TW574357B - TN and STN liquid-crystal displays - Google Patents

Description

574357 A7 B7 V. Description of the invention (ο (Please read the notes on the back before filling out this page) This invention relates to twisted nematic (TN) and super twisted nematic (STN) liquid crystal displays, with short switching time and variability The angle dependence is good, and it is also related to the novel nematic liquid crystal mixture used therein. It has been known that displays such as: M. Schadt and W. Helfrich, Appl. Phys. Lett., 18, 1 27 (1 97 1). Know STN displays, such as: EP 0 131 216 Bl; DE 34 23 993 Al; EP 0 098 070 A2; M. Schadt and F. Leenhouts, 1 71h Freiburg Conference on Liquid Crystals (8- 1 0/04/87); K. Kawasaki et al., SID 87 Digest 391 (20.6); M. S chadt and F. Lee nh outs, SID 87 Digest 372 (20.1); K. Katoh et al., Japanese Journal of Applied Physics, Vol. 26, No. .11, L1 784-L 1 786 (1987); F. Leenhouts et al., Appl. Phys. Lett. 50 (21), 1468 (1987); HAva n Sprang and HG Koopman, J. Appl. Phy s. 62 (5), 1 734 (1 987); TJ Scheffer and J. Nehring, Appl. Phys. Lett. 45 (10), 1021 (1984), M. Schadt and F. Lee nh outs, Appl. Phys.L ett. 50 (5), 236 (1 987), and EPRay nes, Mol.Cryst.Liq.Cryst.Letters Vol.4 (1), pp.1-8 1986). The so-called STN here includes any rather strongly distorted display element with a twist angle between 160 ° and 360 °, for example, according to Waters et al. (CMWaters et al., Proc. Soc. Inf. Disp. (New York) (1985) (3rd Intern. Display Conference, Kobe, Japan), STN-LCD (DE-A-35 03 259), SBE-LCD (TJScheffer and J. Nehring, A ppl. Phy s. Lett. 4 5 (1 9 84) 1 02 1) ^ OMI-LCD (M. Schadt and F. Lee nh outs, Appl. Phys. Lett. 50 (1987), 236, DST-LCD (EP-A -0 246 842) or BW-STN-LCD (K.Kawasaki et al., SID 87) This paper size is applicable to China National Standard (CNS) A4 specification (210X297 mm) -4- 574357 A7 _ _B7_______ 5. Description of the invention (2 )

Digest 391 (20.6)). (Please read the precautions on the back before filling this page) The difference between STN displays and standard TN displays lies in the better variability of the electro-optic characteristic curve and the mild and quite high multiple signal ratio due to better contrast, such as: 32 to 64. On the other hand, TN displays have higher contrast ratios because of better darkness, and the angle dependence of contrasts is lower than STN displays with low multi-signal ratios (eg, less than 16). TN and STN displays of particular interest have very short switching times, especially at low temperatures. To achieve short switching times, the optimum rotational viscosity of liquid crystal mixtures has previously been adjusted by using monotropic additives with relatively high vapor pressures. But the switching time reached is not sufficient for all applications. To achieve the steep electro-optical characteristic of the display according to the present invention, the liquid crystal mixture must have a relatively large elastic constant κ33 / ΚπΚ and a relatively small Δε / Δεε, where Δε is the dielectric anisotropy 値, and ε 丄 is The dielectric constant perpendicular to the longitudinal axis of the molecule. In addition to the most suitable comparison and the most suitable switching time, there are other important requirements for such a mixture: 1. Wide d / p range Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 2. High long-term chemical stability 3. Resistive High 4. The frequency dependence and temperature dependence of the critical voltage are low. The achieved combination of parameters is still insufficient, especially for highly multi-transmit STN displays (multi-transmission ratio of about 1/4 00), for low or medium multi-transmission STN displays (multi-transmission ratio of approximately 1/6 4 and 1/1 6) and TN displays as well. One reason is that the material parameters are negative for a variety of requirements. The paper size applies the Chinese National Standard (CNS) A4 specification (210X 297 mm) -5- 574357 Α7 __ Β7 V. Description of the invention (3). Therefore, there are still TN and STN displays (especially low- and moderate-multiple-transmission STN displays) that meet the aforementioned requirements for short switching time, wide operating temperature range, steep characteristic curves, good angular dependency, and low threshold voltage High demand exists. The object of the present invention is to propose a TN and STN display, which does not have the aforementioned disadvantages or has a reduced degree of shortcomings, a short switching time (especially at low temperature) and / or excellent anisotropy. It has been found that this can be achieved by using a nematic liquid crystal mixture comprising one or more compounds of the formula I

r11- {〇 ^ -c = c Among them, printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling this page) R11 is an alkyl or alkoxy group with 1 to 12 carbon atoms Or alkenyl, in addition, one or two non-adjacent CH2 groups are substituted with -CH = CH-, -C0-, -0-C〇-, or -C〇〇-, respectively, so that the 0 atoms are not directly to each other Linked, R12 is an alkyl group having 1 to 8 carbon atoms, wherein one or more fluorene atoms are replaced by F, and L1 to L4 are fluorene or F, respectively. The compound of formula I is used in the mixture used by the TN or STN according to the present invention, so that the paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) -6- 574357 A7 _ B7 V. Description of the invention (/) 4 / • The switching time is extremely short, especially at low temperatures. • The electro-optical characteristic curve is steep, (please read the precautions on the back before filling this page) • The temperature dependence of the threshold voltage is low. In particular, the compound of formula I significantly shortens the switching time of TN and STN mixtures, especially at low temperatures, and at the same time, has high variability, low threshold voltages and operating voltages. The mixtures according to the invention are further characterized by the following advantages:-their low viscosity,-their long shelf life in LC displays at low temperatures,-their low temperature dependence of operating voltage and critical voltage, and-their dielectric constants Frequency dependence is low. Therefore, the present invention relates to a liquid crystal display, which includes-two outer plates that form a battery with a frame, a nematic liquid crystal mixture with positive dielectric anisotropy located in the battery 5-an electrode layer, and an alignment layer thereof On the inside of the outer plate, the consumer cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs printed a tilt angle between the longitudinal axis of the molecule at the surface of the outer plate and the outer plate from 0 to 30 degrees, and the twist angle of the liquid crystal mixture in the battery (from Alignment layer to alignment layer) is between 22.5 ° and 600 °. The nematic liquid crystal mixture contains a) 15-80% by electricity of liquid crystal component A, which is composed of one or more compounds having a dielectric anisotropy of more than +1.5. H) 20-85% by weight of liquid crystal component B, which is anisotropic by one or more dielectrics

