TW434310B - Liquid crystal composition - Google Patents

Abstract

The invention relates to a nematic liquid crystal composition which exhibits a resistivity of at least 1i 10<SP>11</SP> Ωcm which contains 1 to 10,000 ppm of a crown ether and to a method of improving the electrostatic behavior of a liquid crystal display device with the aid of such a composition.

Description

A7 B7 V. Description of the invention (1) Background information of the present invention 1 Related field of the present invention The present invention relates to a nematic liquid crystal composition having a resistivity of at least 1 X 1 011 ^ cm, It is characterized in that it contains a crown ether (cf〇wn ether) of 1 to 10 '00 00 Ppm ° 2. Previous technical description ·. 'A liquid crystal display element (L CD) with a high resistivity liquid crystal has encountered the following problems: • During the LCD manufacturing process, when the protective film is peeled off from the polarizer, static electricity will form an electric field on the sample element. This electric field will align the liquid crystal compounds, and the element will become &quot; ON state &quot;. Therefore, the manufacturing of the component must be interrupted until it has been discharged. • If the cloth is used to touch or rub the LCD for work, it will be printed by Shelley Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (read the notes on the back and then fill out this page). Such components may still have the same static electricity. Effect and becomes &quot; Startup state &quot;. It is an object of the present invention to provide a solution to this disadvantage, that is, to find a method for shortening the discharge time of the LC without adversely affecting the liquid crystal resistivity. Japanese published applications; IP 4 — 028 — 7 _8 8 It is recommended that cryptand be doped into the liquid crystal to reduce its specific resistivity. •-· — This paper size is applicable to China National Standard (CNS) A4 specification (210X297mm) ^ 4 3 ^ 310 Annex II (A) Chinese Specification for Patent Application No. 841 10329 Amendment to the Republic of China Amended in March ____

Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs. 5. Description of the invention (2) p ^ Further, the specific resistivity of the liquid crystal composition obtained by improving 100 is less than 1 x 1 〇αα cm. 〇 This application JP 5- 0 8 8 — 1 4 8 explains the method of adding crown ether to the liquid crystal to reduce the sodium ion in the LCD. Japanese published application J P 54 — 1 06 — 08 4 states that the cross-linking of multiple CD can be reduced by adding a crown ether or a hole compound to the liquid crystal. However, no one has suggested that the nematic liquid crystal composition doped with 1 0, 0 〇 〇 P pm crown ether resistivity of 1 X 1 0 1 1 Ω cm can be suitable to reduce the electrostatic problem of L C D. SUMMARY OF THE INVENTION Accordingly, it is an object of the present invention to provide a nematic liquid crystal composition having a resistivity of at least 1 X 1 0 11 Ω cm, which is characterized in that it contains a crown ether of 1 to 10,000 ppm. Another object of the invention is to provide a method for improving the electrostatic behavior of an LCD by means of such a composition. The preferred system is more preferably doped with crown ether into the nematic liquid crystal composition of the present invention. The crown ether expression includes a cyclic polyether and a corresponding benzo derivative. They are preferably cyclic compounds such as chemical formula A or B [(CH2) 2 〇] „— — —, ((CH2) 2 〇U2 * (C6H40) 2 B, (Please read the precautions on the back before filling (This page) r This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) 4 3 10 A7 B7 V. Description of the invention (3) where m is an integer from 4 to 8 'They are especially as the chemical formula

