Liquid crystal composition and liquid crystal display element

Abstract

The present invention provides a liquid crystal composition formed by combining a polymerizable compound represented by formula I with a specific liquid crystal component, particularly a PSVA liquid crystal composition for displays or TV applications and a PSA-IPS liquid crystal composition for an IPS mode, and a liquid crystal display element or liquid crystal display comprising this liquid crystal composition; in particular, the polymerizable compound has a faster polymerization rate, and a “material system” formed from the selected polymerizable component and liquid crystal component should have the lowest rotary viscosity and the best photoelectric properties, and has a high VHR after (UV) photoradiation, this avoiding the problem of the occurrence of residual images to final displays. ##STR00001##

Claims

1. A liquid crystal composition, comprising one or more polymerizable compounds represented by formulas I-1 to 1-3, I-8 and I-9 as a first component, one or more compounds represented by formula II as a second component, and one or more compounds represented by formula III as a third component: ##STR00036## ##STR00037## ##STR00038## wherein R.sub.1, R.sub.2, R.sub.3, and R.sub.4 each independently represent an alkyl group having a carbon atom number of 1-10, a fluorine-substituted alkyl group having a carbon atom number of 1-10, an alkoxy group having a carbon atom number of 1-10, a fluorine-substituted alkoxy group having a carbon atom number of 1-10, an alkenyl group having a carbon atom number of 2-10, a fluorine-substituted alkenyl group having a carbon atom number of 2-10, an alkenoxy group having a carbon atom number of 3-8 or a fluorine-substituted alkenoxy group having a carbon atom number of 3-8, and any one CH.sub.2 or several CH.sub.2 that are not adjacent in the groups represented by R.sub.3 and R.sub.4 may be substituted with cyclopentyl, cyclobutyl or cyclopropyl; Z.sub.1 and Z.sub.2 each independently represent a single bond, —CH.sub.2CH.sub.2- or —CH.sub.2O—; ##STR00039## each independently represent ##STR00040## ##STR00041## each independently represent one or more of ##STR00042## m represents 1 or 2; and n represents 0, 1 or 2.

2. The liquid crystal composition according to claim 1, wherein in said liquid crystal composition, a total mass content of said one or more polymerizable compounds represented by formulas I-1 to I-3, I-8 and I-9 is 0.01-1%, a total mass content of said one or more compounds represented by formula II is 15-60%, and a total mass content of said one or more compounds represented by general formula III is 20-60%.

3. The liquid crystal composition according to claim 1, wherein said one or more compounds represented by formula II are one or more compounds represented by formulas II-1 to II-15; and said one or more compounds represented by formula III are one or more compounds represented by formulas III-1 to 111-12: ##STR00043## ##STR00044## ##STR00045## wherein R.sub.3 and R.sub.4 each independently represent an alkyl group having a carbon atom number of 1-10, a fluorine-substituted alkyl group having a carbon atom number of 1-10, an alkoxy group having a carbon atom number of 1-10, a fluorine-substituted alkoxy group having a carbon atom number of 1-10, an alkenyl group having a carbon atom number of 2-10, a fluorine-substituted alkenyl group having a carbon atom number of 2-10, an alkenoxy group having a carbon atom number of 3-8 or a fluorine-substituted alkenoxy group having a carbon atom number of 3-8, and any one CH.sub.2 or several CH.sub.2 that are not adjacent in the groups represented by R.sub.3 and R.sub.4 may be substituted with cyclopentyl, cyclobutyl or cyclopropyl.

4. The liquid crystal composition according to claim 1, wherein said liquid crystal composition is a negative liquid crystal composition, and further comprises one or more compounds represented by formula IV: ##STR00046## wherein R.sub.5 and R.sub.6 each independently represent an alkyl group having a carbon atom number of 1-10, a fluorine-substituted alkyl group having a carbon atom number of 1-10, an alkoxy group having a carbon atom number of 1-10, a fluorine-substituted alkoxy group having a carbon atom number of 1-10, an alkenyl group having a carbon atom number of 2-10, a fluorine-substituted alkenyl group having a carbon atom number of 2-10, an alkenoxy group having a carbon atom number of 3-8 or a fluorine-substituted alkenoxy group having a carbon atom number of 3-8, and any one or more CH.sub.2 in groups R.sub.5 and R.sub.6 may be substituted with cyclopentyl, cyclobutyl or cyclopropyl; and W represents O, S or —CH.sub.2O—.

