US2828180A

US2828180A - Water-in-oil dyestuff emulsions and their application to the dyeing and printing of cloths and fibers

Info

Publication number: US2828180A
Application number: US488420A
Authority: US
Inventors: Sertorio Francesco
Original assignee: ANONIMA ITALIANA COLORI E AFFI
Current assignee: ANONIMA ITALIANA COLORI E AFFI; ANONIMA ITALIANA COLORI E AFFINI Soc
Priority date: 1952-05-31
Filing date: 1955-02-15
Publication date: 1958-03-25
Anticipated expiration: 1975-03-25
Also published as: GB733099A; NL175307B; DE958380C; CH307607A; NL93555C

Description

nite

tates. Patent Francesco Sertorio, Milan, Italy, assignor to Societa Anonima Italiana Colori e Aifini, Milan, Italy, a corporation of Italy No Drawing. Application February 15, 1955 Serial No. 488,420

Claims priority, application Italy May 31, 1952 31 Claims. (Cl. 8-62) This invention relates to water-in-oil type dyestuif emulsions particularly suitable for dyeing and printing cloths and which penetrate the fibers thereof without formation of a coating thereon. The invention further relates to processes of utilizing these emulsions.

The necessity for increased production in the textile field has led to the development of processes of dyeing piece goods instead of the yarn or fibers. Piece goods dyeing is economically and technically advantageous but presents technical ditficulties of its own, particularly with heavy textiles. Even colors and even shades of colors are diflicult to obtain, and although considerable research has been done, satisfactory resultshave not been obtainable. Uneven and unsightly dyeings can arise when mixtures of vat dyestuffs are used in dyeing, because of a troublesome preferential migration of one of the dyestuffs to the surface or the ends of the piece goods during drying, before the dyes are fixed by the reduction. Furthermore, if the dyestuff is not evenly distributed throughout the fabric, it is liable not to be properly fixed on the goods, and may wash oif in the soaping process, or the goods may tend to crock.

In accordance with the present invention, there is provided water-in-oil type emulsions having as the external continuous or oil phase a volatile stable inert organic liquid boiling within the range from about 60 to about 220 C. and immiscible with water under the conditions of application to the cloth or fiber, and having water as the internal discontinuous phase. The emulsions in addition comprise an organic dyestuff which during the dyeing or printing process displays an affinity for the fibers. The dyestuif is dispersed in the water phase, and both phases are emulsified by an organic emulsifier, as hereinafter defined. These ingredients are the essential ingredicuts.

The terms dispersed and dispersion as used herein in the specification and claims are inclusive of true solutions and of stable dispersions.

These emulsions can be applied to cloths and fibers by conventional dyeing and printing processes, preferably with pressure, as in pad dyeing and roller printing, and the cloths and fibers are dyed homogeneously and deeply by the emulsions in such processes, even at room temperature. Control of pressure and of the amount of emulsion and its viscosity permits regulation of the depth of penetration of the dye into the cloth as required. The emulsions are free from film-forming or polymerizable or hardening agents, so that no coatings are formed on the suface of the cloth or fibers.

The water-in-oil characteristic of the emulsions is significant in the dyeing and printing of cloths and fibers. Because the dyestufi which is employed is dispersed in the internal discontinuous aqueous phase, it is possible to confine the dye area within precise limits in printing, so that design prints can be printed which have sharp edges. There is no tendency for the dyestuif to flow laterally along the surface of the fiber or cloth as is the case frequently with oil-in-water emulsions and aqueous dyestuff solutions. The moir effects obtained with such compositions are not obtained with the water-in-oil emulsions of the invention.

In printing and in dyeing with the water-in-oil emulsions of the invention, the penetration of the fiber or clothby the dyestufi is a function of the pressure applied through the padder or printing rollers. In printing, the amount of emulsion applied to the cloth by the depth of the engraving on the printing roller also is a factor. Hence, by control of pressure, cloths which are uneven in the warp or filling direction can be dyed and printed in an even shade, because the dyestuflt' penetrates to the same extent in both the thin and the thick parts of the fabric. Also, it is possible to print both sides of a cloth with different designs or in different overall shades, while regulating the depth of penetration on each side, and obtain double face printing in which the two faces are in no way intermingled.

This theory also shows that the viscosity of the emulsion is important. The viscosity is controlled by the relative amounts of organic liquid and water, and of emulsifier, and upon the extent or degree of stirring. Best results are obtained with emulsions having a viscosity of at least 0.5 poise at 25 C.; the maximum viscosity limit would be that at which the emulsion is still flowable under the processing conditions.

When the amount of organic liquid is more than about 25%, the viscosity of the emulsion is too low, and the sheath surrounding the water droplets is not strong enough to prevent them from moving laterally along the surface of the fabric under the pressure of the padder or printing rollers. On the other hand, the amount of organic liquid.

must be sufficient to surround the water phase droplets.

completely. The minimum amount of organic liquid is At amounts less than this, the vi's usually about 3%. cosity is too high for practical application. Preferably, the organic liquid is in an amount within the range from about 5% to about 20%.

The emulsifier is chosen with regard to the other constituents of the emulsion and will be in an amount sufiicient to maintain a stable dispersion of the desired viscosity. about 0.05% to about 30% is satisfactory. Optimum results are obtained by using from about 0.3% to about 20% emulsifier.

The proper amount of organic liquid and emulsifier for the constituents employed can readily be ascertained by preliminary tests, according to the desired results and the: intended use of the composition, for example, whether it,

is to be employed for dyeing or for printing. Amountsof organic liquid and emulsifying agent within the limits stated make it possible to obtain the beneficial results of the invention in practice.

The organic dyestuff is selected according to its affinity under the processing conditions for the fiber material which is to be treated. The nature of the dyestufl isnot critical, except that the dye must dye the fiber and must be dispersible in water, inasmuch as it must dwell in the water phase of the water-in-oil emulsions of the invention. The term dyestutf as used in the specification and claims is inclusive both of dyes and of dy intermediates.

The amount of dyestufi will depend upon the dyeing effect desired. The minimum is that needed to dye or print the material, and this will depend upon the dyestufl and its affinity for the fibers being dyed or printed. There is no upper limit beyond that of convenience and sound dyeing practice. Usually from about 0.01% up to about 5% pure 'dyestuff gives an adequate dyeing.

Asthe external continuous or oil phase of the'emulsion there can be used any stable volatile organic liquidwhich under the application conditions is immisciblewith Patented Mar. 25, 1958" Generally, an amount within the range from water and is inert to the dyestutf, to the other components of the composition, and to the cloth and/or fiber material being treated. The organic liquid should be liquid under the conditions of application, which are usually at room temperature, although elevated temperatures, up to 100 C. or higher, can be used, if desired. The liquid should be volatile, that is, it should have a boiling point within the range from about 60 to about 220 C., so that it can be removed from the cloth and/or fiber after application thereto.

The physical properties of the liquid, especially the water solubility and the boiling point, are important in the emulsions of the invention; The chemical properties of the liquid do not come into question, inasmuch as the liquid is under all applicationconditions inert both to the cloth and/or fiber material and to the other components of the emulsion.

Straight and branched chain saturated aliphatic hydrocarbons are preferred, such as the several isomeric hexanes, octanes, decanes, undecanes, nonanes, and heptanes. Aromatic hydrocarbons such as benzene, mesitylene, toluene, ethyl benzene, and the xylenes are especially useful because of their volatility. Cyclohexane and decahydroand tetrahydronaphthalene are representative of the cycloaliphatic hydrocarbons. Mixtures of the aliphatic, cycloaliphatic and aromatic hydrocarbons derived from petroleum, such as the petroleum ethers, gasolines, kerosenes, benzenes, naphtha solvents and white spirits of commerce, are particularly attractive because of their low cost.

The chlorinated hydrocarbons, especially the chlorinated aliphatic hydrocarbons, are desirable because of their low inflammability, presenting less of a fire hazard in commercial use. Carbon tetrachloride, trichloroethylene, tetrachloroethylene, and monochlorobenzene are exemplary of this class of materials. Terpenes, such as dipentene, pine oil and wood turpentine, can also be used.

Ethers and ketones also are useful. Methyl isobutyl ketone, mesityl oxide, diacetone alcohol, methylcyclohexanone are examples of ketones and isopropylether is an example of an ether suitable for these emulsions.

Some solvents which are miscible with water in any proportion when added with a suitable emulsifier within the proportional limits stated above become at least partially water-immiscible and give good emulsions. An example of such a solvent is diacetone alcohol.

Typical water-soluble or dispersible dyestuffs are the vat dyes, sulfur dyes, sulfur-carbazole dyes, direct dyes, acid dyes, naphthol dyes, rapidogen (mixtures of soluble aromatic diazoamino compounds and napthols; see H. Dieserens, Die Neuesten Fortschritte in der Anwendung der Farbstofie," vol. 1, 2nd edition [Birkhausen Basel, Switzerland, 1946], pp. 342 to 357 and chapter 4 starting at page 466 et seq.) dyes, and acetate rayon dyes, of which this non-exclusive list is given as illustrative of the preferred dyes:

Vat dyes such as Indanthrene Brown R (Schultz dye table No. 1227), Indanthrene Olive R (Schultz dye table No. 1224), Indanthrene Brilliant Green B (Schultz dye table No. 1269) and Indantbrene Brown G (Schultz dye tableNo. 1219). I

Sulfur dyes and sulfur carbazole dyessuch as ethylcarbazoleindophenol-sulfur (Schultz dye table No. 113, also sold as Hydron Blue B), Immedial Orange G (Schultz dye table No. 1063), Indocarbon CL (Schultz dye table No. 1114) and Immedial Blue G (Schultz dye table No.

1078). r a Acid and chromium dyes such'as Supramine Red 33 (Prototype 193), Light Fast'Yellow 26 (Color Index Naphthol, rapidogen and acetate rayon dyes such as Naphthol AS-SW (Prototype No. 313), Rapidogen Red R (Prototype No. 169) and Celliton Blue BB (Prototype No. 62).

