merck chemicals - 100 years of liquid crystals

März 2004

Merck KGaACorporate CommunicationsE-Mail: [email protected] Darmstadt

www.merck.de W84

The roots of Merck KGaA reachback into the 17th century. In1668, the pharmacist FriedrichJacob Merck purchased the Engel-Apotheke (“Angel Pharmacy”) inDarmstadt; in 1816, EmanuelMerck took it over; his scientificwork on highly effective alkaloidslaid the foundation for “large-scale production” from 1827 on.

From the beginnings in the phar-macy laboratory evolved a phar-maceutical-chemical factory.Right from the outset, the guidingprinciple was always the especial-ly high purity of the preparations.By intensive research work in thearea of pharmaceuticals and che-micals, as well as by expansionand increasing internationaliza-tion, the economic success ofMerck grew rapidly.

Today Merck KGaA is a globallyoperating group, which concen-trates on pharmaceuticals, special-ty chemicals, and laboratory pro-ducts.

The guarantors of success forMerck are in the year 2003 morethan 34,200 entrepreneuriallyminded employees, who areengaged in application-orientedresearch and development, andwho are consistently responsiveto the desires and needs of theircustomers.

The company headquarters is inDarmstadt, Germany. A total of204 companies operate for Merckin 53 countries, and productiontakes place at 62 locations in28 countries. Merck KGaA gener-ates sales of 7.2 billion eurosworldwide, to which the LiquidCrystals division contributes farmore than 400 million euros.

Merck is the leading manufacturerof LCD materials worldwide. Bythe continuous further develop-ment of customized liquid crystalmixtures, Merck – together withthe display manufacturers –makes tomorrow’s communica-tion technologies possible.

100 years of liquid crystals at Merck

The history of the future

Arial view at Merck Darmstadt

In 2004, now 100 years later,Merck’s situation with its LiquidCrystals division is ideal. In themeantime, Merck has secured itsbusiness with more than 2,500patents for liquid crystals, theirmixtures, and display applica-tions. With a market share of over60%, Merck is the global leaderin the liquid crystal market; inthe area of TV applications, Merckis currently even the dominantsupplier.

The way has been long and some-times stony, but Merck has man-aged to get there. This has beendue to its perseverance, compe-tence, constant technologicalleadership, courageous businessdecisions, and thanks to manypeople with their visions andimperturbable faith in success, aswell as the close and trustingcooperation with its customersfor many years.

Merck’s researchers developed anew generation of superfluorinat-ed liquid crystals for the VAtechnology, which enable ex-tremely short switching timesof 16 milliseconds – and in thelatest devices of only 12 milli-seconds.

The LCD television manufacturerscount on strong growth in thecoming years – a boom, whichwill be comparable only to themobile telephone boom. In orderto guarantee delivery for liquidcrystals, Merck has invested 250million euros in new productionfacilities at the sites in Germany(with a capacity of 100 tons peryear, capable of being increasedto 150 tons per year).

The Future The Company

Pyramid at the main

entrance in Darmstadt

Milestones

The Austrian botanist Friedrich Reinitzerdiscovered the liquid crystalline propertiesof cholesteryl benzoate

The German physicist Otto Lehmanndescribed their physical properties anddefines them as a new state of aggrega-tion in his publication “On flowingcrystals”

At the incentive of Otto Lehmann, Merckoffered the first liquid crystals for researchpurposes in its price list “Substanceswith liquid crystalline properties”

Cholesteric liquid crystals were employedas temperature indicators, in thermogra-phy and medicine, later also in fashionitems and cosmetics

Dynamic scattering (George Heilmeieret. al., RCA, United States)

Merck began research on nematic liquidcrystals

The twisted nematic cell (TN cell) wasinvented by Schadt and Helfrich (Swit-zerland) and Fergason (United States)

George Gray (University of Hull,England) developed cyanobiphenyls and-terphenyls: BDH Chemicals Ltd. (todayMerck) and Hoffmann-La Roche Ltd.marketed them

