhibitor 21 Carob been 2. 5 2 74. 9 1 51. 4 A Without inhibitor 21 .-do 2. 6 2 57. 8 1 2. 1 A W ith inhibitor 21 Methyl cellulose (Methocel 4000).. 3 2 40. 7 4 30. 8 A Without inhibitor- 21 .d0 3 2 40. 6 4 20. 4 A With inhibitor 23 Sweet potato starch 5. 26 2' 34. 2 3 34.1 B Without inhibitor. 23 do 5. 26 2 35. 0 3 28. 0 B with inhibitor 21 3. 5 3 117 4 98 C1 Without inhibitor 21 0 3. 5 3 121 4 57 Cl 1 l or.. gum in xe s are 68 -2 W'th inhib't 21 R P G i d t h 8 4 750 4 730 C Without inhibitor 21 .do 8 4 600 4 335 C2 N0'rE.Relative viscosity measurements are taken as follows: .A-Time in B-Time in seconds for 10 cc. or paste to flow mm a 10 cc. pipette. C1Releti Reading in centipoises taken on Brooktleld viscosimeter.

seconds for glass beads weighing .0975 gram to fall mm. vs readmg, taken on Brookfleld electric viscosimeter. C2

Example 9 An intimate mixture is made of 10 parts of 3- nitro-4-amino anisole, 2.5 parts of allyl isothicurea hydrochloride, and'7.5 parts of common salt. This mixture is useful for the preparation of fast prints on fibers impregnated with ice color coupling components, as is shown in the following example:

1.68 parts of the mixture described above is stirred in a. mixture of 5 parts of 5N hydrochloric acid, 10 parts of ice water, and to the mixture lowing solution. After 'diazotization is complete, the

acidity to Congo red paper is destroyed by the addition of small amount of sodium acetate solution. The resulting diazo solution is intimately mixed with 75 parts of 2% aqueous carob bean gum. The resulting viscous pmte is printed upon cloth impregnated with the anilide oi' Z-hydroxy- '3-naphthoic acid in the customary manner.

BrightBordeaux prints are obtained. 'After four hours, such a printing gum is still sufficiently viscous for proper printing, whereas a similar.

pastemade from a base not mixed with the inusual ice color coupling components, and as in,

Ezamplell In a manner similar to that described in Ex ample 8'printing pastes are made from thezinc v chloride double salt of the diazonium chlorideof 3-nitro-4-amino anisole "and various gum 'thickeners, but with 0.288 part of beta-methylallyl f isothiourea hydrochloridesuhstituted for the allyl isothiourea used in'Example 8. ,Thefresulting printing gums are used for preparationjof. fast colorprints upon the .fiber prepared with the the example shown above, theseprinting pastes maintain their relative viscosity better than siinilar printing pastes which do not contain the inhibitor has become watery and unsuitable for hibitor. Thisis shown by the following table:

Time af- Parts of Time after ml] 8 Method oi Nature of P inting g ggi i g Thickening gum used lit gi mafi reiiiits gf s cond r e i iirg s m a powder printing t in per viscosity viscosity relative viscosity 23 powder cent reading reading reading went I Minutes Hours v i With inhibitor 01 bean 5.? L2 i 48. 0 A 0 2. i A Methyl cellulose (Methocel 4000).. g 2 With inhibitor 23 5. 2e 2 3314 3 3413 B Without inhibitor 23 5. 26 2 35.0 3 28. 0 3 With inhibitor 21 3. 5 3 120 4 102 C1 Without inhibitor 21 0 3. 5 I 3 121 4 57 01 With inhibitor. 21 R. P. G. gum m xed starches 8 4 745 4 735 02 Without inhibitor 21 0 8 4 600 t 4 335 C2 Norm-Explanation of viscosity measurements: A-Time in seconds for glass beads weighing 0.097 gram to fall 1330 mm. B-lime for 10 cc. of paste to flow from a 10 cc. pipette. Brookfleld viscosimeter.

printing. This change in relative viscosity of the gum is shown by the following figures:

m neis tiv s- Relativeflzis- Print gum use cosi r cosi a r g 2 lion. 4 him Printing paste as described above.-." 43. 2 21,1 Same but without inhibitor 32. 8 2. 9

These relative viscosity measurements are the times in seconds taken for glass beads weighing 0.097 gram to fall 130 millimeters.