These classes of dyestuffs are known materials, and those skilled in the dyeing art know many other illustrative members of these classes. Therefore, further details or examples need not be given.

The chemical nature and the structure of the emulsi: fiers are not important, except as these influence their physical properties. A variety of chemically different organic emulsifiers are suitable. However, the organic emulsifiers used in the emulsions of this invention must be nonpolymerizable, thatis, they must not form resins in the course of the dyeing process or printing process. The classes of emulsifiers defined below are illustrative.

Gne class of emulsifiers having operative solubility ratios can be defined by the following general formulae:

where R is a straight or branched chain saturated or unsaturated aliphatic hydrocarbon group having from about twelve to about eighteen carbon atoms or a mixed aliphatic-aromatic group attached to A through the aromatic nucleus, and having one to five straight or branched saturated or unsaturated hydrocarbon groups, of which at least one has from six to about twelve carbon atoms and the others have from one to twelve carbon atoms, and all are attached to the aromatic nucleus. A is selected from the group consisting of ethereal oxygen, sulfur, and carboxylic ester groups, and x is a whole or decimal number representing the average number of alkylene oxide units, and is within the range from about 3 to about 31.

When A in the above formula is a carboxylic ester group, the emulsifiers have the following structure:

where x is a number within the range from about 3 to about 31 and R is as in I, preferably having from twelve to eighteen carbon atoms. R is hydrogen or the same as R in I.

When A is oxygen and R is an aralkyl group, the emulsifiers have the following structure:

a. otonton op-oatomon where n is the number of R groups and is from 1 to 5, x preferably is a number within the range from 5 to 11 and R is an aliphatic hydrocarbon radical, at least one R having from six to twelve carbon atoms, while the other Rs can have from one to twelve carbon atoms.

When A is an ethereal oxygen atom and R is an aliphatic hydrocarbon radical, the emulsifiers have the following structure:

where x preferably is a number within the range from 3 to 24 and R preferably has from twelve to eighteen carbon atoms.

When A is a sulfur atom the emulsifiers have the following structure:

where x preferably is a number within the range from about '5 to about 10 and R is as in I..

A second class of emulsifiers has the following general structure: I1. /[(CHz),,CHz0],H

R A\ V '[KCHzMCHgOhH] where R is a straight or branched chain saturated or unsaturated aliphatic hydrocarbon group having from sees, 180

where x is a number from 1 to 5, the sum of x and y is within the range from 2 to 15, n is a number within the range from to 7 and R is as in II.

When A is an amino nitrogen atom, the emulsifiers take one of the following two forms:

where the sum of x and y is within the range from 5 to and R is as in II. II) /[CH2CH2CH20],H RN

where the sum of x and y is within the range from 3 to 6 and R is as in II.

A third class of emulsifiers which can be employed in accordance with the invention has the general structure:

III.

HO CH Cl-I O] m E CH CH CH O CH CH O 'H These are fully described in U. S. Patent No. 2,674,619 to L. G. Lunsted, dated April 6, 1954; see especially column 3, lines 55 to 71. See also U. S. Patent No. 2,677,700 to D. R. Jackson et al., dated May 4, 1954.

m and m represent the average number of oxyethylene units, and n the average number of oxypropylene units. See U. 5. Patent No. 2,674,619. The sum of m and m preferably is within the range from 15 to 41, and n preferably is within the range from 17 to 31.

The fourth class of emulsifiers which can be used in the compositions of the invention has the formula:

IV(a) RNH and their salts RNH -HX [V(b) R NH and their salts R NH-HX where X is an inorganic or organic salt-forming anion.

A fifth class of emulsifiers are the fatty amides and amide polymers, including quaternary amides:

where R; is an aliphatic straight or branched chain saturated or unsaturated hydrocarbon group having from twelve to eighteen carbon atoms, R and R are selected from the group consisting of hydrogen, a lower alkyl of from one to live carbon atoms and an amide polymer group, and B and X are selected from the group consisting of inorganic and organic salt-forming cation and anion, and are present when the nitrogen is quaternary, and are absent when the nitrogen is trivalent, in the fatty amides.

When R and R, are hydrogen, and B and X are not present, these are fatty acid amides:

V(a) R CONH R CONR R can be a radical of an amide polymer, whereupon they take this structure:

These are fully described in U. S. Patents Nos. 2,304,113, 2,304,369, 2.344.259, 2,344,260 and 2,410,788. See No. 2,304,113, page 1, column 2. line 32 to'page 2, column 1, line 43 for a full description of the above formula.

The sixth class of emulsifiers are esters:

VI. RCOOR of aliphatic polyhydric alcohols having from three to six carbon atoms and of polyhydric carbocyclic ethers having a furan or pyran ring or two condensed furan rings, these polyhydric alcohols having at least one hydroxyl group for each three carbon atoms, preferably one hydroxyl group for each carbon atom, and aliphatic fatty acids having from eight to eighteen carbon atoms.

One class of these can be defined by the following general structure:

VI(a) noonZDomCmopn] where x is a number from 2 to 10, n is a number from 1 to 3, z is a number from 1 to 3, and n plus 2 is the number of hydroxyl groups of the ring nucleus which are esterified and etherified as shown. These compounds have one of the following structures, 2 being the furan or pyran ring:

These are derived from the Spans by addition of polyoxyethylene chains. The Spans have the following general structure:

Vl(b) [RCOLZEH],

where n is a number from 1 to 3 and z is a number from 1 to 3 and z and n are the number of free hydroxyl groups and esterified hydroxyl groups of the ring, respectively.

The Spans have one of the following structures, 2 being the furan, pyran or condensed furan ring:

These are derived by esterification of the hexitans and hexides obtained by loss of water (anhydrization) from sot-bite}. See Atlas Surface Active Agents, a booklet of the Atlas Powder Company, Wilmington, Delaware, copyright 1950. V .7 7

Another group of materials within this class has the following structure:

where R is a straight or branched chain Saturated or unsaturated aliphatic hydrocarbon g'roup having from three to eight carbon atoms and M is an alkali metal cation, such as sodium, potassium or ammonium, or an alkaline earth metal cation, such as calcium, barium or strontium. i i I A seventh group of emulsifiers are the fonates of the general structure VII. RSO M' VIII. [RCOO M where RCOO is derived from an aliphatic fatty acid having from twelve to eighteen carbon atoms and M is a polyvalent metal cation and n is a valence of M.

A ninth group of emulsifiers are the higher quaternary ammonium salts:

petroleum sulwhere at least two of R R R and R are long chain aliphatic saturated hydrocarbon radicals having from about eight to about eighteen carbon atoms, and at least two are short chain aliphatic saturated hydrocarbon groups of not over five carbon atoms, and X is a saltforming inorganic or organic anion. I

Exemplary of aliphatic hydrocarbon groups as R in the above formulae are n-octyl, tert.-octyl, nonyl, decyl,

lauryl, cetyl, myristyl, stearyl, trimethyl nonyl, ricinoleyl,

oleyl, linoleyl, and the mixed fatty aliphatic radicals derived from natural and hydrogenated oils and fats, such as the mixed coconut oil aliphatic radicals, mixed tallow aliphatic radicals, mixed soyabean aliphatic radicals and hydrogenated tallow aliphatic radicals. Typical R alkaryl groups are octylphenyl, nonylphenyl, hexylphenyl, tert.- octylphenyl, decylphenyl, stearylphenyl, isohexylphenyl, heptylphenyl, isooctylphenyl, ethylhexylphenyl;

In addition to the water, organic liquid, organic emulsifier and dyestufi, it may be of advantage to add auxiliary agents such as polyhydric alcohols, for instance, glycerine. If the solubility of the emulsifier in water is too high, it may not give a satisfactoryemulsion; in this event, an inorganic salt can be added to the Water phase of the emulsion to salt out the emulsifier. One or more of the inorganic alkaline salts used in printing emulsions is satisfactory.

When the emulsion is intended for use in printing, the water phase of the emulsion can contain inorganic alkaline salts such as potassium' carbonate, sodium hydroxide, potassium hydroxide, mixtures of sodium and potassium carbonates and sodium and potassium hydroxides, and reducing agents such as sodium formaldehyde sulfoxylate, sodium hydrosulfite and mixtures of sodium hydrosulfite and sodium formaldehyde sulfoxy= late. These. are conventional components of printing pastes and .emulsions.

The. emulsions of the invention are readily prepared ,by conventional emulsion-forming methods which lead to iwater-in-oil emulsions. The important step is that the'organic liquid phase be prepared, with or without emulsifier, and that the water phase be poured into the organic liquid phase with stirring. The order of mixing the other ingredients is less important. It usually is convenient to disperse the dyestutr" and other components of the water phase in a sufiicient quantity of water to form a paste, but this is not necessary.

In one convenient method, a mixture or solution of the emulsifier and organic liquid is prepared, and the water is poured into it while stirring. The dyestuif can be dispersed in the water, or can be added separately afterward.

The total amount of the emulsifier is preferably present in the organic liquid before adding the water and the dyestuif, in order to obtain the maximum emulsifying effect. However, it also is possible to disperse the dyestuff in the emulsifier, dilute this with water, and then pour this into the organic liquid.

Frequently, for commercial purposes it is desirable to prepare and market separately a concentrated dyestulf emulsion and a clear concentrate, suitable for preparing a colorless emulsion. The concentrated dyestuff emulsion is a stable water-in-oil emulsion exactly like the emulsions of the invention in containing water, organic liquid, emulsifier and dyestufi, but it has more dyestufi than is needed, i. e., more than 5% dyestuif, up to 25% or more. The clear concentrate is a dyestuif-free emulsion of the organic liquid and the emulsifier (in the proper proportions for the final dyestuif emulsion). In order to forman emulsion for dyeing or printing, with stirring, a suitable proportion of water is added to the clear concentrate,obtaining a colorless emulsion that can be mixed with the concentrated dyestuff emulsion to obtain a final emulsion having the desired dyestufi content.

