With the exception of the few shades which could be produced solely by means of coloring matters of a chemical character, all dyeings on furs up to about thirty years ago were made with dye substances obtained from the vegetable kingdom, either alone, or in conjunction with the aforementioned mineral colors. The colors of vegetable origin used in comparatively recent times were mainly extracts of the wood of certain trees; so the name “wood dyes” has come to be applied generally to the dyes of this class. The use of the vegetable or natural dyes on furs dates back to quite ancient times, as frequent allusions and descriptions in Biblical and other contemporaneous literature testify. There are numerous pictures on monuments and tablets illustrating the dyeing of furs among the ancient Egyptians, the evidence indicating that the juice of certain berries, and extracts of certain leaves were used for the purpose. At a later period, in the Roman era, henna, which was used over two thousand years ago as to-day for the beautification of the hair of women, was also used to color fur skins. The instances cited here are merely of scientific and historical interest, and are not of practical importance as far as fur dyeing methods are concerned.
It was not until many centuries later that the dyeing of furs took on the aspects of a commercial art, and the substances then employed were chiefly tannin-containing materials such as gall-nuts and sumach, which inconjunctionwith certain metallic salts, particularly those of iron, were capable of producing dark shades. The use of iron compounds to form dark grey or black colors on leather tanned by means of the tannins, had been common for a long time, and it was natural that fur dyers should try to produce such shades on furs in a similar fashion. The use of the iron-tannin compound as a dye proved to be very effective, and to this day the production of blacks by means of the vegetable coloring matters has as a basis an iron-tannate. A formula in common use in the latter seventeenth and the eighteenth centuries for producing black shades on furs, is the following:
All these substances except the gall-nuts, the copperas and half the lime water were boiled up in a cauldron; then the gall-nuts and the copperas were placed in a bucket and the contents of the cauldron poured in, and the rest of the lime water added. The mixture was stirred up, allowed to settle for an hour, and when cool, was ready to be applied by the brush method. For dyeing by the dip process, a similar mixture was used, only considerably diluted with water. A study of the formula discloses the fact that in it are combined killing and mordanting substances as well as dyeing materials. The lime water, in conjunction with the salammoniac serves as a killing agent, the verdigris, copperasand alum are mordants, while the litharge and the minium, both compounds of lead, could possibly act as mineral dyes, and the iron filings and the antimony took virtually no part at all in the dyeing, except, perhaps to act in a mechanical way.
The formulas for other shades were made up along similar lines, the chief constituent of vegetable nature being either gall-nuts, sumach, or both. A mixture for a chestnut brown, for example, contained gall-nuts, sumach, and the various other mineral constituents as in the black dye, litharge, alum, copperas, verdigris, salammoniac, antimony, and in addition, red lead and white lead. It is evident in both these instances that the shade obtained was as much the result of mineral dyeing as of vegetable dyeing.
The discovery of America introduced into Europe many new dye substances, chiefly wood extracts such as logwood and Brazilwood, but it was not until the nineteenth century that these materials found their way into the dye formulas of the fur dyer. Most of the processes used in the dyeing of furs were adaptations of methods employed in silk dyeing, the silk fibre being considered as most nearly approaching fur-hair in nature and characteristics. By devious and circuitous paths the formulas of the silk dyers reached the fur people, and so, in the middle of the nineteenth century, dye mixtures containing the various dyewoods as well as the tannin-containing substances were in general use for the dyeing of furs. The following is a typical recipe of that time for the production of black on furs like wolf, skunk, raccoon, etc.:
The mixture was boiled up, and after cooling was ready for application by the brush method, the skins being first killed by a killing mixture also applied by the brush. The dye substances in this case are the gall-nuts, sumach and the logwood extract, with the iron mordant, copper vitriol, and alum as mordants. For brown shades a similar formula was used containing Pernambuco wood extract, logwood extract, quercitron bark, gall-nuts and dragonblood, together with iron, copper and alum mordants.
Formulas such as the above were mainly empirical, that is, they were compounded as a result of trial of various combinations of the constituents, without considering the nature and quantitative character of the reactions, as long as the desired shades could be obtained. Such dye mixtures were frequently found to yield results varying from those expected or originally obtained, because the effectiveness of the formulas depended upon the exact duplication in every detail, of conditions which had given satisfactory results previously, and it was not always possible to attain such an accurate reproduction of circumstances, especially when the fur dyers were quite ignorant of the scientific relationships of the materials used. So when more light had been shed on the nature and chemical characteristics of the vegetable dye substances, formulas like those described were no longer employed, although the essential ingredients were the same in the new processes. Unnecessary constituents were eliminated, and proper ones substituted where it was required, and the quantities of the materials used were made to conform to the chemical laws governing the reactions. Since these new formulas were based on a rational understanding of the constituents andtheir reactions, it is desirable to study the latter briefly, before further discussing the formulas themselves.
The substances of vegetable origin used in modern fur dyeing may be grouped into two classes, one, the tannin-containing materials, and the other, the dyewoods proper. The most important of the tannins are gall-nuts, sumach and chestnut extract. Cutch, which also comes under this class, is more frequently used for the production of brown shades, so it is grouped with the dyewoods. Among the latter are logwood, fustic, Brazilwood, quercitron, turmeric, and several others of less significance.
First and foremost under this heading are the nutgalls. These are ball-shaped excrescences produced on certain plants by the punctures of insects in depositing their eggs. There are two chief varieties, the European, and the Chinese. The European galls are formed by the female gall-wasp which drops an egg in the rind of young branches of certain oaks. A swelling (the nutgall) is produced, in which the young insect develops, and from which it finally escapes by piercing a hole through the shell. Those galls which are not pierced have a fresh bluish or green color, are heavy and contain most tannic acid. After the insect has gone out, the galls are of a lighter, yellowish color, and also of inferior quality. The best oak-galls are the Aleppo, and the Turkish or Levant galls, containing 55–60% of tannic acid, and about 4% of gallic acid. The Chinese galls are produced by the puncture of a plant-louse on the leaves and leaf-stalks of a species of sumach, and not on oaks. The galls are very light, and very rich in tannic acid, containing often as much as 80%. For dyeing purposes, nutgalls are usually ground to a powder, and in some instances they are even roasted first and then ground.
