Oct., 1912
T H E JOURNAL OF I N D U S T R I A L A N D ENGINEERING CHEMISTRY.
cent. I n order t o make liquid driers, the paste or solid driers can be melted alone or in combination with gum-resins, bodied linseed oil, or both, and then thinned t o liquid consistency with volatile oils. Among other cobalt salts, some of the chemical manufacturers offer the acetate, with directions for its use as a drier. All agree t h a t between two- and four-tenths of one per cent. are necessary t o dry linseed oil. The oil should be a t a temperature between 300’ and 400’ F., and be carefully stirred until all the salt is dissolved. Soya and China wood oil may be similarly manipulated. I t is still a little too soon t o make a positive statement as t o how oils thus treated with the acetate withstand wear and exposure. Cobalt oxide, like the acetate, can be directly added t o oil during boiling. I t however dissolves slowly and necessitates heating t o high temperature ; the resulting product is also very dark, and mostly consists only of bodied oil. Rosin also will directly combine with cobalt compounds on heating together in a suitable kettle or container. The product possesses a number of objectionable features. It still is mostly unchanged rosin, has become much darker and lost considerably in weight due t o volatilization. I have tried the effect on oils of quite a number of cobalt compounds, but found none equal in efficiency t o those described in the foregoing. RESEARCH LABORATORY.
TOCHBROTHERS, NEW
PORK.
_____._
THE DEVELOPMENT OF HYDROSULPHITES IN THEIR RELATION TO MODERN DYESTUFFS.’ B Y PHILIP
s. CLARKSON.
I n 1869 when Schuetzenberger first made sodium hydrosulphite and in 1872 when he, together with Lalande, applied it t o the preparation of indigo-white and introduced a vat for indigo dyeing based on its use, a basic foundation was laid for the practical application t o the fibre of the latest and the most desirable group of synthetic dyestuffs. These are now known technically as “vat colors” but some better term should be applied to them than one derived from the large vats or dye vessels necessary on account of the quantity of sediment in the old style method of indigo dyeing. As is well known. these products are insoluble in water and require reduction, generally in a n alkaline solution, t o render them soluble and suitable for use in the dye kettle. The old methods of fermentation, etc., used with indigo are not applicable here and the hydrosulphites are found t o be the most satisfactory agents, being most energetic in reducing action, and in the form of their sodium salts giving no insoluble combinations with the dyestuffs. Before the discovery and invention of the now large group of vat dyestuffs, the use of hydrosulphite in dyeing was small, and the improvement in manufacture of hydrosulphites not marked, but coincident with the discovery of new coloring matters suitable for use in vat dyeing came new interest in the use of hydrosulphites as discharging agents in calico printing. 1 Paper presented at the Eighth International Congress of Applied .Chemistry, New York. September, 1 9 1 2 .
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This led t o the discovery of the formation of stable compounds with formaldehyde for which the first American patent appeared in 19041 followed by t h a t for the production of pure sodium hydrosulphite powder in 1905,sthat for sodium formaldehyde sulphoxylate in the same year and finally the two zinc salts in the year 1911. These may be said t o represent the products now in commercial use, the pure , sodium hydrosulphite powder (Na,S,O,) representing the products used for dyeing, the formaldehyde compounds those used for printing and for discharging. These are a s follows: Sodium-formaldehyde-sulphoxylate, NaSO,.CH,O 2H,O, which is commercially known as hydrosulphite N F conc., Rongalite C and hyraldite C extra, accord! ing t o the maker. This is the compound of especial interest to the calico printers. Di-zinc- f o r m a l d e hyde sulphoxylate,3 ZnSO,CH,O, is known t o the trade as hydrosulphite A 2,decrolin or hyraldite 2. This is used only for stripping or removing dyestuffs f r o m d y e d materials. Mono-zinc-formaldehyde sulphoxylate,4 2 n ( H S 0 ,C H , 0 ) z , which is hydrosulphite -4 2 soluble conc. This is used for the same purpose as the di-zinc salt, but is moreeffective and is soluble in r#oE‘ virwater. The other commercial marks represent mixtures with various substances for special purposes. Practical Applications.-These comprise dyeing, printing, discharge-printing on dyed materials, and stripping or the removal of dyestuffs and coloring matters from previously dyed material. The dyestuffs which require the use of hydrosulphites are a s commonly classed: indigo and substituted indigoes, usually halogen substitution for hydrogen ; indigoids, those having the molecular construction of indigo but having other replacements; and anthracene compounds. Dyeing.-The method of application for all these classes of dyestuffs is practically the same; the dyestuff is reduced with 1 1 / ~ times t o twice the amount of sodium hydrosulphite in the presence of alkali t o dissolve the leuco compound formed. This reduced dyestuff is then applied t o the fibre in the well known manner and the color finally developed by oxidation. Various assistants are added t o secure technically
+
f
r
2
C.S. Patent KO.769,593, Des Camp. E. S . Patent No. 793,559, Bazlen and Wohlfart.