The water-in-oil emulsions of the invention can be applied to cloths, textiles, fabrics, yarns and fibers of all kinds, and made of all types of natural and synthetic fibers and fiber-forming materials. The term cloth as used herein is inclusive of woven and unwoven cloths, textiles and fabrics as Well as knitted cloths, and the term fiber is inclusive of single filaments, bundles of filaments, twisted and untwisted, such as yarn, roving, silver, warps, and cards. All of these can be dyed and printed by emulsions'of the invention. Cloths and fibers made of cotton, mohair, angora, camels hair, silk, cashmere, cellulose derivatives, such as cellulose acetate, cuprammoniurn cellulose and viscose rayon, Wool, ramie, jute, linen, sisal, and synthetic materials and resins such as glass (Fiberglas), polyamides (nylon), casein protein (Aralac), copolymers of acrylonitrile and vinyl chloride (Vinyon N and Dynel), polyacrylonitrile (Orlon), copolymers of terephthalic acid and ethylene glycol (Terylone and Dacron), copolymers of vinylidene chloride and vinyl chloride (Saran) and polyvinyl chloride (Vinyon) can be dyed and printed with the emulsions of the invention. The invention is especially useful for the dyeing and printing of piece goods.

The emulsions in accordance with the invention are best applied in dyeing and printing by equipment which permits application of pressure, such as by passing the materail through a padder or a roller printing machine, between high pressure squeeze rollers, to thoroughly impregnate the cloth and fibers with the emulsion. See, for example, American Cotton Handbook, second edition, Textile Book Publishers (1949), chapters 15 and 16, pp. 573-689. The impregnated cloth can be dried, although this is not necessary before fixing the dye on the fibers. In the drying'step, the water and organic liquid are evaporated, leaving behind the dye and the emulsifying agent,

asastse if present. During the later aqueous treatments of the fibers, the emulsifying agent is removed and the dye is fixed onthe fiber so that only the dye remains. For example, a cloth impregnated as above described with a vat dyestuif emulsion will pass through another padder in which it picks up in the bath chemicals which are necessary to reduce and solubilize the dye to be fixed on the fibers, while the emulsifier is dissolved in the bath. Such processing of course forms no part of the instant invention.

The emulsions according to the present invention are generally applied at room temperature, but can be applied at elevated temperatures up to 100 C. or higher if desired. The upper limit depends upon the stability of the emulsion components. The emulsion is stable and shows no tendency to separate, and therefore it is not necessary to utilize special devices to maintain the emulsion homogeneous.

The following examples illustrate water-in-oil emulsions of the present invention and their use. The first or A series of examples shows various emulsifiers and organic liquids. The second or B series of examples in addition shows various methods of preparing the emulsions, and various dyestuffs. The third or C series shows various methods of application of the emulsions.

A SERIES All of the emulsions of Examples 1A to 97A, inclusive, were prepared as follows: The full amount of dyestufi' was dispersed in the quantity of water stated to form a paste. In some cases, as stated, salts-potassium carbonate, sodium formaldehyde sulfoxylate were then added in order to reduce the solubility of the emulsifier in the water phase; these salts converted these emulsions into printing pastes. A dispersion was prepared of the full amounts of the emulsifier and of the organic liquid. The aqueous dyestufi dispersion, containing the salts if present, was poured into the emulsifier dispersion, with stirring, at room temperature, and stirring continued until the emulsion was homogeneous.

References in the A series examples to R, x, n, z, etc. in identifying the emulsifiers are to the emulsifier formulae at the head of each group of the examples.

EMULSEFIERS OF GROUP I (a) RCOO [CI-I CH O 1 CH CH OR' Example 1A parts Glyco 200 Monolaurate (x=3.5, R=lauryl), parts white spirit (mixed aliphatic petroleum hydrocarbons, boiling range 110l60 C.), 84.5 parts water and 0.5 part Vat Brown R (Indanthrene Brown R).

Example 2A 10 parts Glycol 400 Monolaurate (x=8, R=lauryl), parts solvent naphtha, 12 parts sodium formaldehyde sulphoxylate, 12 parts potassium carbonate, 60.5 parts water and 0.5 part Vat Brown R (Indanthrene Brown R).

Example 3A 10 parts Glyco 600 Monolaurate (x=12, R=lauryl), 10 parts solvent naphtha, 12 parts sodium formaldehyde sulphoxylate, 12 parts potassium carbonate, 55 parts water and 0.5 part Vat Brown R (Indanthrene Brown R).

Example 4A 10 parts Glycol 6 00 Monostearate (x=l2, R=stearyl), 10 parts solvent naphtha, 12 parts sodium formaldehyde sulphoxylate, 12 parts potassium carbonate, 55.5 parts water and 0.5 part Vat Jade Green (Indanthrene brilliant green F. F. B.).

10 Example 5A 10 parts Glycol I500 Monostearate (x=31, R=stearyl), 10 parts toluene, 12 parts sodium formaldehyde sulphoxylate, 12 parts potassium carbonate, 55.5 parts water and 0.5 part Vat Jade Green (Indanthrene brilliant green F. F. B.).

Example 6.4

10 parts Glyco 200 Monoleate (x=3.5, R=oleyl), 15 parts white spirit (mixed aliphatic petroleum hydrocarbons, boiling range 110-160 C.), 74.5 parts water, and 0.5 part Vat Brown R (Indanthrene Brown R).

Example 7A 10 parts Glycol 400 Monoleate (x=8, R=oleyl), 15 parts toluene, 74.5 parts water, and 0.5 part Vat Brown R (Indanthrene Brown R).

Example 8A 5 parts Glyco 400 Dioleate, Emulphor A (x=8, R and R=oleyl), 13 parts white spirit (mixed aliphatic petroleum hydrocarbons, boiling range ll0160 C.), 81.5 parts water and 0.5 part Vat Brown R (Indanthrene Brown R).

Example 9A 10 parts Glyco 400 Di-Triricinoleate (x=8, R and R=ricinoleyl; the remaining four ricinoleyl groups are esterified through their carboxylic acid group to the hydroxyl groups of other ricinoleyl radicals, including those attached through their carboxylic acid groups to a terminal hydroxyl group of the polyoxyethylene radical),

10 parts white spirit (mixed aliphatic petroleum hydrocarbons, boiling range l'10-l60 C.), 79.5 parts water and 0.5 part Vat Brown R (Indanthrene Brown R).

Example 10A 10 parts Neutronyx 330 (x: 12, R=mixed soyabean fatty alkyl), 10 parts solvent naphtha, 12 parts sodium formaldehyde sulphoxylate, 12 parts potassium carbonate, 5 5 .5 parts water and 0.5 part Vat Jade Green (Indanthrene brilliant green F. F. B.). 7

Example 11A 5 parts Renex (x=20, R=mixed fatty alkyl and abietyl), 10 parts solvent naphtha, 12 parts sodium formaldehyde sulphoxylate, 12 parts potassium carbonate, 60.5 parts water and 0.5 part Vat Jade Green (Indanthrene brilliant green F. F. B.).

(See also Examples 93A, 94A, 95A, 96A, 97A, infra.).

EMULSIFIERS OF GROUP I(b):

R" OlCHzCHnOhCHaCHzOH Example 12A 5 parts Emulphor A Extra (n=2, R=isohexyl and heptyl, x=5), 18 parts white spirit (mixed aliphatic petroleum hydrocarbons, boiling range l10160 C.), 72.5 parts water and 0.5 part Vat Brown R (Indanthrene Brown R).

Example 13A 5 parts Megapal M Extra (n:2, R=octyl and p-methyl, x=6), 10 parts solvent naphtha, 84.5 parts water and 0.5 part Vat Brown R (Indanthrene Brown R).

Example 14A 5 parts Triton X45 (11:1, R=isooctyl, x=4 to 5), 15 parts white spirit (mixed aliphatic petroleum hydrocarbons, boiling range 1lO-l60 C.), 79.5 parts'water and 0.5 part Vat Brown R (Indanthrene Brown R).

Example 15A 10 parts Triton X100 (R=isooctyl, x=7 to 9), 10 parts solvent naphtha, 12 parts sodium formaldehyde sulphoxylate, 12 parts potassium carbonate, 55.5 parts water and 0.5 part Vat Jade Green (Indanthrene brilliant green F. F. B.).

Example 16A 10 parts Triton X-l02 (R=isooctyl. x=ll), 10 parts solvent naphtha, 12 parts sodium formaldehyde sulphoxylate, 12 parts potassium carbonate. 55.5 parts water and 0.5 part Vat Jade Green (Indanthrene brilliant green F. F. B.).

Example [7.4

10 parts Tergitol NPX (R=ethylhexyl, x=8 to 9), 10 parts solvent naphtha, 12 parts sodium formaldehyde sulphoxylate, 12 parts potassium carbonate, 55.5 parts water and 0.5 part Vat Jade Green (Indanthrene brilliant green F. F. B.). Example 18A parts Neutronyx 600 (R=nonyl, x=9), parts solvent naphtha, 12 parts sodium formaldehyde sulphoxylate, 12 parts potassium carbonate, 60.5 parts water and 0.5 part Vat Jade Green (Indanthrene brilliant green F. F. B.).

EMULSIFIERS OF GROUP I(c) RO [CH CH O CH CH OH Example 19A 10 parts Brij 30 (R=lauryl, x=3), 10 parts White spirit (mixed aliphatic petroleum hydrocarbons, boiling range ll0160 C.), 79.5 parts Water and 0.5 part Vat Brown R (Indanthrene Brown R).

Example 20A 5 parts Permulsin FO Extra Concentrate (R=mixed palmityl stearyl, x=), 10 parts solvent naphtha, 12 parts sodium formaldehyde sulphoxylate, 12 parts potassium carbonate, 60.5 parts water and 0.5 part Vat Jade Green (Indanthrene brilliant green F. F. B.).

Example 21A 5 parts Permulsin 0 Extra Concentrate (R=oleyl, x=24),'10 parts solvent naphtha, 12 parts sodium formaldehyde sulphoxylate, 12 parts potassium carbonate, 60.5 parts water and 0.5 part Vat Jade Green (Indanthrene brilliant green F. F. B.). e

Example'ZZA 10 parts Tergitol TN (R=trimethylnonyl, x=7 to 9), 10 parts White spirit (mixed aliphatic petroleum hydrocarbons, boiling range 110160 C.), 12 parts sodium formaldehyde sulphoxylate, 12 parts potassium carbonate,

55.5 parts Water and 0.5 part Vat Jade Green (Indanthrene brilliant green F. F. B.).