- Example 10 A printing gum is made as described in Exam Dle (except for the fact that 0288- parts of betamethyl allyl isothi'ourea hydrochloride of thefolformula (obtainabl from thiourea and beta-methylallylchloride) is used in place of 0.264 part of allyl isothiourea preserving its relative viscosity for a longer period than similar. paste not containing the in- 1 hibitor. This is shown in the following table:

I These relative measurements are the times in seconds for glass beads weighing 0.097

gram each to tall 130 mm.

(ll-Relative readings taken on Brookfleld-viscosimter. C2-Reading in centipoises taken on 0 Example 12 the-same manner as that described in Example 9 above. The printing paste thus prepared is useful for the preparation of fast color prints on the fiber which has been impregnated with ice color coupling components; for example, when this-paste is printed upon cotton cloth impregmated with the anilide of 2-hydroxy-3-naphthoic acid, bright bluish red prints of very good fastness properties are produced. The ability of such a paste to maintain its relative viscosity, and

hence its utilityfor printing is shown in the foilowing table:

' Relattive vtils- Relggiveegvascosiyrea cosiyr Prmtmg paste ing alter mg after I 2 min. 4 hours Paste containinginhibitor so. 2 29.1 Same but without inhibitor 38. 2 0. 1

These relative viscosity readings indicate the time in seconds for glass-beads weighing 0.097 am to fall 130 millimeters.

Example 13 5.48 parts of a mixture ofthe zinc chloride double salt of the diazonium chloride derived from 3- nitro--aminoanisole and partially dehydrated aluminum sulfate, corresponding to 15.35% real whichi's suitable for the production of fast Bor-' ing paste maintain its relative viscosity, and

hence its utility for printing, much better than a similar printing paste which does not contain the allylamine hydrochloride. This advantage is shown in. the following table:

Reiattive vs- Relative vcilscosi y rea cosity rea Printing paste used mg 2 min mg 2 hours after mixing aiter mixing Containing allylamine hydrochloride 38. 5 14. 6

Without allylamine hydrochloride 40. l l. 4'

The relative viscosity readings are the times in seconds for copper plated steel shot "weighing 0.107 gram each to fall 130 millimeters.

Example 14 1.575 parts of the zinc chloride double salt of the diazonium chloride derived from 3-nitro-4- amino anisole is dissolved in 21.5 parts of water containing 0.23 part of diallylainine hydrochloride. with '75 parts of 2.5% carob bean gum. The resulting printing paste is suited for the production of fast Bordeaux prints upon cotton cloth impregnated with the anilide of 2-hydroxy-3-naphthoic acid. The printing paste so prepared retains its relative viscosity, and hence its utility The resulting solution is intimately mixed for printing, much better than a similar paste prepared in exactly the same manner but without the diallylamine hydrochloride. This advantage is shown in the following table:

Relative vs- Relattive vtiiscosity rea oosi yrea Printing paste used mg after inggiter 2 min. 2 ours Containing diallylamine hydrochlor' e 53. 6 20. 0 Without diallylamine hydrochloridc 45. 6 1. 3

These relative viscosity readings are the times in seconds for copper plated steel shot'weighing approximately 0.10'1 gram each to fall 1-30 millimeters. Example 15 1.5? parts of the zinc chloride double salt -of the diazonium chloride of 3-nitro-4-amino anisole, and 0.446 part of tetra-allyl ammonium bromide are dissolved in 21 parts of-water and the resulting solution is intimately .mixed with '75 aseaeee deaux prints on cloth impregnated with the ani- .lide of 2-hydroxy-3-naphthoic acid. This print- 7 ltelatiitre l'telatige Diazotized amine in Thinning inhibitor in 500$ y SW51 y printing paste printing paste gfgi E -12 min. hours 3-nitro-4-amino ani- Tetra-allyl ammoni- 69. 5 48. 2

sole. um bromide.