4
Ber. d . chem. Ges.. 1908, p. 4657. B. Fran., 435,260.
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T H E J O U R N A L OF I N D U S T R I A L A N D E N G I N E E R I N G C H E M I S T R Y .
Oct., 1 9 1 2
perfect results. The shades obtained are generally speaking much in advance of any previously known in regard t o fastness to all injurious influences combined with brilliancy of shade. Printing.-It is in this branch of the art of coloring t h a t the most marked change has taken place. Previous t o the development of the application of vat colors in this industry, the dyer was far ahead of the printer in the production of shades of extreme fastness. Especially the manufacturing and finishing process depends on the production of insoluble color lakes in the process of coloring. The hydrosulphite-vat color process of printing provides this nearly in perfection. The required installation of machinery is not extensive, the success or failure of the operation
nish shades which can be guaranteed a s fast to light, washing, wearing and other injurious influences. in fact almost t h a t the color will last longer than the fibre. This condition has undoubtedly been brought about b y the discovery and perfection of the hydrosulphiteformaldehyde compounds. This is the present state of the direct printing industry; now the printer is ahead of the dyer for he can work more economically and the results are in every way satisfactory t o the consumer. One of the very apparent results is " laundry-proof shirts for one dollar. " The method of discharging azo colors by the use of these salts has been used for sometime and cannot be said t o have been very recently developed-only improved by the use of sodium-formaldehyde-sulph-
depending mainly on the proper construction and condition of the steamer, preferably a Mather-Platt. This must be arranged so t h a t all access of air is excluded and suitable steam plates provided for heating so t h a t the interior is at all times a t a temperature of 1 0 2 ~ - 1 0C. 4 ~(see figure). With proper conditions here a n d the usual care in making u p the print colors failure is not t o be anticipated. The present application of the v a t colors in the printing process depends on the use of sodium-formaldehyde-sulphoxylate. This is stable a t ordinary temperatures and enables the pastes t o be made up without difficulty, and the prints from the machine are uniform throughout the length. On steaming, the sulphoxylate is liberated and a t once reduces the dyestuff t o its soluble condition in which i t combines with the fiber. After steaming, the material is treated with either soap or oxidizing agents which fully develop the color in a n insoluble condition. By the proper selection of dyestuffs the printer can fur-
oxylate in place of the zinc-dust-bisulphite mixtures of the original formulas. But the use of formaldehyde-sulphoxylate for discharging white patterns on material dyed with indigo is the most recent and the most notable advance in the printing industry brought about b y the use of hydrosulphites. I t has long been known, and use has been made of the fact that oxidizing agents would destroy indigo blue and render i t colorless and all t h e discharge printing on indigo has been based on this. The great disadvantage has been, however, t h a t these agents also acted on the cotton fiber and the formation of oxycellulose with material loss of strength h a s occurred. By the use of reducing agents this could be avoided but the difficulty was t o remove the indigowhite produced in the pattern before it became reoxidized. I n I907 one of the foreign manufacturers of indigo. suggested the use of anthraquinones in the printing
Oct.,
,
1912
T H E J O U R N A L OF I E D U S T R I A L A N D E N G I N E E R I i V G C H E i W I S T R Y .