ΪThe paper size is applicable to the Chinese National Standard (CNS) A4 specification (210'〆297 male H -7- 574357 Α7 Β7 ______ V. Description of the invention (5) Compound composition between -1.5 and +1.5 'c) 0-20 Lightning% liquid crystal component D, which consists of one or more dielectric anisotropy (please read the precautions on the back before filling this page) compounds below -1.5, and d) the photoactive component C selected The amount is such that the ratio between the layer thickness (outer plate spacing) and the natural pitch of the palm nematic liquid crystal mixture is from about 0.2 to 1.3. It is characterized in that component A contains at least one compound of formula A

Wherein, R11 is an alkyl, alkoxy or alkenyl group having 1 to 12 carbon atoms. In addition, one or two non-adjacent CH2 groups are respectively -0, -CH = CH-, -C〇- , -0-C〇- or -C〇〇-, so that. Atoms are not directly connected to each other, R12 is an alkyl group having 1 to 8 carbon atoms, wherein one or more η atoms are replaced by F The consumer cooperatives of the Intellectual Property Bureau of the Ministry of Economy printed L1 to L4 as Η or F, respectively. The present invention also relates to related liquid crystal mixtures for use in TN and STN displays, particularly moderate and low-level multi-signal STN displays. Particularly preferred liquid crystal mixtures include one or more compounds of formula 丨 wherein R11 is a linear 1E · alkenyl group having 2 to 7 carbon atoms or a 3E-alkenyl group having 4 to 7 carbon atoms. Another preferred liquid crystal mixture contains one or more compounds of formula I. The paper size applies to the Chinese National Standard (CNS) A4 specification (2) 0X 297 mm. -8-574357

5. Description of the invention (β 6 R11 is a linear alkyl group with 1 to 8 carbon atoms. (Please read the precautions on the back before filling out this page) Another preferred liquid crystal mixture contains one or more compounds of formula I , L i and L2 are fluorene, and among other preferred liquid crystal compounds, L 1 and / or L 2 are F. Among other preferred liquid crystal compounds, L 3 and L 2 are F. And L4 is fluorene, and among other preferred liquid crystal compounds, one or more compounds of formula I, L3 and / or L4 is F. In another preferred liquid crystal mixture, one or more compounds of formula I, R12 is 1 to A straight-chain alkyl group of 8 carbon atoms in which 2, 3 or more fluorene atoms are substituted by F such that the alkyl group contains at least one -CF2- and / or {cardio group. Particularly preferred R12 is 1, 2 Perfluorinated straight-chain alkyl group of 3, 4 or 5 carbon atoms. Therefore, the preferred R12 is -CHF2, -CF3, -CH2-CHF2, -CH2-CF3 > -CF2-CF3 > -CF2 -CHF2 '-CH2-CH2-CHF2 > -CH2-CH2-CF3 ^ -CH2-CF2-CHF2' -CH2-CF2-CF3 '-CF2-CF2-CHF2 or -CF2-CF2-CF3. Particularly preferred R12 Is -CF3. Particularly preferred compounds of formula I From the following persons: Ministry of Economic Affairs Intellectual Property Office employees consumer cooperatives printed

18 This paper size is in accordance with Chinese National Standard (CNS) A4 (210X 297 mm) -9-574357 A7 B7 Printed by the Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs

(Please read the precautions on the back before filling out this page.) The size of this paper applies to the Chinese National Standard (CNS) A4 (2j〇X 297 mm) -10- 574357 A7 B7 V. Description of the invention (8 ^

This paper size is applicable to China National Standard (CNS) A4 specification (210X297 mm) -11-574357 A7 B7 V. Description of invention (9)

(Please read the notes on the back before filling out this page.) Among them, R °° is Η, CH3, C2H @ 11-C3H7, and particularly preferred is Η or CtL. 'The base is a hospital with 1 to 8 carbon atoms. base. Excellent are the compounds of formulas ic, if, I i, I η, I q and 11. The compound of formula I is used in the liquid crystal mixture according to the present invention for TN and STN displays, and the resulting variation is high and the switching is rapid, especially at low temperatures. Compounds of formula I have low viscosity. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs In addition to the compound of formula I, the mixture according to the present invention preferably contains one or more alkenyl compounds of formula 11

The paper size 4 uses the Chinese national county (⑽) A4 specifications (2 Xian 297 public fantasy -12-574357 A7 B7 V. Description of the invention (d R3 is an alkenyl group with 2 to 7 carbon atoms, (Please read the back first Please note this page to fill in this page) R4 is an alkyl, alkoxy or alkenyl group having 1 to 12 carbon atoms, in which, in addition, one or more non-adjacent CH2 groups can be -0-, -CH = CH-, -CO-, -0C〇- or -C〇〇- is substituted such that 0 atoms are not directly connected to each other, and a is 0 or 1. Particularly preferred compounds of formula II are selected from the formulas Ila to Ilg