Iio None 62.4 1.3 2, 5-d1chlor aniline... Tetra-allyl emrnoniv96. 8 90. 3

um bromide. Do None 83.3 19.0

These relative viscosity measurements are the times in seconds for copper plated steel shot weighing approximately 0,107 gram each to fall 130 millimeters.

Example 16' 1.575 parts of the zinc chloride double salt of the diazonium chloride derived from 3-n'itro-4- amino anisole and 0.34 part N-allyl-N,N-dimethyl-N-phenyl ammonium chloride are dissolved in Relative yis- R 1 cosity reading a we Printing paste used after H) 2 to 4 cgfstlgyzriidlnsg .rmn.

Containing thinning inhibitor 44. 6 25. 4 Without thinning inhibitor: 45. 0 1.0

These relative viscosity readings are the times in seconds for copper plated steel shot weighing approximately 0.107 gram each to fall 130 millimeters. 1

Example 17 5.4:; parts of a. mixture of'the" z'ii'i chloride double salt of the diazonium chloride vderived from 3-nitro-4-amino anisole and partially dehydrated aluminum sulfate, corresponding to a strength of 15.35% real base, are-dissolved in 21 parts of water along with 0.20 partof N-allyl urea. The resulting solution is intimately mixed with 75 parts of 2.5% carob bean gum. The resulting printing paste is valuable for the preparation of fast Bordeaux prints upon cotton cloth parts of 2.5% carob bean gum. The resulting printing paste is used for the production of test Bordeaux prints upon cotton cloth impregnated with arylides of 2-hydroxy-3-naphthoic acid.

In a similar manner, 1.63 parts-of the zinc chloride double salt of the diazonium chloride of 2,5- dichloraniline is mixed'with 0.46 parts of tetra allyl ammonium bromide and the resulting mixture is dissolved in 21 parts of water. This solution is then intimately mixed ,with 75 parts of 2.5% carob bean gum to form a printing paste which is eminently suited for the production of bright scarlet prints upon cloth impregnated with the anilide of 2-hydroxy-3-h'aphthoic acid.

The advantages that these printing pastes possess over similarly prepared pastes not containing tetra allyl ammonium bromide, are shown in the following table:

impregnated with arylides of 2-hydroxy-3-naphthoic acid, and is superior to a. similar paste which does not contain the allyl urea because of the fact that it retains its relative viscosity and, hence, its utility for printing much better. This advantage is shown in the following table:

Relative vis- Relative vis- Prmtingpaste used cosity reading cosity reading after 2 min. after 2 hours Containin allyl urea. 39. 8 1B. 6 Without lyl urea 40. 1 1. 4

These relative. viscosity measurements are the times in seconds for copper plated steel shot weighing approximately @107 gram each to fall millimeters.

manner: v An amount of the zinc chloride double salt of ous mineral acids and containing at least one oleflnic double bond for 12 carbon atoms, organic nitrogenous bases soluble in aqueous mineral acids containing at least one acetylenic triple also free from primary and secondary aminogroups it used together with amines before. diazotization, the amount of the nitrogenous base of a carbohydrate thickener.

2. A printing paste containing a carbohydrate thickener, at least one water soluble diazonium salt derived from an ice color diazo component and an organic compound having not more than 16 carbon atoms belonging to the group consistbeing sufiicient to substantially inhibit thinning 7 7 g g i gg g fg ggg 'gzfi fiz 23 3x 22: bond for 12 carbon atoms, and water soluble salts arts is mixed with 0 512 parts of 'anyl guanidme of the above bases, this compound being free from p constituents capable of azoic coupling, of consulfate and the mixture is dissolved. in enough densation with the diazomum salt to form dlazowater to make 25 parts'of solution. The resultmg Solution is mtimatel mixed with 75 parts ammo or diazoimino compounds under acid conditions, or catalyticall'y decomposing the discoof Carob bean These Punting pastes nium salt at room temperature the amount of the i are used for the preparation of fast color prints .r e

