Vegder's Blog

June 26, 2011

Seeing Red in Japan – Part One

The Kunimatsu triptych from 1886 shown above is a great way to kick off this post – especially because of its use of aniline red dyes.
It was contributed to this site by my friend M. B. in Houston. I am particularly grateful because visually it makes such a spectacular statement.

Take a look around you – No, really! Take a look and you will see something or a lot of things that relate back to the (re-)discovery of aniline dyes: New colors, objects and items in your medicine cabinet all came from this – modern organic chemistry included. Oh the marvels. That is the crux of the issue I will try to cover in this post.

But back to Japan for the moment -There are at least 10 red dyes – give or take one or two – which have been used in Japan over the ages. 8 of these would count as traditional, but I have decided to start with one of the non-traditional ones, aniline red, and to discuss its impact and implications and anything else I can think of.

    ©Victoria and Albert Museum, London

The aniline color craze began in Europe and the wife of Napoleon III, the Empress Eugenie (ウージェニー皇后: 1826-1920), was a real trend setter. She started wearing her skirts high enough for her feet to be seen. This called for a new style in footwear which was no longer hidden beneath long skirts and numerous crinolines. Fortunately for her aniline dyes, like the vibrant aniline red used to color the ribbed silk boot shown above, had just been discovered. This boot is one of a pair in the Victoria and Albert Museum. It is in the ‘military’ style with the heel covered too. The Museum is not sure if this item is French or British, but do know that it dates from ca. 1865-75.

Aniline dyes アニリンせんりょう – So, ask yourself: How did the search for a treatment for malaria lead to those screamingly garish colors imported into Japan starting in the early 1860s? Well… I’ll try to give you some of those answers. But, I warn you, it is a circuitous route.

An Oooops! turns into an Ooooh! – In 1856 young William Henry Perkin (ウィリアム・ヘンリー・パーキン: 1838-1907) spent most of his Easter vacation in his lab on the top floor of his father’s house in London fiddling with his chemistry set. Others say it was a shed behind the house. In any case, Perkin’s efforts were a bit more than just fiddling with a bunch of chemicals. Although he was only 18 years old at the time he was determined to discover a synthetic quinine as a derivative of coal tar. At that time quinine was the only known treatment for malaria*. His German born professor, August von Hofmann (1818-92), had already been trying to do this for years.

What he came up with was a glob of black goo. Goo. Only goo. Definitely goo. According to Simon Garfield, Perkin’s biographer, this young scientist went about his research in a “rather nonchalant” way. Perkin himself wrote: “I was endeavouring to convert an artificial base into the natural alcoloid quinine, but my experiment, instead of yielding the colourless quinine,  gave a reddish powder. With a desire to understand this particular result, a different base of more simple construction was selected, viz. aniline, and in this case obtained a perfectly black product. This was purified and dried, and when digested with spirits of wine gave the mauve dye.” Garfield added that “In effect, the discovery at this time of one apparently simple molecule could rarely claim such a far-reaching impact on the development of science and industry.”

*What was so urgent about fighting malaria in 19th century England?1) You can’t run a decent empire when your soldiers are suffering from malaria in places like India and Africa. 2) But it isn’t just overseas that was plagued with malarial fevers. James I and Oliver Cromwell may have died from it. Cardinal Wolsey and later Charles II were said to be a sufferers. Even fictional characters were endangered. Take for example Pip in Great Expectations. He was one lucky fellow that he wasn’t felled in his youth by this disease despite his visits to nearby marshes.

   Portrait of James I (d. 1625) by John de Critz the Elder in the collection of the Dulwich Picture Gallery. All that power and still it didn’t help.

3) And elsewhere? Charles V, the Holy Roman Emperor, Pope Sixtus V and his successor Urban VII – all dead. St. Augustine? Dante? 8 cardinals and 30 scribes at the Conclave of 1623 succumbed. A lot of others fell ill but survived. And that sublime painter, Caravaggio, was done in by it in his prime in 1610. Sigh! Below is a painting by Caravaggio from the National Gallery, London. Appropriately it is of a boy bitten by a lizard.