Sumach consists of the leaves and sometimes of the small twigs and stems of a species of sumach plant known as the Rhus coriaria. The Sicilian variety is the finest commercial quality, with the Virginian ranking next. It is sold as a powder, but also in the form of the whole or crushed leaves. The best sumach contains 15–25% of tannin. Extracts are also manufactured, a liquid extract of 52 degrees Twaddell, which forms a dark brown, thick paste; and a solid extract, formed by evaporating the liquid extract to dryness.
Chestnut extract is prepared from the wood of the chestnut oak, which contains 8–10% of tannin. The solid extract has a bright, black color, while the liquid extract is a dark brown paste with a smell like that of burnt sugar.
The tannins all give greyish to black shades with iron salts, and it is this fact which renders them important for fur dyeing.
One of the most important of all the natural dye substances, especially for the production of blacks, is logwood. The color is really a red, but with the common mordants it forms blue, violet or black shades. Logwood, or campeachy wood, as it is sometimes called, is the product of a large tree growing in the West Indies, and Central and South America. When freshly cut, the wood is practically without color, but when exposed to the air it soon becomes a dark reddish-brown on the surface. The coloring principle of logwood is called hematoxylin, which is a colorless substance when pure, and is of itself incapable of dyeing; but when it is exposed to the air, especially when moist and in the presence of some alkaline substance, it is converted into hematein, which is the real coloring matter of logwood. To prepare the wood for use, the logs are chipped or rasped, the chips being heaped up and moistened with water. Fermentation occurs, and the heaps are frequently turned to allow free access of air to the wood, and to prevent overheating.As a result of this process, a great part of the hematoxylin is converted to the hematein. The logwood may be used for dyeing in this state as chips, but logwood extracts can now be obtained of a high degree of purity and are easier to work with. The commercial forms of the extract, are the liquid of 51 degrees Twaddell, and the solid extract. Hematein crystals can also be obtained. All these extracts contain mainly hematein, together with a small percentage of hematoxylin which is converted to the former during the dyeing process. Logwood is never used as a direct dye, but is used to form color lakes with the various mordants, the following colors being produced:
By combining several of the mordants, any desired shade of black can be obtained, and if other dyewoods are used in conjunction with the logwood, the range can be further increased.
Fustic, yellow-wood, or Cuba wood, as it is variously called, is obtained from a tree also growing in the West Indies, Central and South America. It is used either as wood chips, or as a paste extract of 51 degrees Twaddell, and occasionally as solid extract. Fustic contains two coloring matters, morintannic acid, possessing the characteristics of a tannin, and which is quite soluble in water, and morin, which is rather insoluble, and which settles out from the liquid extract. Fustic is the most important of the yellow dyes of natural origin, and is used considerably in fur dyeing with logwood for shading the blacks, or for producing compound shades. With the usual mordants fustic gives the following colors:
Brazilwood, or redwood, is the product of a tree found in Brazil, and exists in several varieties, such as peach wood, Sapan wood, Lima wood, and Pernambuco wood. They all yield similar shades with the various mordants, and all seem to contain the same coloring principle, brasilin, which, like the hematoxylin, has no dyeing power, but by fermentation and oxidation it is converted to brasilein, corresponding to the formation of hematein. Brazilwood and the related woods are used either as chips or extract, but seldom alone, usually in conjunction with other dyewoods. By combining logwood, fustic and Brazilwood in various proportions, and by employing suitable mordants, all the shades required by the fur dyer can easily be produced.
Quercitron is the inner bark of a species of oak (Quercus tinctoria) found in the United States. It contains two coloring principles, quercetrin and quercetin. The fresh decoction of quercitron bark is a transparent dull orange-red which soon becomes turbid and deposits a yellow crystalline mass. It is generally used in conjunction with other dyes.
Cutch is the dried extract obtained from a species of acacia, the principal varieties being Bombay, Bengal, and Gambier cutch. It contains two coloring principles, catechin and catechu-tannic acid. Cutch acts as a tannin, and like other tannins discussed above, can be used for the production of grey or black shades with iron mordants. It is employed chiefly, however, for dyeing browns. Aluminum salts give with cutch a yellowish-brown, tin salts give alighter yellow, copperas gives a brownish-grey, and chrome and copper salts give brown shades.
Turmeric is the underground stem of theCurcumatinctoria, the coloring principle being called curcumin. It may be used as a direct dye, but usually a mordant is used. Turmeric is sometimes used in place of fustic.
While the tannins can be used alone with an iron mordant for producing greyish to black shades, the dyewoods alone yield colors which would be too bright to be suitable for dyeing furs. In order to tone down this brightness, and to give to the dyeings that greyish undertone which is characteristic of the natural furs, and which can only be imitated by means of the iron-tannin compound, it is customary to combine the tannins with the wood dyes. The iron-tannate constitutes the foundation of the color which gets its intensity, and necessary brilliancy and bloom from the wood dyes. Moreover, the presence of the iron-tannin compound helps considerably to increase the fastness of the dyeing. Furs dyed with the combination of the tannins and the wood dyes obtain an additional tanning treatment which materially improves the quality of the leather, for not only do the tannin substances exert this tanning action, but the dyewoods as well, for they are themselves either of the nature of tannins, or contain a coloring principle which is a tannin. It is to the combined effects of the tannin substances and the dyewoods that furs dyed with vegetable dyes owe their beauty of color, lustre, naturalness of shade, permanence of the dyeing, and durability of the leather. Wood dyeings on furs have for this reason acquired a just renown, but owing to the introduction of the new kinds of fur dyes, the use of the vegetable dye substances has been greatly reduced.
The dyes of vegetable origin can be applied to furs by either the brush method or the dip method, or both, and since mordants are required with the dyes of this class, they are applied in one of the three ways mentioned in aprevious chapter: first, by mordanting before dyeing; second, by applying mordant and dyesimultaneously; and third, by mordanting after the skins have been treated with the dye.