ogenous base present being suflicient to subupcn mpregnated the amide 2415" stantially inhibit thinning of the carbohydrate droxy-a-naphthoic acid. These printing pastes tmckener retain their relative viscosity and hence their util- 1 ity to the printer, very much better than similar composltmn j j w 9 01mm 1 whtch pastes Similarly prepared but without the any] the diazonium salt 15 a diazoniumchloride-zinc guanidine sulfate. Thisadvantage may be seen chloride double Saltby consulting the following table: 4. A composition according to claim 2 inwhicli Relative vis- Relativevis- Color of print on Base used for zinc chloride Thinniug'inhibitor in cosity meascoslty measanilide of 2-hydouble salt printing paste urement urement droxy-3-nsphthoic after2min aiterihrs. acid 2,5-dichloraniline.. Allyl guanidine sulfate. 66.8 66.0 Yellowish scarlet.

' DQ v None 61.2 10.2 Do. 4-nitro-2-amino anisolo- Allyl guanidine sulfate... 69. 4 65. 6 Reddish scarlet. Do None 76.2 18.2 Do. 3-nitro4-amino aniso Allylguanidine sulfate. 85.6 40.0 Bordeaux.

None 83.2 0.4 o.

Allyl guanidine suliate-. 66.4 49.6 New blue. None 71. 4 9. 2 Do.

These relative viscosity measurements are the the diazonium salt is a diazonium chloride zinc times in seconds for copper plated steel shot chloride double salt. I v weighing 0.107 gram each to fall 130 millimeters. 5. A composition according to claim 1 in which This application is in part a continuation oifour 40 the nitrogenous base is an allylguanidine. co-pending application, serial No. 437,201, filed 6. A-composition according to claim 2 in which April 1, 1942. the nitrogenous base is an allylguanidine.

We claim: p 7. A composition according to claim 1 in which 1. A composition suitable for the preparation the nitrogenous compound is a tetra-allylammoof printing pastes containing carbohydrate gum nium compound. thickeners comprising an ice color forming com- 8. A composition according to claim 2 in which ponent included in the group consisting of comthe nitrogenous compound is a tetra-allylammopositions containing water soluble diazonium salts nium compound. 1 r and intermediates therefor consisting of amines 9. A'composition comprising water soluble didiazotizable to produce compositions containing 59 azonium salts derived from an ice color diazo I water soluble diazonium salts, the color forming component and an organic compound with not component having admixed therewith'an organic more than 16 carbon atoms selected from me compound with not more than sixteen carbon group consisting of organic nitrogenous bases sol-' atoms selected from the group of organic nitroguble in aqueous mineral acids and containing at enous bases soluble in aqueous mineral acids least one olefinic double bond for 12 carbon and containing at least one oiefinic double bond atoms, organic nitrogenous bases soluble in aquefor twelve carbon atoms, organic nitrogenous ous mineral acids containing at least one acetbases sol bl in q eousmineral acids containing ylenic triple bond for twelve carbon atoms, and at least o a ty t pl b nd for tw lve water soluble salts oi the above bases, this combon atoms, and water soluble saltsoi! the above 60 poundbemg f 1mm constituents capable f bases, this compound being free from constitazoic coupling, f forming dim amino or diam uents capable of aizoic coupling, of torminigddiazo unmo c'ompounds under acid conditions and of amino or diazo im no compounds under ac conditions, of catalytically'decomposing diazonium gggg gg' gf g ggg 2 :5 gz g z g z i gi az salts at room temperature, this compound being pe I g base being sumcient to substantially inhibit thinning of a carbohydrate thickener.

'10. A composition according to claim 1 in the nitrogenous compound is an allyl urea.

FREDERIO H. ADAMS; HANS z. :LECHER. WILLIAM B. HARDY.

ing of organic nitrogenous bases soluble in aque-'