5. The liquid crystal composition according to claim 1, wherein said liquid crystal composition is a negative liquid crystal composition, and further comprises one or more compounds represented by formula V: ##STR00047## wherein R.sub.7 and R.sub.8 each independently represent an alkyl group having a carbon atom number of 1-10, a fluorine-substituted alkyl group having a carbon atom number of 1-10, an alkoxy group having a carbon atom number of 1-10, a fluorine-substituted alkoxy group having a carbon atom number of 1-10, an alkenyl group having a carbon atom number of 2-10, a fluorine-substituted alkenyl group having a carbon atom number of 2-10, an alkenoxy group having a carbon atom number of 3-8 or an fluorine-substituted alkenoxy group having a carbon atom number of 3-8; and ##STR00048## each independently represent 1,4-phenylene, 1,4-cyclohexylene or 1,4-cyclohexenylene.

6. The liquid crystal composition according to claim 1, wherein said liquid crystal composition is a negative liquid crystal composition, and further comprises one or more compounds represented by formula VI, ##STR00049## wherein R.sub.9 and R.sub.10 each independently represent an alkyl group having a carbon atom number of 1-10, a fluorine-substituted alkyl group having a carbon atom number of 1-10, an alkoxy group having a carbon atom number of 1-10, a fluorine-substituted alkoxy group having a carbon atom number of 1-10, an alkenyl group having a carbon atom number of 2-10, a fluorine-substituted alkenyl group having a carbon atom number of 2-10, an alkenoxy group having a carbon atom number of 3-8 or an fluorine-substituted alkenoxy group having a carbon atom number of 3-8; and ##STR00050## represents 1,4-phenylene, 1,4-cyclohexylene or 1,4-cyclohexenylene; and each (F) independently represents H or F.

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

8. The liquid crystal display element or liquid crystal display according to claim 7, wherein said active matrix display element or display is a PSVA-TFT liquid crystal display element or display.

Description

DETAILED DESCRIPTION OF EMBODIMENTS

(1) The present invention is further described in conjunction with particular examples below, but the present invention is not limited to the following examples. Said methods are all conventional methods, unless otherwise specified. Said raw materials are all commercially available, unless otherwise specified.

(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 of the liquid crystal (T.sub.CL), as measured by means of a DSC quantitative method;

(5) S-N represents the melting point (T.sub.m) for the transformation of a liquid crystal from a crystal state to a nematic phase;

(6) Δn represents optical anisotropy, n.sub.o is the refractive index of an ordinary light, n.sub.e is the refractive index of an extraordinary light, with the test conditions being: 25±2° C., 589 nm and using an abbe refractometer for testing;

(7) Δε represents the dielectric anisotropy, Δε=ε.sub.∥ε.sub.⊥, wherein the ε.sub.∥ is a dielectric constant parallel to a molecular axis, and ε.sub.⊥ is a dielectric constant perpendicular to the molecular axis, with the test conditions being: 25±0.5° C., using 20 micron parallel cells, and using INSTEC: ALCT-IR1 for testing;

(8) γ1 represents a rotary viscosity (mPa.Math.s), with the test conditions being: 25±0.5° C., using 20 micron parallel cells, and using INSTEC: ALCT-IR1 for testing; and

(9) ρ represents an electrical resistivity (Ω.Math.cm), with the test conditions being: 25±2° C., and the test instruments being a TOYO SR6517 high resistance instrument and an LE-21 liquid electrode.

(10) VHR represents a voltage holding ratio (%), with the test conditions being: 20±2° C., a voltage of ±5 V, a pulse width of 10 ms, and a voltage holding time of 16.7 ms. The test equipment is a TOYO Model 6254 liquid crystal performance comprehensive tester.

(11) τ represents a response time (ms), with the test instrument being DMS-501 and the test conditions being: 25±0.5° C., a test cell that is a 3.3-micron IPS test cell, an electrode spacing and an electrode width, both of which are 10 microns, and an included angle between the frictional direction and the electrode of 10°.

