US2173824A - Composition for printing textile fibers - Google Patents

Description

Patented SEP I93? Search Ragga PATENT OFFICE COMPOSITION FOR PRINTING TEXTILE FIBERS Ivan F. Chambers, Wilmington, Del., assignor to E. I. du Pont de Nemours & Company, Wilmington, Del., a corporation of Delaware No Drawing. Application March 17, 1937, Serial No. 131,525

6 Claims.

This invention pertains to an improved process for printing textile fibers and fabrics with vat dyes, and to vat dye compositions especially adapted for such purposes. More particularly it relates to the preparation of printing compositions containing a vat dyestuff and a material adapted to facilitate the printing operation. Still more particularly it relates to the preparation of printing pastes which contain materials adapted to facilitate the penetration of the dye during a printing operation. Still more particularly it relates to the printing of fabrics composed of. natural or artificial or mixed fibers, and particularly lustrous or. delustered regenerated cellulose fibers, with pastes containing agents which facilitate the printing operation. In a more limited sense it relates to vat dye powders or pastes containing agents which give improved penetration and levelness, and to fabrics printed with the above compositions.

By the term vat dyestufi as used hereinafter I refer to dyestuffs such as those of the anthraquinone, indigo, thioindigo and sulfur series which are capable of being reduced by the aid of alkaline hydrosulfite.

The fixation of vat colors on textile fabrics by reduction and subsequent oxidation is one of the most important dyeing procedures in the textile field. In calico printing, the reduction is effected partially or wholly when the printed material is subjected to the action of steam. During the steaming or aging operation the dyestuff is mechanically held on the cloth by a vehicle consisting of a starch, dextrin or other paste.

Printing compositions may contain the vat dyestuff in its oxidized form or its reduced, that is, the leuco form. A suitable printing composition may be prepared by mixing the dyestuff paste with a thickening containing an alkaline reacting substance and a reducing agent. As examples of alkaline' reacting substances may be mentioned potassium carbonate, sodium carbonate and sodium hydroxide. The reducing agents referred to may be an alkali metal aldehyde sulfoxylate, alkali metal hydrosulfite or glucose. The usual thickening agents are British gum (dextrin), starch and/or gum tragacanth. A small percentage of glycerin is usually added to the printing composition as an assistant.

Processes are also known which employ sta bilized water-soluble forms of the vat dyestuffs,

such as the leuco-esters of the vat dyestuif,

known as Indigosol colors. These colors are water-soluble and require no reducing agent. Application consists in impregnating the fabric with the color and fixing the dyestuff on the fiber by subsequent hydrolysis and oxidation.

In the processes just described and others, special assistants are generally added to the dyestufl composition or printing paste, to facilitate the dispersion of the dyestuff, penetration, reduction, oxidation, etc. The state of perfection, however, has not yet been attained, and the printer generally has to cope with such problems as poor penetration of the color into the fiber, low tinctorial yield, lack of brilliancy in the prints, specky or mottled prints. He is also quite restricted in the conditions of operation, and will frequently obtain inferior results if. the aging time is curtailed or if the percentage of reducing agent in the printing composition is appreciably reduced. In printing with the Water-soluble forms of the vat dyestuffs, the additional problem enters of obtaining deep shades. Light shades are, as a rule, obtained readily with leucoesters but only a few of the latter have sufiicient solubility and penetrating power to produce a satisfactory deep shade.

It is an object of this invention to provide a process for printing with vat dyestuffs which is characterized by the productionof uniform prints, free from speckiness, and of good penetration. It is a further object of. this invention to produce novel dyestufi compositions and/or printing pastes which are particularly adapted for the process aforementioned. It is a still further object of this invention to provide novel vat dyestufi compositions which possess good wetting, penetrating and dispersing power, and permit of efficient utilization of the color. ,A still further object'of this invention is to produce vat dye powders or grains which are essentially nonhygroscopic and which possess good wetting, penetrating and dispersing power. A still further object is to produce prints of exceptional strength, brilliancy, penetration on natural and particularly on lustrous and delustered regenerated cellulose fibers. Another object is to produce dyeings of exceptional levelness, penetration, strength and brilliancy by the pigment-pad method or by continuous or intermittent machine method. Other and further objects of this invention will appear hereinafter.

