US2078388A - Dyeing process and composition - Google Patents

Description

Patented Apr. 27, 1937 PATENT OFFICE DYEING PROCESS AND COMPOSITION Jean Georges Kern, Hamburg, N. Y., assignor to E. I. du Pont de Nemours & Company, Wil-' mington,-Del., a corporation of Delaware No Drawing. Application February 12, 1935, Serial No. 6,261

11 Claims.

This invention relates to the application of icecolors to cellulosic material and more particularly to dyeing and printing compositions comprising an ice-color coupling component anda diazo-imino compound having the general formula:

in which formula R1 represents hydrogen, alkyl, hydroaryl (for example, cyclo-pentyl, cyclo-hexyl, methyl-cyclo-hexyl, and analogous groups) alkylol or hydroarylol, and R2 represents alkylol V or hydroarylol, or R1 and R2 together represent a tetramethylene or penta-methylene chain substituted by one or more hydroxyl groups and to 0 dyeing and printing processes utilizing such compositions. 1

Ice-colors are a class of azo dyes insoluble in water, always produced on the fibers by the cou-. pling thereon of diazotized aryl amines with coupling components. The name ice-colors" is derived from the early practice in applying these dyes. At that time their application involved the use of diazo solutions cooled with ice. When these colors were first discovered they were applied to the fiber by a two step process in the first of which the fiber was impregnated with the coupling component, for example, beta-naphthol, and in the second of which the impregnated fiber was passed through an ice-cooled (hence the name ice-color) solution of a diazotized base (aryl amine). As a modification of this process thickeners were added to the diazo solution to produce a viscous paste and the padded goods (padded with the coupling component) were printed from engraved rolls with the said paste (thus producing colored patterns).

The unused coupling component, that is, the portion on the fabric where no thickened diazo solution was applied, was subsequently washed from the unprinted portions of the fabric. The use of this process was limited because it was necessary (because the instability of the diazo solutions required that they be prepared in small batches and at .frequent intervals) for the dyer (usually unskilled in such matters) to prepare his own diazo solutions. This was a serious problem and one which hindered the expansion of this type of dyeing and printing.

In an effort to overcome some of these difii culties there was developed a process in which the diazotization was carried out by the manu- 10 facturer of the aryl amine. The diazotized amine so obtained was precipitated and stabilized by the addition of various agents such as zinc chloride and naphthalene-1:5-di-sulfonic acid. The r resultant dry powders were sold to the dyer. In the use of such products it was only necessary for the dyer to dissolve the stabilized body in water to obtain a solution capable of being used in the application of ice-colors as described above.

The application of ice-colors to fabrics was reduced to a single step process by the utilization of mixtures of nitrosamines (prepared from the aryl amines) and coupling components. Certain diazotized aryl-amines when treated with strong I alkali are changed to anti-diazotates (nitrosamines) which are stable over long periods of time and do not couple with the usual coupling components under alkaline conditions. Mild acids convert the nitrosamines to the parent diazo salts.

Making use of the above properties, textile fibers were impregnated with alkaline pastes containing both the nitrosamines and coupling components. The fabrics were then treated with mild acids, resulting in reversion of the nitrosamines to diazo salts and coupling of the latter with the coupling components to produce fast dyeings or printings. The one step process resulting from the introduction of the nitrosamine products however, suffered from disadvantages. The colors produced by this method were usually duller than the colors produced by the two step method previously used. Further, only a few of the aryl-amines commonly used as diazo components could be economically converted to the nitrosamines.

This invention had for an object the devising of an improved and simplified method of applying ice-colors to fabrics. Other objects were the production of new printing and dyeing compositions, new printing and dyeing processes, a more complete impregnation of the fiber or fabric prior to the coupling and development of the color thereon and the production of brighter shades of ice-colors than are obtainable according to the one-step process of the prior art. A general advance of the art and other objects which will appear hereinafter as the description of the invention proceeds, are also contemplated.

