TW200528597A - Nematic liquid crystal composition and liquid crystal display device - Google Patents

Abstract

A nematic liquid crystal composition wherein a resistivity value of the composition is 1.0×10<SP>11</SP>Ω.cm or more and 1.0×10<SP>13</SP>OHgr;.cm or less, and the composition comprises one or more kinds of at least one of a semi-polar organic boron compound and a charge-transfer complex comprising the semi-polar organic boron compound, and a liquid crystal display device using the composition.

Description

200528597 IX. Description of the invention: [Technical field to which the invention belongs] The present invention relates to a nematic liquid crystal composition and a liquid crystal display element using the same. [Previous technology] In the manufacturing process of liquid crystal display elements starting with twisted nematic, super twisted nematic or active matrix, etc., when the protective film attached to the surface of the liquid crystal display element is peeled off, static electricity may occur in the element. An electric field is generated (stripping and charging). The electric field system often aligns the liquid crystal composition of the non-lighting portion, that is, the non-lighting portion 'is in a lighting state, and the alignment state continues until the electric field is discharged. The time required for the electric field to discharge must not be ignored, and it is not only the case that the operation must be interrupted in the shipping process such as the inspection process of the manufacturing process or the operation of cleaning the surface of the component, which results in a product (tact) time (equivalent to (On average production time of one product). It has been revealed that the problem of abnormal alignment due to charging can be mitigated by reducing the specific resistance 液晶 of the liquid crystal composition (see Patent Document 1). For a liquid crystal composition having a low specific resistance ，, even when a voltage is applied due to static electricity or the like when one of the voltages is applied, the specific resistance 値 is low, so that the charges can be quickly discharged and the liquid crystal molecules can return to the aligned state when no voltage is applied. For example, a nematic liquid crystal display device generally has a liquid crystal composition having a specific resistance ratio of 1 X 1 011 Ω · cm or more, and the relaxation time of the liquid crystal molecules is relatively long when voltage is applied due to one of the charges. When a substance that reduces specific resistance 値 is added to this composition and the specific resistance 値 is reduced to about 1 X 1 09 Ω · cm, the charge relaxation becomes very rapid. Therefore, even when a voltage is applied when one of the charges is caused by static electricity or the like, there is almost no change in the alignment state. However, a liquid crystal display element using a liquid crystal composition having a specific resistance 値 less than lx 101% · cm usually causes an increase in power consumption and causes defective display such as character sintering due to electrical short circuit. Therefore, it is desired to develop a liquid crystal composition having a specific resistance 値 with an appropriate size and an improved behavior of voltage application when the liquid crystal display element is charged due to static electricity or the like. Molecule relaxes very fast liquid crystal composition. The method for alleviating the abnormal alignment of liquid crystal molecules caused by static electricity or the like in the liquid crystal composition described above discloses a method of adding an ionic substance such as Cryptand to the liquid crystal composition (see Patent Document 2). However, the ionic components in the liquid crystal composition are adsorbed on the injection ports of some liquid crystal panels, etc., and are adsorbed on the polymer film such as polyimide in the liquid crystal display element, and there are problems that cause various display spots. In addition, a method of similarly alleviating abnormal alignment of liquid crystal molecules due to static electricity or the like has been disclosed by adding a nonionic surfactant such as ethylene glycol and a copolymer thereof (Patent Document 3). However, in this antistatic mechanism, the effect is easily affected by the amount of ions in the liquid crystal or the alignment film or the alignment state, and a sufficient antistatic effect cannot be obtained. In addition, when a large amount is added to obtain a sufficient effect, as the addition ratio increases, there is one of the reliability items of the liquid crystal display element, the nematic-isotropic phase transition temperature of the liquid crystal composition (the liquid crystal phase). Upper limit temperature). In addition, a method of similarly mitigating the abnormal alignment of liquid crystal molecules due to static electricity has been disclosed by adding a crown ether such as a cyclic polyether (Patent Document 4). However, crown ethers have a strong irritant effect on human skin or eyes -6-200528597, which may cause problems in the operating environment for manufacturing liquid crystal display elements. In addition, when the conventional non-liquid crystal compound is added, the compatibility with other liquid crystal compounds is not good, and the liquid crystal properties are impaired. Furthermore, no additives have been found that do not decrease the specific resistance and display quality, and can quickly alleviate the abnormal alignment of liquid crystal molecules in a momentary voltage application due to static electricity or the like. [Patent Document 1] Japanese Patent Publication No. 59-4676 (2 pages) [Patent Document 2] Japanese Patent Publication No. 4-28788 (2 pages) [Patent Document 3] Japanese Patent Publication No. 4- 1 80993 ( (4 pages) [Patent Document 4] Japanese Patent Publication No. 11_508286 (2 pages) [Summary of the Invention] The object of the present invention is to provide a material having an appropriate size without significantly reducing the specific resistance 値 and the upper limit temperature of the liquid crystal phase. It is a liquid crystal composition that has a specific resistance that can quickly alleviate abnormal alignment of liquid crystal molecules in the case of a momentary voltage application caused by static electricity or the like. The present inventors reviewed a nematic liquid crystal composition containing a semipolar organic boron compound or a charge transfer complex formed using the semipolar organic boron compound. As a result, they have found that these compounds can quickly alleviate abnormalities in liquid crystal molecules caused by static electricity and the like. The effect of the alignment phenomenon completes the present invention. 200528597 In other words, the present invention provides a nematic liquid crystal composition, which is characterized in that it contains at least one semipolar organic boron compound or a charge transfer complex composed of a semipolar organic boron compound, and the semipolar organic boron compound The number of boron atoms in a molecule of the compound is 5 or less, and the specific resistance 値 is 1.0 × 101 () Ω · cm to 1.0 × 1013Ω · cm, and a liquid crystal display device using the same. [Effects of the Invention] The nematic liquid crystal composition of the present invention is characterized by having a specific resistance 适当 of an appropriate size, and can quickly alleviate the abnormal alignment of liquid crystal molecules with respect to the application of voltage when one of them is charged due to static electricity or the like. Due to this feature, a liquid crystal display element can be efficiently manufactured in a manufacturing process, which can shorten the discharge time of charge caused by charging. [Embodiment] [Best Mode for Carrying Out the Invention] An example of the present invention will be described below. However, the present invention is not limited to the following examples. For example, the constituent elements of these examples can be appropriately combined. The present invention relates to a nematic liquid crystal composition having an improved behavior of voltage application when one of them is charged due to static electricity or the like, and a liquid crystal display element using the same. In the present invention, the nematic liquid crystal composition contains one or more semi-polar organic boron compounds or a charge transfer complex composed of a semi-polar boron compound. Any one or both of the above compounds and complexes may be contained. Therefore, compared with the conventional liquid crystal composition, the 200528597 time in which the abnormal alignment of the liquid crystal molecules with respect to the voltage application when the voltage is applied due to static electricity can be improved can be improved. In general, a semipolar organic boron compound refers to an organic boron compound having a semipolar bond. Since boron is trivalent, boron forms a bond with three oxygen atoms when a boric acid derivative is formed. At this time, an empty electron orbital exists in the boron atom, and the orbital is stabilized by a special structure coordinated by an isolated electron pair such as an oxygen atom and bonded to four oxygen atoms. Since the coordination bond is called a semipolar bond, an organic boron compound generally having a semipolar bond is called a semipolar boron compound. The term semi-organic boron compound used in the present invention means that. The semi-polar organic boron compound added to the liquid crystal composition of the present invention includes bis (glycerol) borate, bis (glycerol) borate monobasic borate, and bis (catechol) borate. , Bis (1,2-propylene glycol) borate, bis (2-ethyl-1,3-hexanediol) borate, or a compound having a skeleton represented by the following general formula (I) is preferred. [化 1] _nun ΩΗΠ—