Merck patented phenylcyclohexanes(PCHs), biphenylcyclohexanes (BCHs)and cyclohexylbiphenylcyclohexanes(CBCs)

Cyclohexylcyclohexanes (CCHs) intro-duced by Merck

Merck developed the “Viewing Independ-ent Panel” (VIP display), the basis of allactive matrix flat panel LCDs

Merck constructed an applications labo-ratory for liquid crystals in Atsugi, Japan

The extensive liquid crystal patent port-folios of Brown Boveri & Cie. (BBC) waspurchased by Merck

Merck constructed an applications labo-ratory for liquid crystals in Seoul, Korea

Joint venture between Merck and Balzersfor the production of ITO glass; construc-tion of a fully automated coating plantin Taiwan (since 1997, a wholly ownedMerck subsidiary: “Merck Display Tech-nologies Ltd.”)

Merck and Hitachi Ltd. cooperated inthe development of In Plane Switching(IPS), a new technology for LCD monitorsbased on a patent filed in 1990 by theFraunhofer Institute for Applied Solid-State Physics in Freiburg, Germany. Thispatent was acquired by Merck in 1994

Merck sold its patents on ferroelectricliquid crystals to Hoechst

An applications laboratory for liquidcrystals constructed by Merck in Taiwan

Merck took over the nematics businessof Hoffmann-La Roche Ltd.

Together with Fujitsu Ltd., Merck devel-oped an LCD video monitor based onVertical Alignment (VA) technology

The production capacity for ITO glasswas expanded in Taiwan

Merck Ltd. was established in Hong Kong,responsible for the liquid crystal businessin Hong Kong and China

A third ITO coating line was installedfor color STN displays and OLEDs

The German Future Prize was awardedby the President of the Federal Republicof Germany to Merck for the liquidcrystal technology that makes flat tele-visions possible

Inauguration of the new production plantfor liquid crystals in Darmstadt, with aninitial annual capacity of 100 tons. Theinvestment totals approximately 250million euros at the Darmstadt and Gerns-heim locations

Would you like to know more? Youwill find detailed informationabout the success story of liquidcrystals in the book “The history ofthe future – 100 years of liquidcrystals at Merck”.

The current development at Merckis documented in the Annual Re-ports and at www.merck.de.

New production plant

for liquid crystals

in Darmstadt –

inauguration in 2004

Thus display manufacturers arenow able, for the first time, tomass-produce flat, energy-saving,large LCD television screens. Thiswas so great a technological ad-vance that, in November 2003,Merck’s researchers received theGerman Future Prize from thePresident of the Federal Republicof Germany.

While the liquid crystals are pro-duced predominantly in Germany,the liquid crystal mixtures aremanufactured directly in theproximity of the actual customers.Thus Merck established a newliquid crystal center in 2002 atPoseung near Seoul, Korea, andfounded Merck Ltd. in Hong Kong,which is responsible for the liquidcrystal business in Hong Kongand China.

In the 1980s, the electronic in-dustry developed their displaysand technology ever faster, sothey always required new andmore effective liquid crystal mix-tures. Due to their advantages –low energy consumption, lightweight and freedom from radia-tion – LCDs now displaced otherflat screen technologies such aslight emitting diodes (LED) orvacuum fluorescence displays(VFDs), and gradually also theconventional cathode ray tubedisplays.

More and more demands wereplaced on Merck by its customers.Consequently, Merck intensifiedits own efforts and expanded itsresearch team, while also enteringinto numerous co-operations –some of which still exist today –with universities and researchinstitutes. Merck also licensed oracquired patents of other liquidcrystal manufacturers, such as,for example, in 1985 the completepatent portfolio on liquid crystalsfrom Brown Boveri & Cie. (BBC),Baden, Switzerland.

A concentration process was alsonow underway, with a clear sep-aration between major liquidcrystal manufacturers and majordisplay producers. Several thou-sand inconvenient kilometers laybetween them since the ones werein Europe and the others in Asia.That was not a good basis for aclose cooperation.

