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792 Paranitrotoluol Dinitrotoluol
Koch’s Acid NaDhtholic Acid
Xylol Nitroxyl01 Cumidine DiDhenvlamine Niohtdalene Dinitronaphthalene Nitronaphthalene Hydroquinone Metol and Rubber Accelerator H-Acid D r y Distilled Benzidine Nitrobenzol Dinitrochlorbenzol Paraamidoacetanilid Faranitraniline Chromotropic Acid Cleve’s Acid
Acetamino Cleve Acid Carbazol Crude Anthracene Refined Anthracene Anthraauinone Alpha Naphthol Dimethylaniline Ethyl Benzylaniline Nitroso Dimethylaniline Diazo 1,2,4-Acid Purified Diethvlaniline Anthraruffin Resorcine Phthalic Acid Dinitrophenol Monochlorbenzol
The basis of the dye-making industry is the foregoing, for without the intermediates the dye maker is unable to proceed. Fortunately a t the Marcus Hook Works, Buffalo Works, and Brooklyn Works a staff of chemists and workmen were already in a position to undertake and carry on the dye-making operations as soon as the American factories were able to deliver the intermediates, and this work has continued, uninterrupted, to the present time. At the moment, owing to the war situation, certain much needed derivatives of toluol are not to be obtained for the reason previously mentioned. Certain small amounts of toluol, however, are permitted to be used for the manufacture of some few dyestuffs necessary for soldiers’ uniform material, but the general public is for the time being debarred from using dyes in which toluol constitutes an important ingredient. Almost every dye chemist and colorist has been asked what progress American chemists have made, whether we are looking to the production of dyestuffs better than the Germans formerly made or whether we are devoting our attention to the production of new dyes. Answering the queries i t might be well t o state a t once, that we produce dyes in every respect the equal in shade, strength, and working qualities of the pre-war type. This the American dye manufacturer has been successful in doing. He has not been able to produce every dye formerly imported, but with a catalogue of about 175 dyes actually made in the United States to-day from American raw materials and intermediates, in quantity and variety sufficient for the wants of the textile industry, one can regard the progress made as being remarkable. Referring to the second question, the American chemist has not had the time nor the opportunity during the high pressure period of the war to devote his energies to discovering new dyes, his whole time has been devoted to devising successful methods for producing intermediates and dyes, the chemistry of which required little or no further investigation. Among the important dyestuffs that have been made in the United States may be mentioned direct black, a product of great interest to cotton dyers and useful for many purposes. This dye has been manufactured a t the Buffalo Works of the National Company in immense quantities, and since the war commenced, entirely from domestic raw materials. Another dye of great technical value is chrome blue, applicable chiefly to wool. This dye possesdes in a marked degree properties of extreme fastness to light and weather, and therefore is almost exclusively employed for dyeing sailors’ uniform fabrics. The dyes now being manufactured number about 175 and include members of all the groups of colors used in American mills prior to the outbreak of hostilities. This list is being added to from time to time as progress is made in the production of necessary intermediates. In addition to the foregoing the manufacture of synthetic indigo is not to be omitted. At one of the Works of the National Company it is being produced and as rapidly as present conditions of labor and material permit, the plant is being expanded
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to a size that will deliver a quantity of indigo equal to, if not exceeding, over half the requirement of the American market. Another product of importance is alizarine. This is now being produced from American anthracene a t the Brooklyn Works, in quantities equal to the total requirement of the market, and is of a quality equal to any alizarine in paste form that was ever imported. The manufacture of alizarine is an industry within itself. When it was suggested that it be produced in this country, the problem a t once arose as to the source of anthracene, since none of this raw material had ever been recovered from domestic tars. It was known that anthracene existed in our tars, but i t was not until the necessity of supplying our dyers with alizarine arose that steps were taken to isolate the crude anthracene and refine it. This required a complete revision of our usual mode of procedure, but i t was successfully accomplished. There is no doubt but that the alizarine industry will be permanent. THE DEVELOPMENT OF THE DYESTUFF INDUSTRY SINCE 1914 By J. F. SCHOELLROPF, JR , of the War Industries Board