These compounds may be used alone or in combination of two or more. In addition, when considering the compatibility with the liquid crystal composition, the number of boron atoms contained in one molecule is preferably one atom. More specifically, the semi-polar organic boron compound is preferably a compound represented by the following general formula (1-1) or general formula (1-2). These compounds represented by the general formula may be used singly or in combination as necessary. [Chemical 2]

200528597 (where R1 or R2 each represents an independent hydrogen atom, a hydroxyl group, an alkyl group having a carbon number, an alkoxy group having a carbon number of 1 to 12, an alkenyl group having a carbon number of 2 to 12, or an alkenyl group having a carbon number of 2 to 12 Oxygen, alkyl with 1 to 12 carbons substituted with halogen, alkoxy with 1 to 12 carbons substituted with halogen, alkenyl with 2 to 12 carbons substituted with halogen, or carbon with halogen substituted Alkenyloxy groups 2 to 12, A1 and A2 each represent an independent single bond, an alkylene group having 1 to 10 carbon atoms, an aryl group having 6 to 18 carbon atoms,-(-(CH2) n〇-) m -(n represents an integer of 1 to 10, m represents an integer of 1 to 30), -CH2-0-C0-R3-C0- (R3 represents a hydrocarbon group of 1 to 60 carbons) or -CH2- 0-C0-NH-R3-NH-C0-, p and q are each independent! ~! The integer 'when there are several A1 and A2' may be different or different) contained in the liquid crystal composition The content of these semi-polar organic boron compounds is preferably 0.00001 to 1% by mass, and more preferably 0.0001 to 0.1% by mass. The specific resistance 値 of the liquid crystal composition of the present invention is 1 · χχ1〇1 () Ω · cm ~ 1 · 〇χ1013Ω · cm, and the lower limit is preferably greater than 1 · 〇χ1〇 &quot; Ω · cm, and the upper limit is greater than 1 · 〇χ1〇12Ω · cm is preferable, and 1.0 · χΙοΗβ · cm to 1.0 × 1012Ω · cm is more preferable. The semi-polar organic boron compound described above has the property of easily forming an electron donor, and forms a charge transfer complex by combining an appropriate electron capacity acceptor. The charge transfer complex composed of the semi-polar organic boron compound also has the effect of rapidly alleviating the abnormal alignment of liquid crystal molecules in a momentary voltage application caused by static electricity or the like. In order to form the charge transfer complex used in the present invention, a semi-polar organic boron compound and an electron donor serving as an electron capacity acceptor are required. Electron donor-10-200528597 It is known that there are fulvalene derivatives such as tetrathiofulvalene, tetraselenofulvalene, phthalocyanine and its derivatives, amine compounds, and hydroquinone. 'Amine-based compounds are preferred. Amine compounds are divided into aliphatic amine compounds and aromatic amine compounds, such as ethylenediamine, hexamethylenediamine, dimethylaminopropylamine, phenylenediamine, methyliminobispropylamine, piperidine, and polyethylenediamine Amine and its ethylene oxide adduct, polyvinylpyridine, poly (dimethylaminoethyl) acrylate, poly (dimethylaminopropyl) acrylamide, diallylamine-isobutylene cross-copolymerization Things. These can be used alone or in combination as needed. The charge transfer complex formed by such a semipolar organic boron compound has a content ratio of 0.00001 to 1% by mass in the liquid crystal composition, and more preferably 0.0001 to 0.1% by mass. The nematic liquid crystal composition of the present invention preferably contains one or two or more compounds represented by the following general formula (II), more preferably 1 to 20 types, and even more preferably 1 to 15 types. [Chemical 3]

