LOCATIONOF DYESTUFF AND SYNTHETIC ORGANICCHE~U~CAL MANUFACTURERS ACCORDING BULLETIN No. 89 (1933)
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DYESTUFFS
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HE h i s t o r y of o u r d y e stuff industry dates back
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to cotton which displaced the dye crop. almost to the founding of Another s u c c e s s f u l n a t u r a l Wilmington, Del. the colonies in North A m e r i c a . dyestuff business was started in I n d i g o w a s the f i s t commercial 1798 in a small s h o p i n Greenp r o d u c t , and the records show wich V i l l a g e , N e w Y o r k . The t h a t i t was i n t r o d u c e d i n t o founder was W i l l i a m P a r t r i d g e Louisiana as early as 1718 and beand his plant consisted of a mill came an article of export within ten years. I n the eastern driven by one mule. This enterprise has never died out, states the first record of any effort to cultivate indigo is that and the two largest individual plants for the manufacture of Julian Van Rensselaer made experiments with indigo seed near dyewood extracts in the world are its successors. The basis Albany in 1658 and Augustus Heerman in the neighborhood of this industry was, in the early days, the extraction of the of New Amsterdam. Apparently there was some indigo procoloring matter from the bark of the black oak tree, a dye duced shortly after the development of the plantations in the discovered by Bancroft in 1795. This is quercitron. South, but the real foundation of the industry resulted from More than 100 years after the start of indigo production, the efforts of Eliza Lucas, the daughter of the governor of the the manufacture of synthetic dyestuffs came into being, for it Island of Antigua. She obtained seed from her father in 1740, was only in 1856 that the seed with which Perkin worked cultivated it on her plantation in South Carolina, and in a produced the new strain that since then has proved so sturdy very short time learned how to process the harvest to produce and prolih. That America demanded the most recent in indigo capable of competing with the French product. It is the world’s goods even then as now, is evident from the fact astonishing to find what a successful crop this was. It was that already in the early sixties August Partz attempted to said, apparently without exaggeration, that “it proved more make fuchsin in Brooklyn. Almost with the discovery of the beneficial to Carolina than the mines of Mexico or Peru are, new dyes in Europe, the important place they held was or ever have been, either to old or new Spain.’’ South Carorecognized in this country. We find that the Scientific lina in 1757 sold a crop for which it obtained 150,000 pounds American in its issue of January 10, 1860, presents an outline of the method of manufacture of the new aniline dyes and sterling, an enormous income at that time. The industry declined rapidly after the Revolutionary War because the stresses a point which seems strange, since i t refers to what British encouraged the cultivation of indigo in India and in are now considered the most fugitive of dyes-namely, the West Indies. Also the attention of the South turned their extraordinary stability. I n this first article which de368
E.I. du Pont de Nemours & Company, Inc.,
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scribes the manufacture of aniline violet (a mixture of basic violets), the following statement is made: “The violet tints have generally been made with archil, but in consequence of the small stability of that coloring principle, violets thus made change under the influence of light alone, and they are altered by the feeblest acids. Aniline is now replacing archil; it constitutes the base of a fast violet color, which does not fade in the light, and which is acted upon by neither acids nor alkalies. It is to this great stability that it owes all its importance.” This article also quotes the price as $245 to $326.88 a pound, emphasizing thereby a condition obtaining a t the time-namely, that bright colors belonged to the rich upper classes and not to the poor. At present the fastest colors are used on the most inexpensive goods. I N 1865Thomas and CharlesHollidaystarted making these @ new aniline dyes in the suburbs of Williamsburg on Long Island. The offices of the concern were on Chambers Street, New York, and according to its advertisement, magentas, blues, and violets of various shades, purple, yellow, orange, and green were made, as well as blacks and browns for the use of “printers, publishers, manufacturers of paper hangings, lithographers and others.” These works produced picric and carbolic acid, methyl spirits, and nitrobenzene. Within ten years, however, it appears that all the dyes produced in America were made from imported aniline. I n 1882 we find it stated that there were two firms in America, both in New York State, producing approximately 300,000 pounds of dye-that is, one-third of the total consumed, 700,000 pounds being imported. Ry 1892 the industry was a t a standstill, but it refused to die out and struggled along in the succeeding years in spite of adverse tariffs and merciless foreign competition. This dogged perseverence was responsible for the fact that, when the Great War broke out, there were seven dyestuffs concerns here producing about 10 per cent of the domestic consumption. Then these stalwarts had their reward, because immediately on the disruption of traffic across the Atlantic the importation of dyes ceased and these firms were our only resource. They were of tremendoug importance. It is true that their efforts were not always as successful as the dyer would have liked, even admitting that a great many of the ludicrous and horrible results obtained by using dyes during that period were due to the misuse of products already in the country a t the time imports ceased. These manufacturers and others who came into the field with unlimited zeal and capital changed the situation rapidly. Whereas in 191314 seven companies produced 6,600,000pounds of the 60,000,000 pounds consumed, in 1927 fifty-five companies were operating to produce 95,000,000 pounds, about 94 per cent of the domestic demand. This development was not without its struggles. It was much too special a field to be of easy access to the ordinary organic chemical establishment. I n fact the organic chemical industry was not too well provided with men who could be thrown into this new development.