Printed by the 8th Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, where R3a and R4a are Η, CH3, C2H5 or, respectively;!: The basic paper size applies the Chinese National Standard (CNS) A4 specification (210X 297 mm) -13 -574357 Μ ___ _B7_ V. Description of the invention (^ is an alkyl group having 1 to 8 carbon atoms. Particularly preferred are compounds of formula Ila (especially 1 ^ 33 and 1 ^ "are CH3) and formula lie, Ilf and Ilg compounds (especially η) ° Compounds of formula II used in the liquid crystal mixture according to the present invention will have low rotational viscosity and high variability of the TN and STN displays, and will switch quickly, especially at low temperatures In addition to the dielectrically neutral alkenyl compounds of formula II, the mixtures according to the invention preferably comprise one or more positive dielectric formal II * alkenyl compounds

ir where R3 is an alkenyl group with 2 to 7 carbon atoms, Q is CF2, 0CF2, CFH, 0CFH or a single bond, printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs (please read the precautions on the back before (Fill in this page) Y is F or C1, and L1 and L2 are Η or F, respectively. Particularly preferred compounds of formula II * are those in which L1 and / or L2 are F and Q-Y is F or 0CF3. In a preferred compound of formula II *, R3 is a 1E-alkenyl or 3E-alkenyl group having 2 to 7 (preferably 2, 3 or 4) carbon atoms. Polar formula II with a dielectric anisotropy higher than + 1.5 * Compounds are regarded as the previous standard paper size applicable to China National Standard (CNS) A4 specifications (210 × 297 mm) -14- 574357 A7 B7 V. Description of the invention (d meaning Component A ° Component A is preferred to contain one or more cyano compounds of the formula L3 R— < 〇 > one ~ ^ 0 / -CNV2

Ilia

lllb ----- il-# 衣-(Please read the precautions on the back before filling this page)

R— (〇 > --COO CN lllc, order

R— (H > -C00 CN llld f Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs

R— (H V-CH2CH2 CN

R- < H 0/000

CN llle lllf This paper size is applicable to Chinese National Standard (CNS) A4 specification (21 OX 297 mm) -15- 574357 A7 B7 V. Description of the invention (^

Among them, (please read the precautions on the back before filling this page) The R & D system produced by the 8th Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs is an alkyl, alkoxy or alkenyl group having 1 to 12 carbon atoms. In addition, one or Two non-adjacent CH2 groups are substituted with: 〇-, -CH = CH-, -C〇-, -0-C0-, or -COO-, respectively, so that the 0 atoms are not directly connected to each other, and L1 to L3 are respectively Is n or F. Particularly preferred among these compounds is a fluorenyl or alkoxy group having 1 to 8 carbon atoms or an alkenyl group having 2 to 7 carbon atoms. Particularly preferred mixtures comprise one or more compounds of the formulae Illb and / or IIIc and Illf, in particular Li and / or ρ. An excellent mixture comprises one or more compounds of formula IIIb and / or IIIc ', wherein R is an alkenyl group having 2 to 7 carbon atoms, L1 and L2 are fluorene or F, and preferably Η is Η. Particularly preferred is the compound represented by the following formula: This paper size applies the Chinese National Standard (CNS) A4 specification (210X 297 mm) -16- 574357 A7 B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs

Ο >-CN

R ^ JT

CN lllb-2

I llc-2 wherein R3a is H, CH3, C2H5 or n-C3H7, in formulas IIIb-1 and IIIb-2, H or CH3 is preferred, and in formulas IIIc-1 and IIIc-2, H or C 2 Η 5 is preferred. Preferred other mixtures include one or more compounds of formula πιι, wherein L2 is Η and L1 is Η or F, especially F. In a specific embodiment, preferably, component A contains one or more 3,4,5-trifluorophenyl compounds represented by the following formula: R— < Η (Please read the precautions on the back before filling this page)

F

F

0 / -F F IVa The paper size is applicable to Chinese National Standard (CNS) A4 specification (210X 297 mm) -17- 574357 A7 B7 V. Description of invention (d

F

F IVb

F

F IVc

F F

F IVd —------- yi --- 1 (Please read the precautions on the back before filling in this page)

F

F

F IVe

, 1T

F

F

F IVf Consumers' Cooperative, Yinxian Bureau, Intellectual Property Bureau, Ministry of Economic Affairs

F

r- / hV < hVcoo f IVg This paper size is applicable to China National Standard (CNS) A4 (210X 297 mm) -18- 574357 Μ

7 B Explained Mingfa 5) 0 1

R

Η Η

C

F

F

R

H

H

CH

F

F

R

H

CH

F --- ^ --- $!-# 衣-(Read the precautions on the back before filling in this page)

R

H F F’v 〇

Ivrrl Order

R

H c

F

F Printed by the Consumer Cooperative of the Intellectual Property Office of the Ministry of Economy

R

H

F This paper size applies to Chinese National Standard (CNS) Α4 specification (210X297 mm) -19- 574357 A7 B7 V. Description of invention (j

F

R

C2F4 —F F IVp

F

F

R- < H >-< 〇 ^ C2F4— ~ ^ 〇 > -F IVq

F

F

F

F

r —〇 / -c2f4- ^ o > -f V IVr (Please read the notes on the back before filling this page)

F

F order

R

0 > -F IVs

F and, if applicable, one or more compounds having polar terminal groups represented by the following formula:

P Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs L3

R-Λ Η > — < H > -C00 — (> -F

Va L3

R- < H >-< H > -CF9〇- (0) -F

Vb This paper size is in accordance with Chinese National Standard (CNS) A4 (210X 297 mm) 20- 574357 A7 B7 Printed by the Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs

_ 、 Order I — — ~~ (Please read the notes on the back before filling this page) This paper size applies to China National Standard (CNS) A4 specification (210X 297 mm) -21-574357 A7 B7 Printed by Bureau of Industry and Industrial Cooperatives

