US2058418A

US2058418A - Dyeing process

Info

Publication number: US2058418A
Application number: US14270A
Authority: US
Inventors: Miles A Dahlen; Stanley R Detrick; Robert E Etzelmiller; Zwilgmeyer Frithjof
Original assignee: EI Du Pont de Nemours and Co
Current assignee: EIDP Inc
Priority date: 1935-04-02
Filing date: 1935-04-02
Publication date: 1936-10-27
Anticipated expiration: 1953-10-27

Description

Patented Oct. 27, 1936 UNITED STATES PATENT OFFICE DYEING PROCESS of Delaware Serial No. 14,27

No Drawing. Application :prll 2, 1935,

18 Claim.

This invention relates to new dyeing and printing processes and more particularly refers to improved processes for dyeing and printing cotton and related textile materials by means of mixtures of ice color coupling components and di-- azoimino compounds to be more fully described hereafter.

Certain classes of diazoimino compounds which are well adapted for use in the dyeing and printing of textile materials have been described in the prior art. The stabilizing components of these compounds are all characterized in that they are hydrocarbons containing an amino or imino group and one or more carboxylic or sulfonic acid groups. With the exception of the aforementioned substituents, however, the stabilizing components are composed entirely of carbon and hydrogen. For a more detailed description of compounds of this type reference may be made to U. S. Patents 1,882,560, 1,882,561, 1,882,- 562 and 1,982,681.-

Since the coupling of diazotized 'af'ylamines and tetrazotized .arylene diamines with various components is profoundly affected by the structure of such components it is exceedingly important that-great care be exercised in selecting coupling components. This is true to an even greater extent in the production of diazoimino compounds because of additional characteristics which these compounds must possess. For example, a satisfactory diazoimino compound must couple in such manner that the resulting product is stable in neutral or alkaline solution. Moreover, the product must be readily soluble. f equal importance is the ability of these compounds to hydrolyze readily and completely in order that the diazo base might be satisfactorily regenerated. It is obvious from a consideration of these factors that the structure of the stabilizing component is of utmost importance and that the presence thereon of certain substituents,

as well as the position of these substituents, produces a far reaching efiect upon the characteristics of the resulting compound.

It is an object of this invention to devise an entirely new process for dyeing and printing textile materials. A further object is to produce a color imparting medium which may exist in the form of dry powders, aqueous pastes, aqueous solutions, or other types of solutions. A still fur ther object is to produce a dyeing and printing medium which contains a class of diazoimino compounds which is entirely unrelated to any heretofore used; A still further object is to utilize a unique and heretofore unknown class of diazoimino compounds in the production of ice colors on, cotton fibers. Additional objects will become apparent from a consideration of the following description and claims.

These objects are attained according to the herein described invention wherein dyeing and printing compositions are made which contain the customary coupling components, assistants and the like, in addition to diazoimino compounds produced by coupling a diazotlzed aromatic 10 amine or tetrazotized aromatic diamine with a heterocyclic' compound having an imino-containing radical substituted thereon. In a more restricted sense this invention 'is concerned with dyeing and printing compositions containing an ice color coupling component and a water and alkali soluble diazoimino compound produced by coupling a diazotized aromatic amine, capable of use in the production of ice colors, with a heterocycllc compound having an imino-containing radical substituted thereon through the imino group of which coupling takes place, and furthermore containing one or more water-solubilizing groups; This invention pertains, in its preferred embodiment, to dyeing and printing composi tions containing approximately molecular equivalent quantities of an ice color coupling component, preferably arylamides of 2-3-hydroxynaphthoic acid or acyl-acet-arylides, and diazoimino compounds produced by coupling diazotized aromatic amines, capable of use in the production of ice colors, with" furfuryl-aminoacetic acid or tetra-hydro-furfuryl-amino-acetic acid.