EMULSIFIERS OF GROUP 1 a RS CH CH O] CH CH OH Example 23A 10 parts Nonic 261 (R=dodecyl, x=5 to 6). 10 parts solvent naphtha, 79.5 parts water and 0.5 part Vat Brown R (Indanthrene Brown R).

Example 24A 10 parts Nonic 218 (R=dodecyl, x=9 to 10), 10 parts toluene, 12 parts sodium formaldehyde sulphoxylate, 12 partspotassium carbonate, 55.5 parts Water and 0.5 part Vat Jade Green (Indanthrene brilliant green F. F. B.).

Example 25A 10 parts Sterox SK (R=dodecyl, x=5 to'6), 10 parts solvent naphtha, 79.5 parts water and 0.5 part Vat Brown R (Indanthrene Brown R).

12 Example 26A.

10 parts Sterox SE (R=-dodecyl, x=5 to 6) 10 parts solvent-naphtha, 79.5 parts water and 0.5 part Vat Brown R (Indanthrene Brown R).

EMULSIFIERS OF GROUP II(a):

R-C-NHKCHzhCHzOhH Example 27A 2 parts lauroyl ethanolamide (n=1, R=la'uryl, x=1, lauric acid-ethanolamine condensation product), 9 parts white spirit (mixed aliphatic petroleum hydrocarbons, boiling range ll0l60 C.), 88.5 parts water and 0.5 part Vat Brown R (Indanthrene Brown R).

Example 284 2 parts stearoyl ethanolamide (n=1, x=1, R=stearyl, stearic acid-ethanolamine condensation product), 15 parts toluene, 82.5 parts water and 0.5 part Vat Brown R (Indanthrene Brown R) Example 29A 2 parts oleoyl ethanolamide (n=1, R=oleyl, x=1, oleic acid-ethanolamine condensation product), 15 parts toluene, -82.5 parts water and 0.5 part Vat Brown R (Indanthrene Brown R).

. EMULSIFIERS OF GROUP II(b):

' ormnomoprr Example 30A 10 parts Ethomid HT/l5 (n=1, R=hydrogenated tallow fatty alkyl, x-i-y=5), 10 parts solvent naphtha, 79.5 parts water and 0.5 part Vat Brown R (Indanthrene Brown R). Example 31A 10 parts Onyxol 9162 (n=1, x+y=2,.R=mixed coconut oil alkyl, coconut fatty acid-diethanolamine condensation product), 15 parts solvent'naphtha, 12 parts sodium formaldehyde sulphoxylate, 12 parts potassium carbonate, 50.5 parts Water and 0.5 part Vat Jade Green (Indanthrene brilliant green F. F. B.).

Example 32A 10 parts Onyxol 336 (n=1, x+y=2, R=lauryl, laun'c acid-diethanolamine condensation product), 10 parts solvent naphtha, 12 parts sodium formaldehyde sulphoxylate, 12 parts potassium carbonate, 55.5 parts Water and 0.5 part Vat Jade Green (Indanthrene brilliant green F. F. B.).

EMULSIFIERS OF GROUP II(c):

' lcnionio n R-N l Hadflzols V Example 33/! 10 parts Ethomeen T/ 15 (R=rnixed tallow oil fatty alkyls, x+ 1=5 15 parts toluene, 74.5 parts water and 0.5 part Vat Brown R (Indanthrene Brown R).

Example 34A Example 35A 10parts Ethomeen 18/25 (R=stearyl, x-l-y--l5), 20 parts Solvesso (hydrogenated solvent naphtha), 12

'fgreen F. F. B.).

f ri od m t 'm hy u q t zt s basslum carbonate, 45 .5 parts Water and 0.5.part Vat Jade Green (Indanthrene brilliant green F. F. B.).

EMULSIFIERSIOF GROUP 11(d): I

lonzomomopn Example 36A 7 pans G-3763 (R=mix e d tallo'w oil fatty 'alkyls,

Ix+y -3), 13 parts solvent naphtha, 7955 parts water and 0.5 part Vat Brown R (Indanthrene Brown R).

Example 37A 10 parts G3646 (R=mixed tallow oil fatty alkyls,

x+y =6), 10 parts solvent naphtha, 12 parts sodium Yformaldehyde sulphoxylate, 12 parts potassium carbonate,

EMULSIFIERS OF GROUP III:

HO [CH CH O] [CH CH CH O] b [CH CH O] H Example 38A parts Pluronic L-62 (b=2631, a+c=l5-18), 15 parts solvent naphtha, 79.5 parts water and 0.5 part Vat "Brown R (Indanthrene Brown R).

Example 39A parts Pluronic L-44 (b=17-20, a+c=23-27), parts solvent naphtha, 12 parts sodium formaldehyde sulphoxylate, 12 parts potassium carbonate, 50.5 parts water and 0.5 part Vat Jade Green (Indanthrene brilliant Example 40A 10 parts Pluronic'L-54 (b=263l, a+0=33-41), 15 parts solvent naphtha, 12 parts sodium formaldehyde sulphoxylate, 12 parts potassium carbonate, 50.5 parts water and 0.5 part Vat Jade Green (Indanthrene brilliant green F. F. B.).

EMULSIFIERS OF GROUP IV (a): RNH

Example 41A 10 parts Armeen CD (R=mixed coconut oil fatty alkyls), 10 parts white spirit (mixed aliphatic petroleum hydrocarbons, boiling range 110-160 C.), 79.5 parts water and 0.5 part Vat Brown R (Indanthrene Brown R).

Example 4221 5 parts Armeen 12D (R=lauryl), 15 parts solvent naphtha, 79.5 parts water and 0.5 part Vat Brown R (Indanthrene Brown R).

Example 43A 10 parts Armeen 18D (R=stearyl), parts solvent naphtha, 64.5 parts water and 0.5 part Vat Brown R (Indanthrene Brown R).

Example 44A 7 parts Armac 12D (R=lauryl, acetate salt), 23 parts solvent naphtha, 69.5 parts water and 0.5 part Vat Brown R (Indanthrene Brown R).

Example 45A 6 parts Armac 18D (R=stearyl, acetate salt), 25 parts solvent naphtha, 68.5 parts water and 0.5'part Vat Brown R (Indanthrene Brown R).

Example 46A 5 parts Armac TD (R=mixed tallow fatty .alkyls, acetate salt), 25 parts white spirit (mixed aliphatic petroleum hydrocarbons, boiling range 110160 C.),

10 parts Ahcovel A /E/C/F (U. S. Patents Nos. 2,304,113, 2,304,369, 2,344,259, 2,410,788 and 2,344,- 260), '15 parts White spirit (mixed aliphatic petroleum hydrocarbons, boiling range 110-160" C.), 74.5 parts water and 0.5 part Vat Brown R (Indanthrene Brown R).

EMULSIFIERS OF GROUP VI(a):

moo zbomomolrn] Example 49A 5 parts Tween 21 (n=1, z=3, R=lauryl, x=2), 10 parts white spirit (mixed aliphatic petroleum hydrocarbons, boiling range 110-160? C), 84.5 parts water and 0.5 part Vat Brown R (Indanthrene Brown R).

- Example 50A 5 parts Tween 61 (n'=1,-z=3, R=stea'ryl, x=2), 10 parts white spirit (mixed aliphatic petroleum hydrocarbons, boiling range 1l0-160 C.), 84.5 parts water and 0.5 part Vat Brown R (Indanthr'ene Brown R).

Example 51A 5 parts Tween 81 '(n=1, z=3, R=oleyl, x=2), 10 parts white spirit (mixed aliphatic petroleum hydrocarbons, boiling range 110160 C.), 84.5 parts water and 0.5 part Vat Brown R (Indanthrene Brown R).

Example 52A 5 parts Tween (n=3, z=3, R=oleyl, x=10), 10 parts white spirit (mixed aliphatic petroleum hydrocarbons, boiling range 110160 C.), 845 parts water and 0.5 part Vat Brown R (Indanthrene Brown R).

Example 53A 5 parts Tween 65 (n=3, z=3, R=stearyl, x=10), 10 parts white spirit (mixed aliphatic petroleum hydrocarbons, boiling range 110-160 C.), 84.5 parts water and 0.5 part Vat Brown R (Indanthrene Brown R).

. Example 54A 10 parts Tween 60 (n==1,' z'=3, R=stearyl, x -10), 15 parts Solvesso (hydrogenated solvent naphtha), 12 parts sodium formaldehyde sulphoxylate, 12 parts potassium carbonate, 60.5 parts water, and 0.5 part Vat Jade Green (lndanthrene brilliant green F. F. B.).

Example 55A 10 parts Tween 80 (n=l, z=3, R=oleyl, x=10), 18 parts solvent naphtha, 12 parts sodium formaldehyde sulphoxylate, 12 parts potassium'carbonate. 47.5 parts water and 0.5 part Vat Jade Green (lndanthrene brilliant green F. F. B.).

EMULSIFIERS OF GROUP VI(b): [RCO],, Z [H] Example 56A 10 parts Span 20 (n= l, :3, R=lauryl), 20 parts white spirit (mixed aliphatic petroleum hydrocarbons,

.. 1 boiling range 110-160 C.), 69.5 parts water and 0.5 part Vat Brown R (Indanthrene Brown R).

Example 57A parts Span 40 (nu-=1, z=3, R =palmityl), 25 parts solvent naphtha, 64.5 parts water and 0.5 part Vat Brown R (Indanthrene Brown R).

Example 58A 5 parts Span 60 (12:1, z=3, R=stearyl), 25 parts solvent naphtha, 69.5 parts water and 0.5 part Vat Brown R (Indanthrene Brown R).

