Highly vertical dielectric liquid crystal compound, liquid crystal composition, and liquid crystal display device

Abstract

Disclosed are a liquid crystal composition comprising a liquid of formula I and formula II-B, and a liquid crystal compound and a related liquid crystal display device ##STR00001##
wherein R.sub.0, R.sub.1, R.sub.2 and R.sub.3 each independently represent an alkyl group having a carbon atom number of 1-10, a fluoro-substituted alkyl group having a carbon atom number of 1-10, an alkoxy group having a carbon atom number of 1-10, a fluoro-substituted alkoxy group having a carbon atom number of 1-10, an alkenyl group having a carbon atom number of 2-10, a fluoro-substituted alkenyl group having a carbon atom number of 2-10, an alkenoxy group having a carbon atom number of 3-8 or a fluoro-substituted alkenoxy group having a carbon atom number of 3-8, and any one or more non-connected CH.sub.2 in R.sub.0, R.sub.1, R.sub.2 and R.sub.3 may be substituted with cyclopentyl, cyclobutyl, cyclopropyl or O; Y represents ethyl or ethenyl; ##STR00002##
each independently represent one of ##STR00003##
and any fluorobenzene; ##STR00004##
represents benzene or fluorobenzene; and m represents one of 1, 2 and 3, and n represents one of 1 and 0.

Claims

1. A liquid crystal composition, comprising one or more compounds of formula I and further comprising one or two compounds of formula II-B, ##STR00059## wherein R.sub.1, and R.sub.2 each independently represent an alkyl group having a carbon atom number of 1-10, a fluoro-substituted alkyl group having a carbon atom number of 1-10, an alkoxy group having a carbon atom number of 1-10, a fluoro-substituted alkoxy group having a carbon atom number of 1-10, an alkenyl group having a carbon atom number of 2-10, a fluoro-substituted alkenyl group having a carbon atom number of 2-10, an alkenoxy group having a carbon atom number of 3-8 or a fluoro-substituted alkenoxy group having a carbon atom number of 3-8, and any one or more nonadjacent CH.sub.2 in R.sub.1, and R.sub.2 may be substituted with cyclopentylene group, cyclobutylene group, cyclopropylene group or O; Y represents ethyl or ethenyl; ##STR00060## each independently represent one of ##STR00061## and any fluorobenzene; ##STR00062## represents benzene or fluorobenzene; and m represents one of 1, 2 and 3, and n represents one of 1 and 0.

2. The liquid crystal composition according to claim 1, wherein said one or more compounds represented by formula I are one or more of compounds represented by formulas I1 to I14; said one or more compounds represented by formula II-B are one or two of compounds represented by formulas II-B-1 and II-B-2, ##STR00063## ##STR00064## ##STR00065## wherein R.sub.11 represents an alkyl group having a carbon atom number of 1-6, and R.sub.21 represents an alkyl group having a carbon atom number of 1-5.

3. The liquid crystal composition according to claim 1, wherein in said liquid crystal composition, the content in mass percentage of the compounds represented by formula I is 1-40%, the content in mass percentage of formula II-B is 5-60%, and, said liquid crystal composition further comprises one or more compounds represented by formulas II-1 to II-13, the content in mass percentage of one or more compounds represented by formulas II-1 to II-13 is no more than 50%, ##STR00066##

4. The liquid crystal composition according to claim 1, wherein said liquid crystal composition is a positive liquid crystal composition, and said liquid crystal composition further comprises one or more compounds represented by formula III ##STR00067## wherein R.sub.4 represents an alkyl group having a carbon atom number of 1-10, a fluoro-substituted alkyl group having a carbon atom number of 1-10, an alkoxy group having a carbon atom number of 1-10, a fluoro-substituted alkoxy group having a carbon atom number of 1-10, an alkenyl group having a carbon atom number of 2-10, a fluoro-substituted alkenyl group having a carbon atom number of 2-10, an alkenoxy group having a carbon atom number of 3-8 or a fluoro-substituted alkenoxy group having a carbon atom number of 3-8, and any one or more CH.sub.2 in R.sub.4 may be substituted with cyclopentylene group, cyclobutylene group, cyclopropylene group; ##STR00068## each independently represents one of: ##STR00069## m represents one of 1, 2 and 3; Z.sub.1 and Z.sub.2 each independently represent a single bond, CF.sub.2O, CH.sub.2CH.sub.2, or CH.sub.2O; and Y.sub.2 represents F, a fluoro-substituted alkyl group having a carbon atom number of 1-5, a fluoro-substituted alkoxy group having a carbon atom number of 1-5, a fluoro-substituted alkenyl group having a carbon atom number of 2-5, or a fluoro-substituted alkenoxy group having a carbon atom number of 3-8.