The idea of the present conference seems to me an especially happy one, coming as it does just now when we are in the midst of the greatest war in history and inclined to give attention t o those matters only which are directly concerned with the production of material necessary to win the war. It is, of course, but right and proper a t this time that the production and chemistry of war materials should have the first place in the minds of all chemists, but it is well, a t times, if conditions permit, to sit back and think of what will, or may happen, when we are no longer a t war. I say this because I firmly believe that the problems which the American chemist will have to face in the afterwar period will be greater by far than any he has been confronted with since 1914,and you all know of what magnitude and complexity these have been and how well they have been met. Because of these remarkable achievements of American chemists during the past few years, I look forward to the future with confidence and venture to prophesy that the place which America occupies to-day in the field of chemistry, which is a t the head of the procession, will be maintained hereafter. The chemistry of dyestuffs which we are discussing to-day is, it must be admitted, still in its infancy in this country and the reasons for this will presently become clear. Germany, as is well known, assumed the lead in this branch of chemistry some forty years ago and has up to the present time held this, largely due to tariffs “Made in Germany,” and not as a result of superior chemists. Why, you will ask, does this condition still exist after we have had an almost unsurmountable tariff wall for nearly four years? The answer is simple. For four years our chemists and chemical engineers have been engaged in the work of “catching up” with Germany, a task which is nearing completion, and one which has been done in a remarkably short time, considering the difficulties encountered. For the benefit of those who are perhaps familiar only in a general way with conditions confronting the industry during the past four years, it may be well to state as briefly as possible what some of these difficulties were and how they have been effectively overcome. It must be remembered that in 1914there were only seven manufacturers of dyestuffs in the United States and every one of these was dependent upon a foreign supply of intermediates. The total production was less than 6,000,000 lbs., this representing approximately IO per cent of the consumption. Furthermore, due to the cut-throat competition of the Germans on those products made in this country, aided by an unfavorable tariff, the industry had made practically no progress whatsoever during the preceding ten years and just before the war came upon us its condition was going from bad to worse. When, therefore, in August 1914 the tremendous and sudden
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demand for dyes came, the industry was in no shape to meet it, especially as regards personnel, the working organizations of the companies. as a necessary economic measure, having been stripped to the bone. Most of us thought a t that time that the war would be a short one and hastily erected improvised buildings in which it was attempted to produce some of the more important intermediates such as beta naphthol, paranitraniline, H-acid, etc. As a result, early in November, these products were being made in fair-sized quantities, sufficient a t least to make considerable quantities of the more staple dyes. The situation in the fall of 1914 was not so serious, because the imports from Germany had not ceased and large stocks were still in the country, although these were largely in the hands of speculators. Previous to 1914 between 300 and 400 different dyes had been imported into this country by the Germans, approximately 1 2 0 of which had been produced by American manufacturers. On January I , 1915, we were only making about 16, so that you can see what a big job was ahead of us. In March 1915, the English blockade prevented further imports from Germany and the real developments of the industry may be said to date from th$ time. This brought home forcibly, both t o consumer and manufacturer, the fact that if we were ever to become independent of Germany the opportunity was now here. This opportunity was seized upon and immediately the construction of new and modern plants was begun. In less than six months these plants were producing, but i t was soon found that their capacity was entirely inadequate, although they had served to more than double the pre-war production of the country, and had enabled manufacturers to produce about 40 different colors by January I, 1916, as against 16 the year before. 1)uring the year 1916 older plants increased their facilities tremendously, and the production of those who had newly entered the field also began to be felt with the result that in the early part of 1917 the ordinary needs for dyes were being met in a satisfactory manner. The number of dyes produced by the end of the year had increased to over 150, in other words, we were producing a greater variety than was produced before the war, and all raw materials and intermediates were of American manufacture. According to figures prepared by the Tariff Commission the production for 1917 was nearly 46,000,000 lbs., approximately eight times the pre-war figure, and the value was over $57,ooo,ooo as against $2,500,000 in 1914. Truly these figures are remarkable and show better than words can what has been accomplished. Do not forget that all the men to build and operate these plants had to be trained. It was impossible, as in the case of other industries which have developed as a result of the war, to obtain the services of experienced men by hiring them away from competitors by inducements of a financial nature, or otherwise. This was one of the greatest difficulties to contend with, but was rendered comparatively easy by the remarkable adaptability and ingenuity of the American chemist, engineer, and mechanic. Considerable difficulty was also experienced in obtaining the proper equipment for the plants, the design of which was in most cases new and entirely different from anything previously made by our foundries and machine shops. Here also, through whole hearted and intelligent cooperation, our burdens were reduced to a minimum. Up to a short time ago, owing to the incessant demand for dyes, the one idea of all manufacturers was quantity of production, quality being more or less of secondary importance. Now that the urgent needs of consumers are being filled, the pressure is relaxing and it is possible to develop the various processes in order that they may be made competitive. That is the big problem we are facing a t the moment, and one which is of the utmost importance for the future of the industry. To meet this the larger companies have established research laboratories which will undoubtedly bring about the desired results, and a t
