Merck Chemicals - 100 Years of Liquid Crystals at Merck

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100 Years of Liquid Crystals at Merck

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Merck Chemicals - 100 Years of Liquid Crystals at Merck

  1. 1. 100 Years of Liquid Crystals at Merck Dr. Peer Kirsch Merck KGaA, Liquid Crystals Division, D-64271 Darmstadt, Germany 20th International Liquid Crystal Conference (ILCC-20), Ljubljana, Slovenia, July 4-9, 2004
  2. 2. H F F F R H O F H Active Matrix Display (AMD) R OEt F commercial production: 1989 H F F F concept: B. J. Lechner, 1971 H R F H “Super Fluorinated Materials” (SFM), 1985 F Super Twisted Nematic (STN) R CN R. Eidenschink et al., 1976 T. J. Scheffer et al., 1984 O CN R D. Demus et al., 1975 Twisted Nematic Mode (TN) O M. Schadt, W. Helfrich, R CN G. W. Gray et al., 1972 J. Fergason, 1971 O RO Dynamic Scattering (DSM) RO N N R R. Williams, G. Heilmeier, 1962 N R H3C H3C H H H PhCOO F. Reinitzer, 1888
  3. 3. Vertical Alignment (VA) LCD TV commercial production: 1998 2002 In Plane Switching (IPS) Cellular Phone 2000 commercial production: 1996 PDA Active Matrix Display (AMD) commercial production: 1989 Desktop PC Monitor concept: B. J. Lechner, 1971 1997 Super Twisted Nematic (STN) Notebook PC T. J. Scheffer et al., 1984 1990 1995 Twisted Nematic Mode (TN) M. Schadt, W. Helfrich, Wristwatches J. Fergason, 1971 Pocket Calculators Dynamic Scattering (DSM) R. Williams, G.Heilmeier, 1962 1973
  4. 4. The Pioneers - 1 F. Reinitzer (Prague), 1888 H3C H3C H O H H O C 145 N* 179 I F. Reinitzer, Monatsh. Chem. 1888, 9, 421 Dr. Peer Kirsch ILCC-20 Page 4
  5. 5. The Pioneers - 2 O. Lehmann (Karlsruhe), 1889 • "Apparently living crystals" are mesophases: a new and distinct state of matter • Lehmann asks Merck in 1904 to provide liquid crystals for research Dr. Peer Kirsch ILCC-20 Page 5
  6. 6. The Pioneers - 3 D. Vorländer (Halle), early 1900s • Systematic study on various calamitic liquid crystals O O N N O N N O p-Azoxyphenetole Dr. Peer Kirsch ILCC-20 Page 6
  7. 7. Milestones in the History of Merck 1668 Friedrich Jacob Merck (1621–1678) buys the “Engel-Apotheke” (Angel Pharmacy) in Darmstadt, Germany 1827 Emanuel Merck (1794–1855) starts production on an industrial scale Dr. Peer Kirsch ILCC-20 Page 8
  8. 8. International Successes and Setbacks • On the basis of the international success, local subsidiaries were established in - London (1883) - New York (1887) - Moscow (1899) • The New York branch evolved into an independent US Factory in Darmstadt, 1898 company after the World War I: Merck & Co. Dr. Peer Kirsch ILCC-20 Page 9
  9. 9. Merck Today • Merck groups its operating activities under Merck KGaA, going public in 1995 • Shareholders hold 26% of the total capital, the Merck family holds 74% through E. Merck as the general partner. Factory site in Darmstadt, 1995 Dr. Peer Kirsch ILCC-20 Page 10