5. The liquid crystal composition according to claim 4, wherein said one or more compounds represented by formula III are compounds of formula III1 to III22 ##STR00070## ##STR00071## ##STR00072## ##STR00073## wherein X.sub.1 and X.sub.2 each independently represent H or F; wherein R.sub.4 represents an alkyl group having a carbon atom number of 1-10, a fluoro-substituted alkyl group having a carbon atom number of 1-10, an alkoxy group having a carbon atom number of 1-10, a fluoro-substituted alkoxy group having a carbon atom number of 1-10, an alkenyl group having a carbon atom number of 2-10, a fluoro-substituted alkenyl group having a carbon atom number of 2-10, an alkenoxy group having a carbon atom number of 3-8 or a fluoro-substituted alkenoxy group having a carbon atom number of 3-8, and any CH.sub.2 in R.sub.4 may be substituted with cyclopentylene group, cyclobutylene group, cyclopropylene group; (F) represents H or F; and Y.sub.2 represents F, a fluoro-substituted alkyl group having a carbon atom number of 1-5, a fluoro-substituted alkoxy group having a carbon atom number of 1-5, a fluoro-substituted alkenyl group having a carbon atom number of 2-5, or a fluoro-substituted alkenoxy group having a carbon atom number of 3-8.

6. The liquid crystal composition according to claim 1, wherein said liquid crystal composition is a negative liquid crystal composition, and said liquid crystal composition further comprises one or more compounds represented by formula IV ##STR00074## wherein R.sub.5 and R.sub.6 each independently represents an alkyl group having a carbon atom number of 1-10, a fluoro-substituted alkyl group having a carbon atom number of 1-10, an alkoxy group having a carbon atom number of 1-10, a fluoro-substituted alkoxy group having a carbon atom number of 1-10, an alkenyl group having a carbon atom number of 2-10, a fluoro-substituted alkenyl group having a carbon atom number of 2-10, an alkenoxy group having a carbon atom number of 3-8 or a fluoro-substituted alkenoxy group having a carbon atom number of 3-8, and any CH.sub.2 in R.sub.5 and R.sub.6 may be substituted with cyclopentylene group, cyclobutylene group, cyclopropylene group; Z.sub.3 and Z.sub.4 each independently represent a single bond, CH.sub.2CH.sub.2 or CH.sub.2O; and ##STR00075## each independently represent one of ##STR00076## and m represents one of 1, 2 and 3, and n represents one of 0 and 1.

7. The liquid crystal composition according to claim 6, wherein said one or more compounds represented by formula IV are one or more compound of formula IV1 to IV11: ##STR00077## wherein R.sub.5 and R.sub.6 each independently represents an alkyl group having a carbon atom number of 1-10, a fluoro-substituted alkyl group having a carbon atom number of 1-10, an alkoxy group having a carbon atom number of 1-10, a fluoro-substituted alkoxy group having a carbon atom number of 1-10, an alkenyl group having a carbon atom number of 2-10, a fluoro-substituted alkenyl group having a carbon atom number of 2-10, an alkenoxy group having a carbon atom number of 3-8 or a fluoro-substituted alkenoxy group having a carbon atom number of 3-8, and CH.sub.2 in R.sub.5 and R.sub.6 may be substituted with cyclopentylene group, cyclobutylene group, cyclopropylene group.