(Please read the notes on the back before filling in this page) Order ^ 1. This paper size is applicable to China National Standard (CNS) A4 (210X 297 mm) -22- 574357 A7 ---- B7 V. Description of the invention ( ^ L3

(Please read the notes on the back before filling out this page.) Order, R has one of the meanings above, and L3 and L4 are Η or F, respectively. Particularly preferred among these compounds is an alkyl or alkoxy group having 1 to 8 carbon atoms. Particularly preferred are compounds of formulae IVa, IVb, IVc, IVd, IVm and Vm, especially compounds of formulae IVa, IVm and Vm. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. The preferred liquid crystal mixture contains one or more component A compounds, the proportion of which is preferably 15% to 80%, especially 20% to 70%. The dielectric anisotropy of these compounds is Δ ε 2 +3, particularly Δ ε g +8, and Δ ε 2 +12 is particularly preferable. Preferred liquid crystal mixtures contain one or more component B compounds, preferably in a proportion of 20 to 85%, especially 30 to 75%. Group B compounds (especially those containing alkenyl groups) are characterized by their low rotational viscosity 値 71.

Except for one or more compounds of formula II, in the best case, the paper size of component B is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm " Γ -23- 574357 A7 B7) 5. The invention description (21) contains One or more bicyclic compounds selected from the group consisting of

IV1 IV2 IV3 1 .----- ^^ 1 (Please read the notes on the back before filling this page

R IV4 R1— (Η

R IV5 order

IV6

R1 — ^ (H V-CH2CH2 — ^ (H > —R IV7 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs

R1— (H > -C00-

R IV8

R1— (H CH = CH — (H > -R and / or one or more tricyclic compounds represented by the following formulas) The paper size applies to the Chinese National Standard (CNS) A4 specification (210X 297 mm) IV9 24- 574357 A7 B7 V. Description of the invention (j IV10 R1— (H V-CH2CH2 — < 〇WH > -R2 IV11

IV12 IV13 IV14 (Please read the precautions on the back before filling this page) R1- \ H / — \ O / 一 CH2CH2— \ O / 一 R2 IV15

, 1T R | 〇 y-R " IV16

R— (H > -CH0CK IV17 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs R '

CH2CH2— (0) —R IV18 R1— (H V-CH2CH2— (H > -CH2CH2 ~~ (〇) —R2 IV19

R — < Η > -Λ H IV20 This paper size applies to Chinese National Standard (CNS) A4 (210X 297 mm) -25 574357 A7 B7 V. Description of the invention (R— (Η

• R IV21

R IV22 IV23 R — < H > -CH = CH— < H) ~ (〇 > -R 'IV24 (Please read the precautions on the back before filling this page)

L r1—Λ H >-< H V-COO — (〇 V-R2 IV25 R 丨

COO IV26 and / or one or more tetracyclic compounds represented by the following formula: ^ 1. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs R1-

H 丄

IV27

R < H > -CH 2ch2 ~ (^ y ~ R IV28

H

IV29 The size of this paper applies to the Chinese National Standard (CNS) A4 (210X 297 mm) 26- 574357 A7 B7 V. Description of the invention (

IV30 IV31 IV32 IV33 (Please read the notes on the back before filling out this page) Clothing, 1T Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs, where R1 and R2 are alkyl and alkyl groups with 1 to 12 carbon atoms, respectively Oxy or alkenyl, in addition, one or two non-adjacent CH2 groups are substituted with -0, -CH = CH-, -C0-, -0-C〇- or -C〇〇-, respectively, So that 0 atoms are not directly connected to each other, L is Η or F. The 1,4-phenylene groups in IV10 to IV19, IV23 to IV25, and IV27 to IV33 may also be mono- or polysubstituted by fluorine, respectively. In a particularly preferred case, in the compounds of IV27 to IV33, R1 is an alkyl group, and R2 is an alkyl group or an alkoxy group (particularly an alkoxy group), each of which has 1 to 7 carbon atoms. In preferred compounds of the formulae IV27 to IV33, L is F. Excellent are compounds of formulae IV27 and IV29. This paper size applies the Chinese National Standard (CNS) A4 specification (210X29 * 7mm) 27-574357 A7 B7 V. Description of the invention (d) Among the compounds of formula IV1 to IV33, especially, and r2 have 1 to 12 carbons. Atoms are straight-chain alkyl or alkoxy groups. This liquid crystal mixture optionally contains light-active super 1 'by an amount such that the ratio between the layer thickness (separated from the outer plate) and the natural spacing in the palm nematic liquid crystal mixture値 is greater than 0.2. Various palmar dopants (some of which are commercially available, such as: cholesterol nonanoate, S-811, available from Merck KGaA, Darmstadt, and CB15 (SDH, Poole, UK)) are Those skilled in the art can use it. There is no particular requirement for the selection of dopants. The compound ratio of component C is preferably 0 to 10%, more preferably 0 to 5%, especially 0 to 3%. Except for formula I Other than compounds, the mixture according to the present invention preferably contains one or more other liquid crystal diphenylacetylene compounds. Because the birefringence 高 Δη of the diphenylacetylene compound is high, a smaller layer thickness can be used, making the switching time significantly shorter. This The diphenylacetylene compound is preferably selected from Ta to Ti: (Please Read the Notes on the back to fill out Page} i # Ministry of Economic Affairs Intellectual Property Office employees consumer cooperatives printed

P. This paper size applies Chinese National Standard (CNS) A4 specification (210X 297 mm) -28- 574357 A7 B7 V. Description of the invention (^ L5 L6 L3 L2 R— < 0

〇) -C = C-X 〇) -R

Te

F F R1 ~ (〇 V-c = c- < 〇 Vr2

Tf

R

Tg (Please read the notes on the back before filling this page) ^ > -Z4—C III R2

Th

Ti

, 1T Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs Among them, R1 and R2 are as defined above, Z4 is -C0-〇-, -CH2CH2- or a single bond, and L1 to L6 are H or F, respectively. Particularly preferred are compounds of formulae Ta, Tb and Th. Particularly preferred compounds of the formula Te include one, two or three of the groups L1 to L6

The F is the F, and the remainder is Η. L1 and L2 or L3 and L4 or L5 and L6 are not F at the same time.