The foregoing objects and related ends are accomplished in the manner set out in the following description in which details of what is believed to be the best mode for carrying out the invention are disclosed.

In my'Patent No. 2,078,387, issued Apr. 27, 1937 on application Ser. No. 749,277, filed Oct. 20, 1934, there is described a new type of soluble diazo-amino and diazo-imino compounds which correspond to the formula set out above.

The preparation of diazo-amino compounds by the reaction of diazonium salts withcertain secondary aliphatic amines has been described in the chemical literaure. See, for example, Baeyer & Jaeger (Ber. 8,148,893), P. Griess (Ber. 10, 525), and Wallach (Annalen 235, 233). The secondary amines utilized by these investigators contained no. alcoholic hydroxyl groups and for this reason are ill-suited to accomplish the objects of this invention. I

It has been discovered that if with diazo-amino or diazo-imino compounds of the type described above there is employed known coupling components such as the aryl-amides of beta-hydroxynaphthoic. acid, phenyl-methyl-pyrazolone, etc.,'

effected at the desired time by treatment with steam containing acid vapors or treatment with an acidic substance, for example acetic acid.

The invention will be further understood by a consideration of the following detailed description and illustrative specific examples in which -the quantities are given in parts by weight, it

being understood that the procedures followed and amounts of the reagents employed are set out for purposes of illustration and not by way of limitation.

Example I Fifteen (15) parts of the product obtained by the reaction of diazotized 'meta-nitro-para-- toluidi'ne with di-ethanol-amine, of the following constitution:

were mixed thoroughly with "15 parts of the I anilide of beta-hydroxy-naphtholc acid. This mixture was then made up as a printing paste according to the following formula:

. Parts The above mixture 8 Water .l. 36 Caustic soda of 40 B 3 Monopole I oil 3 Starch-gum tragacanth thickening 50 By the above procedure, the dyestufi was formed on the fabric as a brilliant red printed design. The dyestuif has the probable constitution:

Q Example II A printing powder was prepared by mixing equal quantities of the anilide of beta-hydroxynaphthoic-acid and the reaction product of diazotized 2:5-di-chloro-aniline and di-ethanolamine, of the following constitution:

CHzCHz-OH 1 A printing paste was then prepared according to the following formula:

7 Parts Theabove printing powder 8 Ethyl alcohol 3 Caustic soda of 40 B. strength- 3 Water 30 A neutral thickener (for example starch tragacanth) 48 Sodium chromate 5 Monopole oil 3 Cotton goods were printed at room temperature with the above paste and the imprinted material dried. The color was then developed on the fiber by immersing the goods alternately in a boiling 4% solution. of hydrochloric acid for half a minute and then in a saturated sodium acetate solution for three to five minutes, the procedure being repeated until no further increase in color formation occurred. The goods were then rinsed, soaped, again rinsed, and dried. In this manner the scarlet dyestuff of the following constitution:

Cl-Q-Cl was developed according to the printed pattern.

Example III A printing paste was prepared as follows:

5 grams of the diazo-imino compound produced by reacting diazotized 4-nitro-2-amino-anisole with di-ethanolamine were dissolved in 20 cc. ethyl alcohol, to this solution was added 30 cc. of an 0.5 N solution of the anilide of 2:3-

hydroxy-naphthoic acid (Naphthanil AS) and to this mixture was added 70 grams of a starch-tragacanth thickener.

Cotton piece goods were printed with the above paste, then aged for five minutes. The aged prints were developed at 180-190 F. in a solution of sodium bi-chromate (1%) and acetic acid 1%). After color development was complete, the prints were boiled in a 5% soap solution, rinsed and dried. The printed pattern was a bright red of good fastness properties.

It will be apparent from the above examples that in general the improved process of this inventionembraces the formation on the textile fibers of the azo-dyestufis resulting from the coupling of diazo-salts with the aceto-acetyl arylamides and equivalent coupling components by one of two general methods:

First, the textile is padded with the coupling component with which is present (as dis tinguished fromthe prior art) a suitable medium containing the diazo component in the form of a diazo-amino derivative (of the newly discovered type described above) and the necessary assistants. Thereafter, the color is developed by suitable acidic treatment.