8. The liquid crystal composition according to claim 1, wherein said liquid crystal composition is a negative liquid crystal composition, and said liquid crystal composition further comprises one or more compounds represented by formula V ##STR00078## wherein R.sub.7 and R.sub.8 each independently represents an alkyl group having a carbon atom number of 1-10, a fluoro-substituted alkyl group having a carbon atom number of 1-10, an alkoxy group having a carbon atom number of 1-10, a fluoro-substituted alkoxy group having a carbon atom number of 1-10, an alkenyl group having a carbon atom number of 2-10, a fluoro-substituted alkenyl group having a carbon atom number of 2-10, an alkenoxy group having a carbon atom number of 3-8 or a fluoro-substituted alkenoxy group having a carbon atom number of 3-8, and any CH.sub.2 in R.sub.7 and R.sub.8 may be substituted with cyclopentylene group, cyclobutylene group, cyclopropylene group.

9. The liquid crystal composition according to claim 1, wherein said liquid crystal composition may further comprise a compound of formula VI ##STR00079## wherein R.sub.91 represents an alkyl group having a carbon atom number of 1-5 or an alkenyl group having a carbon atom number of 2-5; R.sub.92 represents an alkyl group having a carbon atom number of 1-5, an alkoxy group having a carbon atom number of 1-5, or an alkenyl group having a carbon atom number of 2-5, and any CH.sub.2 in R.sub.91 and R.sub.92 may be substituted with cyclopentylene group, cyclobutylene group, cyclopropylene group; o and p represent one of 1 and 2; and ##STR00080## each independently represent one of ##STR00081## and any fluorobenzene.

10. A liquid crystal compound represented by formula I-A, ##STR00082## wherein R.sub.1 and R.sub.2 each independently represents an alkyl group having a carbon atom number of 1-10, a fluoro-substituted alkyl group having a carbon atom number of 1-10, an alkoxy group having a carbon atom number of 1-10, a fluoro-substituted alkoxy group having a carbon atom number of 1-10, an alkenyl group having a carbon atom number of 2-10, a fluoro-substituted alkenyl group having a carbon atom number of 2-10, an alkenoxy group having a carbon atom number of 3-8 or a fluoro-substituted alkenoxy group having a carbon atom number of 3-8, and any one or more nonadjacent CH.sub.2 in R.sub.1, and R.sub.2 may be substituted with cyclopentylene group, cyclobutylene group, cyclopropylene group, or O; m represents one of 1, 2 and 3; ##STR00083## represents one of ##STR00084## and any fluorobenzene.

11. The liquid crystal composition represented by formula I-A according to claim 10, wherein said one or more compounds represented by formula I-A are one or more compound of formulas I1-I3, I5-I8, and I10-I14: ##STR00085## ##STR00086##

12. A liquid crystal display element or liquid crystal display comprising the liquid crystal composition of claim 1, wherein said liquid crystal display element or liquid crystal display is an active matrix display element or display or a passive matrix display element or display.

Description

DETAILED DESCRIPTION OF EMBODIMENTS

(1) The present invention is further described as below in combination with particular embodiments, but the present invention is not limited to the following embodiments. Said methods, if not otherwise indicated, are all conventional methods. Said raw materials, if not otherwise indicated, can all be available through public commercial approaches.

(2) The reaction process is generally monitored through TLC, and the post-treatments after the reaction is completed are generally water washing, extracting, combining organic phases and then drying, evaporating and removing the solvent under a reduced pressure, recrystallization and column chromatographic separation; and a person skilled in the art would be able to achieve the present invention according to the following description.