  10. 10. Merck Enters Liquid Crystal Business • Since 1904 sale of reagents for liquid crystal research: – (Alkyl)ammonium oleates – Cholesterol esters – p-Azoxybenzoate – p-Azophenetole – p-Azoxyphenetole – p-Azoxyanisole Dr. Peer Kirsch ILCC-20 Page 11
  11. 11. The Skeptics "Soft crystals do exist, floating ones may exist, but liquid ones? I tell you, no way!" G. Tammann, around 1920 Dr. Peer Kirsch ILCC-20 Page 12
  12. 12. Thermochromic Cholesterics: Applications • Use of cholesteric liquid crystals as temperature indicators since 1966, e.g., for – Medical diagnostics: mammography, vascular disorders – Non-destructive testing: welds, electric circuits – Radiation sensing: IR, microwave – Decorative: beer labels Dr. Peer Kirsch ILCC-20 Page 13
  13. 13. Thermochromic Cholesterics: Materials • Cholesteric mixture systems TM74A/B and TM75A/B (BDH Chemicals Ltd., Poole, UK): O H3C R O * O H3C R O H3C O * RO O * • Thermotropic devices: – Dispersion of microencapsulated cholesterics – Polymer-dispersed cholesterics Dr. Peer Kirsch ILCC-20 Page 14
  14. 14. Dynamic Scattering Mode (DSM) • Developed since 1963 by R. Williams and G. Heilmeier (RCA) • Presentation in 1968 at the ILCC-2, Kent, OH: Motivation for Merck to enter liquid crystal research pictures: George Heilmeier with DSM prototype (left), F. Vögtle, Supramolekulare Chemie (right) Dr. Peer Kirsch ILCC-20 Page 15
  15. 15. Dynamic Scattering Mode: Materials • Schiff Bases (Eastman Kodak) RO R = CH3: MBBA N C4H9 R = C2H5: EBBA • Azoxy Compounds (Merck) O MeO N MeO N N C4H9 N C4H9 N4 O • Esters (Merck) O H7C3 ME-35 O C5H11 Dr. Peer Kirsch ILCC-20 Page 16
  16. 16. Practical Problems with First Generation Materials • Azoxy Compounds: Sensitivity against light O RO N N R • Schiff Bases: Hydrolysis and transimination R1O 2 N R R1O R1O 2 4 N R N R R3O 4 N R R3O R3O 4 2 N R N R Dr. Peer Kirsch ILCC-20 Page 17
  17. 17. The Twisted Nematic (TN) Mode • Invented in 1971 by M. Schadt and W. Helfrich (Hoffmann- La Roche), and J. Fergason (Kent State University) off on picture: TN display prototype presented to the board of directors at Hoffmann-La Roche in March 1971 Dr. Peer Kirsch ILCC-20 Page 18
  18. 18. Liquid Crystal Production Merck Darmstadt (tons) 0 20 40 60 80 100 120 140 160 180 19 70 Dr. Peer Kirsch 19 72 TN 19 74 19 76 19 78 19 80 VIP 19 82 19 84 STN 19 86 19 88 ILCC-20 TN-TFT 19 Year 90 19 92 19 IPS 94 19 96 MVA 19 98 20 00 PALC 20 Liquid Crystal Production at Merck 02 20 04 20 06 20 08 prognosis Page 19
  19. 19. Cyanobiphenyls and Terphenyls • Developed by G. Gray and coworkers (Univ. Hull) in 1972 • First chemically and photochemically stable materials with a nematic phase around room temperature • Put to the market by BDH Chemicals Ltd. and Hoffmann- La Roche H11C5 N K15: C 23 N 35.1 I ∆εvirt = 21.6 H11C5 N T15: C 131 N 239.9 I ∆εvirt = 20.2 Dr. Peer Kirsch ILCC-20 Page 20
  20. 20. BDH Chemicals Ltd., Poole • Since 1972 sales of liquid crystal mixtures together with Merck • In 2001 opening of Chilworth Technical Centre Dr. Peer Kirsch ILCC-20 Page 21