These and other objects are accomplished by incorporating into a dyestuff composition benzyl alcohol. In a more limited sense they are accomplished by incorporating into a printing paste, directly or by way of first mixing with the vat dyestufi, benzyl alcohol. In a still more limited sense they are accomplished by incorporating into a dye composition containing a printing assistant, and more particularlyaprinting assistant having wetting properties, benzyl alcohol.

While good results are obtained when benzyl alcohol is added to any printing composition containing a dyeing ingredient, improved results are obtained if a sulfonated textile assistant having wetting and dispersing properties is added to the composition together with the benzyl alcohol. Excellent results are obtained if the sulfonated textile assistant is Turkey red oil and/or a watersoluble alcohol sulfate having from six to twelve carbon atoms in which the radical attached to the sulfate group contains a straight chain of not more than six carbon atoms.

In the preferred embodiment of the invention, they are accomplished by incorporating into a printing paste, directly or by way of first mixing with the dyestuif, a mixture of assistants of the following general composition:

Per cent Benzyl alcohol 0.1 to 20 Turkey red oil 1.0 to 40 One or more water-soluble alcohol sulfates as subsequently de scribed 1.0 to 40 Diluent such as water, British gum,

starch, sugar, glucose, etc 97.9 to 0 Each of the components of the above mixture exerts a specific assistant effect in that one component cannot be successfully substituted for another component. The collective assistant eifect obtained from the mixture is more advantageous for our purpose than the effect obtained from the individual components.

The water-soluble alcohol sulfates referred to above contain not less than six and up to twelve carbon atoms per molecule, but in which the radical attached to the sulfate group does not contain a straight chain of more than six CH2 groups.

Typical and most available compounds of the above general definition are the mono-sodiumsulfates of the higher alcohols obtained as byproducts in the synthetic manufacture of methanol. The latter process generally involves catalytic hydrogenation of mixtures of carbon monoxide and carbon dioxide. But in addition to the main desirable product, methanol, and in addition to other organic compounds of low molecular weight, such as ketones and alcohols below amyl, there is generally obtained a series of byproduct branched alcohols, having a total of from seven to twelve carbon atoms. These alcohols are usually not isolated individually, nor is such individual isolation necessary for the purpose of this invention. Instead, the entire mass of by-products is separated into fractions according to boiling point.

The fractions which I found most useful for the purpose of this invention have, as alcohols, the following boiling ranges and dominant composition. For the sake of facility, I shall herein designate them and later refer to them as fractions A, B, C and D.

However, I named these fractions above as the preferred compounds for my invention merely because of their ready availability and cheapness. If available, the individual constituents of the above fractions may be used in pure form. As typical compounds of this series may be mentioned the following individual compounds or mixtures thereof: 4 methyl- 1 -pentanol; 2- methyl-l-pentanol; 2,4-dimethyl-1-pentanol; 3- methyl-2-pentanol; 2,4 dimethyl 3 pentanol (di-isopropyl-carbinol) 2-methyl- 3 -pentanol; 4-methyl-l-hexanol; 2,4-dimethyll hexanol; 2,5-dimethyl-3-hexanol; and numerous others.

It will be noted that the parent alcohols may be primary or secondary. It will be noted further that they are all characterized by containing no long chains at all, or else containing a long chain loaded with side chains.

I found that best results are obtained with compounds wherein the direct chain between the sulfated alcohol function and the nearest branching point is not longer than four, or at most six carbon atoms.