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the same time train men for original work to be done in the future. I do not mean to imply by this that our research laboratories are not doing any original work now. They are. But until the processes for well-known dyes and intermediates are fully as efficient as those of our foreign competitors, it is manifestly more important that these be given preferential attention. As a result of this work the quality of American dyes is continually improving, in fact, I do not believe that there are many to-day which fall short of the former German standard. Naturally, until the line of dyes made in this country is more complete, there will always be complaints of a certain nature, but the quality of the dyes made in this country i s usually not a t fault. The cause of over go per cent of the complaints which are registered is faulty application of the dyes. If the dictators of fashions would take into account the dyes which are available, all would be well, but they do not, for in order to produce some of the prescribed shades, dyes not yet made in this country should be used. The result is that unsatisfactory substitutes must be used and complaints against the quality of American dyes immediately arise. As the complete and full development of the industry will, in my opinion, require a period of a t least another five years, it is important that as much publicity as possible be given this particular phase of the situation. So much that has appeared in the press during the past few years regarding dyes has been absolutely futile and erroneous. What a pity it is this space could not have been used to better advantage. It is interesting to note that one of the large manufacturers is conducting an active campaign along these lines, which is undoubtedly a step in the right direction, counteracting as it does the insidious propaganda against the quality of our dyes. An important factor in the development of the industry is the progress now being made in alizarine and vat dyes. The most important of these, especially the latter, are covered by German patents which have some years to run before they expire. By an Act of Congress the Federal Trade Commission has been given the power to issue licenses under these patents to domestic manufacturers, which fact has been taken advantage of, with the result that this class of dyes may be expected on the market within a short time. The importance of these dyes cannot be over-emphasized, and only with their production in this country will we be truly independent of Germany. It is for this reason that it is imperative that a change be made in our present tariff law which classes these dyes, as well as indigo, separatcly, and provides no specific duty as in the case of other dyes. I t is my understanding that the Tariff Commission which has made a study of the industry during the past two years will report its findings to Congress in the near future. I do not know what will be recommended, but I do know that unless materially higher duties, than called for in the present law, are placed on dyes, when peace does come it will place the industry in great jeopardy. I make this statement because from experience I know how costly it is to develop new processes and work experimentally on a large scale. Unless we can do this regardless of expense for a t least a period of years, our progress will be slow indeed. Given, saya period of not to exceed ten years of very high duties, I believe the industry will then have grown and developed to such an extent that no further duties of any kind, or a t the most only very much reduced duties, will be necessary. Why should not that be the case? We have all the raw materials in this country and certainly our chemists are the equal, if not the superior, of those of any other land. I could talk on about the tariff indefinitely, but believe that I have covered the important points and have demonstrated its importance with regard to the future of the industry. In closing, I wish to pay special tribute to the untiring energy and industry of those chemists and engineers who composed the nucleus of the organizations which existed prior to the war. I t was upon them that the burden of all that has been accom-
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plished during the past four years rested most heavily and how well they have borne i t is not generally known and therefore should be given special mention. The dean of these men is Dr. R. C. R. Taggesell, chief chemist. of the National Aniline & Chemical Company, Inc., whom the writer has worked with and known intimately for a long period of years. I can state frankly that i t is my opinion that without his superior knowledge and untiring efforts the industrywouldnot stand where it does to-day. I am glad the opportunity has presented itself to publicly proclaim this fact, knowing full well that the modesty of the man would prevent it from becoming known in any other way.