Example 59A 10 parts Arlacel C (n=1 /z, z=3, R=oleyl), parts white spirit (mixed aliphatic petroleum hydrocarbons, boiling range 1l0-160 C.), 69.5 parts Water and 0.5 part Vat Brown R (Indanthrene Brown R).

Example 601! 5 parts Glyceryl Oleate SE (n=1, x=l, R oleyl), 10 parts white spirit (mixed aliphatic petroleum hydrocarbons, boiling range 110-160" C.), 84.5 parts Water and 0.5 part Vat Brown R (Indanthrene Brown R).

Example 61A 5 parts Glyceryl Oleostearate 26 (21:1, x=1, R==mixed oleyl and stearyl), 10 parts white spirit (mixed aliphatic petroleum hydrocarbons, boiling range 110-160 C.), 84.5 parts water and 0.5 part Vat Brown R (Indanthrene Brown R).

Example 62/! 5 parts Glyceryl Stearate 866 (n=1, x=1, R=stearyl), 20 parts white spirit (mixed aliphatic petroleum hydrocarbons, boiling range 110160 C.), 74.5 parts water and 0.5 part Vat Brown R (Indanthrene-BrownR) Example 63A 7 10 parts Aerosol QT, (R=octyl, M =sodiurn), lojparts white spirit (mixed aliphatic petroleum liydroearbons,

boiling range 110-160Z.C 12 parts sodium formaldehyde sulphoxylate, 12 parts potassium carbonate, 55.5 parts water and 0.5 pai't..Vat-Jade ,Green (Indanthrene brilliant greenF.F.B.).i :i e 3 f amp 65A I 1 f ial} i 5 parts Aerosol OT transformed (R=octyl, M =calcium), 12 parts solvent naphtha, 84.5 parts water and 0.5 part Vat Brown R (Indanthrene Brown R); T

E2 b 6 j' F ii 5 parts Aerosol AY -(R =amyl, M sodi tu); 1 1m white spirit (mixed aliphatic petroleum hydrocarbons, boiling range 110160..-C 12 parts sodium formaldehyde sulphoxylate, 12parts potassium carbonate, 55.5 parts water and 0.5 piartV'atJadGreen (Indanthrene brilliant greenF.F."BI).'-' i f. i EMULSIFIERS O'FGRQU P yin n'soj M Q W l 7 Example 67A 10 parts Acto.450- (sodium mixed petroleum hydrocarbon sulphonates (M. W."='455/480)45%; unsulphonated hydrocarbons.9%.;" Water33.85%; isopropyl alcohol-12%; allialinityas Na CO -0.15%),. 1.0 parts white spirit-(mixed aliphatic petroleum hydrocarbons,

.16 boiling range 1l 0-160,C.), 12 parts sodium formaldehyde sulphoxylate, 12 parts potassium carbonate, 55.5 parts water and 0.5 part Vat Jade Green (Indanthrene brilliant green-F. F. B.).

Example 684 5 parts Acto 450transformed (calcium mixed petroleum hydrocarbon sulfonates), 5 parts white spirit (mixed aliphatic petroleum hydrocarbons, boiling range 110-160 C.), 89.5 parts water and 0.5 part Vat Brown R (Indanthrene Brown R).

Example 694 3 parts Acto 450 transformed (zinc mixed petroleum hydrocarbon sulfonates), 7 parts white spirit (mixed aliphatic petroleum hydrocarbons, boiling range 110-160 C.), 89.5 parts water and 0.5 part Vat Brown R (In danthrene Brown R).

Example 70,41 10 parts Acto 500 (sodium mixed petroleum hydrocarbon sulfonates (M. W-.=455/480)-50%; uusulfonated hydrocarbons--47.5%; water-2.35%; alkalinity as Na CO -O.l5%), 10 parts white spirit (mixed aliphatic petroleum hydrocarbons, boiling range 110160 C.) 12 parts sodiumformaldehyde sulphoxylate; 12 parts potassium carbonate; 55.5 parts Water and 0.5 part Vat Jade Green (Indanthrene'hrilliant green F. F. B.).

i l Example 71A V 5 parts Acto 500 transformed (calcium mixed petroleum hydrocarbon sulfonates), 5 parts white spirit (mixed aliphatic petroleum hydrocarbons, boiling range 10 parts Acto 600 (sodium mixed petroleum hydrocarbon sulfonates (M. W.=455,/480)60%; unsulfonated hydrocarbons-10%; water-29.75%; alkalinity as Na CO 0.25%), 10 parts white spirit (mixed aliphatic petroleum hydrocarbons, boiling range 110160 C.), 12 parts sodium formaldehyde sulphoxylate, 12 parts potassium carbonate, 55.5 parts Water and 0.5 part Vat Jade Green (Indanthrene brilliantgreen F. F. B.).

Example 744 5 parts Acto 600 (calcium mixed petroleum hydrocarbon sulfonates), 5 parts white spirit (mixed aliphatic petroleum hydrocarbons, boiling range 110-160" C.), 89.5 parts Water and 0.5 part Vat Brown R (Indanthrene Brown R).

Example 75A 3 parts Acto 600 transformed (zinc mixed petroleum hydrocarbon sulfonates), 7 parts white spirit (mixed aliphatic petroleum hydrocarbons, boiling range -160" C.), 89.5 parts water and.0.5 part Vat Brown R (IndanthreneBrown R). v 7

Example 76A 10 parts Acto 630 (sodium mixed petroleum hydrocarbon sulfonates (M. .W.= 455/480)---63 unsulfonated hydrocarbons-34.5%; water-4.3%; alkalinity as Na CO --0.2%), 10 parts white spirit (mixed aliphatic petroleum hydrocarbons, boiling range l10-160 C.), 12 parts sodium formaldehyde sulphoxylate, 12 parts potas'sium carbonate, 5 5 .5 parts Water and 0.5 part Vat Jade Green (Indanthrene brilliant green F. F. B.).

17 Example 77Av g V 5 parts Acto 630 transformed (calcium mixed petroleum hydrocarbon sulfonates), 5 parts white spirit (mixed aliphatic petroleum hydrocarbons, boiling range 110-160 C.), 89.5 parts water and 0.5 part Vat Brown R (Indan-' threne Brown R).

Example 78A 3 parts Acto 630 transformed (zinc mixed petroleum hydrocarbon sulfonates), 7 parts white spirit (mixed aliphatic petroleum hydrocarbons, boiling range 110-160" C.), 89.5 parts water and 0.5 part Vat Brown R (Indanthrene Brown R).

Example 79A 10 parts Acto 700 (sodium mixed petroleum hydrocarbon sulfonates (M. W.=455/480)70%; unsulfonated hydrocarbons27%; water-2.75%; alkalinity as N21 CO 0.25% 10 parts white. spirit (mixed aliphatic petroleum hydrocarbons, boiling range 110-160? C.), 12 parts sodium formaldehyde sulphoxylate, 12 parts potassium carbonate, 55 .5 parts water and 0.5 part Vat Jade Green (Indanthrene brilliant green F. F. B.).

Example 80A 5 parts Acto 700 transformed (calcium mixed petroleum hydrocarbon sulfonates), 5 parts white spirit (mixed aliphatic petroleum hydrocarbons, boiling range 110160 C.), 89.5 parts water and 0.5 part Vat Brown R (Indanthrene Brown R).

Example 81A 3 parts Acto 700- transformed (zinc mixed petroleum hydrocarbon sulfonates), 7 parts white spirit (mixed ali-- phatic petroleum hydrocarbons, boiling range 1l0160 C.), 89.5 parts water and 0.5 part Vat Brown R (Indanthrene Brown R).

Example 82A 10 parts Ahcobase Oil W-lOO and W-200v (sodium salt of sulfonated mixed petroleum hydrocarbons), 10 parts white spirit (mixed aliphatic petroleum hydrocarbons, boiling range ll-l60 C.), 79.5 parts water and 0.5 part Vat Brown R (Indanthrene Brown R).

Example 83A 10 parts Petrosul 750 (sodium mixed petroleum hydrocarbon sulfonates-62%; unsulfonated hydrocarbons 35%; water--%; inorganic salts0.5%; M. W.= 500/520), parts white spirit (mixed-aliphatic petroleum hydrocarbons, boiling range 110-160 C.), 79.5 parts water and 0.5 part Vat Brown R (Indanthrene Brown R).

Example 84A 10 parts Petrosul 745 (sodium mixed petroleum hydrocarbon sulfonates-62% unsulfonated hydrocarbons- 35%; water 5% inorganic salts0.5%; M. W.= 435/450), 10 parts white spirit (mixed aliphatic petroleum hydrocarbons, boiling range l10160 C.), 55.5 parts water, 12 parts sodium formaldehyde sulphoxylate, 12' parts potassium carbonate and 0.5 part Vat Jade Green (Indanthrene brilliant green F. 'F. B.).

Example 85A 10"parts Petrosul 742 (sodium mixed petroleum hydro carbon sultonates62%; unsulfonated hydrocarbons-'- 35% water-5%; inorganic salts- 0.5%; M. W.= 415/425), 10 parts white spirit (mixed aliphatic petroleum hydrocarbons, boiling range l10160 C.), 55.5 parts water, 12 parts sodium formaldehyde sulphoxylate, lZparts potassium carbonate and 05 part Vat Jade Green (Indanthrene brilliant green F. F. B.).

EMULSIFIERS OF GROUP VIII: (R COO L M Example 86A 5 parts aluminum laurate, 25 parts solvent naphtha, 69.5 parts water and 0.5 part Vat Brown R (Indanthrene Brown R).

Example 89A 5 parts aluminum stearate No. 8 (Al O -8-8.5%; water-soluble sa1ts1%; free stearic acid6-9%; water0.5% 25 parts solvent naphtha, 69.5 parts water and 0.5 part Vat Brown R (Indanthrene Brown R).

Example 90A 5 parts aluminum stearate No. 9 '(Al 0 9.510.0%; water-soluble salts-1%; free stearic acid-47%; water-0.5%), 25 parts solvent naphtha, 69.5 parts water and 05 part Vat Brown R (Indanthrene Brown EMULSIFIERS OF GROUP IX: R R R R NX Example 91A 10 parts Arquad 2 HT (R and R =mixed tallow alkyls, R and R =methyl, X =chloride), 10 parts solvent naphtha, 79.5 parts water and 0.5 part Vat Brown R (Indanthrene Brown R).