The use of the brush method in applying the natural dyes to furs is limited to a comparatively few kinds of dyeing, namely to produce special effects on furs, or to give to the upper-hair of furs a coat of dye different from the base color. In a quite recent German patent is described a process for blending a red fox as a silver fox and the procedure affords a good example of brush dyeing with preliminary mordanting. The specification is as follows: “D. R. P. 310, 425 (1918). A process for dyeing red fox as silver fox. The tanned and dressed skin is first superficially decolorized by applying a dilute mixture of milk of lime, iron vitriol and alum, with a soft brush so as only to penetrate the top-hair. Allow to remain for 4–6 hours, dry, and beat out the dust. A dilute solution of iron vitriol is brushed on so as only to wet the top-hair, and the skin is thus allowed to remain moist for 12–24 hours. Then without drying, a solution of iron vitriol, salammoniac, litharge, red argol and wood ashes is brushed on cold with a hard brush so as to penetrate all the hair down to very near the skin. The skin has now completely lost its red color, and has become a pale yellow. It is now ready to be dyed. An infusion of roasted nutgalls, which have been boiled for 3–4 hours with water, is applied cold with a soft brush to the upper hair. Allow to remain so for 2–3 hours, and without drying, apply a weaker solution of the roasted nutgalls with a hard brush so as to saturate the hair thoroughly. Dry and beat out. According to the concentration of the solution applied, the hair will be colored blue-greyto black, and the shade can be varied by varying the strength of the solutions used. The different parts of the skin, or those parts of different shades can be dyed accordingly.”
In this patent all the operations, including killing, mordanting and dyeing are done by the brush method, and the process, from this point of view is quite similar to one which might have been employed a century previous. It is evident that the time and effort required to carry out the details as described in the patent would only be warranted in exceptional cases, where the value of the dyed fur would be considerably greater than that of the natural skin.
An example of the application at the same time of dye and mordant by the brush method is the original French Seal dye, which is still employed to a limited extent to produce a brilliant, deep, lustrous black topping on furs which have already been dyed by the dip process. A typical formula for the old French Seal dye is the following:
This mixture is applied to the top of the hair of the furs, after previous killing, and the skins allowed to remain moist for several hours, and also exposed to the air. The skins are then dried, and beaten out, and if necessary a second coat of dye is brushed on. In dyeing seal-imitation on muskrat, or skunk-imitation on opossum, for example, the black color required on the top-hair, or the upper part of the hair when the furs are sheared, can be produced by applying a mixture similar to the above, to the fursafter they have received their base color by the dip process with natural dyes or with the Oxidation Colors. Occasionally, the dyeing is given an after-treatment with a dilute solution of sodium bichromate to help develop the color, the action in this case being that of an oxidizing agent, and not of a mordant.
As far as the third method of mordanting is concerned, that of first applying the dye, and then the mordant, it is rarely practised with the brush method. The procedure, however, consists in first brushing on a solution of the desired dye, then drying and brushing on a mordant solution. These operations are repeated perhaps two or three times until the proper shade is obtained, exposing the furs to the air for the color to be developed.
It was in the application to furs by the dip process that the use of the vegetable dyes attained great importance, and although at the present time, natural organic dyes have largely been superseded by the Oxidation Colors and Aniline Black dyes, yet for certain purposes, and especially for the production of blacks, the wood dyes still are able to hold their own.
The dyeing of black formerly constituted probably the most important branch of the fur dyeing industry, and was undoubtedly the most difficult one. For it is possible to obtain as many different kinds of black as there are dyers of this color, but only a few certain shades are desirable. The division of the classes of furs into those derived from the various kinds of sheep, and those obtained from other animals is particularly marked in the dyeing of black, and both the composition of the dye formulas and the methods of dyeing are somewhat different for the two groups. For the dyeing of black on Persian lambs, broadtails,caraculs, etc., a combination of logwood and nutgalls with the requisite mordants is used, while on hares, Chinese sheep, foxes, raccoons, opossum, etc., a mixture of logwood and turmeric or fustic, with the proper mordants is used.
The general procedure is as follows: The dye substances to be used are ground up to a powder in a mill constructed for the purpose, after which they are boiled with water in a copper-lined kettle or cauldron, heated from the outside by steam. The customary arrangement is to have a jacketed kettle, supported on a stand, and having taps and valves to enable the liquor to be drawn off, or pivoted, so that the kettle can be tilted, and the contents poured out. The use of the copper-lined vessel is to be preferred, as it is unaffected by any of the dye substances, and so cannot cause any rust stains. After the dyes have gone into solution and have cooled, the mordant chemicals, previously dissolved in water, are added, and the mixture stirred up. The dyeing in this instance is effected by the simultaneous application of dye and mordant. The dye mixture is now run off, or poured out in the proper quantity into a number of small vats of 25–30 gallon capacity, or into a paddle vat, which can be closed, while the paddle is rotating. The latter device is to be preferred because it permits the dye to retain its temperature better and for a longer period of time, but when lambs are being dyed only the open vats are used. The temperature of the dye mixture is between 40° and 45° C., for only at this temperature can the hair absorb the dye properly without injuring the leather. The killed skins are immersed in the dyebath for a time, usually overnight, after which they are removed, drained and hung up, with the hair-side exposed to the air, so as to permit the dye to develop, which takes place with the aid of theatmosphericoxygen. The dyebath is again brought to the proper temperature, and the skins are again entered, to go through the same process as often as is necessary to obtainthe desired depth of shade. The dyed skins are thoroughly washed to remove excess dye, then dried and finished. The following are a few dye formulas used in the production of blacks:
or,
A recently published formula for dyeing China goat skins black, is the following:
Dissolve 50 lbs. of dark turmeric and 45 lbs. of logwood extract and make up to 300 gallons of solution, at 95° F. Enter the killed skins and leave them in the liquor until they rise to the surface. Then take them out and add 25 lbs. of logwood extract, 10 lbs. of sumach, 10 lbs. of blue vitriol, 5 lbs. of fustic extract, and about 60 lbs. of iron acetate liquor. Stir up well, and immerse the skins for 18 hours. Draw them up, and expose to the air for 12 hours. Heat the liquor again to 95° F. and put the skins back for 12 hours. Draw out, hang up in the air for a time, then wash thoroughly, hydro-extract, dry and finish.