(3) In the present specification, the percentages are mass percentages, the temperatures are in degree Celsius ( C.), and the specific meanings of other symbols and the test conditions are as follows:

(4) Cp represents the clearing point ( C.) of the liquid crystal measured by a DSC quantitative method;

(5) n represents the optical anisotropy, n.sub.o is the refractive index of an ordinary light, n.sub.e is the refractive index of an extraordinary light, the test condition is 252 C. and 589 nm, and an abbe refractometer is used for the test;

(6) represents the dielectric anisotropy, =.sub..sub., wherein .sub. is a dielectric constant parallel to a molecular axis, and .sub. is a dielectric constant perpendicular to the molecular axis, the test condition is 250.5 C., a 20 micron parallel cell is used, and INSTEC: ALCT-IR1 is used for the test;

(7) 1 represents a rotary viscosity (mPa.Math.s), the test condition is 250.5 C., a 20 micron parallel cell is used, and INSTEC: ALCT-IR1 is used for the test; and

(8) T (%) represents a transmittance, T (%)=100%*bright state (Vop) luminance/light source luminance, the test device is DMS501, the test condition is 250.5 C., the test cell is a 3.3 micron IPS test cell, both the electrode spacing and the electrode width are 10 microns, and the included angle between the frictional direction and the electrode is 10; therefore, there is a positive correlation between .sub. and T, so in the evaluation of the transmittance, .sub. can be used as an evaluation index for indication.

(9) In the examples of the present invention application, liquid crystal monomer structures are represented by codes, wherein the code representation of cyclic structures, end groups and linking groups of the liquid crystals are shown in tables (I) and (II) below

(10) TABLE-US-00001 TABLE (I) Codes corresponding to cyclic structures Corresponding Cyclic structure code C 0 B B(3F) B(2F,4F) B(3F,4F,5F) B(4F) B(3F,5F) B(2F) B(2F,3F) C[3O] C[3O,5O] 0 Sa

(11) TABLE-US-00002 TABLE (II) Codes corresponding to end groups and linking groups Corresponding End group and linking group code C.sub.nH.sub.2n+1 n C.sub.nH.sub.2n+1O nO OCF.sub.3 OCF.sub.3 CF.sub.2O CF.sub.2O F F CH.sub.2CH.sub.2 E CHCH V CH.sub.2O 1O CHCHC.sub.nH.sub.2n+1 Vn C(5) C(3)1

(12) For example:

(13) ##STR00053##

(14) C(5)CCV1

(15) ##STR00054##

(16) 3BB(3F) B(3F,5F)CF2OB(3F,4F,5F)

Example 1

(17) ##STR00055##

(18) 27.6 g of (1-A), 30 ml of toluene and 30 ml of isooctane are added to a 250 ml three-necked flask, followed by the addition of 14 g of 1,3-dimercaptopropane, the suspension described above is heated to 50 C. with stirring, 19.2 g of trifluoromethanesulfonic acid is added within 30 minutes, after the addition, the temperature is raised to reflux, the generated water is separated out, after the water is completely separated out, the suspension is cooled to 90 C., 100 ml of methyl tert-butyl ether is added at 70-90 C. within 45 minutes, the suspension continues to be cooled so as to precipitate a crystal, filtration is carried out under the protection of nitrogen, and the resulting crystal is washed with methyl tert-butyl ether (25 ml4) followed by vacuum drying to give 45 g of crystal (a dithiane trifluoromethanesulfonate).

(19) A mixed solution of 14.8 g of 3,4,5-trifluorophenol, 10.8 g of triethylamine and 130 ml of dichloromethane is added to a 500 ml three-necked flask and cooled to 70 C., the above-mentioned 45 g of crystal in 120 ml of dichloromethane is added dropwise within 45 minutes and stirred for one hour at this temperature, and then 73.5 ml of NEt.sub.3.3HF is added within 5 minutes. Thereafter, 72.7 g of liquid bromine in 30 ml of methylene chloride is added at 70 C. within one hour, then the reaction continues at 70 C. for one hour, the temperature is raised to 0 C., the reaction liquid is poured into 160 ml of a 32% aqueous sodium hydroxide solution and 300 g of ice, and the pH of the reaction liquid is adjusted to 5-8 by means of dropwise adding about 45 g of the 32% aqueous sodium hydroxide solution. After liquid separation, the aqueous phase is extracted with 80 ml of dichloromethane, organic phases are combined, filtered with 4 g of diatomite and washed with water, and the solvent is evaporated to dryness under a reduced pressure. The resulting crude product is subjected to column chromatography followed by recrystallization with petroleum ether to give 21 g of a product (1-B) with GC: 99.92%.