   © The National Gallery, London

Perkin didn’t discover the properties of anilines, but he got the patent! Ha! – Otto Unverdorben distilled it thirty years before Perkin did. In Classics in Spectoscopy it says “The first to deal with indigo was the German pharmacist Unverdorben, who was an expert in the dry distillation of organic material. In 1826 he obtained a liquid by the dry distillation of Indian indigo in the presence of caustic lime, it was the first aniline!” After that it adds that “Despite this, the constitution of indigo was far from being understood.” It wasn’t until 1928 that the structure of indigo was finally understood using “…X-ray crystallographic means…”

Where does the word aniline come from? – In 1843 a German chemist, Carl Julius Fritzsche (1808–1871), coined the word from the Portuguese anil which means indigo. Where did the Portuguese get it? from the Arabic an-nil for indigo. And the Arabs? from the Persians, nila, same meaning. And the Persians? from the Sanskrit nili. Also, here the suffix -ine has the meaning of ‘having the nature of’ . Besides, it is one of those endings which is used in chemistry to lump groups together. But I am not finished. ‘-ine’ comes to us via the French for ‘derived substances’.

So… where are the Japanese in all this? That is supposed to be the point of this post, isn’t it? So… where are they. Well, here, sort of… アニリン. That is the Japanese for aniline. Remember these dyes didn’t make their appearance into Japan until the 1860s and they arrived thanks some entrepreneurial Germans.

The Mauve Fever – This is the oooh factor mentioned above. It was the first synthetic dye. Wow! Imagine… now there was a color which had once been restricted only to royalty. Of course, it still wasn’t cheap, but now if you had the bucks you could wear this color. Imagine when this dye hit the market. There had never been anything quite like it. The earlier dye had been extracted from a shellfish – murex. Supposedly it would take up to 12,000 shells of Bolinus brandaris to get 1.5 grams of the pure dye. No wonder it was reserved for the royals. But I’ll come back to that later when we talk more about purples in Japanese woodblock prints.

   Detail of a mauve dyed, ruched skirt from 1873 in the collection of the Victoria and Albert Museum. It is either French or British. ©Victoria and Albert Museum, London

   This painting of the Countess Lamsdorff is in the collection of the Metropolitan Museum of Art, but I found the photo posted at commons.wikimedia.org.

The Brits dropped the ball – While the British were first into the game receiving patents for their products there was not enough funding to compete in an international marketplace. Quickly the French came to dominate the synthetic dye market as they had with natural dyes, but their greed and sense of protectionism was self-defeating and short-lived. The French had outplayed the British, but things were moving too quickly and Germans were on a path to victory – at least when it came to the chemical industry.

Not that the British weren’t trying to compete. Initially aniline red was difficult to make and could only be produced in small batches. That is, until 1859-60 when a new method was created using arsenic acids. This was discovered in two different places in England at the same time and both applied for patents in January 1860. Henry Medlock of Coventry won the day and got the patent, but soon sold it to the competing firm of Simpson, Maule and Nicholson. “By 1863, [they] monopolised the British market in aniline dyes through its control of the most important aniline red patent, and rights to patents for derivatives of aniline red, particularly aniline blue and (from late in 1863) the Hofmann’s violets.”

In the late 1850s Heirich Caro, a Polish born German chemist, traveled to England to work with the dying firm of Robert’s Dale & Co. England was, in many ways, where it was at at that time. While there “Caro acquired some nitrobenzene, then sold as essence of mirbane for giving pleasant odours to soaps and perfumes, and reduced it to aniline. By subjecting the aniline to a variety of oxidising reagents he discovered that certain copper salts-those used in dyeing processes-gave the mauve colorant.” Dale and Caro applied for a patent and got it and large scale production was probably underway by early 1862. For whatever reason, one I can’t explain, this new patent did not infringe on Perkin’s original one. French efforts to import and sell their mauve products in England did violate Perkin’s patent, but Caro and Dale’s new technique did not. Now it was nitrobenzene which was needed on an industrial scale.