In a German patent, D. R. P. 107,717 (1898), is described a method for dyeing lambs black, consisting in treating the skins for 24 hours in a logwood bath, then rinsing in cold water, and mordanting for 15 hours in a solution of bichromate of potash. The skins are then washed and treated with a solution of iron salt, then dried.This process, while of not much practical importance, is an illustration of mordanting subsequent to the dyeing treatment.
As far as the production of other shades is concerned, the procedure is quite similar to the regular black method. For a dark brown, for example, the skins are dyed in a mixture containing
employing operations just as in the case of the black.
Greyish-blue shades on white hares, lambs, kids, etc., can be obtained by treating the skins successively in thefollowingbaths:
Bluish-grey tones on the same furs can be produced by treating with
Similar grey shades can be produced by mordanting the skins with an iron salt, and then dyeing in a weak bath containing gall-nuts, sumach and iron vitriol. This method is very effective for making Alaska or silver fox imitations.
Fur seal for a long time has been a fur of distinction and importance in the fur industry, and consequently the dyeing of seal has constituted an important, though not very extensive branch of the art of fur dyeing. In quite recent times the popularity of seal has become so great that imitations have had to be produced to help supply the demand, and as a result, French seal, or seal-dyed rabbit, and the so-called Hudson seal, which is seal-dyed muskrat, have acquired a great vogue. Occasionally opossum, nutria and other furs are also used for the purpose of producing seal imitations. While the supply of real seals is relatively small, and the demand large, the production of seal imitations has assumed large proportions, and as a result, the dyeing of seal and its imitations or substitutes has come to be a great branch of the fur dyeing industry.
During the past thirty years, the long and tedious processes of dyeing seal and seal imitations, involving the use of dyes of vegetable origin, have largely been superseded by what is known as the Aniline Black dye. It was the French who first worked out successfully the application of Aniline Black to furs, and the method has attained much importance and extensive use in the fur dyeing industry.
Aniline Black is the name given to an insoluble black dyestuff produced by the oxidation of aniline in an acid medium. As a finished product it cannot be used in fur dyeing, but if the hair of the furs be impregnated with asuitable preparation of aniline and then treated with certain oxidizing agents, the color will be formed on the hair, being firmly fixed and giving a fast black, resistant to light, washing and rubbing. The basis of the dye, aniline, is an oily liquid, possessing a peculiar fishy odor, colorless when pure, but rapidly turning brown when exposed to the air. It is obtained from benzol, which is distilled from coal-tar, by treating with nitric acid, forming nitrobenzol, which when subjected to the action of reducing chemicals is converted into aniline. The process may be shown schematically as follows:
Coal—coal-tar—benzol—nitrobenzol—aniline oil—Aniline Black. Aniline Black was by no means a new dye when the French succeeded in producing it on furs. It had been used for a long time previous on textiles, chiefly cotton. The history of the development of the Aniline Black process throws considerable light on its nature and constitution, and so presents many features of interest. As early as 1834, the chemist Runge observed the formation of a dark green color when heated aniline nitrate in the presence of cupric chloride. Fritsche, in 1840, noticed that when chromic acid was added to solutions of aniline salt, a dark green, and sometimes a blue-black precipitate was produced, and later the same chemist obtained a deep blue by the action of potassium chlorate on aniline salt. It is interesting to note that Perkin, in 1856, conducting similar experiments on the oxidation of aniline with chromic acid, obtained a blue-black product from which he extracted the first synthetic coal-tar dye, mauve. Thus far, all the experiments on the oxidation of aniline proved to be merely of scientific interest, but in 1862, Lightfoot patented a process for the practical application of colors formed by the oxidation of aniline on the fibre, a greenish shade being obtained by that method, to which the name emeraldine was given, and by subsequent treatment with bichromate of potash, the green was changed to a deep blue color.Since that time, the methods for producing and applying Aniline Black have been developed and improved, although all the processes were based on the principles incorporated in Lightfoot’s original patent. However, it was not until the last decade of the nineteenth century that the dyeing of furs by means of the Aniline Black method was successfully attempted.
A knowledge of the nature and the manner of the chemical changes which take place in the production of Aniline Black is a valuable aid in obtaining satisfactory results in practise; and although Aniline Black was extensively used before the true character of the reaction was understood, since the successful determination of the constitution of Aniline Black and the discovery of the real nature of the process by Green and his collaborators in 1913, the methods have been considerably improved and simplified, with correspondingly better results in dyeing. As a consequence, the methods of dyeing furs with Aniline Black have also become simpler and more efficient.
A discussion of the chemical changes which occur in the Aniline Black process, is out of place here on account of the highly involved and complicated character of the reactions, to understand which requires a considerable knowledge of specialized organic chemistry. But the essential features of practical importance in the production of Aniline Black are the following: As already noted, one of the characteristic properties of aniline is its tendency to turn from a colorless to a dark-brown liquid in the presence of the air. This change is due, together with certain other causes, to an oxidation brought about by atmospheric oxygen. By employing oxidizing agents, this oxidation can be accelerated and carried further, and eventually the Aniline Black is obtained. Among the substances which may be used to bring about the conversion of aniline to the insoluble black dye are manganese dioxide, lead peroxide, hydrogen peroxide, chromic acid, ferric salts, potassiumpermanganate, chloric acid and chlorates in the presence of certain metallic salts, particularly those of vanadium and copper. Chlorates, especially sodium chlorate and potassium chlorate, are the most commonly employed oxidizing agents, bichromate of soda or of potash being used, in addition, to complete the oxidation. When using chlorates it is necessary to have present in the dye mixture a small quantity of a metallic salt, which, while not entering into the reaction itself, is nevertheless indispensable as an oxygen carrier. Vanadium compounds have proved to be the most effective for this purpose, and according to an authority, one part of vanadium salt is sufficient to cause the conversion of 270,000 parts of aniline to Aniline Black, the necessary amount of a chlorate being present of course. Salts of copper, cerium, and iron are also extensively used, but they are not quite so efficient as vanadium.