(20) ##STR00056##

(21) [1 KHz, 20 C.]: 1.0

(22) .sub.: 8.7

(23) .sub.//: 7.3

(24) n[589 nm, 20 C.]: 0.164

(25) Cp: 65 C.

(26) ##STR00057##

(27) [1 KHz, 20 C.]: 0.3

(28) .sub.: 8.0

(29) .sub.//: 8.3

(30) n[589 nm, 20 C.]: 0.230

(31) Cp: 171 C.

(32) ##STR00058##

(33) [1 KHz, 20 C.]: 3.9

(34) .sub.: 8.5

(35) .sub.//: 4.4

(36) n[589 nm, 20 C.]: 0.086

(37) Cp: 126 C.

Example 2

(38) TABLE-US-00003 Classification Liquid crystal monomer code Content (%) II-B 3CCV 60 I 3C[3O,5O]B(3F,5F)CF2OB(2F,3F,4O2) 8 I 5B B(3F,5F)CF2OB(2F,3F,4O3) 9 I 3CCCF2OB(2F,3F,4O4) 6 I 3C[3O,5O]BB(3F,5F)CF2OB(2F,3F,4O2) 7 I 5C[3O,5O]B(3F,5F)CF2OB(2F,3F,4O3) 2 I 4BB(3F)B(3F,5F)CF2OB(2F,3F,4O2) 8 [1 KHz, 20 C.]: 1.2 .sub.: 4.1 n[589 nm, 20 C.]: 0.104 Cp: 96 C. .sub.1: 88 mPa .Math. s.

Example 3

(39) TABLE-US-00004 Classification Liquid crystal monomer code Content (%) II-B 3CCV 33 II 3CC2 4 II 3CBO2 3 II 3CC5 6 I 3BB(3F,5F)CF2OB(2F,3F,4O2) 7.5 VI 3CBB2 4 V C(5)1OSaO4 6 IV 2OB B(2F,3F)O4 4.5 IV 3CC1OB(2F,3F)O2 12 IV 3C1OB(2F,3F)O2 5 IV 2CC1OB(2F,3F)O2 11 IV 4CC1OB(2F,3F)O2 4 [1 KHz, 20 C.]: 3.71 .sub.: 7.7 n[589 nm, 20 C.]: 0.088 Cp: 76 C. .sub.1: 112 mPa .Math. s.

Comparative Example 1

(40) TABLE-US-00005 Classification Liquid crystal monomer code Content (%) II-B 3CCV 33 II 3CC2 4 II 3CBO2 5 II 3CC5 6 VI 3CBB2 8 V C(5)1OSaO4 6 IV 2OB B(2F,3F)O4 5 IV 2OB B(2F,3F)O2 3 IV 3CC1OB(2F,3F)O2 12 IV 3C1OB(2F,3F)O2 5 IV 2CC1OB(2F,3F)O2 11 IV 4CC1OB(2F,3F)O2 2 [1 KHz, 20 C.]: 3.50 .sub.: 7.14 n[589 nm, 20 C.]: 0.091 Cp: 76 C. .sub.1: 96 mPa .Math. s.

(41) Suitable for negative IPS and VA mode displays.

(42) Comparative Example 1 does not contain any component of formula I, and comparing Example 3 with Comparative Example 1, the addition of the component of formula I enables an obvious increase of .sub.. Upon transmittance testing, the transmittance of Example 3 is higher than that of Comparative Example 1 by 5%.