The invention may be more readily understood by a consideration of the following illustrative examples in which the quantities are stated in parts by weight:

Example 1 330 parts of the dry diazoimino compound of the following formula:

| cmcooNa N=N v 0 I \CH:O/. on

i H H o1 obtained by the action of diazotized4-chloro-2- amino-toluene on furfuryl-ammo-acetic acid, were ground with 280 parts of the ortho-toluidide of 2-3-hydroxy-naphthoic acid producing a yellow powder.

A printing paste of the following composition was prepared:

Parts The above mixture 4.0 Cellosolve 4.0 Sodium hydroxide solution (35%) 2.0 Sulfonated castor oil 1.0 Water (warmed to 140 F.) 29.0 Starch tragacanth thickener 60.0

and printed from an engraved roll onto cotton piece goods. The printed material was dried thoroughly and then aged for 2 minutes in the vapors arising from a boiling solution of 4 parts of acetic acid (56%) and 1 part of formic acid (85%) in 15 parts of water. The prints were rinsed, soaped, again rinsed, and then dried. Bright red dyeings of good fastness properties were obtained, due to the formation of the dye of the formula:

Example 2 N t l l.

produced by the action of diazotized 4-ch1oro-2- amino-anisole on furfuryl-amino-acetic acid was mixed with 300 parts of the ortho-anisidide of 2-3-hydroxy-naphthoic acid. Cotton piece goods were printed with a paste prepared from this composition by the procedure similar to that described in Example 1. After color development and soaping of the prints, the pattern was developed as a brilliant bluish red due to the formation of the color of the probable formula:

oom

on 1 0 ONE? om Emdmple 4 350 parts of the water soluble diazoimino compound of the following formula:

N=NN 0 Hz- H:

1 obtained by the action of diazotized 4-chloro-2- amino-anisole on tetra-hydro-furfuryl-aminoacetic acid, and 225 parts of aceto-acetyl-pphenetidine were stirred with 600 parts of ethyl alcohol, 300 parts of sodium hydroxide solution of 30% strength were added, followed by 1400 parts of water. The mass was stirred until complete solution was obtained, then filtered.

A printing paste of the following composition was prepared:

Parts The above solufinn 20 Water 20 Starch tragacanth thickener 0 Cotton goods were printed and aged by the procedure given in Example 1. Bright yellow dyeings of very good fastness to light were obtained, due to the formation of the dye of the formula:

OCH:

COCH:

omoo CHO ONHOQNHCOCHOOCH; 43H: z

Example 3 350 parts of the water soluble diazoimino compound of the following structural formula:

OCH:

CHaCOONa Example 335 parts of the dry diazoimino compound of the following formula:

OCH: CHz-COONa N=NN o CH -CH (3H2 H; CH:

7 .phen'yl,- naphthalene, anthracene, azobenzene, di

obtained by the action of diazotized 4-chloro-2- amino-anisole on tetra-hydro-furfuryl-aminoacetic acid, were ground with 240 parts of acetoacetyl-p-phenetidine producing a gray powder. 12 parts of this mixture were dissolved in 40 parts of sodium hydroxide solution (35%) and 950 parts of water. Cotton piece goods were padded in this solution, then passed through squeeze rollers and dried. The padded goods were aged under the same conditions given in Example 1, rinsed,

soaped, rinsed and dried. Bright yellow dyeings of good fastness to light were obtained. The color was identical with that produced according to Example 4.

The following table lists a number of other representative dyeing and printing compositions, suitable for the coloring of textile fabrics as illustrated in the above examples:

phenyl ether, diphenylamine and carbazole series are quite satisfactory. The aforementioned and related amines may have substituted thereon one or more radicals such'as, for purposes. of illustration, alkyl, alkoxy, halogen, nitro, acylamino, benzoylamino, sulfonamido trifluoro-methyl, and the like groups. It is usually advisable that these amines should be free from groups which confer No. Base Stabilizer Coupling component g g g l 4-chloro-2-aminotoluene Tetra-hydrolurfuryl-omino-aceticacid. 2-hydroxy-3-naphthoy1-o-toluidine Red. 2 do do 2-hydroxy-3-nuphthoyl-o-phenetidine Scarlet. 3 do do Sodium compound of 2-hydroxy-3- Red.