As for the sulfate group, it may be neutralized by a cation which does not impair the watersolubilizing tendencies of the sulfate function. Such cations are the alkali metals, for instance sodium or potassium, and water-soluble organic bases, especially those which contain free OH groups or other groups conferring water-solubility. Examples of such organic bases are the mono-, dior tri-alkylamines, mono-, dior triethanolamine, the corresponding propanolamines, the butanolamines, cyclohexylamine, cyclohexyl-monoor di-ethanolamine, dimethylethanolamine, n-butylamine, guanidine, tetraethylammonium hydroxide, glucamine, n-methylglucamine, diglycerylamine, 1,3-diamino-n-propanol, l-amino-propane-diol, etc.

My invention does not require the use of the above novel assistants exclusively, but on the contrary other assistants of the customary and well known types may be added, and indeed are often very desirable. These subsidiary assistants may be incorporated into the eventual printing paste in any desirable manner. For instance, they may be mixed with the benzyl alcohol of this invention to produce an assistant preparation for the convenient use of the printer. Or they may be incorporated by the dyestuff manufacturer jointly with the benzyl alcohol or mixtures of the same with sulfonated textile assistants having wetting and dispersing properties, directly into the dyestuff preparation, to be marketed thus as a color preparation especially suited for printing. Or one of the assistants may be incorporated into the dyestuff while the other is incorporated into the thickening paste or reducting preparation eventually mixed with the dyestuff.

Among these additional or subsidiary assistants may be mentioned wetting and dispersing agents, reducing agents, reducing catalysts, emulsifying agents, lubricants, inert solid or liquid diluents, etc. The individual representatives of these various classes are well known in the art of printing, and it will be sufficient for the purpose of illustration to name here but a few typical members: for instance, sodium benzyl sulfanilate, isopropyl-naphthalene sodium sulfonate, diethylene glycol, sodium oleate, pine oil, glucose, sucrose, dextrine, sodium carbonate, so-

dium hydrosulfite, sodium sulfoxylate formaldehyde, hydroxy-alkylamines, tetralin sodium sulfonate, tetralin, hexalin, glycerin, etc. As sub- 8. BLEACHWG s DYElNG; Hum

TREATHEN? & CHEs'iiZCAL t-"zODlFl- CATION F TEXTILES & FiBERS,

sidiary assistants not heretofore commonly employed in this art may be mentioned the free alcohols corresponding to the sulfates of this invention, especially the methanol by-products above mentioned, and the carboxylic acids obtained by the oxidation of these fractions, as more particularly described in U. S. Patent 1,856,263 and copending application of Hans C. Duus, Serial No. 735,297.

The sulfuric acid esters or sulfates of the above defined alcohols, forming the major object of this invention, may be prepared in well known manner. A convenient and practically universal method is to react the corresponding alcohol with from 65% to 100% of theory (based on the hydroxyl number) of chlorosulfonic acid, and then neutralizing with the desired inorganic or organic base. The resulting aqueous solution may be used directly, without troubling to isolate the alkylsulfate. The residual free alcohol, where a deficiency of chlorosulfonic acid is employed, is not a detrimentas has already been indicated.

The concentration of the new assistant mixture and the method of application may vary within wide limits depending on the desired results or convenience. The following general procedures may be used:

(a) Addition of an aqueous solution or stable emulsion to the printing composition;

(b) Addition of a dry assistant mixture to the printing composition;

(0) Addition of a dry assistant mixture containing a diluent such as sugar, starch, glucose, or British gum;

((1) Preparation of an assistant color paste whereby the vat color pigment or leuco sulfuric ester derivative is intimately mixed with an aqueous solution or stable emulsion;

(6) Preparation of an assistant color powder whereby the vat color pigment is intimately mixed with a dry assistant mixture and/or an inert diluent such as sugar, starch, glucose, or British gum.

The proportion of assistant with respect to the weight of the printing paste may likewise vary within wide limits, good results being obtained with proportions from 0.1 to 20.0%, and preferably from to 20%, depending on the composition used.