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Now that part of the struggle is over and we have an American dyestuff industry. That industry is no longer following but leading the way; it is producing materials in quality, quantity, and variety, not equal to those of the standards in commerce a t the time the development was started but very much better because American standards are more rigorous than those of any other nation, and the user of dyestuffs has been able to obtain what he wanted by direct contact with the producer t o an extent never before possible. And not only do American firms meet domestic requirements but their products go to the Far East, the Near East, Russia, Southeastern Europe, South America, Central America, and Canada. Other than the producer and user of dyes, few people, not even chemists, realize that since 1913-14, when America reentered the field, the advance in the industry has been t r e mendous. The range of products is much greater; there is greater chemical complexity and previously undreamed of purity; cost has been falling continually, with improved yield; rarities have become commonplaces; the range of hues is greater than ever before; the working properties best suited t o the needs of the user have been studied and new standards established accordingly; fastnesses have been systematically studied so that there are now available whole families of dyes of equal fastness that produce full lines of shades, rather than a few isolated fast dyes. The upward trend in quality has been so phenomenal that the layman would be horrified if he were thrown back into the period of 1900. He would complain about his bookbindings, draperies, socks, shoes, upholstery, the color of his automobile, the baby’s rompers, his wife’s dresses, the rugs, the blankets, hats, wall paper, his dress suit. Everyone knows that dyes are used for cotton, silk, and wool, but people do not appreciate that every new type of textile fiber requires special dyes so that the selection for rayon, although chemically it resembles cotton very closely, must necessarily be different from that for the natural fiber. And such textiles as are made from acetate cellulose can be dyed only with special compounds that the manufacturers have produced within the past six years. The vogue for tinweighted silk followed the development of suitable dyes, and new materials have been designed composed of several fibers because the range of modern dyestuffs includes groups that leave silk white, rayon white, acetate white, cotton white, or wool white. The call for color goes much farther than the dyeing of textiles. T H E R E is the extremely important use of dyestuffs in the 0 lake industry. What this means is not apparent unless attention is called t o the fact that all colored printing is done with lakes; what would our packaged goods be without splashes of colors and our magazines without illustrations, not t o mention tobacco boxes without their alluring scenes from the tropics. The making of typewriter ribbons, carbon paper, and protected check papers is another special field which has
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Du PONTDYE PLANTAT DEEPWATER POINT,N. J., FEBRUARY 4, 1935 called for all kinds of work, and what we used twenty years ago would not be a t all acceptable now. I n the wall paper trade an interesting situation exists, for the cheaper papers are much better in fastness than the more expensive ones. This is characteristic of the development in many products. The vat colors were first used on cheap shirts, and it was a long time before the expensive garments of the elegant gentleman were anything like as fast as those of the working man. In wall papers we have reached a development, thanks to the better understanding of the use of color and the introduction of faster-to-light dyestuffs, of products that are perhaps too permanent because people like to change their decorative scheme. The walls are not only brightly colored but they are washable, and while it is cheaper as a rule t o replace wall paper than it is to wash it, in the household where there are children, it is a great advantage to be able to apply soap and water to the wall. Within the very recent past we find a tremendous swing toward the use of spirit inks in printing. This comes of the development of much better rubber printing rolls. These spirit inks enable the printer to work much faster because they dry almost instantly. They are very bright and do not color a moist hand. This method is used in printing all kinds of special paper bags for packaging food, coffee, etc., and even for bags used for cement.
