US1920987A - Process of dyeing - Google Patents

Description

Patented Aug. 8, i933 IPROCESS 01F DYEING Charles E. Kaltenbach, Cranford, N. 3.; Herman Muhlenbrock, Juana C. Kaltenbach, and lltoger W. Aldrich executors of said Charles E.

Kaltenbach, deceased No Drawing. Application August 15, 1928, Serial No. 299,878. Renewed December 24, 1932 6 Claims.

My invention relates more particularly to improvements in the dyeing of acetate silks but various features thereof will be found useful in various other fibres. The main advantage of the invention is to provide improvements in the dyeing art generally where it serves to extend the usefulness of certain dyes and dye components by extending the field of their applicability making them faster upon the fibre and rendering them capable of producing a greater variety of tones andshades at will than is now possible with a fixed number of dyestuffs.

Further and more specific objects, features and advantages will more clearly appear from the detailed description below.

It has been common in the application of dyes to acetate silk to use dispersing agents or materials capable of maintaining insoluble dyes in so fine a degree of suspension that they freely penetrate and affix themselves to the fibre and seem to be the more resistant to washing because of their insoluble character, excelling in fastness those congruous dyestuffs which are truly soluble during their application to the fibre. Sometimes these dispersing or emulsifying agents have been added by the dyemaker and actually incorporated with .the dyestuff itself in a proportion adapted for direct use in the dyebath. Sometimes they are added to the dye bath apart from the dyestuff and serve either to disperse it if it be insoluble in water and sometimes to both insolubilize and disperse it if it be originally a water soluble dye.

35 In the present invention there is provided a material which functions at one and the same time as a solubilizing and insolubilizing agent seeming to act in a cyclic manner and having the power of dissolving solid matter of gross particles and reprecipitating it in finely divided particles adapted for penetration of a fibre or fabric, the whole action being favorable for fast dyeing of the latter and notattended to any notable extent with a reversible or reciprocal action of dissolving the finer particles off the by distilling the stumps of pine trees (usually of the species Pinus palustris) by the action of steam. This affords an oil useful for various purposes and consisting in large proportions of terpineol. It is to be understood that the same product is derived from other members of the pine family besides Pinus palustris and may be derived from other parts of the tree, though possibly not having all the desirable qualities to the same extent as the product derived from stumps of Pinus palustris, and the use of the substantially equivalent prodnot derived from other sources is considered to be within the scope of my invention. I am aware that sulfonated oils such as Turkey red oil and combinations of the same with soap have been employed to disperse dyestuffs in dyeing acetate silks. I am also aware that certain organic solvents have been proposed as agents for the same purpose but these materials differ radically from the matter of the present invention. The Turkey red oil consists of sodium or ammonium salts of sulphoricinoleic acidand some unconverted castor oils, (a fat-like body) while the pine oil consists essentially of hydrocarbons allied to turpentine and is wholly different in its nature as well as its source. It differs entirely in its solvents and its own solvent power from Turkey red oil. It has been pointed out by many investigators that the dyeing of acetate silk is akin to the dyeing of hydrocarbon oil and here perhaps is an explanation of one of the functions and advantages of the pine. oil in that it first takes up the dyestuff and then passes it on the fibre which has a congruous but stronger afiinity than the oil for the color. Many other organic solvents which have been suggested as dispersing agents lack this similarity to acetate silk in affinity for dye which pine oil as a mixture of hydrocarbons has. Some of these organic solvents while suggested as dispersing agents affect the colors themselves, are true color components and often combine with the dyestuffs in unlocked for ways and lead to improper dyeing and waste or spoiling of the fabric.

Basic dyes especially in the form of bases freedfrom their usually associated acid radical are rendered applicable to acetate silk by the use of this agent and the dyeings are more intense than with the other dispersing agents now employed.

I have taken such acetate silk dyes as Rhodamine B base (DuP), C. I. 749, Malachite green base 0. I. 657, Auramine base C. I. 655, and numerous oil soluble colors and have successfully applied them to acetate silk by the use of my dispersing agent.

According to my invention in its preferred form I take an insoluble dyestufl, for example, known to be free froinany dispersing agent and I mix it by stirring well into pine oil and then into the salve-like emulsion of pine oil and soap. The dyestuif disperses perfectly and on adding water the resulting mixture is a complete solution or at least so finely divided in suspension that the colored liquid would go through a fine filter paper. Into a bath thus prepared of about oz. of dyestufl', about 6 oz. of pine oil soap salve-like emulsion and about 20 gallons of water was placed a one pound hank of acetate silk. I found that the dyestufi started drawing at once on the silk although the most active precipitation on the fibre showed at temperatures between 160 and 170 F. The exhaustion of the bath and precipitation on the fibre were superior to the results obtained by the dispersing agents sold for use with this color.

It was found that the dyestufi's mentioned above dyed on the fibers satisfactorily for which they were adapted. I found further that many dyes were improved by the addition of diand trisodium phosphates. I found in many cases that the addition of sodium hydrosulphite reduced many of the above dyestuffs and that subsequent oxidation in plain water by the atmosphere or by chlorine water or other oxidants resulted not only incolors faster to washing, but also enabled fibres not indicated for some of these dyestuffs, to draw almost as well as on the fibres for which said dyestuffs are indicated.

I have found that in the coupling of diazotized amines with phenols, naphthols, etc. that my pine oil emulsion makes the phenolic body operative as a developer without the addition of caustic soda. I am able not only to apply this to naphthoic acid derivatives such as beta-hydroxynaphthoic acid anilide. Naphthol ASSW (Gr. E.) believed to be beta-hydroxynaphthoic acid beta naphthalide but I am able to couple with amines-such as paranitraniline, etc. with similar advantageous results and thus avoid the deleterious effects of alkali or acid ordinarily necessary for the application of the coupling phenol or amine respectively.