Where these assistants are incorporated in the marketable dye composition, the latter may be prepared in paste form or dry, for instance powder, grains or flakes, with suitable diluents such as sugar, starch, glucose, British gum, etc., as most convenient.

Without limiting this invention the following examples are given to illustrate my preferred mode of operation. Parts are by weight.

EXAMPLE I Illustrating preparation of the thickening pastes.

Thickening SBG 100 parts of wheat starch and 300 parts of British gum were pasted with 600 parts of water 1000 parts This mixture was heated at the boil for ten minutes and cooled to room temperature. A smooth paste was obtained.

eh Room Thickener A 560 parts of Thickening SBG were heated to 170 F. There were then added 170 parts of potassium carbonate. After the potassium carbonate had dissolved, the paste was cooled to 140 F. and the following ingredients added 120 parts of sodium sulfoxylate formaldehyde 50 parts of glycerin 100 parts of water 1000 parts The whole was stirred to form a smooth paste.

Thickener B 550 parts of Thickening SBG 50 parts of potassium carbonate 250 parts of caustic soda (35% solution) 150 parts of glucose 1000 parts Thickener C 520 parts of Thickening SBG were heated to 170 F. There were then added 200 parts of potassium carbonate. The paste was cooled to 140 F. and the following ingredients added 180 parts of sodium sulfoxylate formaldehyde 50 parts of glycerin 50 parts of water 1000 parts The following examples illustrate the preferred embodiment of my invention.

EXAMPLE II 20 parts of Sulfanthrene Orange R Paste (Color Index #1222) were mixed with 78 parts of Thickener A. To this were added 2 parts of benzyl alcohol 100 parts Lustrous and titanium dioxide delustered rayon piece goods were printed with the above printing composition, dried and aged for five minutes at 214 F. in a rapid ager of the Mather Platt type. The printed material was then treated for one minute in an oxidizing bath at 140 F. containing 0.5% of sodium bichromate and 0.5% of acetic acid, rinsed in cold water, soaped for five minutes in a soap bath at 160 F. containing 0.5% of soap, rinsed and dried. Bright orange prints of exceptional penetration were obtained.

In the above example, the dyestuff may be replaced by any other vat dye of the indigoid, thioindigoid or anthraquinone series, as for instance, Ponsol Dark Blue BR. Paste (Color Index #1099), Sulfanthrene Blue 2BD Double Paste (Color Index #1184), Su1fanthrene" Pink FF Paste (Color Index #1211), Sulfanthrene" Violet B Double Paste (Color Index #1222), Ponso1" Yellow G Double Paste (Color Index #1118), Sulfanthrene" Yellow R Paste (Color Index #1170), Ponsol Brown AR Double Paste (Color Index #1151), Ponsol Blue GD Double Paste (Color Index #1113), Ponsol Golden Orange G Double Paste (Color Index #1096), Ponso1" Flavone GC Paste (Color Index #1095), Ponsol Blue BCS Double Paste (Color Index #1114), Ponsol" Jade Green Paste (Color Index #1101), and many others.

4 EXAMPLE III 20 parts of Ponsol Jade Green Paste (Color Index #1101) were mixed with 70 parts of Thickener C. To this were added 1 part of benzyl alcohol and 9 partsof Turkey red oil 100 parts Lustrous and ethylene glycol di-beta-napthyl ether delustered rayon piece goods were printed with the above printing composition, dried, aged, and developed as in Example II. A bright green print of exceptional uniformity and penetration was obtained.

EXAMPLE IV 15 parts of Sulfanthrene Blue 2BD Double Paste (Color Index #1184) were mixed with 60 parts of Thickener A as prepared in Example I 14 parts of Thickening SBG 3 parts of sodium hydrosulfite and 8 parts of a stable emulsion consisting of 25 parts of isopropyl naphthalene sodium sulfonate 60 parts of water and 15 parts of benzyl alcohol 1 00 parts E0 parts i The printing paste was heated to 140 F. during which the color was reduced to a considerable extent and then cooled to room temperature. Piece goods containing viscose rayon, Bemberg rayon, cellulose acetate rayon, and titanium dioxide delustered rayon fibers were printed with the above printing composition, dried and aged for five minutes at 218 F. After aging the print was immersed for two minutes in a bath at 130 F. containing 0.5% of sodium perborate and 0.5% of acetic acid. A brilliant blue dyeing of exceptional levelness and penetration on all types of fibers was obtained.