The ratio of Ta and Tb compounds is preferably from 2 to 40%, especially from 2 to 20%. The proportion of the compound of formula Th is preferably from 2 to 35%, especially from 4 to 25%. This paper size applies to the Chinese National Standard (CNS) A4 specification (210X297 mm) -29- 574357 A7 B7 V. Description of the invention (2) The proportion of the compounds of formula Ta to Ti is preferably 2 to 55%, especially 5 to 35% O The mixture according to the present invention may optionally contain no more than 20% —or a plurality of compounds having a dielectric anisotropy of less than −2 (component D). If the mixture contains a component D compound, these are preferably one or more compounds containing the structural unit 2,3-difluoro-1,4-phenylene, for example, according to DE-A-38 07 801, DE-A- 38 07 861, DE-A-38 07 863, DE-A-3 8 07 864 or DE-A-38 07 908. Particularly preferred is the diphenylacetylene containing this structural unit as described in WO 88/001 33. Other known component D compounds are, for example: DE-A 32 3 1 707 and

Contains structural units as described in CN (27) or DE-A-34 07 01 3

(Please read the notes on the back before filling out this page) 2,3-dicyanohydroquinone or cyclohexane derivative. The liquid crystal display according to the present invention is preferably free of any component D compound. The "alkenyl" as defined in R, R1, R11, R2, R3, and R4 is printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs to cover straight chain And branched alkenyl. 1 ^, 1 ^ 1, 1 ^ 1 and 1 ^ 2 have 2-12 carbon atoms, and 1 ^ and 1 ^ have 2 to 7 carbon atoms. Particularly preferred alkenyls are C2-C7-1E-alkenyl, CVC7-3E-alkenyl, C5-C7-4-alkenyl, CVC7-5-alkenyl and CV6-alkenyl, especially c2-C7-1E -Alkenyl, CVC7-3E-alkenyl and C5-C7-4-alkenyl. Preferred examples of alkenyl are vinyl, 1E-propenyl, 1E-butenyl, 1E-pentenyl, 1E-hexenyl, 1E-heptenyl, 3E-butenyl, 3Ev pentenyl ' 3E-hexenyl, 3heptenyl, 4-pentenyl, 4Z-hexenyl, 4E-hexene basic paper sizes are applicable to China National Standard (CNS) A4 specifications (210X297 mm) -30 574357 A7 B7 V. Description of the invention (g, 4Z-heptyl, 5-hexyl, 6-heptyl and the like. Groups having no more than 5 carbon atoms are preferred. TN and STN displays according to the present invention can be used The compounds of the formulae I, η, III, IV, V, VI and T and their sub-formulae and other compounds are known or can be prepared in a manner similar to known compounds. In a particularly preferred embodiment, this mixture contains One or more compounds selected from the aforementioned formulae Ic, If, Ii, in, Iq and it, of which H or CfL · is preferred, one, two or three compounds of formula I—3 to 40%, 5 to 25 % Is preferred, 6 to 16% is particularly preferred, one or more compounds of formula I,-5 to 60%, especially 12 to 50%, one or more alkenyl compounds of formula Π and Π *, at least one lie and / Or Ilf compounds ,-At least one alkenyl compound selected from the following (please read the precautions on the back before filling this page) Order P.

574357 A7 ____ B7 V. Description of the invention (

Wherein, alkyl is an alkyl group having 1 to 8 carbon atoms, ^ 33 is fluorene or CH3-one or more compounds of formula IV9 and / or IV24, wherein R1 is an alkenyl group having 2 to 7 carbon atoms, and R2 As defined before, especially with! Alkyl or alkoxy groups of from 6 to 6 carbon atoms, in particular one or more compounds of formula IV9a and / or IV24a,

(Please read the notes on the back before filling out this page) This book is printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs, where the ruler is “Η, CH3, C2H5 or n-C3H7, especially Η or CH3 'R2 as before The definition of 'is preferably an alkyl or alkoxy group having 1 to 6 (especially 1, 2 or 3) carbon atoms. The proportion of these compounds in the liquid crystal mixture is preferably 2 to 30%, especially 5 to 25%, --or multiple (especially two to five) formulas Illb, IIIc, Illf and / or this paper size is applicable to China National Standard (CNS) A4 specification (210X297 mm) 1 ~ -32-574357 A7 ____B7___ V. Description of the invention (^