Example 92A 10 parts Arquad 2 C (R and R =mixed alkyls, R and R =methy1, X :chloride), 10 parts solvent naphtha, 12 parts sodium formaldehyde snlphoxylate, 12 parts potassium carbonate, 55.5 parts water and 0.5 part Vat Jade Green (Indanthrene brilliant green F. F. B.).

EMULSIFIERS OF GROUP 1(a) Example 93A 15 parts Glyco 400 Dioleate, Emulphor A (x=8, R and R =oleyl), 10 parts methyl cyclohexanone, 75 parts water, and 0.5 part Vat Brown R (Indanthrene Brown R). 7

Example 94A 15 parts Glyco 400 Dioleate, Emulphor A (x=8, R and R =0leyl), 15 parts diacetone alcohol, 70 parts water and 0.5 part Va't Brown R (Indanthrene Brown R).

7 Example 95A 5 parts Glyco 400 Dioleate, Emulph-or A (x==8, R=oleyl), parts diisopropyl ether, 12 parts sodium formaldehyde sulphoxylate, 12 parts potassium carbonate, 61 parts water and 05 part Vat Brown R (Indanthrene Brown R).

Example 96A 10 parts Glyco 400 Dioleate, Emulphor A (x=8,

R and R =oleyl), 25 parts Carbon Tetrachloride, 65

parts water and 0.5 part Vat Brown R (Indanthrene Brown R).

' Example 97A 7 parts Glyco Dioleate 400, Emulphor A (x'='8, R .and R ='oleyl) 10 parts Monochlorbenzene, 83 parts water and 0.5 part Vat Brown R (IndanthreneBrown R).

B SERIES Example 1B To 84.25 kg. of Water was added 1.5 kg. of Indanthrene Olive R paste (Schultz dye table 1224, 20% dyestufl The diluted dyepaste was poured into a mixture of 12.25- kg. white spirit and 2 kg. of Emulphor A Extra while continuously stirring. The resulting Water-in-oil gees, 180

19 emulsion was used in the pad dyeing of cotton greige piece goods.

Example 23 To a mixture of 11 kg. of mixed petroleum aliphatic hydrocarbons, boiling within the range from 60 to 200 C., amixture of 2 kg. of Brij 30, 2 kg. of Emulphor A Extra and 81.7 kg. of water was added cautiously, with constant stirring. A milky white water-in-oil emulsion was formed having a good viscosity. To this emulsion was added with stirring 3 kg. of Indanthrene Brilliant Green B (Schultz dye table No. 1269), in the form of a paste which was 17% pure dyestuff. The final dyestufi emulsion was used in pad dyeing cotton piece goods.

Example 38 Immedial Blue C powder (Schultz dye table No. 1078), 5 kg., was mixed with 15 kg. of Emulphor A Extra. The paste was mixed just before use with 65 kg. of water, and the resulting mixture was cautiously poured with stirring into 25 kg. of a mixture containing kg. of o-xylene and kg. of white spirit boiling from 100 to 160 C. The resulting water-in-oil emulsion was used in pad dyeing cotton greige goods.

Example 4B Indanthrene Brilliant Green B (Schultz dye table No. 1269), 10 kg., in the form of a paste having 12% pure dye content was mixed with 45 kg. of water, 15 kg. of sodium formaldehyde sulphoxylate, 12 kg. potassium carbonate, 5 kg. urea and 5 kg. glycerine. With stirring, this mixture was poured into 5 kg. of white spirit boiling from 110 to 160 C. and containing 1.5 kg. of lauroylmonoethanolamide and 1.5 kg. of calcium mixed petroleum hydrocarbon sulphonates having a molecular weight of 455-480 (Acto 450). The resulting water-in-oil emulsion was used in printing cotton piece goods.

Example 53 Alizarin Blue B (5 kg.) was dispersed in 80 kg. of water containing 5 kg. of glycerine, thus obtaining 85 kg. of an aqueous dyestufi dispersion. This dispersion was poured cautiously with stirring into a mixture of 5 kg. of Emulphor A Extra and 10 kg. of mixed petroleum aliphatic hydrocarbons boiling within the range from 110 to 200 C. The mixture was stirred at at least 2000 R. P. M. The water-in-oil emulsion which was obtained was applied by the pad dyeing process to a wool fabric. The fabric imbibed with the emulsion was dried and passed into a solution containing 10 g./l. of sulfuric acid at a temperature of 100 C. to develop and fix the dyestutf. This required 5 to 10 minutes.

The water-in-oil emulsion thus prepared can be transformed into a printing emulsion for printing wool piece goods either mechanically or by hand if 10 kg. of ammonium sulfate is added to the initial 85 kg. of aqueous dyestuif dispersion, before mixing with the emulsifier. The fabric printed with the emulsion is steam-treated and finished according to the conventional methods. The ammonium sulfate is capable of developing an acid during the steam treatment in order to fix the dyestuff.

In place of the Alizarin Blue, Fast Direct Yellow Example 6 B Fast Light Yellow 26 (1.3 kg.) was dissolved in 84.75 kg. of water containing 0.25 kg. of sodium lauryl sulfonate. This was poured with vigorous stirring into a mixture of 4 kg. Emulphor A and 10kg. of white spirit. The water-in-oil emulsion thus formed was applied to.

nylon-woolen piece goods by the pad dyeing process. The fabric was impregnated and, without drying, immersed for 5 to 10 minutes in a solution containing 10 g./l. of sulfuric acid at 100 C. The fabric was then washed and finished.

The emulsion may be transformed into an emulsion suitable for fabric printing either mechanically or by hand, by dissolving in the initial aqueous dyestutf solu tion a salt capable of developing an acid during steam treatment, such as, for instance, 10 kg. of ammonium sulfate, before mixing with the mixture of emulsifier and white spirit. The fabric printed with the emulsion is then steam-treated and finished according to the conventional method.

In place of the Fast Light Yellow 2G, there can be used 1.3 kg. of Direct Fast Red 83L (Color Index No. 278). The remaining steps are the same. The Direct Red water-in-oil emulsion obtained is applied to the cotton piece goods to be dyed through a padder, then steamed in a conventional steamer for printing direct dyestuffs, washed and finished. The emulsion could also be used in printing, printing and dyeing processes being practically the same for direct dyestuffs.

Example 7B Chrome Black PV (Schultz dye table No. 234), 5 kg., was dispersed in kg. of water. The dispersion was poured into a mixture of 5 kg. Emulphor A Extra and 10 kg. of white spirit with high speed stirring. A waterin-oil emulsion was obtained, which was applied to cotton greige piece goods in a pad dyer. The padded cloth was developed without drying in a boiling solution of 10 g./l. of surfuric acid. The dye was fixed and developed in about 10 minutes. The fabric then was treated with bichromate according to the conventional procedure.

Example 8B Naphthol AS-RL (prototype No. 312), 4.2 kg. was dispersed in 4.2 kg. of glycerine and 76.6 kg. of water. This dispersion was poured with vigorous stirring into a mixture of 10 kg. of petroleum aliphatic hydrocarbons boiling within the range of 110 to 200 C. and 5 kg. of Emulphor A. The water-in-oil emulsion thus obtained was applied by the pad dyeing process to cotton piece goods, after which the fabric was dried and passed into a solution having the following composition: kg. of water, 3 kg. 36 B. caustic soda, 25 kg. anhydrous sodium sulfate. The bath was kept at 40 C., and the fabric held in the bath about 5 minutes. After this treatment the fabric was pressed out and coupled in a 0.5% solution of diazo Base K, and finished by the usual method.

Example 9B Naphthol AS (prototype No. 302), 15 kg., was dissolved in 835 liters of water and 30 kg. of 36 B. caustic soda. The caustic solution was cautiously poured with stirring into a mixture of 20 kg. oleoylmonoethanolamide, 20 kg. calcium mixed petroleum hydrocarbon sulphonates having a molecular weight. of 455 to 480 (Acto 450) and 80 kg. of white spirit.

The resulting water-in-oil emulsion was applied to cotton cloth through a padder and then dried. The dried cloth may be coupled with a base as described in Example 8B, or it may be printed with a diazo of a base using a conventional printing system.

Example 10B Fast Red KB base (prototype 270), 5 kg., was dissolved in 50 liters of boiling water containing 6 kg. of 20 B. hydrochloric acid. The solution was diluted with 54 kg. of water, and the temperature brought to 5 C. Sodium nitrite (2 kg.) dissolved in 10 liters of water was cautiously added, keeping the temperature at about 5 C. The

thus-obtained diazo compound was neutralized with 3.777

eaaa rso 21 kg;;of sodititnacetate and 2.5 kg. ofacetic acid dissolved in 2l-liters of water. The diazo solution was diluted with 7301;75 liters of water, keeping the temperature of 5 C., and then poured with stirring into a mixture of 7.5 kg; oleoylmonoethanolamide, 7.5 kg. lauroylmonoethanolamide, and 30 kg. of white spirit.

The resulting diazo Water-in-oil emulsion is very stable and can be used for dyeing as well as for printing cotton piece goods, naphtholated by conventional or emulsion processes, such as those in Examples 813 and 9B.

Example 11B Celliton Fast Red GCA (prototype 236), 3 kg., was dispersed in 85 liters of water. The dispersion was cautiously poured into a mixture of 2 kg. oleoylmonoethanolamide, 2 kg. lauroylmonoethanolamide (Onyxol 336) and 8 kg. of white spirit. The water-in-oil emulsion thus obtained was applied to fabrics made of acetate rayon, silk, nylon and other synthetic fibers by the pad dyeing process, or with a roll printing machine, or by screen printing. The fabric was dried and passed to steam treatment following the usual specification.

In place of steam treatment a hot treatment by a salt solution containing 100 kg. of water and 30 kg. of sodium sulfate can be used. a

The following examples, the C series, illustrate methods of application of the water-in-oil emulsions of the invention.