Aa or Ba compounds

From the nematic compound of the present invention, it is possible to achieve a high specific resistivity value, accompanied by a rapid discharge of electrostatic charges, and as a result, L C D having excellent performance can be obtained. The specific resistivity of the composition of the present invention is greater than 1 X 1 0 1 1 Ω cm, preferably between 2X1011 and lxl014Qcm. The end of the discharge time depends on the amount of crown ether added. Generally speaking, even a crown ether with only 1 P pm can shorten the discharge time by at least 30%. Depending on the type of composition that is not doped, a crown ether with 1 P pm can shorten the discharge time by 50 to 8 5%. Therefore, the content of crown ether in the composition should be less than that printed by the Shellfish Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs. — L · — — i Q —------ Order (Please read the precautions on the back before filling this page } 10, 000 ppm: more preferably between 1 and 1,000 ppm. In principle, it is possible to add the crown ether to any kind of nematic composition. It is more suitable to apply the present invention to TN or S TN. Devices, especially for TN-L CDs or active matrix LCDs with high threshold voltages. Nematic components of these two types of display elements are more suitable for the first recommended by Gooch and Tarry. Operate at a minimum transmission value (for example, see C, .H. G0och, HA Tarry, Electron. Lett. 10) The paper &amp; scale is applicable to China National Standard (CNS) A4 (210X 297 mm) -6-

434310 A7 _____B7 V. Description of the Invention (4), 2-4, 1974). Therefore, the birefringence value (Δη) of the nematic composition of the present invention is preferably 0.1 1 or less, especially 0.07 to Q. 105, and most preferably 0.090 to 0 _ 10 2 ° The viscosity of the composition of the present invention at 20 ° C is more preferably $ 2 5 c S t. The nematic phase range is preferably at least 70 ° C, especially at least 80 ° C and at least between 20 ° C and + 70 ° C. The nematic composition usually contains at least 3, preferably 5 to 20, especially 8 to 15 mesogenic compounds. The dielectric anisotropy of the composition of the present invention (an isotropy). (Δ ε) is usually greater than +1. It is preferably between + 3. 0 and. + 1 ◦. 0. The threshold voltage of the composition of the present invention It is preferably smaller than 3.5 V, especially smaller than 3.0 V. The nematic liquid crystal composition of the present invention preferably contains at least one liquid crystal compound such as Chemical Formula I and at least one compound such as Chemical Formula II, (please read the precautions on the back before filling this page) • 'll Staff of Central Standards Bureau, Ministry of Economic Affairs Consumer cooperative printing

This paper size applies to Chinese National Standard (CNS) A4 specification (2 丨 0X 297 mm) 43431 〇 Α7 Β7 V. Description of the invention (5) where R1, R1QR3 are independent of each other's alkyl, alkoxy or olefin base,

For up to 12 C

X is a C N, fp, c

-0 C F 2H

Rings A, BC, and D are independent of each other. They represent Λ, 4 _cyclohexyl '1, 4 ~ hexenylene 1 4 and 1 phenylene. Each ring is selectively twisted by one or two It is replaced by a fluorine atom, independently of each other: _ C ξ C —, CH 2 C Η C〇0 — or single bond (+ please read the notes on the back before filling this page) L 1 and L 2 η 〇 in Independent of each other, Η or F is 0 or 1, and 0 _ +, 1 or 2. Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs

There are formulas. The chemical composition of the chemical substance is self-selecting, and the liquid is less singular to the harmonious: the material is compounded into the natural chemical, the middle ee of the II body to the a of I and the appropriate I—- b is suitable for ί Do n’t choose a specific one, in one a. Less I to I Chinese standard home country i country T one with a moderate ruler-paper I centimeter-8-4 3 431 〇 Α7 Β7 V. Description of the invention (6 )

R M 'x &gt; &quot; C00Kr la V

F R

C = Ni 'i \) lc (Please read the notes on the back before filling this page) R1 &lt; IK &gt;

OCF, Id L2 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs

lib —RJ lie This paper size is applicable to China National Standard for Ladder (CNS) A4 (2IOX297 mm) 1 9 43431 〇 A7 B7 Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (7)