Since little mauve could be produced initially from the processes developed by both Perkin and Caro – maybe 5% or so – there was a lot of goop left over. “From this residue Caro in 1862 obtained the first commercial aniline black, a product that brought considerable profits to Roberts, Dale & Co., since, unlike the other coal-tar colorants, it adhered readily to cotton.” It proved very successful on the mainland European market.

The Germans picked it up and ran with it – Admirably the English were showing rugged individualism, but got no government backing. It was each man and each firm competing with each other man and firm to see who would be king of the hill. In France pettiness and parochialism prevailed. But in Germany many of the 39 states of the Confederation were backing their own scientists – men like Liebig, Kekulé and Bunsen – and research was on a tear and only going to grow more rapidly. About 150 years previously central Europe had seen a similar state-sponsored competition to create and develop the hard-paste porcelain market. Now it was pure chemistry which was on the line and the growth rate was exponential.

To try and get a grasp on what this meant at the time all we have to do is think of the growth of the computer industry: silicon chips, quantum leaps, Twitter! Where would the world be without Twitter? Just ask the fine people in Tunisia or Egypt’s Tahrir Square. That headiness is what it must have felt like to the average German researcher. By the 1860s they had started building their own synthetic dying plants after working for and learning the secrets of British ones a few years before. R & D. Everything was R & D – and market share. As the English languished and the French were overly paranoid in a “we-have-to-protect-ourselves-at-all-costs” sort of way, the Germans were forging onward.

The same year Perkin made his discovery “…a dealer in dyewoods, K.G.R. Oehler, established a tar distellery in Offenbach and started making picric acid, fuchsine and mauve.” By 1863 Friedrich Bayer was producing fuchsine and working with other aniline dye derivatives.

Did you ever wonder what BASF stood for? Well, I’ll tell you: Badische Anilin und Soda Fabrik. Get it? Anilin! Anilin! for goodness sake. Anilin! Said to be the largest chemical industry giant on the whole planet. That includes Japan.

In 1867 Paul Mendelssohn-Bartholdy, son of the composer Felix Mendelssohn, started another aniline dye factory near Berlin. He was partnered with a man who had just returned from England. In 1873 their company became the Aktien Gesellschaft für Anilin Fabrikation or AGFA. AGFA, AGFA. My scanner – which my great friend Mike gave to me – is an AGFA.

Bayer, BASF and AGFA: Clearly it was dust-eating time for the Brits and the French. Who could compete with a trio like that?

The role of toluidine – First, I have to tell you that I know next to nothing about this substance. I barely passed high school chemistry. But that doesn’t stop me from being interested – even fascinated – even amazed. That said – Carl Martius, one of the founders of AGFA, wrote to Caro on July 8, 1863:

Pure aniline alone produced by all different methods and pure toluidine alone do not give dyestuffs. Instead
mixtures of the two bases give immediately aniline red. All commercial anilines (even if boiling between 182-188°C)
contain toluidine.

Martius wrote again on July 12:

I hope that you have received the two samples of aniline and toluidine which I sent you some days ago. It is a pity
that I cannot send you more because my stock is diminishing due to the many trials. The toluidine is produced from
the oxalate-itself from the highest boiling fraction of commercial aniline. The aniline is from the [salts] of aniline
which distil over from the production of aniline red. It boils constantly at 182°C and with sublimation there is no
trace of aniline red. The relation of one equivalent (93 parts of aniline) and two equivalents (214 parts of toluidine)
is the best to produce aniline red. The result of our trials with the mauve reaction is that the pure aniline gives the
best results. Perkin claims the contrary. We are busy now with trials concerning the synthesis and constitution
of rosaniline. Iodine when heated with aniline gives no trace of fuchsine. By contrast, aniline red is obtained immediately
if aniline is replaced by toluidine.

Heady days or just a fad? – Let’s step back to 1856 and Perkin’s discovery of an aniline based mauve dye. It was followed two years later by the brightest red yet known in France or anywhere else for that matter. Other colors quickly followed. But would they stick?