naphthoyl-m-xylidine. 4 4-chloro-2-amino- .do 2-hydroxy-3-naphthoyl-o-anisidine. Do. 5 4-nitro-2-amino-nnisnle do 2-h droxy-3-naphthoyl-3'-nitro-ani]i11e- Bluish-red. 6 Diamsidine .do So ium compound of 2-hydroxy-3- Blue.

- nafhthoyl-aniline. 7 4-iuroyl-arnino-2,5-diethoxy-aniline do o.-. Do. 8 4-carilliomethoxy-amino-2,5-dimethoxydo 2-hydroxy-3-naphthoyl-anili Do.

an 1118. 9 3-chloro-aniline .do 2-hydroxy-3-naphthoyl-o'anisidinen" Red. 10 5-nitro-2-amin0-anisoIe do Sodium compound of 2-hydroxy-3- Bordeaux.

- naphthoyl-wnaphthylamirw. l1 2,5-dichloro aniline 'l-(iugiuryl-amino)-ethane-2-sulfonic Diaceto-acetyl-o-tolidine Yellow.

' aci 12 4-iuroyl-amino2,5-dimethoxy-aniline---. Sodium compound of 2-hydroxy-3- Red-blue.

. naphthoyl-o-toluidine. 13 4-ethoxy-4-amino-2-5'-dimethoxy-azo- Sodium compound of 2-hydroxy-3- Black.

7 benzene. naphthoyl-a-nephthylamine. 14 4-chloro-2-amino-anisole Aceto-acetyLp-phenetidine Yellow. 15 4-benzoyl-amino-2,5-diethoxy-aniline.- 2-hydroxy-anthracene-3-carboxyl1c Green.

acid-o-toluidide. 16 4-chloro-2-amino-toluene Sodium compound of 2-hydroxy-3- Red.

. naphthoyl-o-toluidine. 17 do Diaceto-acetyl-o-tolidine-sulione l8 Aniline do 19 4'-ethoxy-i-aminodiphenyl-amine 2-hydroxy-3-naphtboyl-amline 20 Dianisidine .do d0 o. 21 do Fmfuryl-amino-acetic acid 2-hydroxy-3-naphtboyl-o-tpluidme Do. 22 3-benzoyl-amino-4-methoxy-aniline ..do Z-hydroxy-El-naphthoyl-amhne. Bordeaux. 23 4- l:arbomethoxy-amino-2,fi-diethoxyani- .-.do 2-hydroxy-3-naphthoyl-o-tolu1dme Blue.

1116. 24 4-benzoyl-amino-2-methoxy-5-methyldo' Sodium compound of 2-hydroxy-3- Violet aniline. naphthoyl-aniline. 25 4-ch1oro-2-amin0-toluene Amixturc oi lurluryl-amino-acetic Sodium compound of 2-hydroxy-3- Red.

acid and:gtra-hydro-furiuryl-aminonaphthoylb-toluidine. ace 1c ac 26 do B-hydroxy othyl-iurluryl-amine- Sodium compound oi 2-hydroxy-3- Scarlet.

. naphthoyl-o-phenetidme. 27 do a-pyrldyl-amino-ecetic acid Sodium compound of 2-hydroxy-3- D0.

na hthoyl-o-phenetidine. 23 4- h10 2-amino-anisole Amixtureofturiuryl-amino-aceticacid p-ch or-anilide oi2-hydroxy-carbezole- Brown.

and ticltra-hydro-iuriuryl-amino-ace- 3-carboxylic acid.

cac 29 4-benzoyl-amino-2.5-diethoxy-anilinc..;. .do o-toluidide oi2-hydroxy-anthracene-3- Green.

, carboxylic acid.