(Wherein R4 represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, at least one alkyl group having 1 to 12 carbon atoms substituted with halogen, an alkenyl group having 2 to 12 carbon atoms, or at least one carbon number substituted with halogen Alkenyl groups of 2 to 12, one or two or more of these groups (: 112 groups, under the condition that 0 atoms of each independent group are not directly bonded to each other, can be an oxygen atom, a sulfur atom,- CO-, _COO-, _OCO-, or -0C0-0- substitution, 200528597 B1 and B2 each represent an independent trans-1,4-cyclohexyl group (there is one CH2 group in this group or no adjacent 2 CH2 groups can be substituted by oxygen or sulfur atoms, 1,4-phenylene (1 or more CH groups present in this group can be substituted by nitrogen atoms), 1,4-cyclohexene Base, 1,4-bicyclo [2.2.2] octenyl, piperidine-1,4-diyl, naphthalene-2,6-diyl, decalin-2,6-diyl, or 1,2 , 3,4-tetrahydronaphthalene-2,6-diyl, the hydrogen atoms present in these groups may be substituted by methyl, -CN or halogen, and s and t each represent independent 0, 1 or 2, s and The sum of t is 3 or less, and Z1 and Z2 each represent independent -CH2CH2-, -CH = CH-, -CH (CH3) CH2- -CH2CH (CH3)-, -ch (ch3) ch (ch3)-, -CF2CF2-, -CF = CF-, -CH2O-, -OCH2-, -OCH (CH3)-, -CH (CH3) 0- ,-(CH2) 4-,-(CH2) 30-, -o (ch2) 3-, -c three c-, -CF20-, -OCF2-, -COO-, -OCO-, -COS-,- SCO- or single bond, L1 and L3 each represent independent -H, -F or -Cl, L2 represents -F, -CM, -CN, -CF3, -OCH2F, -〇CHF2, -OCF3 or-CH2CF3 When there are several B1, B2, Z1, and Z2, they may be the same or different.) The content of the compound represented by the general formula (II) contained in the liquid crystal composition is preferably 1 to 80% by mass, and preferably 1 to 50% by mass is more preferred, and 1 to 20% by mass is most preferred. In the general formula (II), R4 is an alkyl group having 1 to 12 carbon atoms, an alkoxy group, and 2 to 12 carbon atoms. An alkenyl group or an alkenyloxy group having 2 to 12 carbon atoms is preferred, and a linear alkyl group and a linear alkenyl group are more preferred. Each of B1 and B2 is preferably a structure selected from the group of formulas. -12- 200528597 [Chemical 4]

Among them, B1 and B2 each have a structure independently selected from Formula Group 2 as

Better. [Chemical 5]

F 200528597

Z1 and Z2 in the general formula (II) each represent an independent single bond, -CH2CH2-, -ch (ch3) ch2-, -ch2ch (ch3)-, -CH (CH3) CH (CH3)-, -CE C-, -COO-, -OCO_ are preferred, single bonds, -CH2CH2-, -C Ξ c-, -COO-, -0C0_ are more preferred, and single bonds or _COO- are most preferred. L1 and L3 each independently represent -F, -CN, -CF3, or -OCF3, and -F or -CN is more preferable. s and t are preferably s + t as 1 or 2. The compound represented by the general formula (II) specifically includes the general formula (11-1), the general formula (11-2), the general formula (11-3), the general formula (11-4), and the general formula (Π -5), a compound represented by the general formula (11-6), the general formula (11-7), or the general formula (II-8) is preferable. [Chemical 6]

(Where L1 and L3 each represent independent -H, -F, or -Cl, and L2 represents -F, -CM, -CN, -CF3, -OCH2F, -OCHF2, -OCF3, or -CH2CF3, X1, and x2 (H-H or -F) each represents an independent -H or -F) nematic liquid crystal composition preferably contains one or two or more compounds represented by the following general formula -14-200528597 (III), preferably contains 1 to 20 kinds More preferably, it contains 1 to 15 types. [Chem. 7] R5 ^ C1_Z3 ^ C ^ Z ^ C3-Z ^ R ^ (, „)