Among them, R1, R2, R3, li, L2, Z1 and B ring and C ring have the meanings as given in item 5 of the patent application scope, Q is 0 or 1 '~, and L 3 is Η or F. : Another feature of the present invention is a method for improving the discharge time of an electrostatically charged liquid crystal display element by means of the composition of the present invention. EXAMPLES After a general description of the invention, a more complete understanding can be obtained by reference to certain specific examples provided herein, unless otherwise specified, for illustrative purposes only, and not for limitation. In the following examples, the temperature properties of the mesophase are expressed in a conventional manner as corresponding temperatures (° C). Three different methods were used to study the LCD discharge time after the cell gap of 5. 7 # πι was filled in the twisted nematic cell (TN) after it was filled with the composition of the present invention: Experiment A: using an electrostatic discharge simulator A voltage of 10 kV was applied; • Experiment B: A DC power supply was applied with a voltage of 10 V for .10 seconds; • Experiment C: The cell was rubbed with paper to generate static electricity. This paper size is applicable to Chinese National Standard (CNS) A4 specification (2 丨 0X297mm) &quot; ~ 10-II 丨 ™! T! ΓΟΙ ---- Order (please read the precautions on the back before filling this page) ) 434310 A7 B7 V. Description of the Invention (δ) The composition of the mixture of Examples 1 to Γ 0 is designated as follows.

The compound number is as follows: Abbreviation (acrynym) ME-nN.F Chemical formula

Hm + iCn

COO

F

C ^ N

HP-nN.F

-C = N Η2η + ι ^ η PCH-nOm Hsn + iCn CCH-nOm Hin + i ^ n CH-nm H2n + icn— CP-nm H2n + icn ~ \

〇CmH2mH-i OCmH ^ nrH (Please read the precautions on the back before filling this page) CBC-nm

CBC-nmF Consumer Cooperatives, Central Standards Bureau, Ministry of Economic Affairs

PCH-nF CCP-nOCFj

BCH-nF.F H: nf i ^ n Hirtf i ^ n

Η2η + ΐ ^ η

F H2n + iC H211 + 1

This paper size applies Chinese National Standard (CNS) A4 specification (21 OX297 mm) 11 3 43 1 0 A7 B7 V. Description of the invention (9) ECCP-nOCFs / tWiCn— (II ^ __ ^ ~~ ^ -ch2ch2- ECCP -nF HurfiCn ~ \ 2 ^) ~ f ECCP-nF.FF H2n + iCn '

BCH-nmF CPTP-nOm CCPC-nm

〇CmH2m + i (Please read the precautions on the back before filling this page) D-nOrm Η2η + ι〇η.

COO

Printed in Example 1 by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs The formula of nematic composition A contains: This paper scale is applicable to Chinese National Standards (CNS) A4 specifications (2! OX: 297 mm) 12 ™ 43 4310 A7 B7 V. Description of the invention (10) Content of compound printed by employees 'cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs (%) Physical properties' ME2N.F 2.00 ME3N.F 3.00 Clarity: + 1 0 5 ° C ME5N.F 1.80 △ η 0. 0 9 6 8 HP-3N.F 2.30 Δ e +4. 1 PCH-30 1 18.80 PCH-302 7. 00 CCH-303 12.30 CCH501 12.30 CCH-503 2.40 CH-33 3.70 CH-35 3. 70 CH-43 3.70 CH-45 3. 00 CBC-33 4. 00 CBC-53 4.70 CBC-33F 5.00 CBC-53F 5.30 CBC-55F 5.30 Add different amounts of 1 8 —Crown ether — 6 to this paper size Applicable to China National Standard (CNS) A4 specification (210X297 mm) —I —. 1----t ^ 'i-----^ 1f ^--I—1 11 I ...... — ^ 1 Yi ^ (Please read the cautions on the back before filling in this page) -13-43431 〇 Α7 Β7 5. In the description of the invention (η). The concentration, discharge time (r) and specific resistivity (ρ) are listed in Table I below.