EXAMPLE V 20 parts of Ponsol Brilliant Violet RR Paste were mixed with 70 parts of Thickener C. To this were added 10 parts of a solution consisting of parts of diethylene glycol 15 parts of benzyl alcohol M) parts Id) parts Piece goods containing cotton, viscose rayon, cuprammonium rayon, and barium sulfate delustered viscose rayon fibers were printed with the above printing paste, dried and aged for five minutes at 216 F. The print was then developed as in Example II. A bright level violet print of exceptional color value and penetration was obtained.

EXAMPLEVI 5 parts of Sulfogene Fast Black CL (Indocarbon CL) were mixed with 5 parts of glycerin. To this was added 80 'partsof Thickener B as in Example I 3 parts of benzyl alcohol and '7 parts of Turkey red oil 50 parts Cotton, lustrous rayon, and titanium dioxide delustered rayon were printed with the above printing composition, dried, aged for five minutes at 214 F. and developed as in Example II. A brilliant and uniform print of excellent penetration to the reverse side of the fabric was obtained.

' EXAMPLE VII parts Starch tragacanth thickening 100 parts of wheat starch 360 parts of gum tragacanth (6% solution) 540 parts of water 1000 parts Heated at the boil for 15 minutes, cooled.

Piece goods containing cotton, lustrous and titanium dioxide delustered rayon were printed with the above printing composition, dried, and aged for six minutes in the rapid ager. After aging the material was rinsed, soaped for five minutes at 160 F. in a 0.5% soap solution, rinsed, and dried. A brilliant level blue dyeing showing exceptional penetration of color to the reverse side of the fabric was obtained.

EXAMPLE VIII parts of Sulfanthrene Orange R Paste (Color Index #1217) were mixed with parts of benzyl alcohol parts. There were then evaporated parts of water producing parts of Assistant Sulfanthrene Orange R Paste The above was milled in a colloid mill producing a finely dispersed assistant dyestuff paste adapted for handling in commerce.

EXAMPLE IX 100 parts of Ponsol Blue GD Double Paste (Color Index #1113) were mixed with parts of Turkey red oil and parts of benzyl alcohol There were then evaporated of water producing parts. parts parts of Assistant Ponsol Blue GD Double Paste The above was milled for one hour in a rod mill producing a finely dispersed assistant dyestufi paste, especially suitable for printing rayon.

"a UllE/(HES Si H5555 EXAMPLEX 100 parts 100 parts Fabrics containing (a) cotton and lustrous viscose rayon, (b) lustrous and titanium dioxide delustered viscose rayon, (c) lustrous and titanium dioxide delustered cellulose acetate rayon were printed with the above printing composition, dried, and aged for five minutes at 214 F. in a rapid ager of the Mather Platt type. The printed materials were then treated for one minute in an oxidizing bath at 140 F. containing 0.5% of sodium bichromate and 0.5% of acetic acid, rinsed in cold water, soaped for five minutes in a soap bath at 160 F. containing 0.5% of soap, rinsed, and dried. Brilliant level prints were obtained on all fabrics according to the pattern of the printing roll. The prints were very sharp in outline and showed exceptionally good penetration to the reverse side of the fabrics.

In the above example, Assistant A is a 30% aqueous solution of mixed sodium alkyl sulfates obtained by the sulfation of a mixture of Ce primary and 01 secondary alcohols (B. P. 133- 150 C.).

Assistant A may be substituted with equally good results by Assistants B, C or D, as described below. Assistant B is a 30% aqueous solution of mixed sodium alkyl sulfates obtained by the sulfation of a mixture of C7 primary and Ca secondary alcohols (B. P. 150-160 0.).

