II. Dyeing with Vegetable Dyes by the Dip Method

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the vegetable dyes attained great importance, and although at the present time, natural organic dyes have largely been superseded by the Oxidation Colors and Aniline Black dyes, yet for certain purposes, and especially for the production of blacks, the wood dyes still are able to hold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 the atmospheric oxygen. 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 obtain the 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:

Logwood extract100grams
Chestnut extract14c.c.
Turmeric38grams
Iron acetate 6° Bé50c.c.
Water1200c.c.

or,

Cutch15grams
Soda14grams
Logwood extract120grams
Verdigris19grams
Iron acetate 5° Bé.16c.c.
Water1200c.c.

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

Gall-nuts40parts
Verdigris10„
Alum10„
Copperas5„
Brazilwood extract (15° Twaddell)150„
Water1000„

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 the following baths:

1.Logwood extract100grams
Water1liter
2.Indigotine10grams
Alum10grams
Water1liter

Bluish-grey tones on the same furs can be produced by treating with

1.Logwood extract200grams
Indigotine15grams
Water1liter
2.Alum150grams
Salammoniac12grams
Water1liter

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.

CHAPTER XIV
FUR DYEING
Aniline Black

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 a suitable 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, potassium permanganate, 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, an Aniline 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

1. One-bath Aniline Black

A typical formula for this method is the following given by Beltzer:

Aniline salt10kg.
Sodium chlorate1.5kg.
Copper sulphate0.7kg.
Vanadate of ammonia10gr.

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 an oxidizing agent 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 all directions, 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.

2. Oxidation Aniline Black

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:

Aniline oil10liters
Nitric acid 36° Beaumé, or
Hydrochloric acid 22° Beaumé20liters
Cold water20liters

This is solution A, and is merely a solution of aniline hydrochloride, or nitrate, depending on which acid has been used. 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.

Sodium chlorate4kg.
Copper sulphate1kg.
Vanadate of ammonia10gr.
Water50liters

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.

3. Diphenyl Black

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.

4. Aniline Black by Green’s Process

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 dispensing with 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:

Para-amido-phenol0.5kg.
Aniline oil10liters
Hydrochloric acid 22° Bé.10liters
Acetic acid 40%5liters
Cold water25liters

This is solution A. Solution B is prepared by dissolving

Copper sulphate2kg.
Salammoniac10kg.
Cold water50liters

A and B are mixed, and the mixture applied to the hair of the furs several times, drying each 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.

CHAPTER XV
FUR DYEING
Oxidation Colors

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:

D. R. P. 47349
A Process for Dyeing Hair and Feathers

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.