Illh compounds, (please read the notes on the back before filling out this page)-at least two compounds of formula IIIc, and, if necessary, at least one compound of formula Illb whose L1 and / or L2 is F. The proportion of these compounds in the liquid crystal mixture is preferably from 7 to 50%, especially from 10 to 40%,-or more (preferably 1, 2 or 3) diphenylacetylene compounds represented by formula Ta or Tb,- -Or more (preferably 1, 2 or 3) diphenylacetylene compounds represented by formula Th,-or more compounds of formula IV27 and / or IV29, wherein L in formula IV27 is Η or F, particularly preferably It's F. The proportion of these compounds in the liquid crystal mixture is preferably from 10 to 45%, especially from 15 to 40%.-More than 20% of the compounds have a positive dielectric anisotropy, especially Δ ε $ + 12. The characteristic of the mixture according to the present invention is that, especially when used for TN and STN displays with high layer thicknesses, the total switching time (^. 1 = "+ 〖." 『Very short. Printed by the 8th Industrial Cooperative Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs '' The liquid crystal mixture used in the production of STN and TN cells according to the present invention has a dielectric positive Δ ε-1. A particularly preferred liquid crystal mixture Δ ε g 3, especially Δ ε-5. The liquid crystal mixture according to the present invention has a useful threshold. Voltage Vm / Q / 20 and rotational viscosity r 1 値. If the optical path difference d · △ η is predetermined 値, the optical anisotropy 値 η defines the layer thickness d 値. In particular, when d · △ η is quite high The liquid crystal mixture used in the present invention is preferably one having a relatively high optical anisotropy, because a relatively small d 値 can be selected at this time, which is advantageous for obtaining a better switching time 値. However, even according to the invention, Liquid crystal display This paper size applies Chinese National Standard (CNS) A4 specification (210X 297 mm) '-33- 574357 Α7 Β7 Printed by the Consumers ’Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention (3) The liquid crystal mixture with a smaller η 具有 also has a feature that is beneficial to the switching time. Another feature of the liquid crystal mixture according to the present invention is that the electro-optical characteristic curve has a good variation and can be operated in the case of multiple transmissions with high ratio 値, especially Operation above 20 ° C. In addition, the stability of the liquid crystal mixture according to the present invention is still 'with favorable resistance 的 and critical voltage frequency dependence. The liquid crystal display according to the present invention has a wide operating temperature range and has good contrast angle dependence The structure of the liquid crystal display element according to the present invention includes a polarizer, an electrode substrate, and a treated electrode surface (this treatment causes each of the liquid crystal molecules to be arranged next to each other, usually a twist angle of 160 to 720 from one electrode to another electrode. This depends on the general design of the display element. The so-called "general structure" here refers to a broad definition and also includes all changes and modifications of TN and STN batteries. In particular, it also includes matrix display elements and Display elements. The surface inclination angles of the two outer plates may be the same or different. The same inclination angle is preferred. Better TN display The pretilt angle between the molecular longitudinal axis of the device on the surface of the outer plate and the outer plate is 0 ° to 7 °, preferably from 0.01 ° to 5 °, especially 0.1 ° to 2. In STN displays, the pretilt angle It is Γ to 30 °, preferably Γ to 12 °, especially 3 ° to 10 °. The twist angle of the TN mixture in the battery is between 22.5 ° and 170 °, and between 45 ° and 130 ° Between, especially between 80 ° and 115 °. In the battery, the twist angle between the alignment layer and the alignment layer of the STN mixture is between 100 ° and 600 °, between 170 ° and 300 ° is better, especially between 180. and 27 (T. (Please read the notes on the back before filling in this page) clothing. Order IP- · This paper size applies to China National Standard (CNS) Α4 specifications (210X 297 mm) -34- 574357 A7 ____B7 _ 5. Description of the invention (The preparation of the liquid crystal mixture that can be used according to the present invention is performed in a currently known manner. The desired amount of the component is dissolved in a smaller amount in the components constituting the main component, and this can be performed at an elevated temperature. Alternatively, a solution of the components in an organic solvent (such as acetone, chloroform, or methanol) can be mixed, and after being thoroughly mixed, the solution (such as distillation) can be removed. The dielectric may also contain other additives known to those skilled in the art and described in the literature. For example, 0-15% polychromatic dye can be added. In the present specification and the following examples, "the structure of the liquid crystal compound is represented by an abbreviation" is translated into a chemical formula according to the following attached tables A and B. All groups CnHiw and + i are straight chain radicals with η and m carbon atoms, respectively. The commission base is a trans configuration. The codes in Schedule B are self-evident. In Schedule A, only the abbreviations of the parent structure are listed. In each case, the abbreviations of the parent structure are followed by hyphens to list the substituents r1, R2, L1, L2, and L3 codes. (Please read the precautions on the back before filling out this page) The paper size printed by the Employees' Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs applies the Chinese National Standard (CNS) A4 specification (210X297 mm) -35- 574357 A7 B7 (

Code for R1, R2, L1, L2, L3 R1 R2 U L2 L3 nm CnH2n + 1 CmH2m + 1 HHH n〇m 0CnH2n + 1 CmH2m + 1 HHH nO.m CnH2n + 1 〇CmH2nn + 1 HHH gate CnH2n + 1 CN HHH nN.F ^ n ^ 2n + 1 CN HHF nN.FF CnH2n + 1 CN HFF nF CnH2n + 1 FHHH nOF 0CnH2n + 1 F, HHH nF.F CnH2n + 1 FHHF nmF CnH2n + 1 CmH2m + 1 FHH nOCF 3 CnH2n +1 〇cf3 HHH n-Vm CnH2n + 1 -CH = CH-CmH2m + i HHH nV-Vm CnH2n + i ~ CH = CH- -CH = CH-CmH2m + i HHH (Please read the notes on the back before filling (This page) ^^ Clothing and Consumer Cooperatives of the Intellectual Property Office of the Ministry of Economic Affairs print TN and STN displays preferably containing liquid crystal mixtures containing one or more compounds selected from Schedules A and B. This paper size applies Chinese National Standard (CNS) A4 (210X297 mm) -36- 574357 A7 B7 V. Description of the invention (Annex A: (L \ L2, L3 = H or F) r1 ~ c〇〇κί > -ρ2

CH

BCH CCP

CPTP PTP

FT ME

RK Η Η H " ‘CCH

(Please read the notes on the back before filling out this page) Clothing. Order f Intellectual Property Bureau of the Ministry of Economic Affairs g (Printed by Industrial and Consumer Cooperatives)

This paper size applies to Chinese National Standard (CNS) A4 specifications (210X 297 mm) -37- 574357 A7 B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention () Schedule B: CVCP-V- (0 ) m (〇) CmH2m + 1