These were exciting times for dye-makers, even though the new artificial products were often considered to be
nothing more than fads that would disappear as soon as tastes in fashion changed. The main problem was that
they were difficult to apply to cotton, which placed restrictions on their application to calico printing. Their
brilliance, however, made them very striking, and encouraged research into new processes of manufacture and
of fixation onto cotton. The major English centre for the manufacture and use of dyes was Manchester, whose
vitality had impressed Caro in 1857, and it was to this humming industrial city that he travelled in the autumn of 1859.

Quoted from: Heinrich Caro and the Creation of Modern Chemical Industry

©Victoria and Albert Museum, London
This child’s bathing suit was made in England in the 1870s. It is a red-dyed calico print. I can’t say that it is an aniline red, but I can’t say it isn’t. The museum doesn’t tell us. However, what I can tell you is that finally I have bothered to learn what ‘calico’ means. It is dye printed cotton cloth. Now I may have known this at some time in the past and had forgotten it, but then it again calico did not register high on my interest scale. What did rate high for me as a small child was the copy of The Gingham Dog and Calico Cat which my cousin’s owned. I wanted that book so badly and still remember the pain of not having it. Of course, give me a break, my lust for that book came several years before I found out that I wasn’t supposed to covet. Now there’s a word I learned early.

Aka-e – There is a category, a genre, almost a sub-genre, of late 19th century Japanese woodblock prints referred to as aka-e or images where one of the dominant colors is due to use of analine red. This is not to be confused with a different type of earlier aka-e known as hoso-e or images meant to prevent or drive off smallpox. The aniline red results in images which can only be described as gaudy or garish – although some of them do eventually grow on you.

In 1858 2  years after Perkin discovered an aniline purple a Frenchman, François-Emmanuel Verguin, created a red dye he called fuchsin. Later it was known as magenta, too. It was a more popular color for dying textiles than mauve and said to have been easier to make. (An aniline blue – bleu de Lyon – came 2 years later.) A synthetic alizirin red was waiting to be discovered and it was finally in 1869.

   One print from a Kunichika triptych. © Trustees of  the British Museum

You know what’s pathetic? Really pathetic? – I’ll tell you: The dearth of information in English on the history of the use of aniline dyes in Japan – especially those used to color Japanese woodblock prints. Considering, all in all, there is practically nothing out there about these prints with the exception of a few opinions and a lot of generalities. Maybe there is a more to be found written in Pashto or Linear A or… but I don’t think so. It wouldn’t matter anyway because I don’t know those languages. However, looking for answers in Linear A, an ancient Cretan script which dates from the 2nd millenium B.C. and, as far as I know, has not yet been translated, might be as useful a place to state as any.  Learning to read, write, speak and understand English as a child has been just about as helpful as looking for answers elsewhere. They don’t exist or, at least, not in any language I have seen yet.

You ask yourself “How will I know the red is aniline and not another red dye?” – In 1964 in Jacobellis v. Ohio Justice White said that he might not be able to give an exact definition of pornography, but “I know it when I see it.” The same could be said of aniline red in Japanese woodblock prints. Early reds, before the importation of these synthetic dyes, faded easily and generally give us only a hint of what they might have looked like. Anilines, on the other hand, have a much more ‘in your face’ kind of appearance. Their vibrancy is unmistakable. Below are two pre-aniline dye prints from the collection of the Metropolitan Museum of Art. The one on the left is by Toyokuni I dates from ca. 1812 where the reds are brilliant and wonderfully preserved. A rarity. The same could be said for the print on the  right by Hokuei. It dates from 1837 and is equally well-preserved.

          

Now, compare the reds shown above with that of the Chikanobu print of the Meiji Emperor from the British Museum shown below. If the difference doesn’t jump out at you immediately there may be one of two reasons: 1) the color settings on your monitor are less than optimum or 2) there is something wrong with the cones found in your retina. Either way, you have to trust me on this one. There is a huge difference.

   © Trustees of  the British Museum

The Symbolism of Redor “Three cheers for the RED, white and blue”

Long before Betsy Ross is said to have sewn the first American flag Renaissance and pre-Renaissance artists were well imbued with the principles surrounding the use of these three colors. Red stood for the blood of Christ, white for the purity of the Virgin and blue for the celestial nature of her heavenly realm. At the Nelson Art Gallery in Kansas City, Missouri are three paintings which drive this point home. One is a Madonna and Child with John the Baptist by Bugiardini (ブジャルディーニ: 1475-1554) where the predominant color worn by the Virgin is red. She has a particularly sad countenance and that may be because she is aware of the fact that her son was born to die on the cross as redemption of mankind’s original sin. 