Table I Composition A doped with 18-crown ether-6 (please read the notes on the back before filling this page) 18-crown-6 concentration [ppm] Experiment 0 r 10 100 1000 1 0 0 0 0 p [1 0 1 (5 Ω cm) 9 8 0 370 13 0 81 21 9.5 a τ k [sec] 2 15 1 5 0 5 5 18 2 0 B r [sec] n. M. 549 123 61 28 12 C r ^ [sec] 55 17 2 0 0 0 The figure is displayed.显 '' 二 -t 二 .Ξ ξϋ Μΰ Μΰ Reduction of 3 ^ 9 g ^ y Phases of each other When the concentration is strong, the concentration of the ether ether crown is crowned and the ratio of the electricity to the electricity is released when the time is resistance. Put it in the middle and put it in A. Show B. Check it out and check it out. 03 In the picture. 1 in the picture. 4 Printed by the Central Standards Bureau of the Ministry of Economic Affairs-Industrial and Consumer Cooperatives. Validation of the standard I Home | National-Intermediate use of moderate rule paper on paper 29 V. Description of the invention (l2) A7 B7 Compound content (%) Physical properties PCF-5F 10.00 PCH-6F 8.00 Clear point: + 9 3 ° C PCH-7F 6.00 △ n0. 0.969 CCP-20CF3 8.00 Δ ε +5.2 CCP-30CF3 12.00 CCP-40CF3 7. 00 CCP-50CF3 11.00 BCH-3F.F 12.00 BCH-5F. F 10.00 ECCP-30CF3 5.00 ECCP-50CF3 5.00 CBC-33F 2.00 CBC-53F 2.0 0 CBC-55F 2. 00 (Please read the precautions on the back before filling out this page) Order the Central Government Bureau of the Ministry of Economic Affairs and the Consumer Cooperatives to print different quantities of 1 8-crown ether one 6 is added to the composition. The concentration, discharge time (r) and specific resistivity (p_) are listed in the table below. I Chinese paper size is applicable to Chinese National Standard (CNS) A4 specification (210 X 297 mm) 15 — Α7 Β7 V. Description of the invention (13)

Table II Composition B doped with 18-crown ether-6 1 Concentration of 8-crown ether-6 [ppm] Experiment 0 1 10 100 1000 1 0 0 0 0 P [.10] 1 0 Ω cm) 2 4 0 0 140 54 27 6.7 2. 7 A r dc [sec] 6 95 160 52 2 0. 5 0 B τ dc [sec] 240 0 3 3 7 90 48 22 5 C r heart [sec] 84 10: '2 1 0 0 UI- «1 ^ ^^^ 1 I--_ i ^ na ^ n factory shoulder (please read the precautions on the back before filling this page) The correlation between discharge time and crown ether concentration in experiment A is shown in The correlation between the discharge time and the crown ether concentration in Experiment B in Figure 3 is shown in Figure 4. The correlation between the discharge time and the crown ether concentration in Experiment C in Figure 4 is shown in Figure 5. Brief Description of the Drawings Figure 1: Discharge time (r dc) in experiment A as a function of the concentration of 18 -crown ether-6 in composition A (electrostatic discharge simulator, plus 1 kV). Figure 2: The discharge time (r) in experiment A as a function of the specific resistivity of composition A (electrostatic discharge simulator, applied voltage 10 kV) This paper is in accordance with the Chinese National Standard (CNS) A4 specification ( 210X297 mm) Printed by the I-Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs, -16-4 3 4 310 A7 B7 V. Description of the invention (14) Figure 3: Discharge time (τ d.) In experiment A is based on the composition Graph of the specific resistivity of A (-♦-) and B (—) as a function (electrostatic discharge simulator, applied voltage 10 k V). Figure 4: Discharge time in experiment B (a graph of the specific resistivity of composition A (― ♦ a.) And B () as a function (DC 3 0 V, application time 1 ◦ second)). Figure 5: The discharge time eight r in experiment C) is based on the specific resistivity of composition A (— ♦ _) and B a); the graph of A function (friction with paper (please read the precautions on the back before filling this page) The paper size printed by the Employees' Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs applies to the Chinese National Standard (CNS) A4 (210X297 mm) -17 —

Claims (1)