(Wherein R5 and R6 represent the same meaning as R4 of the general formula (II), and C1, C2, and C3 each represent an independent trans-1,4-cyclohexyl group (1 CH2 in the group Group or two adjacent CH2 groups may be substituted by an oxygen atom or a sulfur atom), 1,4-phenylene (one or more CH groups in the group are substituted by a nitrogen atom), 1,4- Cyclohexenyl, 1,4-bicyclo [2 · 2 · 2] octenyl, piperidine-1,4-diyl, naphthalene-2,6-diyl, decahydronaphthalene-2,6- Diyl or 1,2,3,4-tetrahydronaphthalene-2,6-diyl, the hydrogen atoms present in these groups may be substituted by methyl, -CN or halogen, u, v and w each represent independent 0 or 1, Z3, Z4 and Z5 each represent independent -CH2CH2-, -CH = CH-, -CH (CH3) CH2-,-CH 2 C Η (C Η 3)-, -CH (CH3) CH (CH3)-, -CF2CF2-, -CF = CF-, -CH20-, -OCH2-,

-och (ch3)-, -ch (ch3) o-,-(ch2) 4-,-(ch2) 3o-, -o (ch2) 3-, -CeC-, -cf2o-, -ocf2-,- COO-, -OCO-, -COS-, -SCO-, -CH = NN-CH- or single bond) The content of the compound represented by the general formula (III) is preferably 5 to 95% by mass, and 10 to 90 The mass% is more preferable, and 25 to 90 mass% is the most preferable. In the general formula (III), R5 and R6 each independently represent an alkyl group having 1 to 12 carbon atoms, an alkoxy group, an alkenyl group having 2 to 12 carbon atoms, or an alkenyl group having 2 to 12 carbon atoms. Among them, a linear alkyl group and a linear alkenyl group are more preferable. C1, C2, and C3 preferably have a structure selected from the group consisting of the following formula group 3, and more preferably have a structure selected from the group consisting of the following formula group -15-200528597. [Chemical 8] [Chemical 9]

(Z3, Z4, and Z5 of the general formula (II) each represent an independent single bond, -CH2CH2-, -CH = CH-, -CH (CH3) CH2-, -CH2CH (CH3)-, -CH (CH3) CH (CH3)-, -c Triple C-, -COO-, -OCO-, or -CH = NN-CH- is preferred, with a single bond, -16- 200528597 /-»u == NN = CH-

-CH2CH2-, -CH = CH-, -Ce C-, -COO-, -OC0-^-U ^, the sum of v and w is more preferable. u, V, and W each represent independent 0 or 1, and u, is 1 or more, but the sum of U, v, and W is preferably 2 or 3. General formula (1) 2), compounds of the general formula, specifically, general formula (III-1), general formula (IIP) ^ (III-3), general formula (IΠ-4), general formula ( III-5), the general formula (III-6), the general formula (III-7) or the compound represented by the general formula (III-8) is preferred)