C SERIES Example 1C Cotton piece goods. in the greige state were passed through a pad mangle filled with the dyestufi emulsion of Example 1B at room. temperature. The fabric was imbibed with the emulsion and squeezed, reaching a final pickup of 65% by weight of the cloth. The cloth was passed through, a drier wherein the water and white spirit were evaporated. Then the cloth was rolled and treated in a jig containing an aqueous alkaline hydrosulfite solution (40 grams caustic soda, 25 grams sodium hydro? su-lfite and 20 grams sodium chloride per liter) at 60 C. for reduction and fixing of the dye on the cloth.

After the fourth passage of the dye through the jig bath, the dye was perfectly reduced. Only an unappreciable quantity of the dye left the fiber and passed into the bath.

The reducing bath was removed from the jig and a cold water bath substituted. The dyed cloth was passed through the cold water four times. Then the water was replaced with a bathcontaining potassium dichromate and acetic acid solution at 50 C. The dyed fabric was passed into this bath, which oxidized'and fixed the dye on. the cloth andpartially removed the emulsifying agent. Thereafter the cloth was washed, soaped, washed and dried in order to remove the remainder of the emulsifying agent and unfixed dyestuff.

The final dyed piece goods had a very even color and the dye had penetrated deeply into the fibers.

Example 2C Cotton piece goods in the greige state werepassed through a first mangle of a continuous dyeing apparatus containing the dyestufi emulsion of Example lB at room temperature." The cloth next passed into a dryer where the water and white spirit were evaporated, and thence into a second mangle containing an aqueous hydrosulfite solution havingthe composition of Example 10 kept at seconds, to develop the dyestufi, after which the dyed cloth:

was oxidized and washed'as described in Example 1C,

using boxes like Williams units. ,The dyed fabricwas, I

very evenly dyed and-contained no detectable quantities ofwhite spirit or emulsifying agent. There was practically 1 10 bleeding as of dyestutrin the treatments dyestulf emulsion-impregnated piece goods.

Example 3C Cotton flannel piece goods in the greige state were printed with the emulsion of Example 4B, using a roller printing machine with finely engraved rollers. There-- after the printed cloth was dried. The cloth was thenaged in a Mather Platt machine and oxidized, washed, soaped, washed and dried.

A perfectly level dyeing was obtained with a penetration of the dyestuff into the fiber that was so perfect that the flannel appeared to have been dyed in loose cotton or yarn form.

The dyeing was repeated, regulating the penetration of the dyestufi into the flannel to only half the depth of the flannel by adjusting the depth of the engraving on the cylinder of the roller printing machine. The flannel in the first pass was printed on one side with the emulsion of Example 4B. In the second pass it was printed on the other side with the same printing emulsion, using Indanthrene Blue RS (color index No. 1106) instead of the indanthrene Brilliant Green B described in the second paragraph of Example 63, after which. the flannel was steam treated in a conventional steamer used with direct dyestuffs, washed and finished.

The dyed cloth was very evenly dyed and the colors printed on the two faces were in no way intermingled, giving an interesting double-face efiect.

The principle of introduction of a dyestutf or of an intermediate for a dyestutf uniformly into the fibers of a cloth or yarn has been fully set forth in the above speciw troduction of materials other than dyestuffs, in lieu of or in addition to the dyestuffs, and with the same degree of success. The water-in-oil. emulsions of the invention can contain mothproofing agents, fungicides, bactericides, mildewproofing agents, water repellent agents and the like, in order to achieve supplemental and special effects.

The phrase water-in-oil is used in the generic sense to characterize the emulsions in the language familiar to those skilled in this art. It means that water is the dispersed internal, discontinuous phase, and the oil, in this instance the organic liquid, is the dispersant, external continuous phase.

The phrase consisting essentially of as employed in the claims means that the ingredients recited are the essential ingredients and that components may be included which do not alter the essential and desirable characteristics of the composition, but that componentsnot named which would interfere with the action of the composition are excluded. Such interfering components include,

among others, thickening agents, such. as cellulose derivaotherwise indicated, all parts and percentages of comv ponents of the emulsion are by weight of theentire emulsion.

This. application is a. continuation-impart of Serial No.

312,671, filed October 1, 1952 and. Serial No. 412,402, j

filed February 24, 1954, both now abandoned.

I claim:

1. A dyestuff emulsion especially suitable for dyeing and printing cloths and fibers, consisting of water as an internal discontinuous phase dispersed in an external continuous phase of from about 3 to about 25% of a volatile stable. inert. water-immiscible organic liquid having ,a boiling point within the range from about 60 toabout 220 C., the phases being emulsified by from about 0.05 to about 30% of an organic emulsifier selected from.

of the "23 the 'g'roup'consisting of emulsifiers defined by the follow ing general formulae:

where R is selected from the group consisting of aliphatic hydrocarbon groups having from about twelve to about eighteen carbon atoms and mixed aliphatic-aromatic groups attached to A through the aromatic nucleus and having one to five hydrocarbon groups, of which at least one has from six to about twelve carbon atoms and the others have from one to twelve carbon atoms, all attached to the aromatic nucleus, A is selected from the group consisting of ethereal oxygen, sulfur, and carboxylic ester groups, and x is a number representing the average number of alkylene oxide units, and is within the range from about 3 to about 31;

where R is an aliphatic hydrocarbon group having from about eight to about eighteen carbon atoms, 1 is or 1, n is an integer within the range from 0 to 8, x and y are each numbers representing the average number of alkylene oxide units and x is within the range from 1 to about 15, the sum of x and y is a number Within the range from about 2 to about 15, and A is selected from the group consisting of amino nitrogen atoms and amide groups;

where m and m represent the average number of oxyethylene units, and n the average number of oxypropylene units, the sum of m and m is within the range from to 41, and n is within the range from 17 to 31;

where n is l or 2 and R is an aliphatic hydrocarbon group having twelve to eighteen carbon atoms;

where R is an aliphatic hydrocarbon group having from twelve to eighteen carbon atoms, R and R are selected from the group consisting of hydrogen, a lower alkyl of from one to five carbon atoms and an amide polymer group, and B and X are selected from the group consisting .of inorganic and organic salt-forming cations and anions, and are present when the nitrogen is quaternary, and are absent when the nitrogen is trivalent; esters RCOOR of aliphatic polyhydric alcohols having from three to six carbon atoms and of polyhydric carbocyclic ethers having a ring selected from the group consisting of furan and pyran rings and two condensed furan rings, the polyhydric alcohols having at least one hydroxyl group for each three carbon atoms and aliphatic fatty acids having from eight to eighteen carbon atoms; petroleum sulfonates RSO M where R is selected from the group consisting of aliphatic and cycloaliphatic hydrocarbon radicals derived from petroleum and M is a salt-forming cation; polyvalent metal salts of higher fatty acids having from ten to eighteen carbon atoms, [RCOO],,M where RCOO is derived from an aliphatic fatty acid having from twelve to eighteen carbon atoms and M is a polyvalent metal cation and n is the valence of M; the higher quaternary ammonium salts:

two are short chain aliphatic saturated hydrocarbon groups of not over five carbon atoms, and X is a salt forming anion, and an amount of an organic dyestufi' to produce a dyeing or printing effect being dispersed in the water phase.

2. A dye emulsion in accordance with claim 1 in which the organic liquid is an aliphatic hydrocarbon.

3. 'A dye emulsion in accordance with claim 2 in which the organic liquid is petroleum ether.

4. A dye emulsion in accordance with claim 1 in which the organic liquid is an aromatic hydrocarbon.

5. A dye emulsion in accordance with claim 4 in which the organic liquid is toluene.

6. A dye emulsion in accordance with claim 1 in which the organicliquid is a cycloaliphatic hydrocarbon.

7. A dye emulsion in accordance with claim 6 in which the organic liquid is solvent naphtha.

8. A dye emulsion in accordance with claim 1 in which the organic liquid is a chlorinated hydrocarbon.

9. A dye emulsion in accordance with claim 1 in which the organic liquid is a ketone.

10. A dye emulsion in accordance with claim 1 in which the dyestufif is a direct dye.

11. A dye emulsion in accordance which the dyestufl is a vat dye.

12. A dye emulsion in accordance which the dyestufi is an acid dye.

13. A dye emulsion in accordance which the dyestufi is a naphthol dye.

14. A dye emulsion in accordance which the dyestufi is an acetate dye.

15. A dyestuff emulsion in accordance With claim 1 in which the emulsifier is a compound having the general structure with claim 1 in with claim 1 in with claim 1 in with claim 1 in where R is selected from the group consisting of aliphatic hydrocarbon groups having from twelve to eighteen carbon atoms and aralkyl groups having an aliphatic hydrocarbon group of from six to twelve carbon atoms attached to the aryl nucleus and attached to A through the aryl nucleus, A is selected from the group consisting of ethereal oxygen, sulfur, and carboxylic ester groups, and x is a number Within the range from about 3 to about 31.

16. A dyestuif emulsion in accordance with claim 1 in which the emulsifier is a compound having the structure where z is 0 or 1, n is an integer from 0 to '8, x is a number within the range from 1 to 15, the sum of x and y is within the range from 2 to 15, R is an aliphatic hydrocarbon group having from eight to eighteen carbon atoms, and A is selected from the group consisting of amino, nitrogen and amido a 17. A dyestufi' emulsion in accordance with claim 1 in which the emulsifier is a compound having the structure where n is 1 or 2 and R is an aliphatic hydrocarbon group having from twelve to eighteen carbon atoms.