Assistant is a 30% aqueous solution of mixed sodium alkyl sulfates obtained by the sulfation of a mixture of C8 to C10 primary and secondary alcohols (B. P. 160-200 C.).

Assistant D is a 30% aqueous solution of mixed sodium alkyl sulfates obtained by the sulfation of a mixture of C10 and above, primary and secondary alcohols (B. P. 200-260 0.).

In the above example, the dyestufis may be replaced by other vat colors of the indigoid, thioindigoid, or anthraquinone series, for instance Sulfanthrene Red 33 Paste (Color Index #1212), Sulfanthrene Blue 2BD Paste (Color Index #1184), Sulfanthrene Violet B Paste (Color Index #1222), Sulfanthrene Pink FF Paste (Color Index #1211), Sulfanthrene Scarlet Y Paste (Color Index #1228), Sulfanthrene Yellow R Paste (Color Index #1170), Sulfanthrene Brown G Paste (or Ciba Brown G Paste), Ponsol Blue GD Double Paste (Color Index #1113) Ponsol Flavone GC Paste (Color Index #1095), Ponsol Jade Green Paste (Color Index #1101), Ponsol Golden Orange G Double Paste (Color Index #1096), Ponsol Brown AR Double Paste (Color Index #1151), Ponsol Yellow G Double Paste (Color Index #1118), Ponsol Blue BCS Double Paste (Color Index #1114), Ponsol Dark Blue BR Paste (Color Index #1099), Ponsol Violet RRD Paste (Color Index #1104), "Ponsol" Blue Green FFB Double Paste (Color Index #1173), and many others.

Search Room Exmu: XI

50 parts of Ponsol Dark Blue BR (Color Index #1099) press cake containing 26% color solids were mixed with 1 part of formaldehyde-naphthalene sulfonic acid condensation product (30% solution) 40 parts of diethylene glycol and 9 parts of benzyl alcohol 100 parts The above was milled for twelve hours in a ball mill forming a smooth homogeneous assistant dyestufi paste.

EXAMPLE XII The procedure was the same as in Example X except that 70 parts of Thickener B were substituted for '70 parts of Thickener A. Prints of exceptional brilliancy, levelness and penetration to the reverse side of the fabrics were obtained.

Assistants B, C or D may be substituted for Assistant A with equally good results.

Sulfanthrene Orange R Paste may be substituted by the other vat colors mentioned in Example X with equally good results.

EXAMPLE XIII 15 parts of Sulfanthrene Blue 2BD Paste (Color Index #1184) were mixed with 60 parts of Thickener A as prepared in Example I 17 parts of Thickening SBG 3 parts of sodium hydrosulfite and 5 parts of a stable emulsion consisting of 45 parts of Turkey red oil 40 parts of Assistant B 15 parts of benzyl alcohol 100 parts 100 parts The printing paste was heated to 140 F. during which the color was reduced to a considerable extent and then cooled to room temperature. Piece goods containing viscose rayon, Bemberg rayon, cellulose acetate rayon and titanium dioxide delustered rayon were printed with the above printing composition, dried and aged for five minutes at 218 F. After aging, the print was immersed for two minutes in a bath at 130 F. containing 0.5% of sodium perborate and 0.5% of acetic acid. A brilliant blue dyeing of exceptional levelness and penetration on all types of fibers was obtained.

EXAMPLE IHV 5 parts of Sulfogene Fast Black CL (Indocarbon CL) were mixed with 5 parts of glycerin. To this were added 80 parts of Thickener B as in Example I and parts of a stable emulsion consisting of 20 parts of Turkey red oil 60 parts of Assistant B 20 parts of benzyl alcohol 100 parts 100 parts Cotton, lustrous rayon, and titanium dioxide delustered rayon were printed with the above printing composition, dried, aged for five minutes at 214 F. and developed as in Example X. A brilliant and uniform print of excellent penetration to the reverse side of the fabric was obtained.