Second, the textile is printed with a paste containing the coupling component and the diazo component (as a diazo-amino compound), which may thereafter be treated to develop the color on the fiber, for example, by treatment with steam containing acid vapors or treatment with a suitable liquid acidic medium.

Textile fiber or fabric having imprinted thereon (that is, in contact with) the herein described new compositions of matter are new products or articles of manufacture. Because of the stability of the pastes containing the diazo-amino compounds and coupling components such imprinted materials are capable of being stored for varying periods of time, a lapse of a week between imprinting and developing beinga fairly common occurrence.

It will be obvious to those skilled in the art that any one or more of the diazo-amino compounds of the type described above (and in my co-pending application) may be employed with any known or desirable coupling compound, for example, those more particularly mentioned hereabove. The advantages in printing and dyeing afforded by the ability to combine in a printing paste or dye bath the diazo component in the form of a diazo-amino or diazo-imino derivative containing a hydroxyl group and the cour pling compound without immediately effecting coupling to form the insoluble dyestufi' are readily apparent. This advantage is based upon the fact that under ordinary conditions present in the printing art the new diazo-amino and diazo imino compounds show little or no tendency to revert to the diazo salts and amines. Such reversion only takes place when the novel diazo derivatives are treated with acidic substances of suitable strength and/ or at temperatures higher than are commonly required in the printing art, for

example, such temperatures as would be present when the materials are subjected to steaming.

Inasmuch as no appreciable coupling results under the ordinary conditions of printing when printing pastes containing the diazo-amino compounds and suitable coupling components are employed, a maximum of penetration of the fiber and absorption of the diazo-amino compounds (and coupling component) is obtained together with a smooth reversion to the diazo salt by the time actual development of the color is effected on the fiber.

Moreover, when the development has been effected the by-products formed in the coupling are readily removable by washing because of the character of the diazo-amino compound specifically disclosed above (and in my co-pending application). The combined effect of the desirable attributes of this invention are a much more effective penetration of the fiber and a more complete development of an even and richer color on the fabric as well as controlled development of the color.

An additional advantage which is quite important from the economic standpoint is the fact that with the new and improved process it is not necessary to pretreat the cloth or the fiber, thus avoiding an expensive and labor-consuming step.

Moreover, a saving of coupling component (betanaphthol, Naphthanil AS, naphtholides, arylamides of hydroxy aryl carboxylic acids and the like) is effected in the printing because the pretreatment of the entire cloth, necessary in the prior art printing, isavoided.

Another of the advantages possessed by the process of this invention is that fabrics and fibers of cotton, wool, silk (either weighted or not) and the synthetic fibers and fabrics, such as acetyl cellulose and rayon, may be satisfactorily printed and dyed., It is to be understood, therefore, that where in the specification and claims the expression "textile or fiber has been used, it is intended to mean textiles or fibers of vegetable or animal origin or mixtures thereof formed from any of the above-mentioned materials.

The expression cellulosic material is used in its customary sense, namely to cover such fibers as cotton and regenerated cellulose.

Any mildly acidic material may be employed in lieu of those mentioned in the examples for the development of the color upon the fiber or fabric, it being understood, of course, that the acidic material must not be of a nature which will tend to destroy the fiber or fabric. In addition, to weak solutions of hydrochloric acid, formic acid or acetic acid, mentioned above, such acidic materials as bi-chromate of sodium or potassium and any of the acidic reagents or mixtures normally employed in the development of colors may be used.

As examples of aryl nuclei, radicals, residues or groups covered by the term Aryl in the formula on page 1 which are especially suitable for attaining the objects of this invention, mention may be made of the radicals of the benzene, naphthalene, anthracene, diphenyl, diphenylether, diphenyl-sulfide, diphenyl-am-ine, diphenylene-oxide, carbazole, azo-benzene and anthraquinone series. mentioned formula covers nuclei containing substituents, for example, alkyl, alkoxy, halogen, nitro, acylamino, and the like.