It is to be understood that the aforementioned examples are illustrative merely of a relative few of the many modifications of the present inven tion. It is contemplated that the individual components, the proportions thereof, the conditions of reaction and related features thereof may be varied widely without departing from the scope of this invention.

In place of the diazoimino compounds referred to supra it is to be understood that other diazoimino compounds which contain as a stabilizing component a' heterocyclic radical having substituted thereon: an imino-containing radical and one or more water-solubilizing groups may be used. Primary arylamines and arylene diamines which are suitable for use in the production of ice colors may be used in manufacturing these diazoiinino compounds. In this connection it may be stated that amines of" the benzene, di-

ride, 3-amino-carbazole, alpha-amino-anthraquinone, 2,5-diethoxy-aniline, 5-methyl-2-methoily-aniline, 5-chloro-2-amino-anisoie and 4- chloro-4'-amino-2,5'-diethoxy-azobenzene.

As in the case of the arylamines, the stabilizing components may also be varied within a considerable range in accordance with the present invention. These stabilizing components are quite unrelated to any heretofore known or used in that they arenot hydrocarbon derivatives but are heterocyclic compounds containing one or more hetero atoms and having an imino-containing radical substituted thereon. I Coupling takes place through the imino group of the aforementioned radical. It is contemplated that additional groups may be substituted upon the heterocyclic nucleus on the component in such manner, that they interfere or prevent this coupling from taking place in the described manner. In order that the resulting diazoimino compounds may be soluble in water and/or alkali it is advisable to substitute one or more water-solubilizing groups upon the stabilizing component selected. These water-solubilizing groups are, for instance, carboxyl, sulfonic acid, hydroxyl, sulfinic acid, sulfato, and the like. The number and character of watersolubilizing groups which are desirable will depend to a great extent upon the diazo base selected and the purposes for which the resulting compounds are to be used. In general, the carboxylic acid and sulfonic acid groups are preferred. It is ,to be understood, however, that one or more of the additional solubilizing groups referred to or groups suggested thereby may be used in place of or in addition to the carboxylic and/ or sulfonic acid group. A few representative stabilizing compounds selected in accordance with the above instructions are: Furfuryl-sorbitylamine, tetra-hydro-furfuryl-sorbityl-amine, 4- methylamino-Z-furoic acid, 3-methylaminobenzopyrane-ar.-sulfonic acid, dioxanylaminoacetic acid, 3-(l'-methyl-morpholino)-glycine, fl-thienyl-taurine, a-thienyl-glucamine, (1:4-dimethyl-piperazino) -methyl-glycine, p-sulfo-phenyl-furfuryl-amine, p-hydroxy-cyclohexyl-tetrahydro-furfuryl-amine, di-furfuryl-amino-4,4'- dicarboxylic acid and p-sulfato-ethyl-tetra-hydro-furfuryl-amine.

Many of the diazoimino compounds produced in accordance with the present invention may be represented by the following general formula:

wherein aryl represents an aryl nucleus adapted for use as a component of an ice color, R1 represents an alkyl, carbo-cyclyl, carbo-cyclyl-alkyl, hetero-cyclyl, or hetero-cyclyl-allwl radical, R2 represents a hetero-cyclyl or hetero-cyclyl-alkyl radical, and R1 and/or R2 contains one or more water-solubilizing groups.

Diazoimino compounds referred to herein which are .of optimum value over a wide range of. conditions and uses may be represented, for the most part, by the following general formula:

wherein R represents the residue of a diazotized amine of the benzene or naphthalene series, free from water-solubilizing groups, and Z represents a furane derivative having an imino-containing radical substituted thereon, said furane derivative containing atleast one water-solubilizing group.