  21. 21. The Cyclohexane Substructure • D. Demus and coworkers (Halle) in 1975 O N H11C5 O D5: C 47 N 78.7 I ∆εvirt = 14.8 Dr. Peer Kirsch ILCC-20 Page 22
  22. 22. Phenylcyclohexanes • Developed by R. Eidenschink and coworkers (Merck) in 1976 H11C5 N PCH-5: C 31 N 54.6 I ∆εvirt = 17.9 H11C5 N BCH-5: C 96 N 219.3 I ∆εvirt = 17.2 H11C5 C3H7 CBC-53: C 54 SB 237 SA 260 N 317 I Dr. Peer Kirsch ILCC-20 Page 23
  23. 23. Cyclohexylcyclohexanes • R. Eidenschink (Merck), 1979 H H11C5 N H CCH-5: C 67 SB (52) N 86.2 I ∆εvirt = 8.3 Dr. Peer Kirsch ILCC-20 Page 24
  24. 24. Viewing Angle Independent Contrast (VIP) • VIP (1980) is the basis for most modern TN LCDs ⎛π ⎞ sin 2 ⎜ 1+ u2 ⎟ T (u ) = 1 ⎝2 ⎠ 2 1+ u 2 C. H. Gooch, H. A. Tarry, J. Phys. D: Appl. Phys. 1975, 8, 1575-1584 Dr. Peer Kirsch ILCC-20 Page 25
  25. 25. The Super Twisted Nematic (STN) Mode • T. J. Scheffer, J. Nehring (BBC), 1981 • Extension of the limit for multiplexing large pixel arrays: the first high resolution LCDs picture: T. Uchida, Ekisho 1999, 3, 195-204 Dr. Peer Kirsch ILCC-20 Page 26
  26. 26. Alkenyls • Merck purchased in 1996 the NLC portfolio from Hoffmann-La Roche • Advantages: – Increased tendency to form nematic phases – Advantageous elastic constants: large K33/K11 – Often low rotational viscosities (γ1) F H H CH3 F H H CCP-V2-1: C 54 SB 104 N 176.6 I CCG-V-F: C 74 N 108.9 I ∆εvirt = 4.3 H C5H11 CC-5-V: C -9 SB 52 N 62.6 I H Dr. Peer Kirsch ILCC-20 Page 27
  27. 27. Chiral Dopants • Used in low concentration for inducing uniform pitch in TN and STN mixtures F O C6H13 H13C6O O * H11C5 O O C5H11 * CH CH3 6 13 14 µm-1 a O O 9.1 µm-1 c F CH3 F O * O H O H7C3 O H * CH 6 13 F CH3 H11C5 13.6 µm-1 a 39.5 µm-1 b • Newest generation for SSCT mode (2000) O a MLC-6012 C3H7 O b ZLI-1132 c MLC-6260 104 µm-1 c Dr. Peer Kirsch ILCC-20 Page 28
  28. 28. Active Matrix Addressing • Proposed already for the DSM mode by B. J. Lechner in 1971 • First prototypes presented by Sharp in 1987 • Technical basis for all high- resolution full colour LCDs picture left: Scientific American 1997 (11), 87 Dr. Peer Kirsch ILCC-20 Page 29
  29. 29. Super Fluorinated Materials (SFM) • 1989: Trifluorophenyl Derivatives F F H H7C3 F H7C3 F H F F • 1990: Trifluoromethoxyphenyl Derivatives H H7C3 OCF3 H • 1990: Difluoromethoxyphenyl Derivatives F H H7C3 OCHF2 H F Dr. Peer Kirsch ILCC-20 Page 30
  30. 30. Extension of the SFM Concept • Additional lateral fluorine substituents on neighbouring rings: F F H H7C3 F H7C3 F H F F F F F H7C3 F F F • Polar rings and linking groups: F F H O H7C3 F H O F H O H7C3 F H O F Dr. Peer Kirsch ILCC-20 Page 31
  31. 31. Why Fluorinated Liquid Crystals? F F F F F Improved mesophase range by fluorinated bridges 2000 H7C3 F F O F TNI,virt = 128 C F H7C3 CF3 + Good voltage holding ratio, high specific resistivity 1990 H7C3 N + H7C3 CF3 ∆ε ~ 9 High dielectric anisotropy (∆ε) 1985 due to polarized C-F bond H7C3 CN ∆ε ~ 21 F H9C4 Broader nematic phase range, 1980 C4H9 C 34 N 177.7 I lower melting point F H7C3 C2H5 C 171 S? (160) N 216.8 I