Chemical preparations

of Merck with liquid

crystalline properties

patent for the cyclohexylcyclo-hexanes (CCHs). Both classes ofsubstances impressed by theirimproved switching times, greaterstability, and better optical displaycharacteristics.

By the end of the 1970s, Merckwas well established in the do-main of liquid crystals. The hardwon competence that Merck hadgained in chemical, physical andapplications technologies wascrucial here. Also with the licensesfor the cyanobiphenyls and-terphenyls of the subsidiary BDHLtd. as well as with the patentsfor PCHs and CCHs Merck hadthe key compounds in its hand.

Dr. Scheuble, head of

central analytical labo-

ratory of physics with

Dr. Fries, head of central

analytical laboratory,

Dr. Allan, EM Industries

and Mr. Kawamoto,

Merck Japan

Plant for coating of

display glass for TN-

and STN-Displays

The 1990s still had some recordsales figures to offer yet: In 1994,Merck’s liquid crystals passed thethen deemed unattainable salesmilestone of 100 million deutsch-marks. In 1997, the boom in note-books and mobile telephonesbrought an increase in sales ofaround 65%. In 1999, Merck re-corded a sales increase of 60%due to the global boom in thecommunication industry as wellas the boom in mobile telephonesfurnished with STN displays.

Merck changed in the 1990s fromthe pure liquid crystal supplierto the supplier of components forthe display industry also (verticalintegration).

In 1993, Merck and Balzers Hold-ing Zürich, Switzerland, agreedupon a 50/50 joint venture, forcooperation in the productionand sale of transparent conductivelayers (ITO glass). In 1997, Mercktook over Balzers’ share, so thatITO glass production now becamea 100% Merck subsidiary. “MerckDisplay Technologies, Ltd., MDT”concentrated its business in Tai-wan, where a second productionline went into operation alreadyin 1998.

In 1995, Merck cooperated withHitachi Ltd. in the developmentof a new kind of display technol-ogy that substantially improvesthe readability of liquid crystaldisplays. A patent for this so-called In Plane Switching (IPS)had already been filed in 1990by the Fraunhofer Institute forApplied Solid-State Physics inFreiburg, Germany. Merck ac-quired this patent in 1994.

In 1995, Merck sold its patentson ferroelectric liquid crystalsto Hoechst, Frankfurt, Germany.In 1996, Merck took over thenematics business from Hoff-mann-La Roche, Switzerland.

In 1996, Merck opened a newapplications laboratory for liquidcrystal mixtures in Taiwan.

In 1997, Merck and Fujitsu Ltd.jointly developed an LCD videomonitor based on Vertical Align-ment (VA) technology, which isused to produce particularly largedisplays as, for example, monitorsfor Computer Aided Design (CAD)or television screens. The 1999annual report stated: “Merck, witha share of approximately 60%,is market leader in the area ofliquid crystals”.

Therefore, already in 1980, Merckestablished an applications labo-ratory for liquid crystal mixturesin Atsugi, Japan.

In the 1980s, within the MerckGroup, E. Merck in Darmstadt,Germany, and BDH Ltd., GreatBritain, were involved with re-search, development and produc-tion of liquid crystals, while tech-nical applications laboratorieswere located in Atsugi, Japan, aswell as briefly also in Hawthorne,United States. As the Korean dis-play industry became ever largerand more important, Merck alsoreacted there immediately andearly: Already in 1989, Merckopened an applications laboratoryfor liquid crystal mixtures locally:in Seoul, Korea.

In 1984, the liquid crystal activ-ities at Merck were all combinedwithin one unit. Already in 1988,the Industrial Chemicals divisiongenerated sales of 218 millionSwiss francs – more than 20%coming from liquid crystals.

The topic of liquid crystals is oneof Merck’s greatest success sto-ries. The development of liquidcrystals by Merck shows persua-sively how a large economic suc-cess can evolve from a pure re-search topic: Today, liquid crystalinformation displays enhance thequality of people’s life worldwide.