Coupling components which are particularly adapted for use herein are those referred to by one familiar with the art as ice color coupling components. Among these components mention may be made of the following:

(1) Arylamides of hydroxy-aryl-carboxylic acids, such as the arylides of 2-3-hydroxy-naphthoic acids, 2-hydroxy-carbazole-3-carboxylic acid, 7-hydroxy-alpha-naphtho-carbazole-6-carboxylic .acid, hydroxy-indole-carboxylic acids, hydroxy diphenylamine-carboxylic acids, hydroxyphenanthrene-carboxylic acids, etc. The arylamides may be produced from the usual primary arylamines free from water solubilizing groups, such as aniline, the halogenated anilines, toluidines, substituted toluidines, amino-phenol-ethers and substitution products, naphthylamines and their substitution products, etc.

(2) Acyl-acetyl derivatives of arylamines, such as aceto-acetyl, benzoyl-acetyl, and terephthaloyl-bis-acetyl derivatives of primary arylamines and diamines free from water-solubilizing groups.

(3) Naphthols such as alphaand beta-naphthol.

(4) Acyl-naphthols such as 4-benzoyl-1-naphthol and 4-acetyl-1-naphthol.

(5) Aryl-alkyl-pyrazolones.

(6) Dihydroxy-quinolines.

In general, it may be stated that the arylides of. 2-3-hydroxy-naphthoic acid and acyl-acetyl derivatives of arylamines are preferred for use herein. It is to be understood that the invention is not restricted thereto, however, since the other ice color coupling components referred to supra, and the numerous additional components suggested thereby, are also capable of use herein.

purposes it issometimes helpful to select a mixture of. diazoimino compounds and/or coupling components, and the present invention is understood to-be susceptible to such modification. The proportion of diazoimino compound and coupling component present in the mixture may be varied within considerable range, although it is advisable that they be present in approximately molecular equivalent quantities. The customary dyeing and printing assistants may be incorporated in the.

mixture when desired. When the coupling components are arylamides of hydroxy-naphthoic acids or related compounds they may be used in the form of thefree acids or as salts, preferably in the form of alkali metal salts. It is clear from a consideration of the preceding instructions that the resulting mixtures may be in the form of dry powders, aqueous pastes, aqueous solutions or other types of solutions, and "when dyeing and printing compositions are mentioned in the present specification andclaims it is understood that r they embrace the aforementioned types of mixtures. When solutions or aqueous pastes of the diazoimino compounds are produced it is advisable to make them sufficiently alkaline to prevent hydrolysis of the diazoimino compounds to'the parent diazo salts. It is frequently advantageous to utilize organic solvents in the preparation of these dyeing and printing solutions. Organic solvents of particular value in this connection are water-miscible solvents, such as methanol, ethyl alcohol, ethylene glycol, alkyl ethers of. ethylene glycol, diethylene glycol, and the like.

In imparting colors to textile fibers it is contemplated that the various procedures known to the art may be followed. For example, when textile fibers are printed with pastes containing the described compositions color development may be eifected by subjecting the prints to the action of steam and a mild volatile acid, such as acetic and/or formic. acids. Moreover, the prints may be developed by immersion in a boiling saturated salt solution which contains a weak acid; such as acetic, phthalic, oxalic, citric, and the like acids. It is also contemplated that materials may be inmarks, such elevated temperatures may advantageously be achieved either by the use of heated solutions or by the use of steam, and wherein the heated solutions and steam may contain the desired hydrolyzing agents.

For a more detailed discussion of diazoimino compounds suitable for use herein reference may be had to copending application Serial No. 14,271, filed April 2, 1935, wherein these compounds are described and claimed.

By means of the present invention an entirely new class of diazoimino compounds is utilized in the production of superior dyes and prints. These compounds are quite dissimilar to any heretofore used since they are not hydrocarbon derivatives but are derivatives of heterocyclfc compounds. Due to the presence of one or more hetero atoms and due to the configuration of these diazoimino compounds it is possible to produce superior colors readily and economically. The stability of these diazoimino compounds is quite marked, while at the same time the ease with which they revert to the parent diazo salt upon treatment with suitable hydrolyzing agents is most pronounced. The compounds described herein are quite compatible with assistants, penetrating agents, thickeners, alkalies, solvents and the numerous other accessories used in the production of ice color dyes and prints. The resulting colors are exceedingly uniform and level and are exceptionally fast to laundering.