APPLICATION OF DYESTUFFS IN COTTON DYEING By J. MERRITTMATTHEWS Consulting Chemist, New York City
Cotton has become one of the principal textile fibers of the world and now ranks alongside of wool and silk as the three great sources of clothing material to meet the needs of the human race. A great many will probably consider that cotton has always been in a very important position in this respect, but this is not the case. It has been only during the last century that cotton has come to the front, and this has been brought about by the mechanical improvements in ginning, spinning, and weaving, and t o a great extent also by the manufacture of dyestuffs capable of readily dyeing the cotton fiber. Before the introduction of the coal-tar dyestuffs, the dyeing of cotton, like the dyeing of wool or silk or linen, was dependent on the use of the natural dyes and certain mineral pigments. As most of the natural dyes require to be combined with a metallic mordant before they yield useful and serviceable colors, and as the cotton fiber has very little power of combination, or so-called affinity, for metallic salts, the dyeing of cotton was attended with many difficulties which were not present in the case of wool, as this latter fiber readily combines with many metallic salts that serve as useful mordants. In order t o prepare the cotton with a satisfactory mordant of metallic salt i t was frequently necessary to carry out very devious and complicated operations, the very complexity of which caused the results to be uncertain and exceedingly difficult to maintain uniform. This is readily manifest on referring to some of the old recipes employed for the dyeing of cotton with the vegetable dyes. With the advent of the coal-tar dyes i t was soon discovered that many of them could be applied t o cotton by relatively simple and effective methods. The basic colors which were first introduced, it is true, still required a mordant in their application t o cotton, in this case the mordant consisting of tannic acid fixed in the fiber by the use of a metallic salt, such as tartar emetic. However, even this method of dyeing was a great advance in simplicity and a person of average intelligenceand resourcefulness could soon master the art of dyeing by this means. The acid colors which soon came into the market, i t is true, were only adapted t o wool and silk, and found little application to cotton, but when the benzidine or direct cotton colors were introduced a new field in cotton dyeing was opened up and the widespread use of dyed materials was much stimulated. These colors, however, though varied and pleasing, were limited in fastness, and this naturally restricted the utilization of cotton fabrics. The introduction of aniline black as a specialized feature in cotton dyeing, however, greatly helped to extend the use of dyed cotton materials by providing an extremely fast color. The later introduction of various sulfur dyes also stimulated the use of cotton material by providihg a number of fast shades. With the advent of the so-called vat dyes, however, permitting of the production on cotton of a wide range of beautiful shades of the highest possible qualities of fastness, cotton fabrics were lifted out of their previous rather low-grade class and elevated
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t o the rank of fabric aristocracy. At the present time, therefore, it may be said that cotton materials are used for highgrade fabrics, and in consequence demand the application of high-grade colors. I n the application of dyestuffs to cotton we must consider several factors of prime importance. In the first place, the form in which the cotton is dyed will have much influence in the selection of the dyestuff. Cotton may be dyed in the form of raw stock or loose unspun fiber,as cotton sliver; or in a partially manufactured condition, as yarn (either as skeins or hanks), as warps, or as yarns on cops or tubes. Or the cotton may be dyed in the fabric form, either as a woven piece or as a knitted fabric. Dyestuffs that are suitable for raw-stock dyeing may not be suitable for dyeing woven cloth or knit fabrics, and vice versa. Cotton warp dyeing requires special consideration as t o dyestuffs. Cops and tubes are dyed in special machines and the method of dyeing imposes certain restrictions on the kind of dyestuffs to be used. It will be seen, therefore, that the man who contemplates manufacturing and marketing cotton dyestuffs must be more or less familiar with the processes of cotton manufacture to be in a position t o properly select the products that are the more desirable. Another consideration that is important in selecting cotton dyes is the kind of material into which the fabric will be manufactured and the eventual use t o which it will be put. This will determine the qualities of fastness of the dyestuff t o be employed. Cotton goods go into all kinds of materials at the present time; we have shirtings for men, blouse and skirt material €or women. These are more or less in fancy colors, but as a rule the amount of color is only a small proportion of t h e total fabric. These goods are subject to repeated washing and laundering, and they must also stand exposure to light and perspiration, so it can readily be seen that the colors must be fast to these agencies and a high class of dyestuff is required. Before the war the vat dyes were being largely used for these goods and the public was being educated t o expect a color t h a t would last even longer than the fabric under the severe conditions of laundering, especially as most modern laundries now employ strong bleaching agents, such as hypochlorite of soda, for the rapid whitening or bleaching of the cotton goods. Under the present conditions there are practically none of these v a t dyes available, as they are not being manufactured in this country and it is t o be presumed that all the old stocks on hand have been used up. We also have ginghams and fancy cotton goods which have become quite popular as dress fabrics during the past couple of years, replacing light weight woolens and worsteds, and even silk to a considerable degree. The dyeing in this case isalscs chiefly in fancy colors and should possess about the same degree of fastness as just related, for these are all wash fabrics. Next we have cotton denims used so extensively for overalls and similar garments. Though this class of fabrics is perhaps not so much before the eye of the general public as some others, it is one of the great staples of the cotton business and very large amounts of dyestuffs are used in them. The principal color used is blue, the fancy shades being negligible in amount, and the chief dyestuff used is indigo-in fact, this is where t h e great bulk of indigo is used. The color has t o withstand very severe usage and repeated washings. Logwood can be used t o approximate the shade, but the fastness is very inferior. Sulfur blues can be used with good advantage, and there are some who may be inclined to maintain that sulfur blue is as. satisfactory for this work as indigo. Hydron blue, which may also be classed as a sulfur dye, though in reality i t is a vat dye, is eminently satisfactory, in fact, in many respects it may be considered as superior to indigo. But the trade has long been accustomed to indigo and i t will probably stick to it for a long, time to come.