The formation of the Aniline Black in practise takes place in three well-defined steps, which it is important to be able to recognize and distinguish in order to obtain the best results. The first stage of the oxidizing process produces what is called emeraldine, which in the acid medium of the aniline bath is of a dark green, while in the free state it is of a blue color. As the oxidation proceeds, the second stage develops, the emeraldine being converted to a compound called nigraniline. This in acid solution is blue, and the free base is a dark-blue, almost black. It was formerly considered that the nigraniline was the Aniline Black proper, and so when this stage of the oxidation was reached, the process was often interrupted and not carried to the limit. This can account for the fact that Aniline Black dyeings usually turned green after a short time. The reason for this is that nigraniline, when treated with weak reducing agents, as, for example, sulphurous acid, is at once changed to emeraldine, with its dark green color. Since there is usually a small amount of sulphurous acid in the air, especially in places where coal or gas is burned, anAniline Black dyeing which has not been carried beyond the nigraniline stage will be reduced in time to the emeraldine, and cause the dyeing to become green. The last step in the oxidation changes the nigraniline into what is properly called the ungreenable Aniline Black. Weak reducing substances like sulphurous acid do not change this compound to emeraldine, and stronger reducing agents only convert it to a brownish compound, which changes back to the black when exposed to the air. It is quite evident that in order to obtain a black which will not change to green in time, the oxidation of the aniline must be carried to the last stage. By making tests during the dyeing of the furs, it can easily be determined whether the oxidation has proceeded far enough.
In the dyeing of textiles with Aniline Black, it is customary to carry out the operation at comparatively high temperatures, approaching 100° centigrade. With furs such temperatures are out of the question, so it is necessary to repeat the dyeing several times in order to obtain the proper depth of shade working in the cold. Only the brush method can be used in applying the Aniline Black dye to furs, on account of the strong acidity of the dye mixture, which would ruin the leather, if the dyeing were done in a bath. Indeed, great care must be exercised even by the brush method to avoid too great penetration of the dye liquid, otherwise the roots of the hair will be attacked, and the leather may be “burned” from the hair side. Furs dyed with Aniline Black are frequently after-dyed by the dip-process with logwood or some other similar dye, in order to add to the brilliancy of the dyeing. Combined with intensity of color, Aniline Black on furs is the only dye which will also give fast, lustrous shades, and leave the hair soft and smooth.
There are several methods of applying Aniline Black on furs, the most important being
A typical formula for this method is the following given by Beltzer:
All these substances are dissolved hot in 50 liters of water, and allowed to cool, forming solution A. Aniline salt is aniline oil which has been neutralized with the exact quantity of hydrochloric acid to form the hydrochloride. It forms white or greyish crystalline lumps very easily soluble in water. The sodium chlorate is the oxidizing agent, and the copper sulphate and the vanadate of ammonia are the oxygen carriers.
15 kg. of sodium bichromate are also dissolved in 50 liters of water, forming solution B. The bichromate is also anoxidizingagent and serves to complete the oxidation of the aniline to the black.
Immediately before using, solutions A and B are mixed together, both being cool. In general practise it is customary to mix only small quantities at a time, as a considerable precipitate forms when the whole batch is mixed at once, the precipitate being so much waste dye substance. Usually a liter of A and a liter of B are mixed at a time, and the furs brushed with the mixture. The brushing must be varied according as the hair is hard and stiff, or soft and tender. The hair must be thoroughly impregnated in alldirections, and the penetration must not be too deep to affect the leather. With experience and dexterity satisfactory results can easily be achieved. After the skins have been properly treated, they are dried at a temperature of about 35 degrees centigrade. When dry, they are returned to the dye bench, where they receive another application of the dye mixture, and are again dried. This operation may be repeated as often as six or seven times before a sufficiently intense black is obtained. Another way of producing the desired depth of shade with fewer applications is by using more concentrated dye mixtures. Each method has its disadvantages, the greater number of brushings requiring the expenditure of more time and labor, and the greater concentration of the bath resulting in a considerable loss of dye substance due to the formation of a large precipitate when the two solutions are mixed, and moreover, not all furs can be treated with concentrated mixtures. The best results with this method usually require the application of six coats of a mixture of moderate concentration.
In order to overcome the difficulty of employing very concentrated dye mixtures, or of making many applications of the dye, a method was devised whereby the two solutions of the previous process, instead of being mixed together, are applied successively to the hair of the furs, the following formula, also by Beltzer, being an example:
This is solution A, and is merely a solution of aniline hydrochloride, or nitrate, depending on which acid has beenused. Nitric acid, although more costly than the hydrochloric acid, is to be preferred, because it is an oxidizing acid, and so assists in the oxidation of the aniline, and besides, has a more beneficial effect on the hair than the hydrochloric, in the matter of softness and luster.
This is solution B, containing the oxidizing agent, and the oxygen carriers. Just before using, equal quantities of A and B are mixed, and the skins brushed with the mixture. The skins are then dried at 35–45° centigrade, at which temperature the color begins to develop. When almost, but not entirely dried, the skins are subjected to the action of warm vapor, which is allowed to enter the drying chamber, so as to keep the temperature about 40° centigrade, the color developing better in this way. This operation may be repeated, or the skins are directly treated with a solution of 25 kg. of sodium bichromate in 100 liters of water, to complete the oxidation. The moist skins are exposed to the air for a time, and then dried at 35° C.
This method of dyeing has several advantages over the One-bath Aniline Black. It requires fewer brushings, and enables the complete utilization of the dye solutions without loss. With three applications of the dye mixture by the Oxidation process, as deep and intense a black can be obtained as with six brushings by the One-bath method. The dyeings, too, are nearly, but not fully as brilliant and even as in the latter case. The greater the number of coats of dye that are applied the more regular will the dyeing be.
In 1902, the Farbwerke Hoechst, a large German producer of coal tar intermediates and dyes, invented an Aniline Black process to which they gave the name Diphenyl Black. The chief departure from the previous Aniline Black methods was the replacing of part of the aniline oil of the dye mixture by Diphenyl Black Base I, which is para-aminodiphenylamine. This base has the property of being oxidized to Aniline Black, just like aniline oil, and the advantage claimed for the Diphenyl Black is that it produces an absolutely ungreenable black. The method of application is practically the same as for the other Aniline Black processes, chlorates being used as the oxidizing agents, in the presence of oxygen carriers such as salts of copper and vanadium. The use of bichromates is dispensed with. On account of the comparatively high cost of the Diphenyl Black Base I, this method has not found very extensive application, especially as highly satisfactory ungreenable blacks can now be produced by other methods.