As many apparently widely diiferent embodiments of this invention may be made without departing from the spirit and scope thereof, it is to be understood that the invention is not limited to the specific embodiments thereof except as defined in the appended claims.

We claim:

1.Dyeing and printing compositions which comprise an ice color coupling component and a diazoimino compound having the following general formula:

wherein R represents the residue of a diazotized aromatic amine or tetrazotizedaromatic diamine, Z represents the radical ofa heterocyclic compolmd having an imino-containing radical substituted thereon coupling taking place through the imino group of the aforementioned substituent, said heterocyclic derivative containing at least one water-solubilizing group, and n represents the integer 1 or 2.

2. Dyeing and printing compositions which comprise anice color coupling component and a diazoimino compound having the following general formula:

wherein R represents the residue of a diazotized aromatic amine or tetrazotized aromatic diamine of the benzene or naphthalene series, free from water-solubilizing-groups, Z represents the radical of a heterocyclic compound havingan iminocontaining radical substituted thereon coupling taking place through the imino group ofthe aforementioned substituent, said heterocyclic derivative containing at least one water-solubilizing group, and n represents the integer 1 or 2.

3. Dyeing and. printing compositions which comprise an ice color coupling component and a diazoimino compound having the following general formula:

wherein Rrepresents the residue of a diazotized aromatic amine or tetrazotized aromatic diamine, Z represents the radical of a furane derivative having an imino-containing radical substituted thereon coupling taking place through the imino group of the aforementioned substituent, said iurane derivative containing at least one watersolubilizing group, and n represents the integer I or 2;

'4. Dyeing and printing compositions which comprise an ice color coupling component and a diazoimino compound having the following general formula:

wherein R represents the residue of a diazotized aromatic amine or tetrazotized aromatic diamine of the benzene or naphthalene series, free from water-solubilizing groups, Z represents the radical of a furane derivative having an imino-containing radical substituted thereon coupling taking placethrough the imino group'of the aforementioned substituent, said furane derivative containing at least one water-solubilizing group, and n represents the integer lor 2.

\ 5. Dyeing and. printing compositions which comprise. an" ice color coupling component and a. diazoimino compound having the following general formula:

wherein R represents the residue of a diazotized amineof the benzene or naphthalene series, free from-water-solubilizing groups, and Z represents a furane derivative having an imino-containing radical substituted thereon coupling taking place through the imino group of the aforementioned substituent, saidfurane derivative containing at leastone Water-solubilizing group.

6. Dyeing and printing compositions which comprise an arylamide of 2-3-hydroxy-naphthoic acid and a diazoimino compound having the following general formula:

wherein R represents the residue of an aromatic amine of the benzene series, free from carboxylic or sulfonic acid groups. I I

8. Dyeing and printing compositions which comprise an arylamide of 2-3-hydroxy-naphthoic CHaC OONa wherein R represents the residue of an aromatic amine of the benzene series, free from carboxylic or sulfonic acid groups.

' 9. Dyeing and printing compositions which comprise an acyl-acet-arylide and a diazoimino compound having the following general formula:

wherein R represents the residue of a diazotized amine of the benzene or naphthalene series, free from water-solubilizing groups, and Z represents a furane derivative having an imino-containing radical substituted thereon coupling taking place through the imino group of the aforementioned substituent, said furane derivative containing at least one water-solubilizing group.

10. A process for imparting color to textile fihers which comprises treating said fibers with a composition comprising an ice color coupling component and a diazoimino compound having the following general formula:

wherein R represents the residue of a diazotized aromatic amine or tetrazotized aromatic diamine, Z represents the radical of a heterocyclic compound having an imino-containing radical substituted thereon coupling taking place through the imino group of the aforementioned substituent, said heterocyclic derivative containing at least one water-solubilizing group, and n represents the integer 1 or 2, and developing the treated fibers by subjecting them to the action of a hvdrolyzing agent.