INASMUCH as light is destructive to food fats, causing 0 them to become rancid in the presence of air, we have been accustomed to packing such materials in dark containers without knowing just why. Now it is known that the long wave lengths are kept out, transparent containers can be used which will allow a display of the product and keep it as fresh as though it were in the dark. A green transparent bag doubles the life of potato chips, for example, and yet it is scarcely more expensive than plain transparent paper. So
important has color become that there are materials that could be used for the manufacture of a variety of articles which are not being developed commercially for the moment, simply because the proper coloring matters have not yet been discovered. This is true of some of the beautiful new plastics which will some day give us articles of a character and quality undreamed of a short time ago. If we add t o these odd uses the coloring of cosmetics and foodstuffs, and do not forget that every piece of paper is dyed, even the white, just as is every piece of leather, some idea is obtained of the multiplicity of directions in which this industry serves the public. There are innumerable comparatively small but important uses. The coloring of the vulcanized fiber used for radio panels is a specialty. The method of its manufacture necessitates the selection of a group of dyestuffs possessing qualities quite different from those that are considered in making a choice for use on silk or cotton. Nuts are made more attractive by being colored. Tobacco is tinted. And there is a very natural tendency to color wrappers for food in such a way as to make the materials appear attractive. If peas are sold in a bag of sheet cellulose tinted green, they look fresh and stand out as being very attractive vegetables. Chocolates look much less woebegone in hot weather if they are covered by a transparent wrapper which itself is tinted chocolate brown. The use of metal foils for packaging has increased greatly, and these are made attractive by patterns in color which are usually in a lacquer of some kind. A very special study is required of the dyes used in the projection of color images. It is extremely easy for the physicist to state what is necessary, but it is difficult to make synthetic products with the optical characteristics that the physicist calls for and a t the same time the transparency that will allow of colored projection on a screen in a large hall. The problem is twofold-the making of the films and their coloring. Everyone
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knows from personal observation how quickly this problem is being solved. At a popular resort a t the seaside on a warm (day in July, the toenails of the girls, entirely invisible in the day of Queen Victoria, are now brilliant red because they are tinted with a lacquer containing rhodamine.
THE dyestuff industry was born of research and byre@ search it has lived and prospered; that is still true today, perhaps more so than ever. In this country when we first entered this field on a large scale, we were hampered by the fact that research had taken other directions, but we had chemists who were trained in the formal methods of scientific inuestigation. It was they who carried on. Some of them became admirable plant supervisors and others of particular aptitude grew to be research workers of a very special type. The outcome has proved the worth of the American chemist. At the time the dyestuff industry was started in this country, emphasis was laid on the fact that it was without doubt a key industry, not alone because of its relation to national defense, but to an equally important national balanced manufacturing system. The nondyestuff activities of the dyestuffs industry during the short period in which the United States has been a real factor in the field have gone far beyond n hat the coiners of the phrase had in mind. For instance, as a people we are the greatest mers of rubber in the world and we have benefited enormously because of the aid of the organic chemical industry in perfecting the rubber goods we use. The life of articles made of rubber has been increased more than a thousand fold by antioxidants, substances which were found among the intermediates available in the dye works. Previous to that time the development of accelerators of all kinds revolutionized the handling of rubber; and the long life of the automobile tire, which is becoming proverbial, is the result not only of the great strides made by the actual manufacturers of these products, but also of the better understanding of the effect of organic chemicals, produced in connection with dyestuffs, on the life of rubber. Moreover, we have gone a step farther and invented a synthetic material which resembles rubber and is useful just where the natural product fails.