Thus, at first sight, liquid crystals(in the nematic phase) behavelike a liquid that, however, hasphysical properties resemblingsome solids (anisotropy). Exactlythis combination of characteristicsis the formula for success of elec-tro-optical display systems: liquidcrystal displays (LCDs).

LCDs are used in mobile tele-phones, personal digital assistants(PDAs), clocks, and electronicgames. In addition, liquid crystaldisplays are to be found in note-books, PC screens, and many in-dustrial manufacturing controlunits. Increasingly, they are re-placing bulky cathode ray tubesbecause of their characteristics(lightweight, energy efficient andradiation free). This is so not onlyin the area of PC monitors butalso television sets.

The starting point for liquid crys-tals was 116 years ago – andMerck participated almost fromthe outset – now for exactly100 years.

The secret of mobile telephones,flat PC monitors or super-flat TVscreens is based on liquid crystaltechnology – that is, on the spe-cial properties of specifically syn-thesized molecules.

Only organic molecules whichtypically are elongated and whichhave a separation of electriccharges (dipole) within the mo-lecule can be liquid crystalline.These give rise to a physical char-acteristic that is the basis for theirname: With such compounds, afurther state of aggregation existsbetween the liquid and solidstates, namely the liquid crystal-line state.

During his investigations of plantconstituents the Austrian botanistFriedrich Reinitzer encountereda strange phenomenon: Choles-teryl benzoate did not change at145.5°C into a clear liquid, butfirst into a cloudy fluid. And onlywith further heating up to 178.5°Cdid final transition to the clearliquid occur. The substance hadtwo melting points!

This was a sensation leading toviolent protests in the scientificworld, for this new state of matterdid not match prevailing scientificknowledge. Up to this time it washeld that there are three physicalstates of aggregation: solid, liquidand gas – with clearly definedtransitions.

He asked Merck for support, be-cause: “My work in the area ofliquid crystals […] also amongthe experts in this field [remains]misunderstood and unknown.Nobody is able to procure thenecessary materials and instru-ments”. Lehmann saw from the1904 price list that Merck alreadyoffered substances with liquidcrystalline properties in high pu-rity: methylammonium, dimethyl-ammonium and trimethylammo-nium oleate or Acidum oleinicumpurissimum.

Merck immediately declared itselfwilling to help Lehmann with thecomment: “The endeavor of mycompany is always to supportscientific research in every pos-sible way”.

Starting around the 1920s,Lehmann’s liquid crystals were –thanks to the highly puresubstances supplied by Merck –accepted universally in the scien-tific community.

Starting in the mid-1930s theinterest in liquid crystals slowlylapsed. No possible technical ap-plications were seen for liquidcrystals – and it was also scien-tifically believed that all substan-tial problems in this area hadbeen investigated. And so begana rather long Sleeping Beautyslumber for liquid crystals.

Renaissance

At this conference the dream ofthe flat television, which one canhang like a picture on the wall,was born.

In parallel to research on choles-teric liquid crystals, Merck alsoinvestigated the area of nematicliquid crystals. New nematicswere synthesized and examinedfor technical applicability in dis-plays.

By the end of the 1960s, alreadysix scientists at Merck were en-gaged with liquid crystals. Inthe 1969 Merck annual report,liquid crystals were referred tofor the first time under their brandname: Licristal®.

Temperature distri-

bution in a column,

made visible by chol-

esteric liquid crystals

In the early 1970s, the main con-cern of the liquid crystal chemistswas lowering the operating tem-perature of liquid crystal displays.The experts were searching fornew chemical substances withliquid crystalline properties atroom temperature.