CnH2n +

(〇) CmH vice

CnH2n "CVCP-nV- (0) m CC-nV-Vm

CmH2

f 〇nH2n. Where +1

(Please read the notes on the back before filling this page) CCP-Vn-m CCP-V-m

CCG-V-F

CnH2n .- < 〇M〇 ^ 〇 = C ^} cmH2m + 1 C ^ n + 1 ^ CO〇-{^ 〇C ^^ F PPIUl-nm PZP-n-OT f CnH2n > < 2)- C〇〇 一 & Q ^ 〇CF3

PZP-Vn-OT

CnH2n

PTP-Vn-OT

F

CnH2n-< (^ CO〇- ^ > ~ CN F PZU-Vn-N This paper size is applicable to China National Standard (CNS) A4 specification (210X297 mm) _ 38-574357 B7 Employee Consumer Cooperative of Intellectual Property Bureau, Ministry of Economic Affairs Printed 5. Description of the invention (y Schedule C: Schedule C lists possible dopants that are usually added to the mixture according to the invention 0 c2h5-ch-ch2o— (〇CH. 〇 > -CN C2H5- CH-CH2— ^ Ο CH, C 15 CB 15

c6h13-ch-o— (o CK

CM 21 c6H13〇— (0

R / S-811 〇 (Please read the notes on the back before filling out this page) 〇 〇- < 0

o-ch-c6h13 CH, c3h7- \ Η h o > -ch2-ch-c2h5 CH, CM 44

c8h17o

The revised paper size applies the Chinese National Standard (CNS) A4 specification (210X 297 mm)-39- 574357 A7 B7 V. Description of the invention (d Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs

F CH,

---- 1 .--: · --- ^ 衣-(Please read the precautions on the back before filling this page)

、 1T f This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) -40-574357 A7 B7 V. Description of the invention (y The following examples are used to illustrate the present invention without limitation. The meaning of the symbols is as follows: (Please Read the precautions on the back before filling in this page] c 1. p · Crystal point (nematic-anisotropic phase transition temperature), SN dish-like liquid crystal molecule-nematic phase transition temperature, vis c. Flow viscosity ( Mm2 / s, measured at 20 ° C unless otherwise specified), △ η optical anisotropy (5 89 nm, 20 ° C) n〇 general refractive index (5 89 nm, 20 ° C) △ ε dielectric anisotropy (1kHz, 2 (TC) ε 丄 dielectric constant perpendicular to the longitudinal axis of the molecule (1kHz, 20 ° C) r 1 rotation viscosity S characteristic curve variability = V 9 0 / V 1 0

V10 critical voltage = characteristic voltage of 10% relative contrast V90 characteristic voltage of 90% relative contrast tave (Un + Uf〇 / 2 (average switching time) ton time between ON and 90% of maximum contrast The time between and reaching the maximum contrast of 10% is printed by the Intellectual Property Bureau of the Ministry of Economic Affairs and the Consumer Cooperatives of the Consumer Council. Mu X Multiple messages are given above and below. All temperature units are ° c.% Is weight%. Unless otherwise specified, otherwise All series are about 20 ° C. Unless specifically stated, this display is addressed, the multiple signal ratio is 1/64, and the bias is 1/9. Unless otherwise stated, the twist angle is 240 °. Comparative Example 1 Paper Size Applicable to China National Standard (CNS) A4 specification (21 × 297 mm) -41-574357 A7 B7 V. Description of the invention (^ A mixture of TN and STN includes PCH-3N.FF 10.00% cl.p ": 88.0 ° C ME-2N.F 2.00% Δη: 0.1618 ME-3N.F 2.00% η〇: 1.5025 ME-4N.F 10.00% v10: 1.67 V CC-5-V 10.00% S: _ 1.070 CCG-VF 18.00% tave (-20 ° C): 1500 ms CCP-V-1 8.00% tave (+20 ° C): 115 ms CCP-V2-1 5.00% CVCP-V-1 4.00% CVCP-V-01 4.00% CVCP-1V-01 2.00% PTP-102 5.00% PTP-201 3.00% PTP-301 3.00% PPTUI-3-2 14.00% (Please read the precautions on the back before filling this page ) Clothing

、 1T Printed by the Intellectual Property Department of the Ministry of Economic Affairs 1 Consumption Cooperative of Employees 1 A mixture of TN and STN contains PTP-V2-OT 10.00% cl.p. ·: 88.0 ° C PCH-3N.FF 10.00% Δη: 0.1635 ME- 2N.F 2.00% n〇: 1.5017 ME-3N.F 2.00% v10: 1.70 V ME-4N.F 10.00% S: 1.064 CC-5-V 9.00% tave (+20 ° C): 105 ms CCG-VF 7.00% CCP-V-1 8.00% CCP-V2-1 8.00% CVCP-V-1 5.00% CVCP-V-01 5.00% CVCP-1V-01 5.00% PTP-102 3.00% PTP-201 3.00% PPTUI-3 -2 13.00% .f This paper size applies Chinese National Standard (CNS) A4 (210X 297 mm) -42- 574357 A7 B7 V. Description of the invention (^ Example 2 A mixture of TN and STN includes PTP-V2-OT 10.00% cl.p .: 89.0 ° C PCH-3N.FF 10.00% Δη: 0.1625 ME-2N.F 2.00% π〇: 1.5017 ME-3N.F 2.00% Vi〇 '1.64 V ME-4N.F 12.00% S: 1.069 CC-5-V 8.00% tave (-20 ° C): 1300 ms CCG-VF 6.00% W (+20 ° C): 110 ms CCP-V-1 10.00% CCP-V2-1 8.00% CVCP -V-1 5.00% CVCP-V-01 5.00% CVCP-1V-01 5.00% PTP-102 2.00% PTP-201 2.00% PPT UI-3-2 13.00% (Please read the notes on the back before filling this page) Compared with the results of the comparative example, the switching time of the mixture of examples 1 and 2 is shorter, especially at -20 ° C. At the same time, the variability of the comparative example is low or lower. The paper size printed by the Consumer Cooperatives of the Intellectual Property Office of the Ministry of Economic Affairs is compliant with the Chinese National Standard (CNS) A4 (210X 297 mm) -43-