  Bugiardini’s woeful and prescient Madonna from the collection of the Nelson Art Gallery in Kansas City. Notice here blue cloak and just the touch of white near her left arm pit.

A Lorenzo Monaco (ロレンツォ・モナコ: 1370?-1425) altarpiece presents the Madonna dressed mostly in white, but with a touch of blue, while Jesus wears the red which foreshadows his crucifixion. This Virgin is referred to as the Madonna of Humility because she is seated on a pillow placed upon the ground. The decoration of the pillow is a whole other story altogether.

The Madonna of Humility by Lorenzo Monaco – also in Kansas City.

The third painting is by Lorenzo di Credi (ロレンツォ.ディ・クレディ: ca. 1456-1536 or 37). He was a pupil of  the painter and sculptor Verocchio who was also  taught Leonardo da Vinci. Lorenzo’s blues are heavenly and unlike those of any other artist I know of. Here the Madonna is dressed almost completely in blues.  There is a  hint of white at her forearm. The red of the Passion is there too, but you would have to search long and hard before you will find it.

Lorenzo wants us to concentrate on the Virgin’s role as the Queen of Heaven. She is accompanied by the Christ Child and a young John the Baptist who’s shepherd’s staff is a bejeweled cross. Where are they? Some earthly paradise? Probably not. Everything about this painting, especially the blues of the Virgin’s clothes tell us that they are already in heaven – or so it would seem.

Lorenzo di Credi painting from the collection of the Nelson Art Gallery. It was posted at Flickr by jondresner. She is a truly heavenly Madonna.

Over the years I am sure I have given well over 1,000 museum tours. Not just at the Nelson, but also the Met, the Art Institute in Chicago, the National Gallery in D.C., and lots of other places. Very few of these tours have gone badly. But I remember one time a young woman asked me to give her and her mother a tour and I said “Let’s start with the Renaissance and pre-Renaissance paintings.” As we walked into the first room the mother said “I can’t look at this stuff. Once you have seen one Madonna and Child you have seen them all!” She insisted that we leave the room immediately. However, what she said couldn’t have been any farther from the truth if it had tried. The three examples I showed you above tells us that each artist had something different in mind and only a fool would or could fail to see that. Remember this next time you visit a major museum, please. This principle will serve you well. I promise.

Does red attract the eye?  Well, duh! – Once upon a time, years and years and some more years ago, when I was more naive than I am today, I went on a tour – or was it that I attended a lecture – given by a curator at the Nelson Atkins Museum of Art in Kansas City. One piece he discussed was Rubens’ painting of the Sacrifice of Isaac. He said that the artist chose to clothe Abraham in red because no other color attracted the eye more insistently. That seemed reasonable – at the time. Happily, I was about to find a photo of that painting posted at Flickr by jondresner and can share it with you now.

Over the years I have given more than a thousand tours of museums, maybe two, and have repeated this as a ‘cardinal’ rule. If 2 + 2 = 4 is true then red was chosen to draw the eye is just as true. There seemed to be tons of corroborative evidence for this everywhere. See the examples shown below which both come from the collection of the Met in New York.

The use of red in this painting by ter Brugghen (1588-1629) is a case in point. The younger John looks up adoringly (?) at the figure of Christ nailed to the cross. Red blood is pouring forth from his wounds. These touches are made more poignant by the almost sickeningly greenish sky in the upper half of the canvas. (www.metmuseum.org.)

I chose the next painting not only for its red element, but for the drama and the beauty of the composition. It is by Michiel Sweerts (1618-16664) and called Clothing the Naked.

   http://www.metmuseum.org.