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paste with sodium formaldehyde sulphoxylate. This rendered the discharge more energetic and also hindered the reoxidation, but i t was necessary to handle the material very quickly to avoid tarnishing the whites. The usual conditions of the printing rooms rendered the production of uniform results almost impossible and little practical use was made of the process in this country. However, in the last two years a notable advance has been made owing to the discovery that certain bases of the substituted ammonium type would combine with indigo white to form stable compounds which
higher cost the commercial product now represents the standard of indigo prints. The gain to consumers is in the same proportion: for the strength of the material is not affected and after the garments are washed three times the whites are no longer holes but remain the original material. The zinc-formaldehyde-hydrosulphitesare used solely for removing the dyestuff and colors from previously dyed material and have little interest for the phase of the subject under consideration. Their great advantage lies in the fact that the strength of the fiber is not affected.
do not oxidize in the air. Further experiments proved that this property was characteristic of compounds of certain tertiary bases with benzyl chloride, its homologues and analogous bodies and their substitution products. I n the presence of zinc oxide desirable reddish t o yellow shades can be obtained by this method. But in order t o obtain white discharges the compounds obtained in the discharge process had t o be made readily soluble. I t was found t h a t this could be done b y the substitution of a sulphonic group in the benzyl nucleus. The yellow compound obtained by using a substance of this nature in the formaldehyde sulphoxylate discharge paste is readily soluble in alkalies and being easily removed from the material leaves the patterns clear. Thus the problem of satisfactory indigo discharges was solved. For certain considerations the discharge material is not sold as such b u t in combination with sodium formaldehyde sulphoxylate as hydrosulphite C L or rongalite C L, according t o the maker. The practical method of handling is simple. The discharge pastes are made up with 20 per cent. of the sulphoxylate discharge compound, 8 per cent. zinc oxide, 4 per cent. anthraquinone, 30 per cent. paste, with suitable thickening. The material is printed, dried, steamed in the before described steamer for 3-5 minutes a t 1 0 0 ~ - 1 0 3C., ~ washed in hot water, then passed through a n alkaline bath, washed and dried. I n this process, the pastes are perfectly stable and after printing and steaming the material can be left indefinitely before clearing. The writer kept a piece for two months before clearing and the resulting whites were perfect. The process has been adopted by the largest indigo printers in this country. I n spite of the fact of the
The increase in the use of hydrosulphites and the formaldehyde compounds has been most marked and the probable consumption in t,he textile industry in the United States for the year 1 9 1 1 was not far from one million pounds. N E W Y O R K CITY.
THE EFFECT OF “LIME-SULPHUR” SPRAY MANUFACTURE ON THE EYESIGHT.’ By
JAMES
R. WITHROW.
About two years ago, the writer was called upon to take charge of the installing of a “Lime-sulphur” department for a manufacturer engaged in other lines of chemical manufacturing. Preliminary to starting industrial experimentation, a very thorough laboratory study had been carriedout bythe manufacturer’s regular chemist. This work reviewed in a most capable manner about all the recommendations of recent chemical and experiment station literature concerning “lime-sulphur” preparation. As a result of this work a formula was evolved, which was used as a basis for manufacturing experiments. The laboratory experiments themselves were never made in larger than five-gallon apparatus. The writer witnessed, from time to time, these experiments or portions of them and a t no time noticed anything causing discomfort. The laboratory assistant, who did most of the experimental work for the company’s chemist and was constantly in contact with the material and its fumes, never noticed any effect or discomfort a t any stage of the laboratory work, which extended through several months. To be sure, there was the ever present odor of hydrogen sulphide or a t least a similar ndur. This was never offensively strong. At no time was i t 1 Paper presented at the Eighth International Congress of Applied Chemistry, New York, September, 1912.