The term alkylol" as used herein covers the radicals sometimes designated as hydroxy-alkyl.

This term also used as being generic to the phrase poly-hydroxyalky -tion of dyeing and printing compositions.

The invention, of course, is not limited to the diazo components enumerated in the specific examples. Other diazo amino compounds (prepared from other aryl-amines) may be used. Among these, the diazo-amino compounds prepared from thefollowing aryl-amines merit special mention:

Ortho-chloro-aniline Meta-chloro-aniline 4-nitro-2-amino-toluene 4-chloro-2-amino-toluene 3-nitro-4-amino-toluene 5-nitro-2-amino-anisole 3-nitro-4-amino-anisole 4-amino-6-benzoylamino-1 :3-xylene 4'-ethoxy-4-amino-diphenylamine Di-anisidine I 4 :4 -diamino-diphenyl-ether 4-benzoylamino-2 5-dimethoxy-aniline 'Alpha-amino-anthraquinone 3-amino-carbazole Para-methyl-ortho-nitro-benzeneazo cresidine 4:4-diamino-diphenylamine Sulfanilic acid Aniline &

Amino-azobenzene 2 5-di-chlor-aniline Benzidine 4-chloro-2-amino-benzoic acid Para-nitro-aniline 2 S-di-methoxy-aniline Alpha-naphthylamine 4 4 -di-amino diphenyl-sulflde, and

4-nitro-2-amino-anisole (para nitro ortho 'anlsidine) In like manner, other primary and secondary V amines containing alcoholic hydroxyl groups may be utilized as stabilizing agents in the preparation of the diazo-amino compounds. Among those which warrant special mention are:

Methyl- (beta-hydroxy-ethyl) -.amine Methyl- (beta-hydroxy-propyl) -amine Methyl- (Z-hydroxy-cyclo-hexyl) -amine Butyl- (beta-hydroxy-ethyl) -amine Cyclo-pentyl- (beta-hydroxy-ethyl) -amine Cyclo hexyl- (beta-hydroxy-ethyl) -amine (Betamethoxy-ethyl) (beta-hydroxy- I ethyl) amine Methyl-(betazgamma-di hydroxy propyl)-' I amine Propyl-(betazgamma-di amine Di-ethanol-amine Di- (beta gamma-di-hydroxy-propyl) -amlne' Di-(*i-hydroxy-cyclo-hexyl) -amine 4 Gamma-hydroxy-piperidine Alpha-hydroxy-pyrrolidine Alpha-methyl-alpha'-hydroxy-piperidine Mono-ethanol-amine Beta: gamma-di-hydroxy-propyl-amine, and Ortho-amino-cyclo hexanol.

One skilled in the art will, in'view of the above description, be able to select the most suitable soluble stabilizing agents for use with any particular diazotized aryl-amlne. This selection is usually made on the basis of the solubilityprop- ,erties desirable for best results in the prepara- Cost also is to be considered in making a selection. Some of these aliphatic amines having hydroxyl substituents are extremely cheap. Compounds- Dichlor-aniline hydroxy propyD- Arylamine Alkylolamine v Meta-nitropara-toluidine Di-etlianol-amine Para-nitro-ortho-anisidine Di-ethanol-amine Para-nitro-ortho-anisidine Mono-ethanol-amine Dichlor-aniline Di-ethanol-amino Dichlor-aniline Di-pro ane-di-ol-amine Methy ethanol-amine Benzldina Di-ethanol-amine (1 mol.) Benzidine Di-ethanol-amine (2 mol.) Di-anisidine Di-ethanol-amine (2 mol.)