In 1969, Hans Kelker at Hoechstin Frankfurt, Germany, synthe-sized MBBA (p-methyloxybenzy-lidene-p’-butyloxyaniline), whichwas replaced in 1970 by symme-trically substituted phenylbenzo-ates (from the University of Halle,Germany) and in 1971 also byasymmetrically substituted phe-nylbenzoates (the “Merck esters”).In addition, Merck manufacturedazoxy compounds, which alsohad more favorable propertiesthan MBBA did. The first com-pound of this type, p-methoxy-p’-n-butylazoxybenzene (“nema-tic phase IV”), was presentedby Merck initially at ACHEMAin 1970.

A real breakthrough came in1971, when James Fergason, atthat time at Kent State Universityin the United States, as well asMartin Schadt and Werner Helf-rich in Switzerland, almost simul-taneously had developed a newtype of cell, the twisted nematiccell (TN cell).

In 1973, George W. Gray, profes-sor at the University of Hull, GreatBritain, published his works onsubstituted cyanobiphenyls and-terphenyls – substances, whichhave a nematic phase stable atroom temperature and are parti-cularly well suited for use in TNcells. Professor Gray’s biphenylswere marketed successfully byBDH Chemicals Ltd. (British DrugHouse) in Poole, Great Britain –an enterprise that Merck hadbought slightly earlier (in 1972).

The breakthrough for Merck: In1976, Dr. Rudolf Eidenschink suc-ceeded in the synthesis of phe-nylcyclohexanes (PCHs) and, in1978, Eidenschink et al. filed a

At the end of 1966, Merck’s at-tention was drawn back to thetopic of liquid crystals by a sci-entific paper in which the Amer-ican scientist James Fergasondiscussed his ideas concerningpossible technical uses of liquidcrystals. Merck decided immedi-ately to concern itself with thisagain. Thus, at the end of 1966,the renaissance of work on liquidcrystals at Merck began. The Sleep-ing Beauty slumber had ended.

The impulses for the resumptionof the work in this area thus camefrom the United States at the endof the 1960s. Here various possi-ble applications for cholestericliquid crystals were developed,for analytical measuring technol-ogy, for non-destructive materialstesting, and as a diagnostics tool.

James Fergason of WestinghouseCorp., Pittsburgh, and also GeorgeHeilmeier at the Radio Corpora-tion of America, were workingwith their teams also on possibleapplications of nematic liquidcrystals. In 1968, Heilmeier pre-sented to the professional worlda liquid crystal display. That wasa genuine breakthrough, althoughthis display did need an operatingtemperature of about 80°C.

The scientific community wasgreatly impressed. Therefore, in1968, Merck dispatched a chemistto the “Second International Liq-uid Crystal Conference” at KentState University, Kent, UnitedStates. When he returned, he re-ported that the liquid crystalsdomain did not look like a losingproposition from either a scientificor a technical perspective.

SuccessLocalizationLiquid Crystals Beginnings Breakthrough

Digital clock with “liquid

figures” constructed by

Merck in 1972

Temperature profile of a

surface, visualized by cho-

lesteric liquid crystals

UnpolarizedWhite Light

Orientation Film

Color Filter

ITO Layer

Glass Substrate

Liquid Crystal

Glass Substrate

Polarizer

Orientation Film

Polarizer

ITO Layer

Structure of a TFT-

addressed TN cell, visit

www.liquidcrystals.merck.de

First LCD

“television“,

in black and

white and in

Reinitzer could not let this prob-lem rest. In March 1888, heturned to the German physicistOtto Lehmann. Only a year later,in 1889, Otto Lehmann gatheredfrom this fact the revolutionaryconcept that these “phenomena”disclosed a new, not previouslydescribed, state of matter. Heintroduced the name “liquidcrystals”.

First of all, Gustav Tammannrailed against Lehmann, but alsoother renowned scientists suchas Walter Nernst and GeorgQuincke.

To clarify the question regardingthe new state of “liquid crystals”,Lehmannn turned to guidancefrom the company E. Merck inDarmstadt.

