For cream, light sulphur-yellow, maize, salmon, etc.

Combinations of Thioflavine Rhodamine B Irisamine G

For greenish-yellows Combinations of Thioflavine Victoria Blue B

For light pink Rhodamine B Irisamine Rose Bengal Extra N

For purple Methyl Violet 3B6B Crystal Violet

For sky-blue Victoria Blue B

For white Victoria Blue B (Milk-white) Methyl Violet 3B6B Crystal Violet (Ivory-white)

To produce very delicate shades, the moist dyed skins are subjected to a sulphur bleach overnight, to lighten the color, then rinsed, and dried.

Full, brilliant shades may be obtained by dyeing in a bath of 40 C., acidulated with 23 grams of acetic acid per liter of solution, the following dyestuffs being suitable:

For yellow to orange Thioflavine Paraphosphine Rhodamine Safranine New Magenta O

For pink Rhodamine B Rose Bengal Extra N

For light red Safranines

For bordeaux and red Magenta New Magenta Russian Red Cerise

For violet Methyl Violet 6B4R Crystal Violet 5B

For blue Victoria Blue B Methylene Blue BB New Methylene Blue N

For green Malachite Green Crystals Brilliant Green Crystals, or combinations of Thioflavine Diamond Phosphine Victoria Blue B

For brown Chrysoidines Bismarck Browns

In dyeing skins with harder hair than that of sheep or goat, mere killing is insufficient to render the hair capable of taking up the dye. The skins are therefore immersed before dyeing, in a cold, weak solution of chloride of lime, the affinity of the hair for the dye being thereby greatly increased.

Acid dyes are employed when a greater fastness is required than can be obtained with the basic colors. Sulphuric acid in a quant.i.ty equal to half the weight of the dyestuffs used, together with four times that quant.i.ty of Glauber's salt is added to the dyebath. Formic acid may be used in place of the sulphuric acid, very good results being obtained.

The skins are immersed in the dyebath, and worked until thoroughly soaked with the dye liquor, and then allowed to remain until the proper depth of shade is attained, or overnight. The temperature of the solution is about 40 C., and only very light shades can be produced in this manner.

In 1900 and again in 1914, the Ca.s.sella Co., a large German manufacturer of dyestuffs, obtained patents for processes enabling the dyeing of furs in hot solution with the acid dyes. The method required that the skins be chrome-tanned in order to render them resistant to the action of hot solutions, the addition of a small amount of formaldehyde to the chrome solution increasing this effect. The skins are then treated with a solution of chloride of lime in order to increase the affinity of the hair for the dyestuffs. The method as it is now practised is as follows: The skins which have been cleaned and washed are chrome tanned by the method as described in the chapter on Tanning Methods, 60 grams of formaldehyde being added to every 10 liters of the chrome solution. After proper tanning the skins are rinsed, and while still moist they are subjected to a treatment with chloride of lime. They are first immersed for 15 minutes in a cold bath containing 120 grams of hydrochloric acid 3236 Twaddell per 10 liters of water, then without rinsing, they are entered into a bath made up by adding gradually in four portions the clear solution of 24 grams of the chloride of lime per 10 liters of water. After working for an hour, the skins are removed and entered again into the acid solution, in which they are worked for another 15 minutes. In order to neutralize and remove the last traces of the chloride of lime from the furs, they are rinsed in a luke-warm bath containing 12 grams of sodium thiosulphate, or hyposulphite of soda, in 10 liters of water. The skins are then rinsed again, and hydro-extracted, or pressed, and are ready for dyeing. The dyebath is prepared with the required quant.i.ty of dye, to which is added 1020% Glauber's salt and 25% acetic acid (both calculated on the weight of the skins). The skins are entered at 20 C., then after three-quarters of an hour to 40 C., and then after another hour slowly to 5055 C. For blacks, the temperature is raised as high as 65 C. After dyeing the skins are treated with a solution containing per 10 liters

90120 grams of olive-oil soap 1225 grams olive oil 12 grams ammonia

for 15 minutes, then hydro-extracted and dried, without further rinsing.

