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

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

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US2828180A
US2828180A US488420A US48842055A US2828180A US 2828180 A US2828180 A US 2828180A US 488420 A US488420 A US 488420A US 48842055 A US48842055 A US 48842055A US 2828180 A US2828180 A US 2828180A
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parts
water
brown
emulsion
indanthrene
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Sertorio Francesco
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ANONIMA ITALIANA COLORI E AFFI
ANONIMA ITALIANA COLORI E AFFINI Soc
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
    • C09B67/0071—Process features in the making of dyestuff preparations; Dehydrating agents; Dispersing agents; Dustfree compositions
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
    • C09B67/0071—Process features in the making of dyestuff preparations; Dehydrating agents; Dispersing agents; Dustfree compositions
    • C09B67/0084—Dispersions of dyes
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/22—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using vat dyestuffs including indigo
    • D06P1/224—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using vat dyestuffs including indigo using vat dyes in unreduced pigment state
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/90—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using dyes dissolved in organic solvents or aqueous emulsions thereof
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/90—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using dyes dissolved in organic solvents or aqueous emulsions thereof
    • D06P1/92—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using dyes dissolved in organic solvents or aqueous emulsions thereof in organic solvents
    • D06P1/922—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using dyes dissolved in organic solvents or aqueous emulsions thereof in organic solvents hydrocarbons
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/90—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using dyes dissolved in organic solvents or aqueous emulsions thereof
    • D06P1/92—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using dyes dissolved in organic solvents or aqueous emulsions thereof in organic solvents
    • D06P1/922—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using dyes dissolved in organic solvents or aqueous emulsions thereof in organic solvents hydrocarbons
    • D06P1/926—Non-halogenated hydrocarbons
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/90—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using dyes dissolved in organic solvents or aqueous emulsions thereof
    • D06P1/92—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using dyes dissolved in organic solvents or aqueous emulsions thereof in organic solvents
    • D06P1/928—Solvents other than hydrocarbons
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P5/00—Other features in dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form
    • D06P5/001—Special chemical aspects of printing textile materials

Definitions

  • 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.
  • 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.
  • 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.
  • dispersed and dispersion as used herein in the specification and claims are inclusive of true solutions and of stable dispersions.
  • 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.
  • the penetration of the fiber or clothby the dyestufi is a function of the pressure applied through the padder or printing rollers.
  • the amount of emulsion applied to the cloth by the depth of the engraving on the printing roller also is a factor.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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 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.
  • any stable volatile organic liquid which 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 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.
  • 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.
  • the chlorinated 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.
  • 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. 105ens, Die Neuesten Fortriene in der für 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).
  • Sulfur dyes and sulfur carbazole dyes such 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.
  • 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).
  • a variety of chemically different organic emulsifiers are suitable.
  • 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:
  • 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.
  • the emulsifiers have the following structure:
  • 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.
  • the emulsifiers When A is oxygen and R is an aralkyl group, the emulsifiers have the following structure:
  • 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
  • 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.
  • the emulsifiers When A is an ethereal oxygen atom and R is an aliphatic hydrocarbon radical, the emulsifiers have the following structure:
  • x preferably is a number within the range from 3 to 24 and R preferably has from twelve to eighteen carbon atoms.
  • the emulsifiers When A is a sulfur atom the emulsifiers have the following structure:
  • 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
  • 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.
  • the emulsifiers take one of the following two forms:
  • a third class of emulsifiers which can be employed in accordance with the invention has the general structure:
  • n 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:
  • a fifth class of emulsifiers are the fatty amides and amide polymers, including quaternary amides:
  • 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
  • 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.
  • V(a) R CONH R CONR R can be a radical of an amide polymer, whereupon they take this structure:
  • the sixth class of emulsifiers are esters:
  • the Spans have the following general structure:
  • 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:
  • 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:
  • 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.
  • aliphatic hydrocarbon groups as R in the above formulae are n-octyl, tert.-octyl, nonyl, decyl,
  • 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;
  • organic liquid 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.
  • inorganic alkaline salts such as potassium' carbonate, sodium hydroxide, potassium hydroxide, mixtures of sodium and potassium carbonates and sodium and potassium hydroxides
  • 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.
  • 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.
  • 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).
  • 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.
  • cloth as used herein is inclusive of woven and unwoven cloths, textiles and fabrics as Well as knitted cloths
  • 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.
  • 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.
  • 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.
  • 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,
  • the emulsifying agent is removed and the dye is fixed onthe fiber so that only the dye remains.
  • 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 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.
  • 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.
  • 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).
  • 10 parts white spirit mixed aliphatic petroleum hydrocarbons, boiling range 110160 C.
  • 12 parts sodiumformaldehyde sulphoxylate 12 parts
  • 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 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 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 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
  • Vat Brown R Indanthrene Brown R
  • 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.
  • Indanthrene Brilliant Green B Schotz dye table No. 1269
  • 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.
  • 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.
  • a salt capable of developing an acid during steam treatment such as, for instance, 10 kg. of ammonium sulfate
  • 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 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
  • 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.
  • a hot treatment by a salt solution containing 100 kg. of water and 30 kg. of sodium sulfate can be used.
  • 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:
  • 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.
  • 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.
  • 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.
  • thickening agents such. as cellulose derivaotherwise indicated, all parts and percentages of comv ponents of the emulsion are by weight of theentire emulsion.
  • 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.
  • 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
  • x is a number representing the average number of alkylene oxide units, and is within the range from about 3 to about 31;
  • 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;
  • n 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;
  • n is l or 2 and R is an aliphatic hydrocarbon group having twelve to eighteen carbon atoms;
  • 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
  • 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
  • petroleum sulfonates RSO M where R is selected from the group consisting of aliphatic and cycloaliphatic hydrocarbon radicals derived
  • 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.
  • a dye emulsion in accordance which the dyestufi is an acid dye.
  • the emulsifier is a metal salt of sulfonated mixed aliphatic. petroleum hydrocarbons. g V
  • 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:
  • 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.
  • 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.
  • 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:
  • 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
  • x is a number representing the average number of alkylene oxide units, and is within the range from about 3 to about 31;
  • 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;
  • n is l or 2 and R is an aliphatic hydrocarbon group having twelve to eighteen carbon atoms;
  • 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
  • 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
  • X is a saltforming anion
  • 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.
  • 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,
  • 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.

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US3034850A (en) * 1959-03-20 1962-05-15 Metro Atlantic Inc Process of dyeing with vat dyes
US3046076A (en) * 1959-08-25 1962-07-24 Burlington Industries Inc Process for coloring polyolefinic textile materials
US3211512A (en) * 1961-05-25 1965-10-12 Ciba Ltd Paraffin oil dye assistant and wool dyeing therewith
US3468620A (en) * 1961-08-11 1969-09-23 Geigy Ag J R Process for the dyeing of polyamide fibers
US3236583A (en) * 1962-01-25 1966-02-22 Bayer Ag Polyester dyeing with a dye solution containing polyalkylene oxide ether of phenols and a fatty acid ester of polyalkylene oxides
US3519377A (en) * 1962-02-08 1970-07-07 Teijin Ltd Printing polyester textiles with a disperse dye paste containing an alkyl amide or alkylene diamide
US3281201A (en) * 1962-06-22 1966-10-25 Gen Aniline & Film Corp Process for dyeing of nylon fibers with premetallized and acid dyestuffs
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GB733099A (en) 1955-07-06
CH307607A (fr) 1955-06-15
NL175307B (nl)
DE958380C (de) 1957-02-21

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