Example 4

(43) TABLE-US-00006 Classification Liquid crystal monomer code Content (%) II-B 3CCV 46 II 5BBO2 4 II 3CCV1 6 VI VCCB1 12 VI 3CCB3 7 I 3B B(3F,5F)CF2OB(2F,3F,4O2) 8 III 3CCBB(3F,4F) 1 III 3BBB(2F,4F) 4 III C(5)BB(3F)B(3F,5F)CF2OB(3F,4F,5F) 5.5 III C(5)CBB(3F,5F)CF2OB(3F,4F,5F) 5 III C(5)BBB(3F) B(3F,4F,5F) 1.5 [1 KHz, 20 C.]: 2.76 .sub.: 2.98 n[589 nm, 20 C.]: 0.0986 Cp: 84 C. .sub.1: 58 mPa .Math. s.

(44) Example 4 is particularly suitable for positive, high transmittance TV-IPS mode liquid crystals.

Example 5

(45) TABLE-US-00007 Classification Liquid crystal monomer code Content (%) II-B 3CCV 40 II 5BBO2 7 II 3CCV1 7 VI VCCB1 13 VI 3CCB3 6 I 3B B(3F,5F)CF2OB(2F,3F,4O2) 10 III 3CCBB(3F,4F) 2 III 3CCB(4F) 3 III C(3)1BB(3F)B(3F,5F)CF2OB(3F,4F,5F) 4 III C(5)CBB(3F,5F)CF2OB(3F,4F,5F) 3 III C(5)C[3O]BB(3F,5F)CF2OB(3F,4F,5F) 4 III C(5)BBB(3F) B(3F,4F,5F) 1 [1 KHz, 20 C.]: 2.89 .sub.: 3.13 n[589 nm, 20 C.]: 0.0988 Cp: 87 C. .sub.1: 67 mPa .Math. s.

(46) Example 5 is particularly suitable for positive, high transmittance TV-IPS mode liquid crystals.

Comparative Example 2

(47) The liquid crystal composition obtained by removing 10% of the component I from Example 5 is the liquid crystal composition of Comparative Example 2,

(48) and upon transmittance testing, the transmittance of Example 5 is higher than that of Comparative Example 2 by 6%.

Example 6

(49) TABLE-US-00008 Classification Liquid crystal monomer code Content (%) II-B 3CCV 38.5 II 3CCV1 10.5 I 3B B(3F,5F)CF2OB(2F,3F,4O2) 10 VI VCCB1 2.75 VI V2CCB1 4 VI 3CBBV1 4 III 2BBB(2F,4F) 3.5 III 5BBB(2F,4F) 3 III C(5)BB(3F)B(3F,5F)CF2OB(3F,4F,5F) 4 III C(5)BB(3F,5F)CF2OB(3F,4F,5F) 9.75 III C(5)BB(3F)B(3F,4F,5F) 5 III C(5)CBB(3F,5F)CF2OB(3F,4F,5F) 5 [1 KHz, 20 C.]: 5.27 .sub.: 3.47 n[589 nm, 20 C.]: 0.1129 Cp: 76.5 C. .sub.1: 62 mPa .Math. s.

Example 7

(50) TABLE-US-00009 Classification Liquid crystal monomer code Content (%) II-B 3CCV 18.5 II 3CCV1 10.5 I 3B B(3F,5F)CF2OB(2F,3F,4O2) 10 VI VCCB1 12.75 VI V2CCB1 4 VI 3CBBV1 14 III 2BBB(2F,4F) 3.5 III 5BBB(2F,4F) 3 III C(5)BB(3F)B(3F,5F)CF2OB(3F,4F,5F) 4 III C(5)BB(3F,5F)CF2OB(3F,4F,5F) 9.75 III C(5)BB(3F)B(3F,4F,5F) 5 III C(5)CBB(3F,5F)CF2OB(3F,4F,5F) 5 [1 KHz, 20 C.]: 5.37 .sub.: 3.49 n[589 nm, 20 C.]: 0.1139 Cp: 88.5 C. .sub.1: 69 mPa .Math. s.

(51) Suitable for positive TN and IPS mode displays.

(52) The liquid crystal composition of the present invention has a good stability against light and heat, a lower viscosity, a wider refractive index that may be achieved by adjustment, and a higher clearing point (a very wide service temperature range), and in particular, the liquid crystal composition has a higher light transmittance, thus allowing a display device to have a higher brightness or an energy saving effect.