But wait a second! While each of these examples seem to reinforce the point that red draws the eye – which it does and which I can’t deny – I can no longer be sure that that is why each artist chose to use this color to engage the viewer. I mean, look at these paintings. Each is equally dramatic in its own way and each seems to say that the artist was making an aesthetic choice at the time these were painted. The Isaac in the Rubens painting probably draws as many eyes to it first at the red, red robe of Abraham does. Maybe more considering the age. And the pathos of the ter Brugghen lies in the centralized figure of Jesus and not in the figure of John. The Sweerts, on the other hand… well… that red is pretty damned dramatic. Sure there is a naked Christ-like figure on the left, but that red… Oh that red!

Of course, someone more clever than I could use Photoshop or some such program to change the reds to another color to see what that would do, but still… in the end red has probably been the best choice of all. One last point: None of these reds was made with an aniline dye. The point is about the color and not the pigment – which by the way was delivered in oil and not a water-based medium like that of Japanese woodblock prints.

In the case of a headache take two aspirins and call me in the morning


This image, which I have altered somewhat, was posted at Flickr by Fiona Paloma.

Kaboom! – If you don’t like something, like analine red, you can blow it up: In the publication Military Explosives put out by the U. S. Army it says “1826. Aniline was first prepared by Unverdorben. Later, nitration of aniline resulted in the very powerful explosive called tetranitroaniline.

Miscellany

“When pure, aniline is a colorless liquid; has a peculiar, aromatic odor, and an acrid burning taste.” This is from General Medical Chemistry for the Use of Practioners of Medicine  By Rudolph August Witthaus, 1881, p. 333.

“The availability of arsenic acid in the textile industry greatly facilitated the manufacture of the important aniline red dye in the 1860s.” From Heinrich Caro and the Creation of Modern Chemical Industry, p. 31.

According to Webster’s fuchsin (or fuchsine) is ” a dye that is produced by oxidation of a mixture of aniline and toluidines and yields a brilliant bluish red”. In England this color was called magenta.

“Fuchsine served as a base for the production of other dyes as well, such as Hofmann violet, Perkin green, and Manchester brown.” From A History of the International Chemical Industry: From the “Early Days” to 2000 by Fred Astalion, p. 37

In a 1919 article in the American Journal of Physiology aniline red was used to stain slides being studied under microscopes to see if they could come up with a physical reason for ‘shell shock’.

Aniline dyes used for medical purposes went into short supply when the French and British declared a blockade of German products during World War I. The prices for these dyes were said to have jumped in a matter of weeks to 20 times their previous prices. The only answer would be for the Japanese to get their hands on the German patents.

Most synthetic dyes used in the United States around the time of the outbreak of WWI were imported from Germany. When the British and the French blockaded their export a German submarine , the Deutschland, ran the blockade twice to deliver drugs and dyes to the Americans. “Ironically, in 1914, German dyes were used by French dyers to dye the official French Army uniforms.” This information comes from Kent and Riegel’s Handbook of Industrial Chemistry and Biotechnology.

More than 175 different dyes can be made from aniline and many more from its derivatives. Thousands of dyes have been synthesized and between 1,500 and 2,000 are still being used. Prior to 1884 all of the dyes required a mordant to set them permanently against fading when being washed. Then Paul Böttiger, a Bayer employee, created Congo Red which was the first ‘direct dye’. Many more followed.

We have seen the future and it is us! – I was searching on Flickr under the heading for aniline red – in Japanese, I think, when I ran across this photo under the heading iPad2 and posted by Yasuo Kida. It speaks volumes – to me, at least. What do you think?

For more information about Japanese prints and culture please visit our other web site at http://www.printsofjapan.com/.

2 Comments »

  1. Another fascinating investigation. Damn it Jerry, we need to get you a PBS show. I don’t know what the Hell you would call it… Question du jour with Jerry Vegder. Great writing.. Interesting topic.

    Comment by Philip Wassmer — July 27, 2011 @ 9:30 am | Reply

  2. […] you are interested in the history of aniline red and its presence in Japan, I’d recommend this great post. Of course, there are many more colors now part of the Japanese color system that were adopted from […]

    Pingback by The Traditional Colors of Japan: Making Modern History | Tofugu — September 12, 2013 @ 8:31 am | Reply


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