11. A process for imparting color to textile fibers which comprises treating said fibers with a composition comprising an ice color coupling component and a diazoimino compound having the following general formula:

wherein R represents theresidue of a diazotized aromatic amine or tetrazotized aromatic diamine of the benzene or naphthalene series, free from water-solubilizing groups, Z represents the radicalof a heterocyclic compound having an imino-containing radical substituted thereon coupling taking place through the imino group of the aforementioned substituent, said heterocyclic deriva-.

wherein R represents the residue of a diazotized aromatic amine or tetrazotized aromatic diamine, Z represents the radical of a furane derivative having an imino-containing radical substituted thereon coupling taking place through the imino group of the aforementioned substituent, said furane derivative containing at least one watersolubllizing group, and n represents the integer 1 or 2, and developing the treated fibers by sub- .iecting them to the action of a weak acid at elevated temperatures.

13. A process for imparting color to textile fibers which comprises treating said fibers with a composition comprising an ice color coupling component and a diazoimino compound having the following general formula:

wherein R represents the residue of a diazotized aromatic amine or tetrazotized aromatic diamine of the benzene or naphthalene series, free from water-solubilizing groups, Z represents the radical of a furane derivative having an imino-containing radical substituted thereon coupling taking place through the imino group of the aforementioned substituent, said furane derivative containing at least one water-solubilizing group, and n represents the integer 1 or 2, and developing the treated fibers by subjecting them to the action of a weak acid at elevated temperatures.

14. A process for imparting color to textile fibers which comprises treating said fibers with a composition comprising an ice color coupling component and a diazoimino compound having the following general formula:

wherein R represents the residue of a diazotized amine of the benzene or naphthalene series, free from water-solubilizing groups, and Z represents a furane derivative having an imino-containing radical substituted thereon coupling taking place through the imino group of the aforementioned substituent, said furane derivative containing at least one water-solubilizing group, and developing the treated fibers by subjecting them to the action of acetic or formic acid at elevated temperatures.

15. A process for imparting color to-cotton fibers which comprises treating said fibers with a composition comprising an arylamide of 2-3- hydroxy-naphthoic acid and a diazoimino compound having the following general formula:

16. A process for imparting color to cotton fibers which comprises treating said fibers with a composition comprising an arylamide of 2-3- hydroxy-naphthoic acid and a-diazoimino compound having the following general formula:

CHaCOONa R-N=N- o cmo cn wherein It represents the residue of an aromatic amine of the benzene series, free from carboxylic or sulfonic acid groups, and developing the treated fibers by subjecting them to the action of acetic and formic acid at elevated temperatures. g

17. A process for imparting color to cotton fibers which comprises treating said fibers with a composition comprising an arylamide of 2-3- hydroxy-naphthoic acid and a diazoimino compound having the following general formula:

CHaOOONa RN=NN 'o omen cm H:CH:

wherein R represents the residue of an aromatic amine of the benzene series, free from carboxylic or sulfonic acid groups, and developing the treated fibers by subjecting them to the action of acetic and formic acid at elevated temperatures.

18. A process for imparting color to cotton fibers which comprises treating said-fibers with a composition comprising an acyl-acet-arylide and a diazoimino compound having the following general formula:

wherein R represents the residue of a diazotized amine of the benzene or naphthalene series, free from water-solubilizing groups, and Z represents a furane derivative having an imino-containing radical substituted thereon coupling taking place through the imino group of the aforementioned substituent, said furane derivative containing at least one water-solubilizing roup, and developing the treated fibers by subjecting them to the action of acetic and formic acid at elevated temperatures.

MILES A. DAHLEN. STANLEY R. DETRICK. ROBERT E. ETZELMILLER. FRITHJOF ZWILGMEYER;