(12) T (%) represents a transmittance, wherein T (%)=100%* bright state (Vop) luminance/light source luminance, with the test instrument being DMS501, and the test conditions being: 25±0.5° C., a test cell that is a 3.3-micron IPS test cell, an electrode spacing and an electrode width, both of which are 10 microns, and an included angle between the frictional direction and the electrode of 10°.

(13) The conditions for the ultraviolet photopolymerization of the polymerizable compound involve using ultraviolet light with a wavelength of 313 nm and an irradiation light intensity of 0.5 Mw/cm.sup.2

(14) In the examples of the invention of the present application, liquid crystal monomer structures are represented by codes, and the codes for ring structures, end groups and linking groups of liquid crystals are represented as in Tables (I) and (II) below

(15) TABLE-US-00001 TABLE (I) Corresponding code for ring structure Ring structure Corresponding code C P G Gi Y Sa Sb Sc

(16) TABLE-US-00002 TABLE (II) Corresponding code for end group and linking group End group and linking group Corresponding code C.sub.nH.sub.2n+1— n- C.sub.nH.sub.2n+1O— nO— —OCF.sub.3 —OT —CF.sub.2O— -Q- —CH.sub.2O— —O— —F —F —CN —CN —CH.sub.2CH.sub.2— -E- —CH═CH— —V— —C≡C— —W— —COO— —COO— —CH═CH—C.sub.nH.sub.2n+1 Vn- C(5)- 0 C(3)-

EXAMPLES

(17) ##STR00031##

Comparative Example 1 (RM)

(18) ##STR00032##

Comparative Example 2 (RM)

(19) ##STR00033##

Comparative Example 3 (RM)

(20) ##STR00034##

Comparative Example 4 (RM)

(21) ##STR00035##

Comparative Example 5

(22) TABLE-US-00003 Category Liquid crystal monomer code Content (%) III CY-C(5)-O4 11 III PY-C(5)-O2 9 III COY-3-O2 12 III CCOY-3-O2 8 III CY-5-O2 10 II CC-3-V 20 II CC-3-2 29.75 RM RM-1 0.25

Example 1

(23) TABLE-US-00004 Category Liquid crystal monomer code Content (%) III CY-C(5)-O4 11 III PY-C(5)-O2 9 III COY-3-O2 12 III CCOY-3-O2 8 III CY-5-O2 10 II CC-3-V 20 II CC-3-2 29.75 I I-2 0.25

Example 2

(24) TABLE-US-00005 Category Liquid crystal monomer code Content (%) III CY-C(5)-O4 11 III PY-C(5)-O2 9 III COY-3-O2 12 III CCOY-3-O2 8 II PP-5-1 10 II CC-3-V1 15 II CC-3-2 10 IV Sa-C(5)1O-O2 5 V CCP-3-1 10 V CPP-3-2 9 I I-1 1

Example 3

(25) TABLE-US-00006 Category Liquid crystal monomer code Content (%) III CCY-C(5)-O4 11 III CPY-C(5)-O2 9 III CCY-3-O2 12 IV Sa-C(3) 1O-O4 8 II PP-1-2V 10 II CC-3-V1 25 II CP-3-O2 5 V CLP-3-1 12 V CPP-3-O2 7.8 I I-3 0.2

Example 4

(26) TABLE-US-00007 Category Liquid crystal monomer code Content (%) III CCY-3-O2 11 III CPY-3-O2 9 III PYP-3-O2 12 III CLY-5-O2 10 IV Sb-C(5) 1O-O4 8 II PP-5-1 10 II CC-3-V 25 II CC-3-2 5 V CCP-3-1 4.8 VI CPGIP-5-2 5 I I-4 0.2

Example 5

(27) TABLE-US-00008 Category Liquid crystal monomer code Content (%) III CCY-3-O2 11 III CPY-3-O2 9 III PYP-3-O2 10 III CCOY-5-O2 10 III COY-3-O2 10 IV Sb-C(5) 1O-O4 10 II CC-3-V 20 V CCP-3-1 4.9 V CPP-V-1 5 VI CGPC-3-1 10 I I-5 0.1

Example 6

(28) TABLE-US-00009 Category Liquid crystal monomer code Content (%) III CY-C(5)-O4 11 III PY-C(5)-O2 9 III COY-3-O2 12 III CCOY-3-O2 8 III CY-5-O2 10 II CC-3-V 20 II CC-3-2 29.75 I I-7 0.25