(III-5) R6 (IIIIII) (III-7) (III · 8) (wherein R5 and R6 represent the same as r4 of the general formula (Π), and γι, γ2, γ3, and Υ4 each represent Independent -Η, -F or methyl, Z7 represents -CH2CH2-, -CH = CH ·, -COO ·, _0C0-, or single bond, and Z8 represents 彳 三 -C〇〇_, -OCO- or _CH = NN = CH-) In the general formulae (III-1 · 1) to (III-8), Υ1, γ2, Y3, and γ4 &amp; -Η are preferable. Z7 is preferably Ch2CH2-, -CH = CH- or a single bond. Z8 is preferably c- or -CH = N-N = CH-. The upper limit temperature of the nematic phase of the liquid crystal composition of the present invention is preferably 6 (rc or more, more preferably 80 ° C or more, and most preferably 90 ° C or more. 200528597 refractive index anisotropy (Δη) is preferably 0.06 to 0.30 It is more preferable to use 0.07 ~ 0.18, and in the case of TN-LCD, the design of the cell thickness is more preferably 0.07 to 0.16, and in the case of STN-LCD, the design of the cell thickness is more preferably 0.12 to 0.18. Rate anisotropy (△ 0 is preferably from 1 to 20, more preferably from 1 to 15. The liquid crystal composition of the present invention may optionally contain general nematic liquid crystal, smectic liquid crystal, and cholesterol type in addition to the above-mentioned compounds. Liquid crystals, two-color pigments, etc. In addition, in order to prevent the reversible twisting range of TN-LCD or the spiral structure of STN-LCD, palmarizers can be added. Palmarizers can use common commercial products. For example, cholesterol nonanoate (CN), Meilu Valley (transliteration) company's S-811, R-81 1, CB-15, C-15, etc. Depending on the type of palm agent, the spiral pitch will become longer and shorter as the temperature rises Is known, among these, one or two or more of them may be used, or one or two or more of them may be used in combination. For example, in TN-LCD, STN-LCD, TFT-LCD, the quotient d / p 値 of the thickness d between the substrates and the induced spiral pitch p can be selected from the range of 0.001 to 24, preferably 0.01 to 12, and 0.1 ~ 2 is more preferable, 0.1 to 1.5 is more preferable, 0.1 to 1 is very preferable, and 0.1 to 0.8 is most preferable. The nematic liquid crystal composition is dispersed in TN-LCD, STN-LCD, OCB-L CD, and polymer. Type liquid crystal display elements, phase-change type cholesterol liquid crystal display elements, and the like are extremely useful, and TN-LCD and STN-LCD are particularly useful. In addition, they can be used for transmissive or reflective liquid crystal display elements. The TN liquid crystal display element of the present invention, The twist angle may be selected from the range of 80 ° to 130 °, and preferably from 85 ° to 11 °. The STN liquid crystal display element of the present invention may be selected from 180 ° to 270 according to the purpose. The range of 200528597 is preferably 220 ° to 260 °. [Example 1] In the following, the present invention will be described in more detail with examples, but the present invention is not limited by these examples. In addition, the following "%" In the composition of an Example and a comparative example means "mass%" In the Example, the measured physical property is as follows. Τν ^: nematic phase, isotropic liquid phase transition temperature (° C) △ e: dielectric anisotropy (25 ° C) △ η: birefringence (25 ° C) △ P: specific resistance 値 ( Ω · cm) Charging time: The time (seconds) after the liquid crystal composition is injected into the cell and the lamp is turned on using an electrostatic tube, and then returned to the original state without voltage (seconds). • η (number): -CnH2n + 1 (the alkyl side chain is a number, a typical example is R) -OH ·-Ο C n Η 2 η + 1 -ndm:-(CnH2n-M-CH = CH- (CH2 ) mi) ndm-: CnH2n + i-CH = CH. (CH2) mi--Od (m) n: -0 (CnH2n + 1-CH = CH- (CH2) m_2) d (m) nO-: CnH2n + i-CH = CH- (CH2) m-2〇- In addition, the above-mentioned m represents a number similarly to n. Bonding group -VO-: -COO- _T-: -Ce C_ -2-: -CH2CH2- substituent -19- 200528597

-CN: -C tri N -F: -F bad P h: 1,4-phenylene

Phi: 3-fluoro-1,4-phenylene

Ph2: 3,5-difluoro-1,4-phenylene

Ma: pyrimidine-2,5-diyl Cy: 1,4-cyclohexyl (Example 1, Comparative Example 1), a nematic liquid crystal composition (Η1) shown below was prepared, and the The physical properties were poor, and the results are shown in Table 1.

-20- 200528597 Table 1 Composition and physical properties of Η 1 値 Liquid crystal composition HI (%) Composition 2-Ph-VO-Phl-CN 4 3-Ph-VO-Phl-CN 3 4-Ph-VO-Phl-CN 6 5-Cy-VO-Phl-F 6 0dl-Cy-Cy-5 14.5 3-Cy-V0-Ph-02 14 3-Cy-Ph-02 1.5 3-Cy-2-Cy-VO-Phl-F 4 3-Cy-Cy-VO-Phl-F 8 Odl-Cy-Cy-Ph-1 10 0d3-Cy-Cy-Ph-l 14 3-Cy-Cy-VO-Ph-Cy-2 4 3-Cy -Cy-VO-Ph-Cy-3 4 3-Cy-Cy-VO-Ph-Cy-4 4 3-Cy-Cy-VO-Ph-Cy-5 3 TN.i (° C) 119.8 Δ € 7.0 Δη 0.098 ρ (Ω · cm) 7.8xl〇n

The obtained liquid crystal composition Η1 is characterized in that the charging time of the liquid crystal molecules is relatively long for a momentary voltage application, and 300 seconds of -2 1-200528597 elapses after a long period of time without effective countermeasures, and the abnormal alignment may be continued for a long time. In this Example 1, a liquid crystal composition (Yamarubo S-83) or T-20 (Tongbang Chemical Industry Co., Ltd.) added with a semipolar organoboron compound was prepared in Examples 1-2 to 1-4 ( LC1, LC2 and LC3). In addition, for comparison, Comparative Examples 1 to 1 and 1 to 2 are prepared by nematic liquid crystal composition Η1. Tetraethylene glycol dimethyl ether (TEG), which is a nonionic surfactant represented by the following formula, is added. Liquid crystal composition (R1 and R2). [Chemical 11] H3C0 (-CH20CH20-) 4CH3 (TEG) These specific resistances 値 and the charging characteristics of the TN cell injected into 6.0 μm were measured. The results are shown in Table 2.