Claims (1)

574357 Male A8 B8 C8 D8 Scope of patent application 1 1. A TN or STN liquid crystal display, which contains-two outer plates, which form a battery with the frame, (please read the precautions on the back before filling this page)-located at The nematic liquid crystal mixture with positive dielectric anisotropy in the battery-electrode layer has an alignment layer on the inner side of the outer plate, and the inclination angle between the longitudinal axis of the molecule at the outer plate surface and the outer plate is from 0 degrees to 30 degrees, and the twist angle (from the alignment layer to the alignment layer) of the liquid crystal mixture in the battery is between 22.5 ° and 600 °, and the '-nematic liquid crystal mixture contains a) 15-80% by weight of liquid crystal component A, which Consisting of one or more compounds having a dielectric anisotropy exceeding +1.5, b) 20-85% by weight of the liquid crystal component B, which is composed of one or more dielectric anisotropes between -1.5 and + 1. Compounds between 5, · c) 〇-20 heavy halo% liquid crystal component D, which is composed of one or more compounds with dielectric anisotropy lower than -1.5, and printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs D) Photoactive component C is selected in an amount such that the layer thickness (between the outer plates) ) And the ratio between the pitch of natural palm nematic liquid crystal mixture consisting of about 2 to 1.3 billion ·, characterized in that: A group of compounds comprising at least one component A This paper size applies to Chinese National Standard (CNS) A4 specification (2 丨 〇297297) 574357 A8 B8 C8 D8 2 The scope of patent application where RM is an alkyl, alkoxy or alkenyl group with 1 to 12 carbon atoms In addition, one or two non-adjacent CH2 groups are substituted with -0, -CH = CH-, -C〇-, -0-C〇-, or -C〇〇 ·, respectively, so that 0 atoms do not Directly connected, R12 is an alkyl group having 1 to 8 carbon atoms, in which one or more fluorene atoms are replaced by F, and L1 to L4 are fluorene or F, respectively. · · 2. The liquid crystal display of item 1 of the patent application scope, wherein R11 is a linear 3E-alkenyl group having 4, 5, or 6 carbon atoms. 3. For the liquid crystal display of item 1 or 2 of the patent application scope, wherein R12 is a perfluorinated linear alkyl group having 1, 2, 3, 4 or 5 carbon atoms. 4. For example, the liquid crystal display of the first patent application scope, which contains at least one compound of formula II and / or II * (please read the precautions on the back before filling this page) FT 智慧 R Employees ’Intellectual Property Bureau of the Ministry of Economy Consumption Printed by a cooperative Q-Yam, where R3 is an alkenyl group II with 2 to 7 carbon atoms * This paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) 45 574357 A8 B8 C8 _ D8 VI. Application scope 3 R4 Is an alkyl, alkoxy or alkenyl group having 1 to 12 carbon atoms, wherein, in addition, one or more non-adjacent CH2 groups may be -0-, -CH = CH-, -C〇-, -〇C〇- or -C〇〇- is substituted so that the o atoms are not directly connected to each other, a is 0 or 1, L1 and L2 are Η or F, respectively, and Q is CF2, 〇CF2, CFH, OCFH or a single bond And Y is F or CM. 5. The liquid crystal display according to item 丨 of the patent application scope, which contains at least one compound of formula IV9 and / or IV24 (please read the precautions on the back before filling this page) RH > -CH = CH · IV9 R ^ ) -CH = CH IV24 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs, where R1 is an alkyl group having 2 to 7 carbon atoms, and R2 is an alkyl or alkoxy group having 1 to 6 carbon atoms. 6. The liquid crystal display of claim 1, which comprises one or more compounds represented by the following formula: CN lllb The size of this paper applies to Chinese National Standard (CNS) A4 (210X297 mm) -46- 574357 A8 B8 C8 D8 Patent Application Scope 4 ο V CN lllc COO lllf COO printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, where R is an alkyl, alkoxy, or alkenyl group having 1 to 12 carbon atoms, and one or two non-adjacent CH2 groups are each -0 -, -CH = CH-, -C0-,-• 0-C0- or -C〇〇- is substituted so that the 0 atoms are not directly connected to each other, and L1 and L2 are Η or F, respectively. 7. The liquid crystal display according to item 1 of the patent application scope, which comprises one or more diphenylacetylene compounds selected from the following formula: R! RC = C Ta C Tri CR2 Tb (Please read the precautions on the back before (Fill in this page) This paper size applies to Chinese National Standard (CNS) A4 specification (21 OX297 male) -47 574357 Α8 Β8 C8 D8 六 、 Scope of patent application 5 F F R1 and R2 are alkyl, alkoxy, or alkenyl groups having 1 to 12 carbon atoms, respectively. In addition, one or two non-adjacent CH2 groups are respectively -0, -CH = CH-,, _ 〇_C〇- or -C〇〇- is substituted so that 〇 atoms are not directly connected to each other. 〇 As in the liquid crystal display of the scope of application for the patent application, which contains 3 to 40%-or more compounds of formula. ‘9. A liquid crystal mixture with two or more liquid crystal components, characterized in that the liquid crystal mixture contains at least one compound of formula I (please read the precautions on the back before filling this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs, where R11 is an alkyl, alkoxy or alkenyl group having 1 to 12 carbon atoms, and one or two non-adjacent CH2 groups are respectively -0-, -CH = CH-, -CO-, -0-C0-, or -COO- is substituted so that 0 atoms are not directly connected to each other, and R12 is a radical having 1 to 8 carbon atoms, in which one or more Η The atom is replaced by F, and L1 to L4 are Η or F, respectively. This paper size applies to China National Standard (CNS) A4 specification (210 × 297 mm) -48-