EXAMPLE XV 5 parts of Indigosol 04B (leuco sulfuric ester derived from Ciba Blue 2BD-Color Index #1184) were mixed with 5 parts of Cellosolve (ethylene-glycol-monoethyl-ether) 5 parts of a stable emulsion consisting of 10 parts of Turkey red oil parts of Assistant B 10 parts of benzyl alcohol 100 parts 17 parts of warm water (160 F.) and 58 parts of neutral starch tragacanth thickening. There were then added 4 parts of ammonium sulfocyanide (50% solution) 4 parts of sodium chlorate (23% solution) 1 parts of ammonium vanadate (1% solution) 1 part of ammonia (25% solution) 100 parts Starch tragacanth thickening 100 parts of wheat starch 360 parts of gum tragacanth (6% solution) 540 parts of water 1000 parts Heated at the boil for 15 minutes, cooled.

Piece goods containing cotton, lustrous and titanium dioxide delustered rayon were printed with the above printing composition, dried and aged for six minutes in the rapid ager. After aging, the material was rinsed, soaped for five minutes at 160 F. in a 0.5% soap solution, rinsed and dried. A brilliant level blue dyeing showing exceptional penetration of color to the reverse side of the fabric was obtained.

EXAMPLE XVI 20 parts of Ponsol Violet RRD Paste (Color Index #1104) were mixed with 65 parts of Thickener C. To this were added 15 parts of a stable emulsion consisting of 40 parts of Turkey red oil 55 parts of Assistant C 5 parts of benzyl alcohol 100 parts 100 parts Piece goods containing cotton, viscose rayon, cuprammonium rayon, and ethylene-glycol-dibeta-naphthyl-ether delustered rayon were printed with the above printing composition, dried, aged for two and one-half minutes at 214 F. and developed as in Example X. Although the aging time was curtailed, a bright violet print of exceptional strength, brilliancy and penetration to the reverse side of the fabric was obtained.

Equally satisfactory results may be obtained by employing the triethanolamine salts of the alkyl sulfuric acids included in Assistant C rather than the sodium salts.

EXAMPLE XVII 20 parts of Sulfanthrene Pink FF Paste (Color Index #1211) were mixed with 70 parts of Thickener C. To this were added 10 parts of a stable emulsion consisting of 30 arts of Turkey red oil 62 parts of Assistant D 8 parts of benzyl alcohol 100 parts 100 parts Piece goods containing cotton, cuprammonium rayon, and cellulose acetate fibers were printed with the above printing composition, dried, aged, oxidized, soaped, and finished according to the procedure described in Example X. A brilliant red print was obtained which was sharp in outline and which showed exceptional penetration to the reverse side of the fabric.

EXAMPLE XVIII 100 parts of Sulfanthrene Orange R Paste (Color Index #1222) were mixed with 40 parts of Assistant B and 20 parts of Turkey red oil 160 parts. There were then evaporated 65 parts of water producing parts. There were then added 5 parts of benzyl alcohol producing parts of Assistant Sulfanthrene Orange R Paste The above was milled in a colloid mill producing a finely dispersed assistant dyestuff palste adapted for handling in commerce.

Instead of Sulfanthrene Orange R Paste the following colors were employed with equally good results: Sulfanthrene Pink FF Paste (Color Index #1211), Sulfanthrene Scarlet Y Paste (Ciba Brown G Paste), Sulfanthrene Brown G Paste (Color Index #1212), Sulfanthrene Blue 2BD Paste (Color Index #1184), Ponsol Jade Green Paste (Color Index #1101), and Ponsol Flavone GC Paste (Color Index #1095).