According to the present invention and within its scope I may employ solubilized forms, with any of the solubilizing agents before referred to of any such other organic compounds) or coloring matters in or for the dyeing, printing or stenciling of threads, yarns, fibres, filament fabrics,

films or other products made of or containing.

acetyl cellulose or for making solid solutions, pastes, mixtures or concentrated preparations applicable therefor.

By way of example I may employ as solubilizing agents for the purpose pine oil, pine oil soap, or other terpenes, hydrocarbons of a nature and/or source similar to pine oil and I may use any or all emulsifying agents to replace the soap which have the same power of blending terpenes or liquid hydrocarbons with water when used in combination with the terpenes and hydrocarbons found in the destructive distillation of wood.

Many different dyestuffs of almost all classes have been tried and it was found practical to place all of the water insoluble dyestuffs into a water solution by the use bf the pine-oil-soap emulsion and advantages were discovered in the use of the material on all of the common fibres either in changing advantageously the dyeing properties of the color with respect to the particular fibre or in imparting to a regular dye recipe a greater degree of fastness, level dyeing character, speed of dyeing penetration or exhaustion of the bath. For example, Sulfur Bordeaux R, C. I. 1012 can be dyed with my dispersing agent on silk and viscose without alkali. Certain direct dyes not applicable to silk are rendered applicable by the use of my invention. Direct scarlet A, C. I. 326 and Direct black Ciba same as Diamine Fast black mentioned on page 349 of Color Index which are said to merely tint silk are by its use rendered good colors for this fibre. Direct green B, C. I. 593 not ordinarily adapted for silk dyes well and does not bleed after dyeing when heated in water to 170 F. These advantages on fibres other than acetate silk do not depend on the water insoluble character of the dyestufi but my dispersing agent aifects advantageously the soluble dyes also, not only single colors but, because of its leveling effect, it enables dyestuifs to be blended not hitherto advantageously employed in mixtures by reason of their unequal rates of exhaustion or diverse natural leveling power.

Wherever a color is applicable the invention leads to better penetration and leveling despite the increased speed and completeness of exhaustion. With skill and observation some hint as to the applicability of dye to any fibre can be had by the manner in which the dyestuif incorporates with the pine oil. A dye poorly soluble in pine oil is apt to give a better color on cotton than on viscose.

In adapting coloring matters to fibres it is to be understood that I do not limit myself to complete and true dyestuffs capable of yielding color at once to water in a true solution or in a disperse phase. I find it possible to use intermediates, color bases, coloring components not yet rendered soluble or advanced by sulfonation or otherwise to thestate of true dyestuffs as ordinarily understood. These by the operations of padding, coupling, mordanting, fixing with one or more agents producing these actions finally develop the color on the fibre and my dispersing agent can be used in all such operations. The coloring agent, which may be short of being a true dyestufl', as in the case of the base of a basic dyestuff or of sulphonated dyestuil's before sulphonation are by my process rendered capable of forming true colors by reason of the dispersing character of my pine-oil compound, its ability to simulate on the fibre the effect of the solubility ordinarily attained by sulfonation or the conversion of basic dye bases, not ordinarily dyes, to their color salts,-true dyes; this, because of the acidic character of the acetate silk and its power of functioning as a component in the assembly of a final true color by combining with the basic color base to form a structurally rooted dye acetate or in furnishing to a color component ordinarily requiring sulfonation for its completion an acetate radical which functions similarly.

The advantages of my use of pine oil emulsions in the phenolic couplings of diazotized bodies are pronounced and of broad application. Not only does it serve well in preventing the bad effect of caustic on acetate silk but it is equally good for natural silk and protects its strength and lustre. allows the coupling on either fibre to take place at a higher temperature, thus securing a better penetration, and if the naphthols or phenolic bodies are used in the padding style, that is applied to the fibre before diazotization, a much more even dyeing can take place by reason of the good penetration that is secured by the dispersing agent and the ability to warm at will.

The virtues of pine oil, preferably first used to 1,920,987 blend, mix or dissolve the-coloring or dye material and then incorporating with the pine oil dants, and reducing agents, discharges and resists used in color development. Examples of all of these have been found to be assisted by pine oil.

While I havedescribed the application of my improved dispersing agent to certain dyes and fibres, I do not wish to be limited to such dyes and fibres since many other dyes and, other fibres may be usefully combined through the operation of my process and the invention may be embodied in different forms without departing from the spirit and scope of its broader aspects. Hence I desire to cover all forms and features coming within the language or scope of any one or more of the appended claims.

What I claim as new and desire to secure by Letters Patent, is:

1. A composition of matter comprising as essential ingredients a dye material and an aqueous emulsion of pine oil.

2. A process comprising emulsifying pine oil in an aqueous phase and mixing a textile coloring agent with the emulsion.

3. A process of dyeing textiles comprising emulsifying pine oil with water, mixing a textile coloring agent with the emulsion, and impregnating textile fibers with the mixture.

4. A process comprising emulsifying pine oil with waterrmixing a textile coloring agent with the emulsion, and thereafter including the mixture in a dye bath.

5. A process of impregnating cellulose acetate with materials poorly soluble in water comprising forming an aqueous emulsion of pine oil, mixing such materials with the emulsion, and immersing the cellulose acetate in a bath containing the mixture so produced.

6. A process comprising emulsifying in water