,The diazo-amino compounds described above may be mixed with any of the usual ice-color coupling components such as the aryl-amides of 2:3-hydroxy-naphthoic acid and other hydroxy aryl carboxylic acids, alpha and beta naphthols, aceto-acetyl derivatives of aryl-amines, and 'arylalkyl-pyrazolones as previously indicated. Normally the diazo amino compounds and coupling components are used in approximately equimolecular quantities.

' Examples I and II of this application are taken from application Serial No. 566,317, being'Examples I and II respectively of that application;

the present application is a continuation in part of my said application Serial No. 566,317, filed October 1, 1931, and application Serial N01 566,- 318, filed concurrently therewith, to which said application Serial No. 566,317 makes reference.

As many apparently widely different embodiments oi! this invention may be made without departing from the spirit and scope thereof, it is to be understood that I do not limit myself to the specific embodiments thereof except as' defined by the appended'claims.

I claim:

1. A composition or matter comprising a coupling component and a diazoti-zed aryl-amine capable of producing azo dyes, the said diazotized aryl-amine being in the form oi! a diazo-amino compound possessing the following formula:

.in which R1 represents hydrogen, analkyl, a hydroaryl, an alkylol or hydroarylol radical, R2

- in which R1 represents hydrogen, an alkyl, a hydroaryl, an alkylol or hydroarylol radical, R2

represents an alkylol or hydroarylol radical; or R1 and R2 together represent a tetra-methylene or penta-methylene chain, substituted by one or more hydroxyl groups and Aryl represents an aryl nucleus of an ice-color aryl-amine.

3. A printing paste containig a knownv coupling compound and the reaction product formed by coupling a diazotized base and a di-alkylolamine.

4. A printing paste containing a known coupling compound together with the reaction product formed by coupling a diazotized base and an alkylolamine.

5. The process of imparting color to textile fiber by either dyeing or printing which comprises subjecting the textile fiber to a composition containing a known coupling compound and a diazo compound of the formula:

in which-Aryl represents an aryl nucleus, while R1 represents H, an alkyl, hydroxy-alkyl, a hydroaryl or hydro-arylol radical, and R2 represents a hydroxy-alkyl or hydroarylol radical; or R1 and R2 together represent a tetra-methylene or penta-methylene chain, substituted by one or more hydroxyl groups and thereafter developing the color by steaming the fiber.

6. The process of imparting color to textile fiber by either dyeing or printing which comprises subjecting-the textile fiber to a composition containing a known coupling compound and a diazo compound of the formula:

Aryl-N:Nl -l I ia in which Aryl represents an aryl nucleus, while R1 represents H, an alkyl, hydroxy-alkyl hydroaryl or hydroarylol radical, and R2 represents a 40 hydroxy-alkyl or hydroarylol radical; or R1 and R2 together represent a tetra-methylene or penta-methylene chain, substituted by one or more hydroxyl groups and thereafter developing the color by treating the fiber with an acidic medium.

7. A process'of printing which comprises imparting color to textile fiber by subjecting the textile fiber to a composition containing a known coupling compound and a diazo compound of the formula:

in which Aryl represents an aryl nucleus, while R1 represents H, an alkyl, hydroxy-alkyl hydroaryl or hydroaryl radical, and R2 represents a hydroxy-alkyl or hydroarylol radical; or R1 and R2 together represent a tetra-methylene or pentamethylene chain, substituted by one or more hydroxyl groups and thereafter developing the color by treating the fiber with an acidic medium and thereafter developing the color by steaming the fiber.

8. A composition of matter containing a coupling compound together with the reaction product formed by coupling or condensing a diazotized aromatic amino compound with di-ethanolamine.

9. A printing paste containing a known coupling. compound together with the reaction product formed by coupling a diazotized base with an ethanolamine.

10. A composition of matter containing a coupling compound together with the reaction product formed by coupling or condensing a diazotized aromatic amino compound with a propane-di-olamine.

11. A composition of matter containing a coupling compound together with the reaction prod-' uct formed by coupling or condensing a diazotized aromatic amino compound with di-propane-di-ol-amine.

JEAN GEORGES KERN.