4 310 Announcement of this A8 BS CS D8 "、 Appendix I to the scope of patent application: No. 84110329 Patent Application Amended in February, 1989 1. A nematic liquid crystal composition for a TN or STN display, the display resistivity of which is at least 1 X 1 〇 ^ Ω cm, which is characterized in that it contains 1 to 10, 0 0 0 p pm crown ether, and at least one compound of formula I and at least one compound of formula II, (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 RhRqaR3 is an alkyl, alkoxy or alkenyl group with up to 12 C atoms independently of each other, and the X ring A Β is —CN, F, C — 0 CF 2 Ο —Ο CF 3 or C and D independently of each other represents 1, 4-cyclohexyl, 1, 4-cyclohexyl, 1, 4-cyclohexyl 'each ring is optionally substituted with one or two fluorine atoms The good paper size applies the Chinese National Standard (CNS) Α4 specification (210X297 male #) 1-43431 0 Α8 Β8 C8 D8 VI. The scope of patent application Z1 and Z2 is independent of each other as ——, _ch2ch2—, a c00_ or Single bond (please read the notes on the back before filling this page) L1 and L2 represent η or F independently of each other, η is 0 or 1 'and 〇 is 0, 1 or 2. 2. The nematic liquid crystal composition according to item 1 of the patent application range, wherein it contains 1 to 1'000 ppm of crown ether. 3. The nematic liquid crystal composition according to item 1 of the scope of patent application, wherein the crown ether is a cyclic compound such as chemical formula eight or eight [(CH2) 2.〇] m A, [(CH2) 2 0] m- 2 · (CsH4〇) 2 B, where m is an integer between 4 and 8. 4. The nematic liquid crystal composition according to item 3 of the scope of patent application, wherein the crown ether is a compound such as chemical formula A a or B a Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Such as the nematic liquid crystal composition of the scope of patent application No. 1 in which the birefringence value is 0.1 or lower β This paper standard applies 8 4 specifications (210 乂 297 mm) 4 3 4 3 1 0 as Bg C8 D8 _ 6. Application for patent scope 6. For example, the nematic liquid crystal composition of the scope of application for patent No. 1 'where the liquid crystal composition is in the 5V。 The threshold voltage of τ N -LCD operating at a minimum transmission value is lower than 3.5V. 7. The nematic liquid crystal composition according to claim 1 in the scope of patent application, wherein it contains at least one compound selected from the chemical formulae I a to I e and at least one compound selected from the chemical II a, I lb, and II e: ( (Please read the precautions on the back before filling out this page) IX .., Word | F This paper size applies to China National Standards (CNS) A4, see the standard (210X297 mm) 3 4 3 4 ο ABCD Six, the scope of patent application where R1, R2, R3, L1, l2, Z1 and rings B and C have For the meaning of item 1 of the patent application scope, Q is 0 or 1, and L 3 is Η or F. 8. The nematic liquid crystal composition according to item 1 of the application, wherein the dielectric anisotropy (Δε) of the liquid crystal composition is between +3.0 and +1.0. 9. The nematic liquid crystal composition according to item 1 of the scope of patent application, which is used as a dielectric in a liquid crystal display element to improve the electrostatic effect of the display element. 10. The nematic liquid crystal composition according to item 1 of the scope of patent application, which is used as a dielectric in a liquid crystal display element which is electrostatically charged to improve the discharge time of the display element. 1 1. A twisted nematic (TN) or super twisted nematic (STN) type liquid crystal display element (LCD) comprising a liquid crystal composition according to any one of claims 1 to 8 of the scope of patent application. 12. The liquid crystal display element according to item 11 of the scope of patent application, which is an active matrix LCD. 13. The liquid crystal display device according to item 11 of the scope of patent application is a T N type device. 14. The liquid crystal display element according to item 11 of the scope of patent application is an STN type element. This paper is scaled to the Chinese National Standard (CNS) A4 size (210X297 cm) (Please read the note on the back before filling this page) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs -Order ------ I. J -------- ^ ----- ^-4