In 1907, Green, who has done much work in the direction of elucidating the character of the Aniline Black process, obtained a patent for a method of applying Aniline Black in a manner which was different from all the previously known formulas. The invention created great interest, and although in its original form it did not find a wide application, many of the methods used at the present time are in one way or another derived from the idea of Green. A resumé of the patent will therefore be given here: “The invention relates to the production of an Aniline Black, the new process differing from all other known processes by the fact that the oxidation of aniline is effected solely or mainly by the oxygen of air. The possibility of dispensingwith an oxidizing agent depends on the discovery that the addition of a small quantity of a para-diamine, or of a para-amido-phenol to a mixture containing aniline and a suitable oxygen carrier, such as a salt of copper, greatly accelerates the oxidation of the aniline by the atmospheric oxygen. Further, whereas in the ordinary processes of Aniline Black, the quantity of mineral acid employed cannot be materially reduced below the proportion of one equivalent to one equivalent of the base, under the new conditions the mineral acid may be wholly or partially replaced by an organic acid such as formic acid, without the quality of the black being materially affected. As suitable oxygen carriers the chlorides of copper have been found to give the best results, it being preferrable to use the copper in the form of a cuprous salt. This is effected by adding to the dye mixture cupric chloride, together with a sulphite or bisulphite in sufficient quantity to reduce the cupric salt to the cuprous state, and a sufficient quantity of a soluble chloride to keep the cuprous chloride in solution. Among the compounds suitable for the production of this black in conjunction with aniline are, para-phenylene-diamine, dimethyl-para-phenylene-diamine, para-amido-diphenylamine, para-amido-phenol, etc.”
This method may be used alone as the other Aniline Blacks, or the dyed skins may be after-dyed in a bath containing a logwood dye, or it may be used in conjunction with mineral dyes, or with the Oxidation Colors (see next chapter). A typical formula for the black by Green’s process is the following:
This is solution A. Solution B is prepared by dissolving
A and B are mixed, and the mixture applied to the hair of the furs several times,dryingeach time at 35°–40° C. After three coats of dye have been applied, a pretty and fairly intense black shade is obtained, which is developed further by treating with a solution of 25 grams of sodium bichromate per liter of water. The skins are then allowed to dry in air, and then if desired, an after-dyeing is made with some other dye.
On account of its extreme fastness, Aniline Black, produced by any of the methods outlined above, has attained a justifiable popularity for the dyeing of furs, in spite of the necessity of using the more or less cumbersome brush method of applying the dye. Very recently there was issued to a German company a patent in which is described a method whereby furs can be dyed with Aniline Black by the dip process. An abstract of the patent (D. R. P. 33402) is as follows: “As is known, aniline salt, and similar salts, together with oxidizing agents like bichromates, chlorates, etc., cannot be used for dyeing furs by the dip process, because the strongly dissociated mineral acid is injurious to the leather. The dissociation of the acid can be reduced by adding neutral salts, like common salt, or Glauber’s salt, so that good results can be obtained by dyeing in a bath of the dye mixture, the leather retaining its softness.”
Thus far there have been no reports of the successful practical application of this patent, so its value cannot be discussed. It is extremely doubtful, however, that furs will ever be dyed in the dyebath with the present type of Aniline Black formulas, no matter what substances are added to prevent the leather from being affected.
The year 1888 may be considered the beginning of a new era in the history of fur dyeing; the commencement of a period which was to see the time-honored, traditional methods of the masters of the art give way to newer methods of an entirely different character; and moreover, the initiation of an age when science with its basis of fact and logic, was to undertake the rationalization of an industry which had hitherto worked upon a more or less irrational, empirical and uncertain comprehension of the fundamental principles involved. It was not the work of a single day, or even of a year which brought about the virtual revolution in the dyeing of furs, but the result of long, patient, systematic effort. About this time, the German coal tar industry was attaining its real stride along the path of progress and achievement, and had already succeeded in reaching, to an appreciable degree at any rate, most users of coloring matters, with the consequence that the natural dyes, with their time and labor-consuming processes of application were gradually being superseded by the new synthetic dyestuffs which could be simply and quickly applied. It was now the turn of the fur dyeing industry to receive the attention of the scientists and technologists responsible for the growth of the coal tar dye industry, and so there appeared in the above-mentioned year, the following patents, taken out by a German chemist named Erdmann:
If white hair or feathers are soaked in an aqueous or alcoholic solution of para-phenylene-diamine, and then exposed to the slow oxidation of the air, or are treated in a second solution with some oxidizing agent, then the hair or feathers will be dyed. According to the oxidizing agent chosen, and the concentration of the solution used, the color obtained will be light or dark, varying from the palest blond to the deepest blue-black. Particularly suitable as oxidizing substances are ferric chloride, permanganates, chlorates, hypochlorites, bichromates, and hydrogen peroxide. The dyeings are fast, that is, they do not come off, and the color cannot be removed by washing. Following examples may serve to make the process clear:
20 grams pure para-phenylene-diamine and 14 grams caustic soda are dissolved in a liter of water. The hair, previously degreased, is soaked thoroughly in this solution, and while moist is entered into a three per cent solution of peroxide of hydrogen. The action is not instantaneous, but after a day, the hair is dyed a dark shade; by repetition of these operations a blue-black is obtained.
The para-phenylene-diamine can be replaced in this process by other similar bases, such as dimethyl-para-phenylene-diamine, as well as the naphthylene-diamines. Since the substances which can be applied by this process are uninjurious, the method described can be used to dye human hair on the head or beard, and so seems suited to replace for the dyeing of hair, the metallic salts and various pyrogallic solutions which are on the market, and which are harmful to the health.