Example 7

(29) TABLE-US-00010 Category Liquid crystal monomer code Content (%) III CY-C(5)-O4 11 III PY-C(5)-O2 9 III COY-3-O2 12 III CCOY-3-O2 8 II PP-5-1 10 II CC-3-V1 15 II CC-3-2 10 IV Sa-C(5)1O-O2 5 V CCP-3-1 10 V CPP-3-2 9 I I-8 1

Example 8

(30) TABLE-US-00011 Category Liquid crystal monomer code Content (%) III CCY-C(5)-O4 11 III CPY-C(5)-O2 9 III CCY-3-O2 12 IV Sa-C(3) 1O-O4 8 II PP-1-2V 10 II CC-3-V1 25 II CP-3-O2 5 V CLP-3-1 12 V CPP-3-O2 7.8 I I-9 0.2

Example 9

(31) TABLE-US-00012 Category Liquid crystal monomer code Content (%) III CCY-3-O2 11 III CPY-3-O2 9 III PYP-3-O2 12 III CLY-5-O2 10 IV Sb-C(5) 1O-O4 8 II PP-5-1 10 II CC-3-V 25 II CC-3-2 5 V CCP-3-1 4.8 VI CPGIP-5-2 5 I I-10 0.2

Example 10

(32) TABLE-US-00013 Category Liquid crystal monomer code Content (%) III CCY-3-O2 11 III CPY-3-O2 9 III PYP-3-O2 10 III CCOY-5-O2 10 III COY-3-O2 10 IV Sb-C(5) 1O-O4 10 II CC-3-V 20 V CCP-3-1 4.9 V CPP-V-1 5 VI CGPC-3-1 10 I I-11 0.1

(33) 1. Conversion Rate of Polymerizable Compound

(34) A polymerizable compound is added to a composition, and said polymerizable compound is consumed, due to polymerization, to form a polymer. The conversion rate of this reaction is preferably a large conversion rate. This is because: from the viewpoint of residual images, the residual amount of the polymerizable compound (the amount of the unreacted polymerizable compound) is preferably small.

(35) TABLE-US-00014 Residual amount of Polymerizable compound polymerizable compound Conversion (0.5 wt %) (wt %) rate (Comparative Example 1) RM-1 0.42 16% (Comparative Example 2) RM-2 0.42 16% (Comparative Example 3) RM-3 0.41 16% (Comparative Example 4) RM-4 0.37 26% I-1 0.3 40% I-2 0.26 48% I-3 0.29 42% I-4 0.27 46% I-5 0.26 48% I-6 0.28 44% I-7 0.28 44% I-8 0.25 50% I-9 0.24 52% I-10 0.26 48% I-11 0.25 50% I-12 0.28 44%

(36) 2. Response Time

(37) Mixtures prepared from various polymerizable compounds and liquid crystal compounds are injected into devices. After the polymeric compounds are polymerized by means of irradiation with ultraviolet light, the response times of the devices are measured. Where a mixture of a polymeric compound and a liquid crystal compound is not added, the response time is slow. Therefore, it can be concluded that the combination of the polymeric compound and the liquid crystal compound, referred to in the present invention, is effective in shortening the response time.

(38) TABLE-US-00015 Response time Example (ms) Comparative Example 5 15.3 Example 1 11.0 Example 2 7.8 Example 3 10.1 Example 4 8.5 Example 5 9.0 Example 6 10.0 Example 7 9.8 Example 8 9.6 Example 9 8.5 Example 10 9.5

(39) 3. Reliability

(40) Mixtures prepared from various polymerizable compounds and liquid crystal compounds are injected into test cells. After the polymeric compound is polymerized by means of irradiation with ultraviolet light, the voltage holding ratio (VHR) is measured under the conditions of ultraviolet light, high temperature, etc., and a highly reliable liquid crystal, i.e., having a high VHR (16.7 ms), is preferred. The highly reliable liquid crystal avoids the problem of the occurrence of residual images to final displays.

(41) TABLE-US-00016 VHR (16.7 ms) Example (%) Comparative Example 5 99.0 Example 1 99.81 Example 2 99.90 Example 3 99.81 Example 4 99.93 Example 5 99.70 Example 6 99.81 Example 7 99.90 Example 8 99.81 Example 9 99.93 Example 10 99.70