Liquid crystal

production

|1888 –1935 | | 1960s | | 1970s | | 1980s | | 1990s |

and Mr. Kawamoto,

Merck Japan

and STN-Displays

Renaissance

Temperature distri-

bution in a column,

Merck in 1972

Orientation Film

Color Filter

ITO Layer

Glass Substrate

Liquid Crystal

Glass Substrate

Polarizer

Orientation Film

Polarizer

ITO Layer

Structure of a TFT-

First LCD

“television“,

in black and

white and in

Liquid crystal

production

|1888 –1935 | | 1960s | | 1970s | | 1980s | | 1990s |

and Mr. Kawamoto,

Merck Japan

and STN-Displays

Renaissance

Temperature distri-

bution in a column,

Merck in 1972

Orientation Film

Color Filter

ITO Layer

Glass Substrate

Liquid Crystal

Glass Substrate

Polarizer

Orientation Film

Polarizer

ITO Layer

Structure of a TFT-

First LCD

“television“,

in black and

white and in

Liquid crystal

production

|1888 –1935 | | 1960s | | 1970s | | 1980s | | 1990s |

and Mr. Kawamoto,

Merck Japan

and STN-Displays

Renaissance

Temperature distri-

bution in a column,

Merck in 1972

Orientation Film

Color Filter

ITO Layer

Glass Substrate

Liquid Crystal

Glass Substrate

Polarizer

Orientation Film

Polarizer

ITO Layer

Structure of a TFT-

First LCD

“television“,

in black and

white and in

Liquid crystal

production

|1888 –1935 | | 1960s | | 1970s | | 1980s | | 1990s |

and Mr. Kawamoto,

Merck Japan

and STN-Displays

Renaissance

Temperature distri-

bution in a column,

Merck in 1972

Orientation Film

Color Filter

ITO Layer

Glass Substrate

Liquid Crystal

Glass Substrate

Polarizer

Orientation Film

Polarizer

ITO Layer

Structure of a TFT-

First LCD

“television“,

in black and

white and in

Liquid crystal

production

|1888 –1935 | | 1960s | | 1970s | | 1980s | | 1990s |

and Mr. Kawamoto,

Merck Japan

and STN-Displays

Renaissance

Temperature distri-

bution in a column,

Merck in 1972

Orientation Film

Color Filter

ITO Layer

Glass Substrate

Liquid Crystal

Glass Substrate

Polarizer

Orientation Film

Polarizer

ITO Layer

Structure of a TFT-

First LCD

“television“,

in black and

white and in

Liquid crystal

production

|1888 –1935 | | 1960s | | 1970s | | 1980s | | 1990s |

März 2004

www.merck.de W84

The LCD television manufacturerscount on strong growth in thecoming years – a boom, whichwill be comparable only to themobile telephone boom. In orderto guarantee delivery for liquidcrystals, Merck has invested 250million euros in new productionfacilities at the sites in Germany.

Pyramid at the main

Milestones

Inauguration of the new production plantfor liquid crystals in Darmstadt.The investment totals approximately250 million euros at the Darmstadt andGernsheim locations

for liquid crystals

in Darmstadt –

März 2004

www.merck.de W84

Pyramid at the main

Milestones

for liquid crystals

in Darmstadt –

März 2004

www.merck.de W84

Pyramid at the main

Milestones

for liquid crystals

in Darmstadt –

März 2004

www.merck.de W84

The LCD television manufacturerscount on strong growth in thecoming years – a boom, whichwill be comparable only to themobile telephone boom. In orderto guarantee delivery for liquidcrystals, Merck has invested 250million euros in new productionfacilities at the sites in Germany.

Pyramid at the main

Milestones

Inauguration of the new production plantfor liquid crystals in Darmstadt.The investment totals approximately250 million euros at the Darmstadt andGernsheim locations

for liquid crystals

in Darmstadt –

März 2004

www.merck.de W84

Pyramid at the main

Milestones

for liquid crystals

in Darmstadt –

merck chemicals - 100 years of liquid crystals

Documents

area of liquid crystals

topic of liquid crystals

years of liquid crystals

clear liquid

cholesteric liquid crystals

lehmanns liquid crystals

development of liquid

new state of liquid