This patent was an extension of the original patent to include certain oxy and amido-oxy compounds, the methodbeing essentially the same otherwise as in the original patent. An illustration of the process is as follows:
73 grams para-amido phenol hydrochloride are dissolved with 40 grams caustic soda in a liter of water. The solution dyes hair a golden-yellow, which on subsequent treatment with a solution of ferric chloride turns to a red-brown.
In these two patents is to be found the basis of the modern fur dyes and fur dyeing methods. It is interesting to note that furs were not mentioned at all in connection with the process, which was intended mainly for dyeing hair, especially on the human head. It was only several years later that the value of the method for dyeing furs was realized. So about 1894, the Aktien Gesellschaft für Anilinfabrikation put upon the market three fur dyes under the trade name Ursol, Ursol D, giving dark-brown to black shades; Ursol P, giving red-brown colors; and Ursol C, giving a yellowish-brown shade. Pyrogallic acid had been previously used as a hair dye, and also to a slight extent as a fur dye, so it was used in conjunction with the Ursol dyes for shading purposes. The new fur dyes were not dyes in the ordinarily accepted sense of the term. They were really coal-tar intermediates, substances similar in character to aniline, and their dyeing property depended on the fact that they could be oxidized either by atmospheric oxygen, or by means of oxidizing agents, forming colored insoluble products. When the oxidation of the intermediate was caused to take place on the hair the colored product formed on and in the hair fibre, and remained fast. The reactions bringing about the conversion of the intermediate to the colored insoluble compound are quite analogous to those of the Aniline Black process, though possibly not so complicated, with the important difference, however, that, while in the production of Aniline Black acid is essential, in the present instance the oxidation can be carried on in neutral or even alkaline medium. On account of the character of the method used in applyingthe new fur dyes, the name Oxidation Colors has been given to them. Strictly speaking, Aniline Black is also an Oxidation dye, but it is usually considered in a class by itself. The methods used at first in the application of the Ursol dyes to furs followed closely the process as described in the patents. The furs were first killed, usually by brushing on a lime mixture, drying, and then beating out the dust. This operation was repeated, if necessary. Then a solution of the desired dye, mixed with an equal volume of 3% peroxide of hydrogen was brushed on and the fur allowed to lie exposed to the air. The dyeing could also be done by the dip process, less concentrated solutions being used. By varying the concentration of the solution, and prolonging or shortening the time of action, the shades could be varied from very light to very dark, and by combining two or more of the Oxidation Colors, many different color effects could be produced. Soon other fur dyes were developed and put on the market; for example, Ursol DB, giving blue to blue-black shades, and Ursol 2G, yielding yellowish tones suitable for mixing with the other colors. Ursol C was discarded shortly after its introduction. The dyeings obtained with the Oxidation Colors seemed to be very fast, resisting successfully the action of cold or hot water, or even hot soap solution. Moreover, a dyed hair examined under the microscope appeared to be colored through the epidermis to the medulla, and no individual particles of dye could be discerned.
The new fur dyes had many evident advantages over the coloring matters in general use at the time. The simplicity of the dyeing operations, the short duration of the process, the great tinctorial power of the new products, were facts which strongly recommended themselves to the progressive fur dyer. The cost of the dyes was higher than that of the vegetable dyes, but this consideration was largely overbalanced by the saving in time and labor in using them. And yet, the Ursol dyes found only a comparatively smallmarket. The majority of fur dyers, always conservative and reluctant to turn from the traditional ways of the industry were skeptical of, and even hostile towards the new dyes and the new methods of dyeing. In a sense, this opposition was justifiable. It was not an easy task to relinquish all at once methods which had been successfully applied for generations back, and with which they were thoroughly experienced, in favor of processes which were radically different, and with which they had no experience at all. But some enterprising spirits among the fur dyers undertook to try out the new products and it was not long before the skeptics had good cause for condemning the work and achievements of the chemists as far as fur dyeing was concerned. The new type of dyes did possess some of the advantages claimed for them, but they also possessed many highly objectionable features, which had never been manifest with the vegetable dyes. First of all, the dyeings were not so fast as had at first appeared, for the color came off the hair when the furs were rubbed, brushed or beaten. Then it was observed that after a short time some of the dyeings changed color, and at the same time the hair lost its gloss and became brittle. The condition of the leather after dyeing was anything but satisfactory. Most serious of all, however, was the appearance among the workers in the dyeing establishments, and also among the furriers who worked with the dyed skins, of certain pathological conditions which had hitherto been unknown. Various skin diseases, eczemas, inflammation of the eyes, asthmatic affections and intestinal irritations were some of the afflictions which were directly attributable to the use of fur dyes of the Ursol type. Medical science was at a loss to know how to treat these ailments, because their nature was not understood.
Here indeed, were obstacles threatening to destroy all the hopes which the discovery of the new class of dyes had aroused, and to check at the outset the possibility of rationalprogress in the fur dyeing industry. But the men of science were not content to let the matter drop thus. Difficult problems had been solved before, and surely there must be some way of overcoming the objections and deleterious features of a system of fur dyeing which had so much potential merit. Where hindrances sprang up in the path of progress, it was the duty of the chemist to remove them, and when difficulties arose, it was up to him to resolve them, as far as was humanly possible. So the chemists who had been responsible for the introduction of the Oxidation Colors set themselves to the task of eliminating the undesirable or injurious qualities. It was many years before the results of painstaking effort and persistent study cleared up the causes of all the objectionable aspects of the fur dyes, and suggested means of overcoming them satisfactorily. The work had been directed to the improvement of the dyes and of the methods of dyeing with them. Purer intermediates were produced, and more easily soluble ones, so that there would be no possibility of ultra-microscopic particles of the dye being deposited on the surface of the hair from the dye solution, instead of being taken up within the hair fibre. It was this superficial deposition of minute crystals of the dye or of the only partially oxidized intermediate, on the hair, crystals so fine as to be invisible in the ordinary high-power microscope, which caused the color to come off when the furs were brushed or beaten, giving rise to a dust which was frequently very injurious to the health. Then, mordants were adopted to help fix the dyes, compounds of copper, iron, and chromium being used as formerly with the vegetable dyes, and the range of shades was also increased thereby. Certain of the Oxidation Colors had a tendency to sublime off the hair, so the dyed hair was chemically after-treated in such cases to prevent this. The causes of the pathological aspects of dyeing with the Oxidation fur dyes were not so readily disposed of. But the adoption of devices to prevent the formation andcirculation of dust during the handling of the dye, the employment of adequate protection against contact with the dye or its solutions, the use of the most dilute solutions possible in dyeing, the thorough washing of the dyed skins to remove any excess of the coloring matter, the prevention of dust formation in the drying of the skins, and the rigid observance of, and adherence to hygienic laws, were all factors in the elimination of the health-impairing phases of dyeing with the Oxidation Colors.