  32. 32. Property Prediction by Molecular Modelling Predictable: • Dielectric anisotropy (∆ε) • Birefringence (∆n) • "Reliability" parameters (qualitative) Not (yet) predictable: • Mesophase sequence, clearing point (TNI) • Viscoelastic properties (γ1, Kxy) M. Bremer, K. Tarumi, Adv. Mater. 1993, 5, 842-848. M. Klasen, M. Bremer, A. Götz, A. Manabe, S. Naemura, K. Tarumi, Jpn. J. Appl. Phys. 1998, 37, L945-L948. Dr. Peer Kirsch ILCC-20 Page 33
  33. 33. Combinatorial Chemistry and Automated Parallel Synthesis Dr. Peer Kirsch ILCC-20 Page 34
  34. 34. In Plane Switching (IPS) Mode • Patent of the Fraunhofer Institute of Applied Solid State Physics, Freiburg, 1990 • Acquired by Merck in 1994 • Co-development together with Hitachi Ltd. • Advantages: – Dramatically improved viewing angle of up to 170° – High contrast ratio • Requires materials with strongly positive ∆ε Dr. Peer Kirsch ILCC-20 Page 35
  35. 35. Low Birefringent Materials - 1 • Problem: most bicyclohexyl based liquid crystals tend to have only smectic phases or poor solubility • 1998: Trifluoromethyl bicyclohexyls have found wide spread use in reflective and transflective LCDs H CF3 H C 19 SH? (8) SB? 41 I ∆εvirt = 6.8 ∆nvirt = 0.059 Dr. Peer Kirsch ILCC-20 Page 36
  36. 36. Low Birefringent Materials - 2 • Alternative approach: Materials with negative birefringence as internal ∆n compensators in LC mixtures • 2001: Bicyclohexyl "dimers" with triacetylene as perpendicular polarizable bridging group H11C5 C5H11 C 90 N (63) I ∆nvirt = -0.012 ∆n = -0.0104 (T/TNI = 0.95) H11C5 C5H11 V. Reiffenrath, M. Bremer (Merck), 2001 Dr. Peer Kirsch ILCC-20 Page 37
  37. 37. Difluoroethers: The CF2O Bridge • Substance class first characterized by E. Bartmann and K. Tarumi (Merck), 1995 • Technical synthesis developed by P. Kirsch, A. Taugerbeck, M. Bremer and D. Pauluth (Merck), 2000 F F H O F O F R R H F F F F F F F F O F R F F F F Dr. Peer Kirsch ILCC-20 Page 38
  38. 38. Difluoroethers: Properties • Comparison with directly linked materials: – Increased nematic phase range: TNI increased by 10-15 K, melting points decreased – ∆ε increased, ∆n decreased – Reduction of γ1 by 10-15% – Improved solubility F F H H O F H7C3 F H7C3 H F H F F F C 66 N 94.1 I C 44 N 105.3 I ∆εvirt = 9.7 ∆εvirt = 10.5 ∆nvirt = 0.073 ∆nvirt = 0.067 γ1,virt = 171 mPa·s γ1,virt = 145 mPa·s Dr. Peer Kirsch ILCC-20 Page 39
  39. 39. Other Difluoroether Materials • High stability and enhancement of solubility makes use of "unusual" structural elements possible H3C H3C H H H F O H O SF5 F F H R F H F F F F F F F F H7C3 O F F F F Dr. Peer Kirsch ILCC-20 Page 40
  40. 40. Tetrahydropyranes • Tetrahydropyrane derivatives as highly polar SFM materials with improved stability F C 35 N 66.3 I H O F ∆εvirt = 14.0 ∆nvirt = 0.065 H7C3 γ1,virt = 158 mPa·s O H F F F F F F C 83 N (83.0) I O F ∆εvirt = 35.6 ∆nvirt = 0.132 H7C3 γ1,virt = 457 mPa·s O F F F F F P. Kirsch, E. Poetsch (Merck), 2001 Dr. Peer Kirsch ILCC-20 Page 41