Table 2 Composition of antistatic effect Composition P (Ω · cm) Charge time (S) Change of upper limit temperature of liquid crystal phase CC) H1 Additive H1 100% surface 7.8χ10π &gt; 300 LC1 (Example 1-2) 99.99% S- 83 0.01% 6.4xlOu 40 0 LC2 (Examples 1-3) 99.998% T-20 0.002% 5.8xlOn 16 0 LC3 (Examples 1-4) 99.997% T-20 0.003% 4.8 x 10π 5 0 R1 (Comparative Example M ) 99.90% TEG 0.10% 8_〇xl010 &gt; 300 -0.5 R2 (Comparative Example 1-2) 99.80% TEG 0.20% 8.8χ1010 60 -1.0 -22- 200528597 Nematic liquid crystal composition LC 1 Compared with Η1 of the polar organic boron compound, the specific resistance 値 and the upper limit temperature of the liquid crystal phase are not reduced, and the charging time is shortened. The specific resistance 値 of LC2 and LC3 and the upper limit temperature of the liquid crystal phase are not reduced, and the charging time is further shortened. In this regard, when R 1 of TEG is added, even if 0.1% of LC 1 is added at 0.1%, the specific resistance 値 is reduced and the upper limit temperature of the liquid crystal phase is not effective. In addition, by adding 20% of R2, although the effect of shortening the charging time can be obtained, the effect is insufficient and the upper limit temperature of the liquid crystal phase is reduced. When TEG is used in this way, the effect is not increased when the amount of addition is increased. Compared with the composition of LC1 to LC3, the resistance 値 and the upper limit temperature of the liquid crystal phase are greatly reduced. 'It cannot be used as a practical liquid crystal composition. [Example 2] The nematic liquid crystal composition (Η2) shown below was prepared, and the physical property 値 'was measured. The results are shown in Table 3. -23- 200528597 Table 3 Composition and physical properties of H2 値 Liquid crystal composition LC8 _W_ Composition 4-Cy-VO-Phl-F 9 5-Cy-VO-Phl-F 9 Odl-Cy-Cy-5 21 3-Cy- Ph-02 5 Odl-Cy-Cy-Phl-F 20 3-Cy-Cy-VO-Phl-F 8 Odl-Cy-Cy-Ph-1 8 0d3-Cy-Cy-Ph-l 3 3-Cy- Ph-T-Ph-2 5 3-Cy-Cy-VO-Ph-Cy-3 4 3-Cy-Cy-VO-Ph-Cy-4 4 3-Cy-Cy-VO-Ph-Cy-5 4 TN-i (° C) 105.3 5.3 Δη 0.086 ρ (Ω · cm) 1.2xl013

For the obtained liquid crystal composition H2, the relaxation time of the liquid crystal molecules is shorter than that of H2 for one-time voltage application, and the charging time when no measures are taken is about 30 seconds. To this H2, a liquid crystal composition (LC4 and LC5) containing a semi-polar organic boron compound as a charge-shifting complex is added by adding Berberon EB-6 (manufactured by Beron). As Examples 2-1 and 2-2. In addition, Comparative Examples 2-1 and 2-2 based on -24-200528597 comparison were prepared by adding tetraethylene glycol dimethyl ether, which is the same nonionic surfactant as in Example 1, to the nematic liquid crystal composition H2. Liquid crystal composition (R3 and R4). The specific resistance 比 and the charging characteristics when injected into a TN cell of 6.0 μm were measured. The results are shown in Table 4. Table 4 Composition of antistatic effect Composition P Change of upper limit temperature of liquid crystal phase during charging time H1 Additive (Ω · cm) (S) (° C) H2 100% Ore-1.2χ1013 &gt; 30 LC4 (Example 2-1) 99.99 % EB-6 0.01% 3.5χ10π &lt; 0.1 * 0 LC5 (Example 2-2) 99.90% EB-6 0.10% 3.8χ10π &lt; 0.1 * -0.5 R3 (Comparative Example 2-1) 99.90% TEG 0.10% 2 〇χ1012 &gt; 30 -0.5 R4 (Comparative Example 2-2) 99.80% TEG 0.20% 2.8χ1012 4.5 -1.0 When using a liquid crystal composition with a short charge time 电 2 ', 0.0 1% Ε Β-6 LC 4 is added The time charging time can be shortened to less than 0.1 second, and the temperature range of the liquid crystal phase is not reduced. The addition of 0.1% Ε Β-θ's upper limit temperature of the liquid crystal phase will decrease, but the addition of 〇1% as described above for EB-6 can shorten the charging time practically. In this regard, when the R3 of 0.1% TEG is added, 'the specific resistance 値 can be reduced to a minimum 値', but the charging time is not shortened. When the R4 is added 0.2%, the specific resistance 値 is There is no reduction, but the shortening of charging time is still insufficient. Therefore, it is predicted that the upper limit temperature of the liquid crystal phase will be greatly reduced when the amount is more than the above amount, so it cannot be used as a practical liquid crystal composition. [Example 3] A nematic liquid crystal composition (H3) shown below was prepared, and a liquid crystal composed of yamalubo S-83, which is 99.9 9% H3 and 0.01% as a semi-polar organic boron compound, was prepared. Composition (LC6). In addition, a liquid crystal composition (LC7) composed of 99.997% of H3 and 0.003% of T-20 was prepared. Table LC 1 4 Composition Liquid crystal composition H3 (%) 3-Ma-Ph2-CN 10 Odl-Cy-Phl-CN 10 ldl-Cy-Phl-CN 15 0dl-Cy-Cy-5 2.5 0d3-Ph- T-Ph-0d3 10.5 Odl-Cy-Cy-Ph-1 10 0d3-Cy-Cy-Ph-l 15 3-Cy-Ph-T-Ph-2 7 4-Cy-Ph-T-Ph-l 6 3-Cy-VO-Ph-T-Ph-l 6 3-Cy-VO-Ph-T-Ph-5 6 3-Cy-Cy-V〇-Ph-Cy-3 2 -26- 200528597 Known liquid crystal composition LC6 and LC7 have the effect of shortening the charging time. [Utilization price in industry] The present invention provides a liquid crystal with a specific resistance of a suitable size without using a material with a large reduction in specific resistance, and can quickly alleviate the voltage applied when the liquid crystal display element is charged due to static electricity or the like. Liquid crystal composition with abnormal molecular orientation. The nematic liquid crystal composition of the present invention is characterized by having a specific resistance 値 of an appropriate size, and can quickly alleviate the abnormal alignment of liquid crystal molecules in the case of voltage application when one of the charges is caused by static electricity or the like, so it can be shortened in the manufacturing process. Due to the charge discharge time due to the charge, the liquid crystal display element is efficiently manufactured. [Brief description of the drawing] Fig. 1 shows a structural example of the electro-optical element of the present invention. [Description of element symbols] 1 Polarizing plate 2 Substrate 3 Transparent electrode or transparent electrode with active element 4 Alignment film 5 Liquid crystal -27-