THE desire that rubber goods should fit into specific color Q schemesisagood example of a demand stimulating research to produce entirely new products. Only a short time ago there were only white, red, and black rubber articles, while today the designer needs to fear no restraints. Until other substances more nearly inorganic were discovered to be cheaper and just as effective, the flotation agents used by the mining engineer for floating his ores from the gangue were materials obtained im the course of the manufacture of dpestuffs. The production of phthalic anhydride, originally the process which made synthetic indigo possible, has become a major industry because phthalic anhydride plastics are among the most versatile of materials. They can be used wherever tough films are needed. It is only natural that the organic chemical industry should lead in the study of weapons to fight our host of insect enemies. It is true that so far the natural products, rotenone and pyrethrum, are the least toxic to higher animals and the most toxic to insects of any products used, but already the industry has produced a number of excellent insecticides and undoubtedly it will go farther in this direction. Success in suppressing offensive molds and bacteria has already been striking. We can prevent the discoloration of boards from the time they come from the sawmill until they are used, by spraying with a n organic mercury compound. M7e can disinfect seed successfully by using variations on the same theme.
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Important medicinals hare already resulted because of the cooperation of pharmaceutical and dyestuff industries, and if, some day, we become capable of disinfecting the blood stream of our own bodies, the materials used r i l l probably originate with the dyestuff industry or one of its offspring. Certainly it will be a result of the quickening of interest in organic synthetic work because of the industry’s existence. After all, where, other than in the dyestuff industry, should we find the nuclei around which to build inhibitors of corrosion, high-pressure lubricants, new refrigerants, extraordinarily effective detergents, perfumes and photographic materials; and it is well to remember that the nuclei are useless without research.
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LOOKING into the future, our only guide is the past. h guess as to where the curves of progress are taking us is in the realm of pure speculation. However, this much we may hazard-synthetic fibers will gain more and more and new ones will be introduced. These new fibers will be associated with a great many new materials necessary for their proper processing, finishing, dyeing, etc. Even the old fiberscotton, silk and wool-will be in certain directions transformed by the use of processing methods depending on new organic chemicals. The paint industry will continue to benefit from the change which has come during the past ten years, in which linseed oil has ceased to be the only vehicle, and, unless it is used in some modified form, its place will be taken by films of organic chemicals much less prone to disintegration and much quicker-drying than the natural oil. These films will be colored by the use of pigments which are faster and more brilliant than those employed at present. Some of these will be purely inorganic as in the past, but some will be dyes or lakes made from dyes. -4s far as the production of dyes is concerned, it is certain that the future will see materials more perfectly adapted to the user’s needs than a t present. More of this kind of thing has been done in this country than anywhere else. We have even encouraged the abuse of dyestuffs by making them immune to the most brutal handling, if by doing so it was possible for the user to effect economies. Unquestionably the physical conditions in which dyestuffs are marketed, especially in the case of colors used for textile printing, will be improved, although that seems difficult to believe when the products at present available are scrutinized. There will be a tendency toward the selection of dyes for very limited fields. An extreme case of this is the group of sensitizing dyes which have revolutionized photography. There will have to be new dyestuffs to meet the advent of new plastics. This field, which has grown unbelievably, is still only in its infancy. Perhaps in the far distant future we may render some of our dyestuffs obsolete by producing color as Nature does in her birds and butterflies-that is, by interference. It is to be hoped that this may be so, because the purity of these interference colors is so exquisite that we would be able to enter a new era in the use of color. Perhaps we can achieve this by a combination of a great development in mechanical control and the synthesis of special plastics. The future holds one sure fact-there are no limits to the horizon. We seem to have climbed a mountain as the dyestuff industry has advanced, but the only effect has been that our view has become wider and wider. R e can be sure, however, that even in the dimmest future we shall be using dyes and many of them, and that the organic chemist will still be inventive enough for us to say then, as we can now, that the dyestuff industry is the birthplace of a whole group of organic chemicals enormously important in furthering our march to our happier utilization of the chance that has come to humanity. RECEIVED March 5. 1935