  41. 41. Vertical Alignment (VA) Mode • MVA monitors by Fujitsu since 1996 • ASV TV by Sharp since 2002 • Advantages: – Viewing angle of up to 170° – High contrast ratio – Fast response times • Requires materials with negative ∆ε pictures: MVA (Fujitsu), ASV (Sharp) Dr. Peer Kirsch ILCC-20 Page 42
  42. 42. German Future Prize 2003 M. Bremer, M. Klasen-Memmer, K. Tarumi, Nov 13, 2003 Dr. Peer Kirsch ILCC-20 Page 43
  43. 43. 2,3-Difluorophenylene Derivatives • 1989: First SFM materials with strongly negative ∆ε developed within FLC project (sold in 1995 to Hoechst) H O N R H O OEt R R N N H R OEt R OEt H F F F F R OEt F F Dr. Peer Kirsch ILCC-20 Page 44
  44. 44. Difluoroindanes • Fluorinated indanes are the first fundamentally new type of materials with negative ∆ε since the 2,3- difluorophenylene derivatives: M. Bremer, L. Lietzau (Merck), 2001 H H7C3 H7C3 F H F F F F F F F C 85 I C 130 SB 168 N 203.7 I ∆εvirt = -8.6 ∆εvirt = -8.4 Dr. Peer Kirsch ILCC-20 Page 45
  45. 45. The Past 2004: New LC production plant in Darmstadt 2002: Merck Ltd., Hong Kong 1997: Together with Fujitsu co-development of VA mode Merck Display Technologies Ltd., Taiwan 1996: Purchase of NLC patent portfolio from Hoffmann-La Roche Application laboratory in Taiwan 1995: Together with Hitachi co-development of IPS mode Sales of FLC patent portfolio to Hoechst 1993: Joint venture with Balzers on ITO glass 1989: Application laboratory in Seoul, Korea 1985: Purchase of BBC patent portfolio 1980: Application laboratory in Atsugi, Japan 1968: Start of active LC research at Darmstadt Dr. Peer Kirsch ILCC-20 Page 46
  46. 46. The Present: The Liquid Crystals Division • Employees woldwide: 400 people, including 150 people in R&D • Production volume: 60 tons of liquid crystals in 2002 • Sales 2003: over 400 Mio EUR Dr. Peer Kirsch ILCC-20 Page 47
  47. 47. The Future -1: Transition from CRT to LCD Source – iSuppli/Stanford Resources 250.000 225.000 200.000 Thousands of Units 175.000 150.000 125.000 100.000 75.000 50.000 25.000 0 2002 2003 2004 2005 2006 2007 CRT (TV + Monitor) LCD (TV + Monitor) Dr. Peer Kirsch ILCC-20 Page 48
  48. 48. The Future - 2 • In 2004 completion of a new liquid crystal production facility at Merck, Darmstadt • Investment: 250 MioEUR • Capacity: 150 tons per year Dr. Peer Kirsch ILCC-20 Page 49
  49. 49. Acknowledgements Chemistry Physics Dr. M. Bremer Dr. M. Heckmeier Dr. J. Krause Dr. M. Klasen-Memmer Dr. L. Lietzau Dr. G. Lüssem Dr. E. Montenegro A. Manabe Dr. D. Pauluth Dr. K. Tarumi Dr. E. Poetsch V. Reiffenrath Dr. A. Taugerbeck Dr. W. Becker and Dr. S. Bernschneider-Reif is thanked for historical data and market forecasts Financial Support (€ & ¥) Ministry of International Trade and Industry (MITI) Bundesministerium für Bildung und Forschung (01 B 621/1, 01 BM 904) Dr. Peer Kirsch ILCC-20 Page 50
  50. 50. The LC R&D Team at Darmstadt Dr. Peer Kirsch ILCC-20 Page 51

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