For this method of dyeing, the following dyes may be used:

For yellow and orange Fast Yellow S Acid Yellows Naphthol Yellow S Tropaeoline Orange GG, R, II, IV

For reds Acid Reds Lanafuchsine Azo Orseille

For violet Azo Wool Violet Acid Violets

For blue Cyanole FF Azo Wool Blue Naphthol Blue R Formyl Blue B

For green Naphthol Green B Fast Acid Green Cyanole Green

For brown, combinations of Fast Yellow S Acid Yellows Tropaeoline DD Orange GG Lanafuchsine Indigo Blue N Cyanole B Fast Acid Green BN

For black Naphthylamine Blacks Naphthol Blacks Naphthol Blue-black

For grey Silver Grey N Dyed with the addition of 1/21% of alum

The chrome colors are dyed on furs when very fast shades are desired, all the fancy colors being produced in this manner, but for black, only the acid dyes are suitable. The preparation of the skin is exactly the same as for the acid colors, except that the treatment with chloride of lime may be omitted, although for very full shades it is desirable. The dyeing is carried out as follows: The dyebath is prepared with the requisite amount of the desired dyestuff, which is previously dissolved, and to this is added a solution of sodium bichromate, the amount of this substance being half the weight of the dye. The solution is heated and the skins entered and dyed for 12 hours at 7080 C. Then the dyebath is exhausted by the addition of 1/3% acetic acid, the skins being worked for another half hour, then rinsed, hydro-extracted and dried. Any of the one-bath chrome, or after-chrome colors may be used for this method.

Recently methods have been patented for the dyeing of furs by means of the vat colors. Vat dyes are among the fastest coloring matters ever produced, and their application on furs would be a great advantage, if suitable shades could be obtained. The general process for dyeing with vat colors, consists in reducing the dye, which is usually very insoluble, into a soluble "leuco" compound, by means of hydrosulphites in the presence of alkalies. The leuco compound is not a dye itself, but when the fibre absorbs it, and is then exposed to the air, the leuco compound is reoxidized to its original insoluble form, which remains fast and permanent. The use of strong alkalies in vat dyeing has. .h.i.therto been a great obstacle in the use of these dyestuffs, but in 1917, the Farbwerke Hoechst, a large German dye works, patented a process as follows: "A process for dyeing furs with vat colors. The dyeing is done in solutions of the vat dyes (after the addition of gelatine or some other protective colloid), which are rendered neutral or only slightly alkaline with ammonia, by neutralizing the caustic soda of the solution of the leuco compound of the vat dyes by the addition of ammonium salts, or suitable acids. The dyeings thus obtained are uniform and fast, the leather is dyed to only a slight degree, and shows no deleterious effects of the dyebath on the tannage." As a practical application of this process, another patent was taken out by the same company, also in 1917, as follows: "A process for producing fast blacks on furs, consisting of dyeing a ground color with appropriate vat dyes in a hydrosulphite vat, and after oxidation in air, topping with an Aniline or Diphenyl black. The dyeings obtained by the combination of vat dyes which are fast to oxidizing agents, with an oxidation black, have an appearance matching that of logwood black in beauty; and with a dark-blue to blue-black under-color, and a full, deep black top color, cannot be distinguished from logwood.

These dyeings also have the advantage of being faster to light than logwood or other blacks."

While these processes undoubtedly have many meritorious qualities which make them interesting, they do not seem as yet, to have attained any great practical application. However, it is a field of fur dyeing which is worth while developing, and with certain necessary improvements in these processes, the vat dyes may yet supersede partially some of the other methods of dyeing furs.

CHAPTER XVII

BLEACHING OF FURS

Bleaching is for the purpose of lightening the color of furs, and is most generally applied to white-haired skins such as white fox, ermine, and occasionally white lambs of all kinds, and white bears. Among such furs, pelts of a naturally pure white tone are relatively scarce, while in the majority of cases the color ranges from a pale creamy white to a decidedly yellowish shade. Colors which vary from the pure white detract considerably from the attractiveness and consequent value of the fur, and indeed, some pelts are so far off shade that they can only be used when dyed a darker color. Most white skins which are but slightly inferior in color can be brought to a pure white by bleaching, and they can then be used natural. Some pelts, on the other hand, are particularly resistant to the action of bleaching agents and cannot be sufficiently decolorized to render them suitable for use natural, so these are also dyed. For the production of certain delicate or fancy dyed shades on white furs, it is often necessary to bleach the skins in order to be able to obtain pure tones. Such instances are not very common, however. Occasionally dark furs, such as beaver, are bleached on the tips of the hair, a golden shade being obtained thereby, which at one time was quite popular, but recently such effects have not been in vogue.

In the bleaching of furs, two steps may be distinguished, first degreasing, and second, bleaching proper. In the preliminary operations of fur dressing, the furs are treated with soap or weak alkalies to cleanse them and to remove excess oil from the hair. During the various processes and manipulations, the hair, especially on white skins, may become soiled or somewhat greasy again, so it is advisable to repeat the cleaning process. This should in every case be as light as possible, using a weak solution of soap for the softer and cleaner pelts, or dilute solutions of ammonium carbonate or soda ash for the more greasy-haired skins. The skins are then thoroughly rinsed to remove all traces of the degreasing material. This step is very essential in order to obtain uniform bleaching.