EXAMPLE XIX EXAMPLE XX An easily dispersible vat color powder suitable for printing and dyeing was prepared as follows: 75

uLLnuw-iu UILIWU; l'LUlU TREAUFJZF & CHEMICAL MODF- 100 parts of Sulfanthrene Blue 213D Paste (Color Index #1184) were mixed with 25 parts of Assistant B 2 parts of Turkey red oil 1 part of benzyl alcohol 36 parts of British gum 36 parts of sucrose 200 parts Evaporated to dryness and milled the dry mass for eight hours in a rod mill, producing an easily dispersible powder.

Instead of Sulfanthrene Blue 2BD Paste, the colors mentioned in Example X may be employed with equally good results.

EXAMPLE XXI An easily dispersible vat color powder suitable for printing and dyeing was prepared as follows:

100 parts of Sulfanthrene Pink FF Paste (Color Index #1211) were mixed with 36 parts of Assistant A 4 parts of Turkey red oil -2 parts of benzyl alcohol 5 parts of sodium carbonate 147 parts. Evaporated to dryness and added 31 partls of British gum and 31 parts of refined glucose The above was mechanically mixed and then milled for ten hours in a ball mill, producing an easily dispersible powder. Instead of Sultanthrene Pink FF Paste, the colors mentioned in Example X may be employed with equally good results.

This invention has the advantage that vat dye printing compositions may be easily and economically prepared. A further advantage resides in the feature that prints characterized by unusual penetration to the reverse side of the fabric may be easily obtained. A still further advantage resides in the fact that prints which are free from specks, mealy or mottled effects may be obtained on a commercial bcale with facility. The advantages gained are more noticeably apparent in heavy shades than in light shades. This invention has the still further advantage that unusual Search Room penetration of the dye is obtained in printing both lustrous and delustered rayon fabrics.

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

I claim:

1. A dye composition for printing containing in addition to a vat dye ingredient, benzyl alcohol and at least one sulfonated textile assistant taken from the group consisting of Turkey red oil and water-soluble sulfates of aliphatic alcohols having from 6 to 12 carbon atoms in which the radical attached to the sulfate groups contains not more than 6 carbon atoms in a chain.

2. A dye composition for printing containing in addition to a vat dye ingredient, benzyl alcohol and Turkey red oil.

3. A dye composition for printing containing in addition to a vat dye ingredient, benzyl alcohol and a water-soluble sulfate of an aliphatic alcohol having from six to twelve carbon atoms in which the radical attached to the sulfate group contains not more than six carbon atoms in a chain.

4. A dye composition of the type set forth in claim 3 containing from 0.1 to 20.0% of benzyl alcohol.

5. A dye composition containing a vat dye, from 0.1 to 20% of benzyl alcohol, from 1 to 40% of a water-soluble sulfate of an aliphatic alcohol having from six to twelve carbon atoms in which the radical attached to the sulfate group contains not more than six carbon atoms in a straight chain, and from 1 to 40% of Turkey red oil.

6. A dyestufl composition especially adapted for printing on lustrous and delustered regenerated cellulose fibers containing a vat dye ingredient, in finely divided form, and from 5 to 20% of benzyl alcohol, and at least one sulfonated textile assistant taken from the class consisting of Turkey red oil and water soluble sulfates of aliphatic alcohols having from 6 to 12 carbon atoms in which the radical attached to the sulfate groups contains not more than 6 carton atoms in a chain.

IVAN F. CHAMBERS.

CERTIFICATE OF CORRECTION. Patent No. 2,173,82LL. September 26, 1959 IVAN F, CHAMBERS.

It is hereby certified that error appears in the printed specification of the above numbered patent requiring correction as follows: Page 2, second'column, line 58, for "reducting" read reducing; page 5 first column, line 5, Example X, for "79 parts" read 70 parts; page 6, first column, line 25, Example XV, for "l parts'f read 1 part; page 7, second column, line b8, claim 6, for the word "carton" read carbon; and that the said Letters Patent should be read with this correction therein that the same may conform to the record of the case in the Patent Office.

Signed and sealed this lhth day of November, A. D. 1959 Henry Van Arsdale, (Seal) Acting Commissioner of Patents.