It was only after all these improvements had been accomplished that the fur dye intermediates began to acquire a degree of popularity among fur dyers, and strange as it may seem, there was a more ready market for these dyes in America, than in Germany where they were manufactured. Othermanufacturersof coal-tar intermediates also began to produce fur dyes, and so, in addition to the Ursols, there were the Nako brand, the Furrol brand, the Furrein brand, and one or two others. New dyes were invented, until the whole range of colors suitable for fur dyeing had been produced. The black dye, however, presented some difficulty. A black dye which would rival logwood blacks could not be attained. Ursol DB in conjunction with Ursol D was being used to produce bluish-blacks, but the dyeings were not fast, turning reddish after a time. In 1909, a patent was taken out for a dye mixture, which was made up like the DB brand, but instead of using toluylene diamine with para-phenylene-diamine, the new dye was made up of a methoxy, or ethoxy-diamine with para-phenylene-diamine, and it yielded brilliant bluish-blacks, which were fast, and which very nearly approached the logwood black in luster, intensity, and bloom. For some purposes, however, the production of a black color is still dependent on the use of the logwood dye.
When the Great War cut off to a large degree the importation of skins dyed in Europe, the American fur dyeing industry developed tremendously, and in a comparativelyshort time was able satisfactorily to accomplish in the way of dyeing furs, what had taken foreign dyers a much longer period to attain. It had been previously considered that furs could be dyed properly only by European fur dyers, but the achievements in this direction by Americans fully dispelled this belief. But the success of the fur dyers in America might not have been so marked or rapid, had it not been for the work of the American chemists. The war had also shut off the supply of German dyes, upon which the dyeing industries of America had formerly been dependent, so enterprising chemists in this country undertook to fill the need, and in a surprisingly short time, American fur dyes, in every respect the equal of the foreign product were offered to the American fur dyers, and at the present time, the requirements of the fur dyeing industry in this country are being adequately met by domestic producers. Among the brands on the market are the Rodol, Furamine, Furol, and several others. The Oxidation Colors are now being offered in a high state of purity, and easily soluble, free from any poisonous constituents, and there is absolutely no reason for the appearance of any pathological conditions among workers on dyed furs, or users of such furs, provided the necessary precautions have been taken in the dyeing process. The occurrence of any affection which can be traced to dyed fur, cannot possibly be due to the dye itself, but to gross carelessness and negligence in dyeing, and in any such event, the dyer responsible should be brought to account.
In order to get a better understanding of the nature and action of the Oxidation Colors, a typical one will be studied in some detail. The most important one in this class is para-phenylene-diamine, usually designated by the letter D in all commercial brands of this fur dye, while its chemical formula is represented as C6H4(NH2)2. When pure it occurs in colorless, crystalline lumps, which rapidly turn brown when exposed to the air; the technicalproduct of commerce is of a dark-brown color. It dissolves readily in hot water when pure, and also in acids. At one time the hydrochloride was used instead of the free base, on account of its greater solubility, but now a base is made which is sufficiently pure to be very soluble in water. There are several methods of preparing para-phenylene-diamine: first, by the reduction of amido-azobenzol, the product obtained in this way always containing a slight amount of aniline, which reduces the solubility, and also gives rise to poisonous oxidation products during the dyeing process; second, by the reduction of paranitraniline, the quality and solubility of the product in this case depending on the purity of the starting material; and third, by the treatment of para-dichloro-benzol with ammonia under pressure, the best product being obtained by this method. The crude para-phenylene-diamine, made by any of the above processes, is generally distilled in vacuo, the refined base being obtained as lumps with a crystalline fracture.
The first step in the oxidation of the para-phenylene-diamine is the formation of quinone di-imine, NH:C6H4:NH. This is a very unstable compound in the free state, and even in aqueous solution it decomposes within a comparatively short time, or combines with itself to form a more stable substance. Quinone di-imine has a very sharp, penetrating odor, and produces violent local irritations wherever it comes in contact with the mucous membrane. If a small quantity of para-phenylene-diamine is absorbed into the human body, by breathing the dust, or otherwise, the formation of quinone di-imine takes place internally with consequent irritation of the mucous lining throughout the body. The various pathological conditions mentioned before may be ascribed to irritation caused by quinone di-imine. In any dyeing process where there is a possibility of the formation of quinone di-imine, as is the case with most dyes containing para-phenylene-diamine,special precautions must be taken by the workers in handling the dye or coming in contact with its solutions, and no one who is particularly sensitive to irritation should be permitted to work in a place where such dyes are used.
The next step in the oxidation of the para-phenylene-diamine is the formation of what is called Bandrowski’s base. Three parts of the quinone di-imine combine with themselves, forming a substance of a brown-black color, which was formerly regarded as the final oxidation product. The formula of Bandrowski’s base is represented by the following chemical hieroglyphics:
Further investigation has shown that the oxidation proceeds beyond this stage with the formation of a compound of what is known as the azine type, which is depicted by the chemist as
It is by no means certain that this substance is the true coloring matter obtained by the oxidation of para-phenylene-diamine, for the reactions may continue still farther, producing even more complicated oxidation products. Scientific research and study has not as yet gone beyond this stage.
The reactions of the other dyes of the Oxidation type are quite similar to those of para-phenylene-diamine, some being simpler, and others being even more complex. The presence of certain chemical groups in the intermediate, or the relative position of such groups are factors responsible for the variations in shade.
With the various mordants, the Oxidation Colors give different shades, and a great range of colors can be produced either by combining mordants, or combining dyes, or both. The following tables illustrate the shades formed with the customary mordants.