Broadly speaking, there are two general methods which can be used in bleaching furs, one involving the use of what are known as reducing agents, and the other employing oxidizing substances.

Among reducing agents which can be used for bleaching furs are sulphurous acid, and its salts such as sodium bisulphite and sodium sulphite; hydrosulphites, and derivatives.

1. ~Sulphurous acid.~--When sulphur is burned, sulphur dioxide gas is formed. In the presence of moisture, or when dissolved in water, this gas forms sulphurous acid, which is one of the most commonly used bleaching chemicals for all sorts of materials, and is very effective for decolorizing furs. The procedure usually followed is to hang up the moistened skins on wooden rods in a more or less cubical chamber made of stone or brick, and lined with wood or lead. No other metals may be used, because they are quickly corroded by the sulphurous acid. The requisite quant.i.ty of sulphur is placed in a pot in the bleaching chamber, and then ignited, after which the doors are shut tight. The fumes of the burning sulphur in contact with the moist hair readily exert their bleaching action on the furs, and the operation is allowed to proceed for six or eight hours, or overnight. Then by means of fans or other devices, the air filled with sulphur dioxide gas is withdrawn from the chamber, and replaced by fresh air. The door is opened, the skins removed, exposed to the air for a time, then rinsed, and finally dried and finished. Sometimes one operation is not enough to sufficiently bleach the hair, so the process is repeated. Sulphur dioxide gas can now be obtained compressed in cylinders, which are more convenient to handle than burning sulphur.

The flow of gas which is introduced into the bleaching chamber by means of a nozzle attached to the cylinder, can be regulated, and the bleaching thus r.e.t.a.r.ded or accelerated.

2. ~Sodium bisulphite and sodium sulphite.~--These salts of sulphurous acid are effective in their bleaching action only when in solution in the presence of acids. The acids liberate sulphurous acid from the salts, so this method is virtually the same as 1. Instead of using the salts of sulphurous acid, sulphur dioxide may be dissolved in water, and the solution used for bleaching by immersing the furs in it. This procedure, while consuming somewhat less time than the chamber process, is more likely to affect the leather, which would have to be retanned. The principle is the same as that involved in method 1.

3. ~Hydrosulphites and derivatives.~--The bleaching agent can be prepared by adding zinc dust to commercial bisulphite of soda dissolved in about four times its weight of water until no more reaction is evident. Milk of lime is then added to precipitate the zinc, and the clear supernatant liquid of 1.55 Tw. is used for bleaching. The skins are immersed for 1224 hours, taken out, washed and finished. Instead of preparing the hydrosulphite, the commercial products may be used with greater convenience, a solution containing 14% of the hydrosulphite powder being used, and the skins treated in this until satisfactorily bleached.

The bleaching action of sulphurous acid and hydrosulphite is supposed to be due to the reduction of the coloring matter of the hair to a colorless compound; or possibly to the formation of a colorless compound of the bleaching material with the pigment. The former seems the more probable explanation, because the change is not a permanent one, the original natural color returning after a long exposure of the bleached fur to air and light. However, the results are sufficiently enduring to satisfy the requirements of the trade in the cla.s.s of furs on which these methods of bleaching are used.

Bleaching chemicals with an oxidizing action generally used for decolorizing furs are hydrogen peroxide and peroxides; occasionally hypochlorites and permanganates are also used.

1. ~Hydrogen peroxide.~--Hydrogen peroxide is usually employed for bleaching in the form of its 3% solution, to which is added about 20 cubic centimeters of ammonia per liter. The ammonia serves partially to neutralize the acid which commercial peroxide generally contains, and also to facilitate the bleaching action. The thoroughly degreased skins are immersed in the solution until the hair is completely wetted by it, are then removed, and evenly pressed or hydro-extracted, after which the pelts are hung up to dry in the air. As the hair becomes drier, the concentration of the peroxide becomes greater, and consequently the bleaching action is stronger. Where there is a likelihood of the leather being affected by the bleaching solution, the ammoniacal peroxide may be applied to the hair with a fine sponge or brush until sufficiently wetted, and then hanging the skins up to dry. Repet.i.tion of the process is sometimes necessary to obtain pure white, but the results are always excellent.

2. ~Peroxides.~--The most important of these is sodium peroxide, which comes on the market as a yellowish-white powder, which must be kept dry, and away from any inflammable material, as fires have been caused by the contact of the peroxide with such substances. When dissolved in water, it is equivalent to a strongly alkaline solution of peroxide of hydrogen.

Na2O2 + 2H2O = H2O2 + 2NaOH sodium water peroxide caustic peroxide of soda hydrogen