Claims (1)

200528597 10. Scope of patent application: 1. A nematic liquid crystal composition, which is characterized by containing at least one or more semi-polar organic boron compounds, or a charge transfer complex consisting of semi-polar organic boron compounds, and the semi-polar organic The number of boron atoms in one molecule of the boron compound is 5 or less, and the specific resistance 値 is 1 · χχ101 () Ω · cm ~ 1 · 〇χ1〇13ίϊ · cm. 2. According to the nematic liquid crystal composition of item 1 of the scope of the patent application, at least one of the semi-polar organic boron compounds is a compound having a skeleton represented by the general formula ⑴, (I) [化 12] -CHO ^ ^ j ^ OHC --CHc / 3. The nematic liquid crystal composition of the second item of the patent application, wherein the charge transfer complex composed of a semi-polar organic boron compound contains a compound having a skeleton represented by the general formula (I) and an amine compound The composition of the charge transfer complex. 4. According to the nematic liquid crystal composition of item 2 of the patent application, wherein the semi-polar organic boron compound contains a compound represented by the general formula (Bu1) or the general formula (〖-2), [Chem 13] ch20 H 0H2C ? H2〇 \ (-) / OHC ^ a2 ^ r2 Eight (w) I / V) I ㈣ RH ^ $ CH0 ^ 8) HC- (A2 ^ R2 r ^ a ^ cho oh2c ^ + H (wherein R1 and R2 each represents an independent hydrogen atom, a mesogen, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, and a carbon number of 28 to 200528597. 2 to 1 2 Alkenyloxy, 1-12 carbon substituted with halogen, alkoxy 1-12 substituted with halogen, 2-12 alkenyl substituted with halogen, or halogen substituted Alkenyloxy groups having 2 to 12 carbon atoms, A1 and A2 represent independent single bonds, alkylene groups having 1 to 10 carbon atoms, aryl groups having 6 to 18 carbon atoms,-(-(CH2) nO-) m- (n is an integer from 1 to 10, m is an integer from 1 to 30), -CH2-0-C0-R3-C0- (R3 is a hydrocarbon group having 1 to 60 carbons) or -CH2-0 -C0-NH-R3-NH-C0-, p and q each represent an independent integer from 1 to 10, but may be the same or different when there are several A1 and A2). 5. If the scope of patent application is the fourth item A nematic liquid crystal composition in which a charge transfer complex composed of a semipolar organic boron compound contains a compound represented by general formula i (1-1) or general formula (1-2) and an amine compound Charge transfer complex. 6. If the nematic liquid crystal composition of the scope of the patent application No. 5 in which the amine compound is a tertiary amine. 7 · If the nematic liquid crystal composition of the scope of the patent application No. 1, Which contains one or more compounds represented by the following general formula (II), and contains one or more compounds represented by the following general formula (III), [Chem. 14] (Wherein R4 represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, at least one alkyl group having 1 to 12 carbon atoms substituted with halogen, an alkenyl group having 2 to 12 carbon atoms, or at least one carbon number substituted with halogen 2 ~ 1 2 alkenyl groups, which exist in these groups-29- 200528597 One or more CH2 groups can be independently 0 atoms which are not directly bonded to each other oxygen atom, sulfur atom, -CO- , -COO-, -OCO-, or-0C0-0-, B1 and B2 each represent an independent trans-1,4-cyclohexyl group (1 CH2 group in this group or no adjacent 2 CH2 groups may be substituted by oxygen atom or sulfur atom), 1,4-phenylene (1 or more CH groups in the group may be substituted by nitrogen atom), 1,4-cyclohexenyl , 1,4-bicyclo [2.2.2] octenyl, piperidine-1,4-diyl, naphthalene-2,6-diyl, decahydronaphthalene-2,6-diyl, or 1,2, 3,4-tetrahydronaphthalene-2,6-diyl, the hydrogen atoms present in these groups may be substituted by -CN or halogen, s and t each represent independent 0, 1 or 2, 8 and 1 Below 3, Z1 and Z2 each represent independent -CH2CH2-, -CH = CH-, -CH (CH3) CH2-, -CH2CH (CH3)-&gt; -CH (CH3 ) CH (CH3)-, -CF2CF2-, -CF = CF-, -CH20-, -OCH2-, -OCH (CH3)-, -CH (CH3) 0-,-(CH2) 4-,-(CH2 ) 30-, -0 (CH2) 3-, -CE c-, -CF20-, -OCF2-, -COO-, -OCO-, -COS-, -SCO- or single bond, L1 and L3 each indicate Independent -H, -F or-(M, L2 means -F, -Cl, -CN, -CF3, -OCH2F, -OCHF2, -OCF3 or -CH2CF3, when there are several B1, B2, Z1 and Z2 May be the same or different. [Chem. 15] R5- ^ C1-Z3 ^ C2-Z4 ^ C3-Z5 ^ R6 (III) (wherein R5 and R6 represent the same meaning as R4 of the general formula (II), C1, C2, and C3 each represent an independent trans-1,4-cyclohexyl group (one CH2 group present in the group or no two adjacent CH2 groups can be oxygen or sulfur atoms from the 200528597 generation) 1,4-phenylene (1 or more ch groups in this group may be substituted by nitrogen atom), 1,4-cyclohexenyl, 1,4-bicyclo [2.2.2] Octenyl, piperidine-1,4-diyl, naphthalene-2,6-diyl, decalin-2,6-diyl, or 1,2,3,4-tetrahydronaphthalene-2,6- Diyl radicals. The hydrogen atoms present in these radicals may be substituted by methyl, _cn or halogen. U, v and w each represent an independent 0 or 1 Z3, Z4 and Z5 each represent independent -CH2CH2-, -CH = CH-, • CH (CH3) CH2 ·, _CH2CH (CH3) _, _CH (CH3) CH (CH3)-, -CF2CF2-, -CF = CF-, -CH20-, -〇CH2-, -OCH (CH3)-, -CH (CH3) 〇-,-(CH2) 4-,-(CH2) 30-, -o (ch2) 3 ,, -c triple c-, -CF20-, -〇CF2-, -coo-, -OCO-, -COS-, -SCO-, -CH = NN = CH- or single bond). 8 · The nematic liquid crystal composition according to item 7 of the patent application scope, which contains more than one general formula (11-1), general formula (11-2), general formula (11-3), general formula (11- 4) The compound represented by the general formula (11-5), the general formula (11-6), the general formula (11-7), or the general formula (II-8) is a compound represented by the general formula (II), [Chemical 16] -3 1- 200528597 L2 αι-8) (where R4 each represents an independent alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms or an alkenyl group having 2 to 12 carbon atoms, X1 and X2 each represent an independent hydrogen or fluorine atom, L1 and L3 each represent an independent -H or -F or-CM, and L2 represents -F, -CN, -CF3, -OCH2F, -ochf2,- ocf3 or -ch2cf3). 9. The nematic liquid crystal composition according to item 7 of the scope of patent application, which contains more than one general formula (III-1), general formula (III-2), general formula (III-3), general formula (III) -4), as a compound represented by the general formula (III), a compound represented by the general formula (III-5), a general formula (III-6), a general formula (III-7), or a general formula (III-8), 【化 Π】 (111 * 5) R6 (III-6) (ΠΙ-7) (111-8) (where R5 and R6 each represent an independent alkyl group and carbon number of 1 to 12 carbon atoms -32- 200528597 Alkoxy group 1 to 12, alkenyl group 2 to 12 or alkenyl group 2 to 12 carbon, 1 to 12 alkyl group substituted with halogen, carbon substituted with halogen The alkoxy group of 1 to 12, the alkenyl group of 2 to 12 carbons substituted with halogen, or the alkenyl group of 2 to 12 carbon substituted with halogen, Y1, Y2, Y3, and Y4 each independently represent -H, -F or methyl, Z7 represents -CH2CH2-, -CH = CH-, -COO-, -OCO-, or a single bond, and Z8 represents-CeC-, -COO-, -OCO · or- CH = NN = CH-). 10. The nematic liquid crystal composition according to item 1 of the scope of patent application, wherein the content of the semipolar organic boron compound and the charge transfer complex containing the semipolar organic boron compound is 0.0001 to 1% by mass. 11. The nematic liquid crystal composition according to item 1 of the scope of the patent application, wherein the liquid crystal composition has a dielectric anisotropy of 1 to 20, and Δη representing a refractive index anisotropy of 0.06 to 0.16. 1 2. A liquid crystal display element characterized in that a liquid crystal composition such as item 11 of the scope of patent application is used as a constituent member. -33-