18. A dyestufl emulsion in accordance with claim 1 in which the emulsifier is a compound having the structure R CONR R BX wherein R is an aliphatic hydrocarbon group having from twelve to eighteencarbon atoms, R and R are se-v lected from the group consisting of hydrogen, lower alkyl radicals of fronr one to five carbon atoms-andgamide polymer groups, and B and X are selected from the group consisting of organic and inorganic salt-forming cations and anions, are present when the nitrogen is quaternary, and are absent when the nitrogen is trivalent V 19. A dyestuii emulsion in accordance with claim 1 in which the emulsifier is a metal salt of sulfonated mixed aliphatic. petroleum hydrocarbons. g V

20. A dyestufi emulsion concentrate consisting of water as an internal discont-i-nuous phase dispersed in an external continuous phase of from about 3 to about 25% of a volatile stable inert water-immiscible organic liquid having a boiling point within the range from about 60 to about 220 C., the phases being emulsified by from about 0.05 toabout 30% of an organic emulsifier selected from the group consisting of emulsifiers' defined by the following general formulae:

where R is selected froin'the group consisting of aliphatic hydrocarbon groups having from about twelve to about eighteen carbon atoms and mixed aliphatic-aromatic groups attached. to A. through the aromatic nucleus and having one tofive hydrocarbon groups, of which at least one has from six to about twelve carbon atoms and the others have from one to twelve carbon atoms, all attached to the aromatic nucleus, A is selected from the group consisting of ethereal oxygen, sulfur, and carboxylic ester groups, and x is a number representing the average number of alkylene oxide units, and is within the range from about 3 toabout 31;

onnncrno zn where m and m represent the averagenumber of-oxyethylene units, and n the average number of oxypropylene units, the sum of m and m is within the range frpmlto 41, and n is within the range from IT to 3lj l. (autumn-n where n is 1 or 2 and'R is an aliphatic hydrocarbon group having twelve to eighteen carbon atoms;

R CONR R BX where R lis an aliphatic hydrocarbon group having from twelve to eighteen carbon atoms, R andR are selected from the group consisting of hydrogen, a lower alkyl of from one to five carbon atoms and anamide polymer group, and B and X are selected from the. group; com sisting of inorganic and organic salt-forming cations and anions, and are present when the nitrogen is quaternary, and are absent when the nitrogen is trivalent; esters RCOOR of aliphatic polyhydric alcohols having from three to six carbon atoms and of polyhydric carboxylic ethers having a ring selected from the group consisting of furan and pyran rings and two condensed furan rings, the polyhydric alcohols having at least one hydroxyl group for each three carbon atoms and aliphatic fatty acids having from eight to eighteen carbon atoms; petroleum sulfonates RSO M where R is selected from the group consisting of aliphatic and cycloaliphatic hydrocarbon radicals derived trom petroleum v; and M is a salt-formingcation; polyvalent metal salts of higher fatty acids having from ten to eighteen carbon atoms, [RCOO1,,M where RCOO is derived from an aliphatic fatty acid having from twelve to eighteen carbon-atoms and M is a polyvalent metal cation and n isthe valence of M; the higher quaternary ammonium salts:

where at least two of R R R and R are long. chain aliphatic saturated hydrocarbon radicals having from about eight to about eighteen carbon atoms, and at least two are short chain aliphatic saturated hydrocarbon groups of not over five carbon atoms, and X is a saltforming anion, and an organic dyestuff in a concentration too high for dyeing or printing dispersed in the water phase, said emulsion being adapted, upon dilution with a water-in-oil emulsion of water, volatile stable inert water-immiscible organic liquid and organic emulsifier in proportions within the limits of the concentrate, to form a dye emulsion suitable for dyeing and printing cloths and fibers.

21. A process for the preparation of a dye emulsion in accordance with claim 1 which comprises dispersing a dyestuff in Water and then dispersing the aqueous dyestufi dispersion thus obtained in a volatile stable inert water-immiscible organic liquid having a boiling point within the range from about 60 to about 220 C. in the presence of an organic emulsifier selected from the group consisting of emulsifiers defined by the following general formulae:

wherein R is an aliphatic hydrocarbon group having from about eight to about eighteen carbon atoms, 1 is O or 1, n is an integer within the range from 0 to 8, x and y are each numbers representing the average number of alkylene oxide units and. x is within the range from 1 to about 15; the sum of x and y is a number within'lhe range from about 2 to about 15, and A'is selected from the g'roup'consisting of amino nitrogen atoms and amide groups;

HO [CH CH O] m CH CH CH O [CH CH O] 'H where m and m represent the average number of oxyethylene units, and n the average number of oxypropylene units, the sum of m and m is within the range from 15 to 41, and n is within the range from 17 to 31;

R CONR R BX where R is an aliphatic hydrocarbon group having from twelve to eighteen carbon atoms, R and R are selected from the group consisting of hydrogen, a lower alkyl RCOOR of aliphatic polyhydric alcohols having from three to six carbon atoms and of polyhydric carboxylic ethers having a ring selected from the group consisting of furan and pyran rings and two condensed furan rings, the polyhydric alcohols having at least one hydroxyl group for each three carbon atoms and aliphatic fatty acids having from eight to eighteen carbon atoms; petroleum sulfonates RSO M where R is selected from the group consisting of aliphatic and cycloaliphatic hydrocarbon radicals derived from petroleum and M is a salt-forming cation; polyvalent metal salts of higher fatty acids having from ten to eighteen carbon atoms, [RCOO],,M where RCOO is derived from an aliphatic fatty acid having from twelve to eighteen carbon atoms and M is a polyvalent metal cation and n is the valence of M; the higher quaternary ammonium salts:

where at least two of R R R and R are long chain aliphatic saturated hydrocarbon radicals having from about eight to about eighteen carbon atoms, and at least two are short chain aliphatic saturated hydrocarbon groups of not over five carbon atoms, and X is a saltforming anion, the foregoing being in amounts to form an emulsion consisting of water as an internal discontinuous phase dispersed in an external continuous phase of from about 3 to about 25% of the organic liquid, the phases being emulsified by from about 0.05 to about 30% of the emulsifier, and the dyestuff being dispersed in the water phase.

22. A process for dyeing and printing cloths and fibers which comprises applying thereto a dye emulsion in accordance with claim 1, and applying a pressure sufficient to cause the emulsion to penetrate the fibers and color the same.

23. A process in accordance with claim 22 which includes fixing the dye on the treated material.

24. A process for dyeing and printing cloths to produce a double-face efliect, wherein the treated cloth is dyed with one dyestuff on one side and another dyestuif on the other, which comprises applying to one face of the material a dye emulsion in accordance with claim 1,

applying pressure to the material, the amount of emulsion and the pressure being suflicient to cause the emulsion to penetrate the fibers and color the same, but insuficient to penetrate to the other side of the cloth, applying to the other side of the cloth a similar emulsion containing a difierent dyestutf, applying pressure to the material, the amount of emulsion and the pressure being sufiicient to cause the emulsion to penetrate the fibers and color the same, but insuflicient to mingle with the other dyed portion of the cloth.

25. A process in accordance with claim 1 which ineludes-fixing the dye on the treated material.

26. A dye emulsion in accordance with claim 1 in which the dyestufi is a rapidogen dye.

27. A dye emulsion in accordance with claim 1 in which the dyestutf is a sulfur-carbazole dye.

28. A dyestufi emulsion in accordance with claim 1 in which the emulsifier is a compound having the structure' where n is an integer from 1 to 3, R is an aliphatic hydrocarbon radical having from eight to eighteen carbon atoms, A is the residue of a polyhydric alcohol having at least one hydroxyl group for each three carbon atoms, and x is a number within the range from 2 to 10.

29. A'dyestufi emulsion in accordance with claim 1 in which the emulsifier is an ester of an aliphatic polyhydric alcohol having fromthree to six carbon atoms and at least one hydroxyl group for each three carbon atoms and a higher aliphatic fatty acid having from eight to eighteen carbon atoms.

30. A dyestufi emulsion in accordance with claim 1 in which the emulsifier is a compound having the structure RCOO-CH-SOaM ROOO-CH:

where R is an aliphatic hydrocarbon group having from three to eight carbon atoms and M is a cation selected from the group consisting of alkali metal and alkaline earth metal cations.

31. A 'dyestufr emulsion in accordance with claim 1 in which the emulsifier is a quaternary ammonium salt having the formula RKIia R1 R; where at least two of R R R and R are aliphatic hydrocarbon radicals having from about eight to about eighteen carbon atoms and at least two of R R R and R are aliphatic hydrocarbon radicals having from one to five carbon atoms, and X is a salt-forming anion.

References Cited in the file of this patent V UNITED STATES PATENTS 1,275,771

OTHER REFERENCES Pharmaceutical Emulsions and Emulsifying Agents, by L. M. Spalton, published by Chemist and Druggist, London, 1950, pages 16-20 and 28-39.

Journal Society Dyers Colourists, for December 1951, pages 582-584. W I

U. S. DEPARTMENT OF COMMERCE PATENT OFFICE CERTIFICATE OF CORRECTION March 25, 1958 Patent No. 2,828,180

Francesco S'ertorio It is hereby certified that error appears in the printed specification of the above numbered patent requiring correction and that the said Letters Patent should read as oorreoted below.

Column 5, line 42, for "In GO l'luns'tod road L. G, Lundsted column 7, line 45, for "hydrocarbon" read me hydrocarbon -=-=5 column 8, lines 66 and 67, for "materail" read. material g, column 18., lines 42, 47, 59 and 65, for "R each ooourrenoe, read R e Signed and sealed. "this 6th day of May 1958,

(SEAL) Atteet:

KARL AXLIBE ROBERT c. WATSON attesting Officer I Conniasioner of Patents

Claims

1. A DYESTUFF EMULSION ESPECIALLY SUITABLE FOR DYEING AND PRINTING CLOTHS AND FIBERS, CONSISTING OF WATER AS AN INTERNAL DISCONTINUOUS PHASE DISPERSED INB AN EXTERNAL CONTINUOUS PHASE OF FROM ABOUT 3 TO ABOUT 25% OF A VOLATILE STABLE INERT WATER-IMMISCIBLE ORGANIC LIQUID HAVING A BOILING POINT WITHIN THE RANGE FROM ABOUT 60 TO ABOUT 220*C., THE PHASES BEING EMULSIFIED BY FROM ABOUT 0.05 TO ABOUT 30% OF AN ORGANIC EMULSIFIER SELECTED FROM THE GROUP CONSISTING OF EMULSIFIERS DEFINED BY THE FOLLOWING GENERAL FORMULAE: