the early history of the synthetic dye industry

7
146 WKLFIAM- EARLY HISTORY OF THE SYNTHETIC‘ DYl3 1NDIJSTRY-- TT .T s n C. 79 TABLB: vlll Bleaching Mildewed Cotton Fabrics Reflectance (yo) Fabric 13leaching agent Mcthod Prctrcatment Not mildewed HZO, Cold pad None 89.6 Mildewed H20, C’old pad None 76.9 Mildewcd H*02 Cold pad NaOCI, 3 g/l. 82.0 Not mildewed NaCIO, Cold pad-steam None 88.0 available C1, Mildewed NaCIO, Cold pad-steam None 87.1 Mildewed NaCIO, Cold pad-steam NaOC1. 3 g/l. 88.6 available CI, hypochlorite (Table VIII) which consists in pad- ding to lOOyo take-up and leaving for 30 min at room temperature before washing off. The greater sodium chlorite is apparent. References Davidson and Spedding, J. Textile I d., 49, TO21 (1958). Chesner and Woodfordp J.S.rj.C., 74. 534 (1958). Clegg, J. Textile Inat., 31, T57 (1940). Garrett, J.Y.D.c., 71, 830 (1955). Tekatil. prom., 17, 40 (Mar 1957). safety margin provided by the ‘Orre& Use Of 4 Laporte CheInicals Ltd., BP 812,752 (1959). * * * Weber, J. Textile Inst., 24, P178 (1933). 9 Easton, Amer. Dyestuff Rep., 46, 5 (1957). The author thanks the Lace Research AMsocia- 8 Wood arltl Richmond, J.S.D.C., 68, 337 (1952). tion, as well as Dr. R. Preston, Mr. R. A. Leigh, and other colleagues in the laboratory, for their In Nichol and Smith, Id. Eng. Chetn., 47, 2548 (1955). assistance. LAPORTE CHXMIC‘ALS LTD LUTON BEDFORDSHIRE (MS. received 17th September 1963) l1 Schirl6 and Meybeck, Bull. Znnt. Test. Prance, No. 45, le Leigh, J. Tmtile Ins/., 52, T556 (1961). I3 Giertz, TAPPI, 34, 209 (1951). I* Baier, Mellinnd Testilber., 32, 141 (1951). IG Meybeck, Teintex, 17, 71 (1952). 31; No. 46, 29 (1954). COMMUNICATION The Early History of the Synthetic Dye Industry* 11- The Industrial History (1856-1900) R. D. WELHAMt An account of the development of tho industry from 1856 to 1900 is given. The carly years of the dye-making companies are ctescribed, with roferenre also to tho chemists who were revponsibltt for many of the important discoveritis. The effect on the industry in Britain of the loss of many of those chemists arid of the best mariagors is contrasted with the rapid increaso in tho efticiency and size of the Gorman companies. Accounts are given of the main British companics and of the ways in which they at,tempted to meet the almost overwkkdriiing competition from the Continent. Tho evidence on the decline of the industry in Britain, prusented by Mdtlola arid, later, by Grecn, is ruviewcd. The Period 1856-1 864 1864 Perkin had so improved the process that the When W. H. Perkin received Pullar’s favo1lrable commercial product was available as crystals 3. report on the capabilities of Aniline Purple, he and Although the dye was in use at Keith’s dyeworks his brother, T. D. Perkin, had already begun to by December 1857, the English market did not make it in small quantities in a laboratory at their react very quickly to Aniline Purple and it was its home. The dye was patented on 26th August 1856 popularity in France, where a void patcnt had and the Perkin brothers and their father, G. F. permitted free manufacture, that caused the Perkin, began to build a works for its production growth of the fashion for it hem4. It returned a t Greenford Green, Middlcsex in June 18571,2. from France with the name Mauve, from the Other dyers, notably Thomas Keith, a silk dyer of French for the mallow plant. Bethnal Green, were interested, but the reception The firm of Simpson, Maule & Nicholson began of the new dye by the calico pritit,ers was not a t all production. in 1858, of nitrobenzene and aniline 5, enthusiastic. Prospects were good enough, how- with which they supplied Perkin & Sons, who ever, to persuade G. F. Perkin to support his sons’ began also to make Magenta 6. venture with a great part of his life’s savingst. A third company, Roberts, Dale & Co., founded The works undertook the nitration of benzene, in 1852, began to make dycs in 1860. They reduction of nitrobenzene to aniline, and the employed Caro as chemist from 1859 and he and clichromate oxidation of anilino to Aniline Purple. Dale took out a patent for violet dyes. These were It was originally sold in an amorphous form but by not, however, as satisfactory as those of Girard and Uuscd on a thesis submitted for Part I1 of the Fin,il Honour School of Natural Science (Chemistry), Oxfnrd University. t Present address: Fosoco Interuational Ltd., Long Acre, Birmingham 7. $ When the calico printers were not intereatcd. Poll;w doubted whether production would be proRtaldc for dyers alone; it. was Keith’s approval that persuaded the l’erklna to go uhead.

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Page 1: The Early History of the Synthetic Dye Industry

146 WKLFIAM- EARLY HISTORY OF THE SYNTHETIC‘ DYl3 1NDIJSTRY-- TT .T s n C . 79

TABLB: vlll Bleaching Mildewed Cotton Fabrics

Reflectance (yo) Fabric 13leaching agent Mcthod Prctrcatment Not mildewed HZO, Cold pad None 89.6 Mildewed H20, C’old pad None 76.9 Mildewcd H*02 Cold pad NaOCI, 3 g/l. 82.0

Not mildewed NaCIO, Cold pad-steam None 88.0 available C1,

Mildewed NaCIO, Cold pad-steam None 87.1 Mildewed NaCIO, Cold pad-steam NaOC1. 3 g/l. 88.6

available CI,

hypochlorite (Table VIII) which consists in pad- ding to lOOyo take-up and leaving for 30 min a t room temperature before washing off. The greater

sodium chlorite is apparent.

References Davidson and Spedding, J . Textile I d . , 49, TO21 (1958). Chesner and Woodfordp J.S.rj.C., 74. 534 (1958). Clegg, J. Textile Inat., 31, T57 (1940).

Garrett, J.Y.D.c., 71, 830 (1955). Tekatil. prom., 17, 40 (Mar 1957).

safety margin provided by the ‘Orre& Use Of 4 Laporte CheInicals Ltd., B P 812,752 (1959).

* * * ’ Weber, J. Textile Inst., 24, P178 (1933).

9 Easton, Amer. Dyestuff Rep., 46, 5 (1957). The author thanks the Lace Research AMsocia- 8 Wood arltl Richmond, J.S.D.C., 68, 337 (1952).

tion, as well as Dr. R. Preston, Mr. R. A. Leigh, and other colleagues in the laboratory, for their In Nichol and Smith, I d . Eng. Chetn., 47, 2548 (1955). assistance. LAPORTE CHXMIC‘ALS LTD LUTON BEDFORDSHIRE

( M S . received 17th September 1963)

l1 Schirl6 and Meybeck, Bull. Znnt. Test. Prance, No. 45,

le Leigh, J . Tmtile Ins/ . , 52, T556 (1961). I3 Giertz, T A P P I , 34, 209 (1951). I* Baier, Mellinnd Testilber., 32, 141 (1951). IG Meybeck, Teintex, 17, 71 (1952).

31; No. 46, 29 (1954).

COMMUNICATION

The Early History of the Synthetic Dye Industry* 11- The Industrial History (1856-1900)

R. D. WELHAMt

An account of the development of tho industry from 1856 to 1900 is given. The carly years of the dye-making companies are ctescribed, with roferenre also to tho chemists who were revponsibltt for many of the important discoveritis. The effect on the industry in Britain of the loss of many of those chemists arid of the best mariagors is contrasted with the rapid increaso in tho efticiency and size of the Gorman companies. Accounts are given of the main British companics and of the ways in which they at,tempted to meet the almost overwkkdriiing competition from the Continent. Tho evidence on the decline of the industry in Britain, prusented by Mdtlola arid, later, by Grecn, is ruviewcd.

The Period 1856-1 864 1864 Perkin had so improved the process that the When W. H. Perkin received Pullar’s favo1lrable commercial product was available as crystals 3.

report on the capabilities of Aniline Purple, he and Although the dye was in use a t Keith’s dyeworks his brother, T. D. Perkin, had already begun to by December 1857, the English market did not make it in small quantities in a laboratory a t their react very quickly to Aniline Purple and it was its home. The dye was patented on 26th August 1856 popularity in France, where a void patcnt had and the Perkin brothers and their father, G. F. permitted free manufacture, that caused the Perkin, began to build a works for its production growth of the fashion for it hem4. It returned a t Greenford Green, Middlcsex in June 18571,2. from France with the name Mauve, from the Other dyers, notably Thomas Keith, a silk dyer of French for the mallow plant. Bethnal Green, were interested, but the reception The firm of Simpson, Maule & Nicholson began of the new dye by the calico pritit,ers was not a t all production. in 1858, of nitrobenzene and aniline 5, enthusiastic. Prospects were good enough, how- with which they supplied Perkin & Sons, who ever, to persuade G. F. Perkin to support his sons’ began also to make Magenta 6.

venture with a great part of his life’s savingst. A third company, Roberts, Dale & Co., founded The works undertook the nitration of benzene, in 1852, began to make dycs in 1860. They reduction of nitrobenzene to aniline, and the employed Caro as chemist from 1859 and he and clichromate oxidation of anilino to Aniline Purple. Dale took out a patent for violet dyes. These were It was originally sold in an amorphous form but by not, however, as satisfactory as those of Girard and

Uuscd on a thesis submitted for Part I 1 of the Fin,il Honour School of Natural Science (Chemistry), Oxfnrd University. t Present address: Fosoco Interuational Ltd., Long Acre, Birmingham 7. $ When the calico printers were not intereatcd. Poll;w doubted whether production would be proRtaldc for dyers alone; it. was Keith’s approval

that persuaded the l’erklna to go uhead.

Page 2: The Early History of the Synthetic Dye Industry

A p r i l 1903 WELHAM- EARLY HISTORY OF THE SYNTHETIC DYE INDUSTRY- I1 147

de Laire ?, who transferred their patent to Simpson, Maule & Nicholsona. Martius, who joined Caro a t Dale’s, discovered the important dye Bismarck (or Manchester) Brown in 1863 7.

In France, Renard Frhres of Lyon began, in 1859, the manufacture of Magenta ?. Other French firms started very soon afterwards and, a t the Exhibition of 1862 in London O, four French manufacturers of dyes were represented-

Renard Frhres, Lyon Gerber Keller, Mulhouse Monnet et Dury, Lyon Guinon, Marnas et Bonnet, Lyon

and only the three English firms already mentioned, Simpson, Maule & Nicholson having begun the manufacture of dyes in 1861 lo. Under Nicholson the firm developed the first commercially successful manufacture of Magenta lo, using Medlock’s arsenic acid process to produce a dye of high purity. They also made the spirit-soluble blues and violets and the water-soluble acid dyes prepared from them by Nicholson in 1862 ?, There were, however, other British firms in production a t this time, two having started to manufacture dyes in 1860.

At Huddersfield the firm of Read Holliday, who had been tar distillers since 1830, began in 1860 to make Magenta, nitrobenzene, aniline, and toluidine. They fought a lawsuit with Simpson, Maule & Nicholson over the manufacture of Magenta. Simpson’s had injunctions out against all Magenta makers for patent infringement, and Read Hollidays defended themselves on the grounds that Medlock’s patent 7 specified dry arsenic acid, which would not work, and Nicholson’s, although correctly des- cribing the reaction, had not been taken further than the preliminary specification and the process was thus “common knowledge”. This defence was successful and the industry became free to produce Magenta 4.

Also a t Huddersfield, Dan Dawson, a dyer with some self-taught chemical knowledge, made Magenta in secret (until the result of the Holliday action was known) in his kitchen and sold the dye a t such profit that he abandoned dyeing and set up the firm of Dan Dawson Bros. to make Magenta and, later, Bismarck Brown, Aniline Yellow, Safranine, and Chrysoidine ll.

Calvert’s notes on the Exhibition of 1862 show, however, that the coal-tar dyes were still far from being generally accepted. Initially they were extremely expensive l2 and, very often, incorrect methods of application had given poor results and discouraged users.

“ . . . if the use of coal-tar colours were properly encouraged, they would doubtless gradually decrease in price, and this country, instead of being tributary to others for its dyestuffs, would in time become the purveyor of dyeing materials, or of the substances yielding them, to the whole world.”

1864-1874

Calvert wrote 13, however-

There are in existence documents to show that, about 1864, there was a move to convert Perkin & Sons into a limited company in amalgamation with Renard Brothers & Franc, who were manufacturers

of Magenta a t Brentford. Draft articles of incor- poration were drawn up which indicate a fairly close asvociation between Perkin & Sons and Renard Frhres of Lyon. Perkin & Sons had soon given up the manufacture of Magenta 7 and it is probable that the supplies of Magenta needed for making Britannia Violet and Perkin Green* came from the French-owned factory a t Brentford 14.

But no limited company was formed and, in general, dye manufacture in England remained in the hands of private companies. Chemists of the highest ability were, however, employed. Simpson, Maule & Nicholson had Nicholson himself and employed Hofmann as consultant. Roberts, Dale & Co. employed Caro, Martius, and Leonhardt and had the services of Griess, who worked for AUsopps, brewers, of Burton on Trent, as consultant a. Perkin is known to have employed a t least four chemists, but appears to have done research work himself, using the others as works chemists. Greville Williams was a t Greenford Green from 1863 to 1868, when he left to help found the firm of Williams, Thomas & Dower.

In 1864 another dye-making firm was started, near Manchester, by a Berliner, Ivan Levinstein, who came to England a t the age of eighteen and began making Magenta in a converted cottage a t Blackley. He soon made Bismarck Brown and other dyes15. In the next year the increasing production of dyes caused Simpson, Maule & Nicholson to start a factory a t Walworth to supply Perkin & Sons with intermediates 18.

But the industry was also expanding rapidly in Germany, with several firms being established. In 1860 a t Elberfeld, Bayer, an agent in natural dyes, began manufacture of synthetic dyes a t the kitchen stove level. In 1863 the firm of Meister, Lucius & Briining (MLB) was founded a t Hoechst. In 1864 the firm of Kalle was founded a t Biebrich and the Badische Co. a t Ludwigshafen. The AG fur Anilin Fabrikation, Berlin (Agfa) was founded in 1867, and in 1870 the dye-retailing firm of Leopold Cassella began manufacturing near Frankfurt-am- Main 17. In Germany, however, there was little in the way of new discovery in the early days of the industry and these companies were content to copy the British and French processes for the rosaniline dyes. As they grew larger, however, and the opportunities in Germany for chemists became greater, those German chemists in England began to return home to posts both in industry and a t the universities. Hofmann left in 1865 for the University of Berlin and, a year later, Caro went to Heidelberg. In 1867 Martius returned to Germany and started, with Mendelsohn-Bartholdy, the Agfa works l7.

In 1868 Nicholson also left the industry, the works of Simpson, Maule & Nicholson being made over to the new partnership of Brooke, Simpson & Spiller. Nicholson seems to have effectively retired on the money he had made from ten or so years in a very profitable industry, although he was only just over 40 years of age. Similarly,

Britannia Violet was repared by heating a niethsnolic solution of Magenta. with broniynated turpentine under pressure. Perkln Qceen is its acetyl derivative.

Page 3: The Early History of the Synthetic Dye Industry

148 WELHAM- EARLY HISTORY OF THE SYNTHETIC DYE INDUSTRY- I1 J.S.D.C. 79

Dawson retired in 1874, a t the age of 38, and went to study chemistry a t Berlin under Hofmann ll.

A new British company was formed a t this time by Greville Williams, a talented chemist and a former employee of Perkin & Sons. With John Dower and Edouard Thomas he is thought to have taken over the Brentford works owned by Renard Brothers & Franc that was mentioned earlier j4

(p. 147). By 1869, however, the new industry only pro-

duced some 10% of the dyes used and it had not affected the trade in natural dyes to any appreciable extent la. It was the discovery in 1869 of a com- mercially successful process for the manufacture of Alizarin that introduced real competition with the natural dyes. Within a few years the Madder industry had virtually disappeared l8 and the manufacture of synthetic dyes was established on a large scale.

Although Perkin’s patent for Alizarin was a day later than that of Graebe, Liebermann, and Caro’s, it was sealed first and an arrangement was entered into by which Perkin & Sons were to be the only English manufacturers of the dye. But the absence of an effective patent law in Germany gave no such protection there and when, after being delayed by the Franco-Prussian War, the Badische Company started production in 1871 they were unable to prevent the other German companies from manu- facturing the dye.

Perkin & Sons expanded considerably in the years 1869 to 1873, during which time they had no real competition in the synthetic Alizarin market and could sell the dye a t 3s. a pound, a price which represented a very considerable profit. In March 1874, in a statement prepared in connexion with the sale of the firm, T. D. Perkin calculated the production cost of Alizarin a t just under 1s. 5d. a pound and, by this time, the price of anthracene, which represented about 6O1Y0 of this cost, had doubled or trebled compared with 1871 14.

W. H. Perkin himself laterz0 gave figures for the manufacture of Alizarin a t Greenford Green.

Year Production (ton)

1889 1 1870 40 1871 220 1872 300 1873 436

But the limit of Alizarin production a t Greenford had been reached by 1873 and competition forced the price down to 2s. 3d. a pound a t the end of that year. To increase both the volume and efficiency of production would have required reinvestment of the profits gained by the Perkin brothers and, in addition, W. H. Perkin made no secret of his wish to leave the chemical industry for pure research.

The Sale of Perkin 81 Sons In 1873 the works were offered to the Badische

Company for purchase, but this offer was declined and successful negotiations were opened with the firm of Brooke, Simpson & Spiller in November of that year 14. Brooke, Simpson & Spiller took over the works in 1874 and, later that year, filed a Bill

of Complaint in Chancery against the Perkin brothers, alleging wilful misrepresentation and praying for a rescission of the agreement. Although this Bill of Complaint was not proceeded with, Herbert Levinstein, reminiscing in 1949, wrote-

“Old Mr Simpson, a member of the firm of Simpson, Maule and Nicholson, (sic) who bought them, told me a few years ago, with some warmth. how they had been ‘done’ when they bought Perkin’s works. I certainly do not subscribe to this but they were not a wise pur- chase for Simpson, Maule and Nicholson.”

Despite his mistake over the name of the firm, Levinstein’s conclusion would appear to be the correct one. From statements made by T. D. Perkin a t the time, the directors of Brooke, Simpson 6 Spiller appear to have made no effort to see the books of the firm before purchase nor, when they had bought it, did they give i t the con- tinuous close personal attention that the Perkin brothers had found necessary 14. They were unwilling to expand and diversify the plant or to maintain a scientific control over the processes and, in a period of rising costs of raw materials and increasingly severe German competition, they were bound to run into trouble. The difficulties that were appearing in Alizarin manufacture should have been obvious to those already in the dye- making industry and, unless they were prepared to deal with them, they should not have bought this factory and expected it, as they did, to continue making a profit a t the old rate with less supervision and control.

W. H. Perkin told the Departmental Committee on Industrial Alcohol 22 in 1905 that

“After we left those who bought our works used only a small amount of scientific aid, whereas they should have increased it very much. In Germany they used it with great success; and the use of scientific aid was really the second step* in the developinent of the industry in Germany.”

On the other hand, the claim of W. H. Perkin Jnr.23 that, a t the time of the sale, the Greenford Green works were “in the most prosperous con- dition” and (‘muoh in advance of anything that existed in Germany” must be considered a little nafve, as production by the Badische Company had reached 900 tons in 1873 20.

In preparing an obituary notice for W. H. Perkin in 1908, Raphael Meldola wrote to Heinrich Caro about the sale and Caro, in his reply, pointed out the difficulties of the position of Perkin & Sons. The brothers had profited greatly from the early years of Alizarin manufacture but were later faced with considerable problems. The price of Alizarin was dropping, Perkin could not rely upon the pro- tection of the shared patent in Britain?, and the German dye was not only cheaper but of better quality, since reRearch there had lcd to individual processes for making alizarin, flavopurpurin, and

The Rrat atcp. :iriaorillnu to Perkin. ~ $ 1 1 1 thi. iilnenre of‘ a pfltent IHW in Qerninnv at this timr.

t In the samc lcctnrr Prrkin rrfrr8 to illxrreliaiirirr i n the iniport Rgurcn for Garancine (a rrRiied nflturfll Inadder) for the year 1878 (15,306 cwt quoted initiflll.v and 0,436 cwt quotrd a year later) and he conaidered that tho 0.000 cwt difference represented synthetic Allearln Ininorted as Qnranclne to avoid the ~ossibllltv of flctloo belng taken-by the pfltentees agalnst the irnporh8.

Page 4: The Early History of the Synthetic Dye Industry

April WELHAM- EARLY H18TOHY OB THE SYNTHETIC: DYE 1NllUSl’RY- 11 140

anthrapurpurin from the mono- and di-sulphonic acids of anthraquinone l9. Perkin’s dichloro- anthracene process could not supply enough alizarin and flavopurpurin to meet the growing demand. Caro wrote 24-

“The brothers Perkin felt therefore in 1873 the urgent necessity not only of enlarging, but more so of entirely reforming and remodelling, their manufacture in order to march at the head of their trade. But they must have also foresee11 that their works had not only to be trebled or more and thoroughly changed, but altogether removed from Greenford Green and rebuilt in another more suitable place.”

So the Perkin brothers sold out, having profited enough to ensure a very comfortable retirement for them both*.

The other British firms were, if anything, in a worse competitive position. Alizarin manufacture had been extremely profitable but none of them had shared in those profits. Those firms that had employed German chemists had by now lost them, with the excepbion of Witt, and, of the English chemists who had developed the industry, only Williams remained. Research in the German firms, which does not seem to have started until 1868 or so, rapidly increased in scope, its advantages soon becoming manifest in the im- provement of the Alizarin processes. Production in Britain was nowhere on so large a scale and competition was beginning to be felt in earnest?.

The Period 1874-1900 It was during the seventies that the supremacy

of the German industry was established. In the report on the Paris Exhibition of 1878 Lauth gave details of the production of dyes which indicate the extent to which the German manufacturers now dominated the industry. The value of Germany’s annual production was 50-60 million francs (26 F=E1 approx.) (of which F30 m. was Alizarin, 75% of this Alizarin being exported). British production was F11 m., Switzerland’s F7 m., and that of France F4-5m.=. It was in this decade also that the investigation of azo dyes began on a large scale and in this the ability of German industry to call upon large numbers of trained chemists was important. It was later estimated that, by 1876, 1700 trained chemists were employed in German industry and a large number of these must have been a t dye-making worksz6.

An account of the industry in this period is best given by treating the main British firms indi- vidually and then comparing their progress with that of the German companies.

.

THE BRITISH ALIZARIN COMPANY

Brooke, Simpson & Spiller retained Perkin’s works for only two years, selling them in 1876 to the firm of Burt, Boulton & Haywood, who very shortly stopped manufacture a t Greenford and moved to Silvertown in East Ham. Despite

The Bnal price obtained was €105,000 plus stock at €47,000. f H Levinstein said in evidence to the Departmental Committee on

Iidustrlal Alcohol’ In 1805. that liiv Brnr had Rrst fclt Oerinan competition 30 years earlier.

the improvement in management brought about by this sale 22, the British production of Alizarin dwindled rapidly until, by 1880, loss than 10% of the country’s requirements were supplied 27.

The rapidly falling price of synthetic Alizarin had led to the establishment of an Alizarin Con- vention, which stabilised prices and apportioned quotas. Burt, Boulton & Haywood were the only British members of the Convention, the others all being German firms. In 1882 a common policy was decided upon by the members in respect of the British market because the patents were due to expire in 1883 and production might well have been started by British firms other than Burt, Boulton & Haywood, who were the succcssors to Perkin’s patents z8.

The Convention attempted to have the patents extended and also to force consumers into extension of contracts, a t a price 50% higher than before, for a year beyond the end of the patent rights. This was despite a considerable drop in the price of the raw material, anthracene. The Convention had, however, overplayed its hand here, the threatening circular i t sent to the dye users did not have the expected effect and, although the circular was withdrawn, it inspired a group of Alizarin users in Britain- notably calico printers and the Scottish Turkey Red Dyers- to take steps to ensure their own supplies 28.

A company with a capital of $200,000 was formed, with dyers and printers as shareholders, and this bought, in 1883, the Silvertown works of Burt, Boulton & Haywood and began to manu- facture Alizarin as the British Alizarin Company. The capacity of the works was 600-700 tons a year of the 20% paste, whereas British consumption a t the time was over 3000 tons a year.

In a lecture on this subject to the newly formed Society of Chemical Industry in 1883, Ivan Levinstein 2g said that the United Kingdom possessed special advantages for Alizarin pro- duction-

(a) a large supply of anthracene- then mainly exported,

( b ) cheaper caustic soda, (c) cheaper fuel, ( d ) a large internal consumption, and ( e ) special export facilities.

He hoped that, if research were devoted to improving the process, the British Alizarin Com- pany would soon be in a strong competitive position and would, as well, encourage other chemical industries. The introduction of mordant dyes based on alizarin (faster than dyes based on naphthalene derivatives) was also increasing demand 20.

Figures quoted by Meldola 27 for the consumption of Alizarin by one of the largest firms, thc Alexandria Turkey Red Works, Dumbarton*, show a substantial reaction to the formation of the new company-

* They used over two inillion pounds of 10% Alizarin a year. WRH & h u t one sixth of tiic British total.

This

A4

Page 5: The Early History of the Synthetic Dye Industry

150 N’mt iAhi - EARLY HlS’l’OSY OF THE SYNTHETIC! DYE 1NDUS’I’RY- 11 J.Y.D.0.79

Sourcc of Alizarin (%) German y Britain

1 XXO 98 2 1881 99 1 188.2 100 0 1883 77 23 1884 50 44 1886 47 63

An immediate result of the formation of the company was the reduction in the price of Alizarin from 2s. 6d. to 1s. IOd. per lb (of 20% strength) which was proposed by its representative, S. B. Boulton, a t a Convention meeting on 1st May 1883 a t Brussels and which was accepted 30.

The Convention broke down in 1885 and the price fell to l l d . a pound31, but the company had the guaranteed market of its shareholders and was thus able to wcather competition that might other- wise have been too much for it. It continued to improve the quality of its products* and, by restricting itself to lines for which there was a large demand, it prospered and the German firms were unable to buy it off in 1900 when the second Alizarin Convention, in which it joined, was formed.

This firm, whose foundation has already been mentioned (p. 147), was one of the most successful British manufacturers during this period, although in no way comparable with the German companies. New works were bought and extended in 1885 and the production of intermediates was steadily increased, both for making into dyes and for sale. When negot,iations for its purchase by Bayer and Agfa fell through in 1890 i t was converted into a limited company with a capital of S70,OOO. Bayer and Agfa each took up one third of this. The new company took over tho licences for all the patents of the two German firms in Britain. Production of 2-naphthol, 1-naphthylamine, chamber acid, and other intermediates went forward a t a greatly increased rate. 1-Naphthylamine was made a t the rate of 100 tons a month and 2-naphthol a t 30 32,

Bottiger was chairman of the company, Levinstein managing director, and von Martius another director. Research chemists and tech- nical staff were recruited from the technical schools of Manchester, Salford, and Bury but, in general, Germans were employed and i t was Levinstein’s policy to have a rapid turnover in these. According to Green’s account, research a t Levinsteins was confined t o diazo compounds and, referring especially to Levinstein’s works, he said 33-

‘‘ . . . conditions in the English works aH tt whole at this time were unfavourable to the exploitation of new inventions, so that men like Dr. Hem found insufficient scope for their abilities.”

Herz left Levinsteins and went to Cassella, whcrc he played a large part in the development of the Hydron dyes34. The turnover of chemists a t Levinsteins a t this time was so great that Manchester contained many chemists who had worked for him and these were referred to as “Die Gesellschaft der ehemahligen Levinsteiner” 33.

IVAN LEVINSTEIN

The oompany won R gold medal nt. the Exhibition of 1885.

The company paid reasonable dividends, in 18Yd 6% on SlO0,OOO and in 1894 6% on sE120,OOO. It was wound up in 1895 and a new company, Levinstein’s Ltd, with a capital of 2190,000 and free of the German interest, was formed. Levinstein himself was responsible for severing the German connexion, and this action, coupled with his con- tinual agitation for reform of the British Patent Laws in a manner that would prove unfavourable to the German firms, led to their considerable hostility towards him and his company 33.

READ HOLLIDAY & SONS

This Huddersfield firm, which had begun dye manufacture in 1860 (p. 147), was during thi8 period the largest in the country, Production of the triphenylmethane dyes was carried on, although manufacture of those based on dimethylaniline was stopped in 1884 because of the duty on alcohol. Developments were, however, made in the use of azo dyes. The “ice-colour” process was developed here in 1880, although it was not much used for some years, being mainly exploited by others. The firm did, however, have a dyehouse for this pro- cess, the existence of which was a sore point with dyers and which was thus bad for sales3j. Primuline36 was made here from 1888 and the direct dyes from 1890.

The firm was converted into a limited company in 1890 with capital of S200,000, management remaining in the hands of the Holliday brothers. Not only did the firm have a dyehouse but it made electric dynamos, acetylene gas installations, and calcium carbide until the beginning of this century.

In general it did not have a very good reputation for the quality and standardisation of its dyes. Much colour faking was done. For example, it was found that, if sodium thiosulphate (hypo) was padded on cotton dyed with some direct dyes, the dyeing became faster to light- as long as the fabric was not washed. This last qualification was with- held from customers. For this purpose hypo was given the name Fastogene and was even sold in Germany 38. However, as a long-term policy, this sort of sale did not enhance the reputation of a business that was in competition with German companies which paid a great deal of attention to standardisation and giving an efficient service to the customer.

BROOKE, SIMPSON & SPILLER

After the sale of Greenford Green this company, once (1868) the largest in the world, continued to show the same lack of enterprise that had marked its purchase and operation of those works. It did not enter the azo dye field very early; there are no dyes of this type in the list of its products in 1879 given by Green 37.

It did, however, employ two very talented chemists during this period whose discoveries, if properly exploited, should have ensured commercial success. During the period 1877-85 Meldola worked there; in 1879 he discovered the Oxazines (such as Meldola’s Blue; (3.1. 51175), of which twenty different types were made by 1894 but none in Britain38, and in 1885 the salicylic acid dyes. Green succeeded him until 1894, discovering in

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Bpril19tiJ WELHAM- EARLY HIBTOHY OF THE SYNTHETIC DYE INDUSTRY- 11 151

1887 Primuline (C.I. 49000) and the “ingrain colours” 36, which were not patented by the firm. He also produced Thioflavine T (C.I. 49005) 36 whilst working there.

Both Meldola and Green complained of the lack of support they received and of the lack of interest of the management in their discoveries. Referring to Meldola, Friswell 3* said in 1905-

‘‘ , . . his discoveries were never appreciated by those at the head of the affair. They had an idea that unless the dye could be sold at such a profit that all the plant erected for it could be paid for in the course of a year or two, it was folly to do anything of the kind.”

The firm was converted to a limited company earlier than the others (in 1885 with a capital of €100,000) but continued to decline even when it began to seem possible to make a limited success of the industry in Britain40. It had, however, a number of loyal customers, especially London printers and polish makers. It had also a con- siderable trade with the Far East, to whose dyers, familiar with the large quantities of natural dyes usually required, it sold large tins of much diluted dyes with attractive labels carefully designed to avoid offending and, if possible, to appeal to the religious faith of the area. Imitation Magenta crystals- a tinted starch-gum base sprayed with a solution of the dye- were also sold to the un- suspecting Asian 4l. The business skills of this firm seem to have been remarkably misdirected.

The company had begun to employ, in 1884, Ernest Hickson, a founder-member of the Society of Dyers and Colonrists, who was by 1890 a director but who left in 1893 to found his own firm, considering that Brooke, Simpson & Spiller was falling too far behind in research and develop- ment and that not enough profits were being ploughed back. This was a common criticism of the firm among its employees 41.

ROBERTS, DALE & CO.

This pioneer firm, which once employed Caro and Martius, had already given up the manufacture of dyes when it was destroyed by a picric acid explosion on 22nd June 188742. Dale died two years later and production stopped altogether.

THE CLAYTOK ANILINE C O .

This company was founded near Manchester in 1876 by Charles Dreyfus, an Alsatian43. I ts pro- duction was confined to little more than aniline and aniline salt until 1894, when A. G. Green became manager of its dyestuffs department 33. He found this department almost non-existent, but he had a reasonable laboratory and began to put the manufacture of Primuline and dehydrothio- toluidine sulphonic acid on a proper basis. Later Chlorophenine Orange (C.I. 40055), Clayton Yellow (C.T. 19540), Rosophenine 10B (C.I. 14780) and the Stilbene Yellows ((2.1. 40000-l), as well as p-nitro- aniline, were made.

Research was done on various manufacturing problems, as well as on the mechanism of the stilbene condensation, and on attempts to obtain systematic results in the preparation of the sulphide dyes.

Green’s efforts were responsible for the intro- duction of much more efficient and controlled manufacture and helped greatly to improve the firm’s position. I n tlie eighties competition resulted in very small profits, with losses being recorded in 1884 and 1890. While Green was there, however, the works wcre greatly cnIarged and research on new products and processes was carried on. Green introduced the usc of an aluminium vessel with silver condenser for the manufacture of p-nitroaniline and patents were taken out every ycar during this period. The services of such chemists as W. H. Perkin Jnr., a t Owen’s College, Manchester, were used but, despite this, Green found that the attitude of the manage- ment towards his work was not as encouraging RS

he had hoped and he left the firm in 1901 49.

WILLIAMS, THOMAS & DOWER

This firm, founded in 1868, cmployed scvcrul talented chemists. Apart from Williams himself, MeldolaU was there from 1870 to 1872 and Witt from 1875 to 1879, during which timc he discovered Chrysoidine (C.I. 11270) 45 and worked on his theory of chromophoric groups. But exploitation of these discoveries did not occur on a large scale and Williams gave up his connexion with the industry in 1877“. After Witt lrft there do not seem to have been any further developmcnts eitlicr in dyes or in manufacturing processes.

THE GERMAN COMPAXIES

The rapid advance of the German industry during this period is illustrated by the fact that, by 1883, the combined profits of tlie three largest firms reached Elm47. The Budisclie Co. bought Thomas Frhres of Neuville sur S a h e and there followed a series of German infiltrations into the industry in France. In 1884 MLB built a factory near Paris, in 1885 Cassella bought the Manufacture Lyonnaise des Matieres Colorantes and, in the same year, both Bayer and Weiler tcr Meer (the Farbenfabrik ter Meer, founded in 1877 a t Uedingen near Krefeld) built factories near Lille gH.

I n 1885 Germany exported 4284 tons of Alizarin paste, 4646 tons of aniline dyes, and 1713 tons of intermediates. Heinrich Caro estimated these exports to be about 80% ofthe German production. The Badische Company had a t this time 2 5 w employees and MLB 1600, of whom 54 were trained chemists. In contrast, the British firm of Read Holliday employed about 100-140 up to the turn of the century and was the largest in the country 4, 27.

The expansion continued and by 1894 the German export of dyes was valued a t over E2.5m.49. Its exports to China rose from E189,115 in 1889 to S296,550 in 1894 and to tJapan from $22,850 to 261,071. These figures must be seen against a background of falling dye prices, and figures for the quantity of dyes exported give a better picture. Between 1885 and 1895 German exports of alizarin dyes rose from 4284 tons to 8927 tons and exports of aniline dyes from 4646 tons to 15,780 tons These figures reprtwnted in 1805 xo111(~ !)Oq/b of world consumption 60. Both MLB and Ba lischt. paid dividends of around 25% during this periocl and Bayer 18 ”/o.

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152 WELHAM- EARLY HlSTOHY OF THE SYNTHETIC DYE 1NDUS‘l’RY- 11 J.Y.D.C. 79

The industry also affected other fields. Heavy chemicals and coal-tar distilltltion, for both of which Germany had been for a long time dcpendent upon Britain, expanded to fill the dcinands of the dye-making industry and, in addition, the com- panies moved into the photographic and pharma- ceutical fields l7.

Summary of the Period 1874-1900 A reasonably detailed survey of the state of the

British dyc industry was made, almost in the middle of this period, by Meldola in 1886. In a lecture to the Society of Arts he called attention to the state into which the industry had fallen. Thc annual coal-tar production a t that time was estimated a t 500,000 tons, which was a t lcast half the European total. But the production of dyes was far below that to be expected from the tar production. Meldola circularised various dyc users in an attempt to determine the proportion of British-made dyes they used.

He found that, although the consumption of British-made Alizarin was rising, because of thc formation of the British Alizarin Company in 1883, the position with regard to the other dyes was by no means as favourable. No user said that more than 40% of his firm’s dyes were British and most quoted a figure of a t least 80% for the proportion of imported dyes. Ripleys of Bradford, one of the largest firms, used 86.5% foreign dyes; Walkers of Dewsbury 800/,; Newtons, silk dyers of Maccles- field, 80%; Hey8 of Barrhead, calico printers, 930/, and so on. Mcldola had difficulty in getting information from manufacturers, but Ivan Levinstein considercd that German production was six times the British in dyes dcrived from benzene and toluene, seven times in those from naphthalene, and five timcs in those from anthracenr. From information supplied by the producers of these raw materials Meldola estimated that 75% of the British production of benzene and aniline was exported to the Continent. Levinstein put the British consumption of benzene and toluene a t half a million gallons a year, compared with the Gcrman figure of two million gallons a year 27.

A similar survey of the industry was presented to the British Association for the Advancement of Science in 1901 by Green 51. He too circularised dye-users and received answers which indicated that the situation was unchanged from that in 1886. The British Cotton and Wool Dyers Association Ltd. said that 78% of their aniline dyes and 98y0 of their alizarin dyes were foreign in origin. The Bradford Dyers Association Ltd. used 90% foreign dyes and the English Sewing Cotton Company 9 1 % .

Green also pointed out that, since 1886, 948 British patents for the manufacture of dyes had been taken out by German firms, compared with 86 by British. The loss to India of the .€3m indigo industry was one which, he said, Badische wcre certain of inflicting. Attention was also drawn to the growth of subsidiary industries in Germany.

A t this time the total employed in the five largest German works was 20,000 and, although Green does not give a figure, the total for the British works must have bccn below 1000, since

Hollidays, the largest, only employed 200 or so. Thus it is clear that the British dye industry,

except in the manufacture of Alizarin, only managcd during this period to maintain the share of sales that it had in 1886. As the total volume of sales increased this does, of course, indicate some expansion in production, which took place notably a t Levinsteins, the Clayton Aniline Company and, but to a lesser cxtent, Read Hollidays. But it must also be remembered that the industries that had developed in Germany from the manufacture of dyes- photographical and pharrnaccutical chemicals- werc entirely abscnt here. TRINITY COLLEGE: OXFORU (Receioed 17th August I M 2 )

I Porkin, (Sir) W. H., J.C.S., 69 ( l ) , 696 (1896). References

Morris, L. E., Dyer, 115, 747 (1956) . Porkin, (Sir) W. H., Proc. Roy. Soc., 13, 170 (1864). Brightman, R., private publication. Miall, S., “A History of tho British Chcinical Industry”

Perkin, (Sir) W. H., J . Soc. Chem. Ind., 4, 427 (1885). See Part I, J.S.U.C., 79, 99, 100 (Mar 1963).

Hofmann. A. W.. “International Exhibition 1862:

(London, 1931).

ti Levinstein, I., J . SOC. Chem. Ind., 21, 893 (1902).

Report.by the Juries”, Class 11, Section A, p. 118. lo Ref. 6 , p. 75.

Obituary notice: D. Dawson, J.s.D.c.. 24, 48 (1908). Hofniann. A. W.. Proc. Rou. Inst.. 3. 46d (1862).

~I ~ I

13 Calvert, F. c., “‘Lectures” on Coal-tar Colouru, etu.”

l4 Cliffe, w. H., .J.s.D.c., 73, 312 (1957). (Manchester, 1863).

Obituary notice: I. Levinstein; J . Soc. Chem. I d . , 35, 458 (1916I.

Ref, 6,‘p. 76. Thiessen, F.. “Die Stellune der doutschen Teorfarbon-

industrie in der Weltwir&haft”. I s Pennington, W. H., J.s.D.c., 35, 272 (1919).

See Part 1, ihid., 79, 101 (Mar 1963). ao Perkin, (Sir) W. H., J . Soc. Arts, 27, 572 (1879). 21 Lcvinstoin, H., J.s.I).c., 65, 269 (1949).

Porkin, (Sir) W. H., “Evidence to tho Departmciital Committee on Industrial Alcohol”, Cd 2477, lxiv 29, question 1161 (1905).

*3 Perkin, W. H. (Jnr.), J.C.S., 107, 557 (1915). a4 Cliffe, w. H., J.s.D.C., 73, 312 (1957).

2o Dewar, (Sir) J . , Proc. Brit. Assocn., 3 (1902).

anBoer, J . J. , “Tho Emergence of the German Uyo Industry” (Urbana: University of Illiiiois Prc~sn, 1960).

28 Levinstein, I.. J . SOC. Chem. Ind.. 2. 313 (1883).

Wahl, A., Rev. Sci., 54, 5 (1916).

Meldola, R., J . SOC. Art s , 34, 759 (1886).

8o Boulton, 8. B., ihid. , 2, 220 (1883).‘

3a Wyler, M., lecture to Manchestor Chom. Club, 5.10.37. J .S .D.C. , 1, 361 (1885).

38 Green, A. G., lecture to Manchester Chcm. Club, 22.1 1.38. 84 See Part I, J.s.D.c., 79, 104 (Mar 1903).

Whittaker, C. M., ibid., 72, 557 (1956). 38 See Part I, ihid., 79, 102 (Mar 1963). 37 Green, A. G., Dyer, 62, 557 (1929). 38 Schultz, G. , and Julius, P., “A Systematic Survey of the

Organic Colouring Matters”, 1st odn. (London, 1894). Friswell, R. J., “Evidence to the Departmental Com-

mittee on Industrial Alcohol”, Cd 2477, lxiv (1905). 40 J.S.D.C. , 2, 33 (1886). 41 Wilkinson, H., ibid., 13, 508 (1967). 4a J.S.D.C., 3, 182 (1887). 43 Clayton Aniline Co., private communicat,ion. 44 Obituarv notice: R. Meldola. J.C.S.. 1 I 1 IT). 349 (1917).

\ ,I 3 I

46 See Pari I, J.s.D.c., 79, 101 (Mar 1963i.- 48 Obituary notice: C. Ct. Williams,J.C.S., 99 (T), 606 (1911). 47 Levinstein, I., J . Soc. Chem. Ind.. 3 . 69 11884).

, I . , Ref. 5, p. 89. .

“J.R.D.C., 16, 38 (1900). Ibid., 12, 146 (1896).

61 Green, A. G., Rept. of Britieh Assocn., 252 (1901).