JPH1192763A - Nematic liquid crystal composition and liquid crystal display prepared therefrom - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a nematic liq. crystal compsn. decreased in the change in display characteristics with temp. by incorporating a liq. crystal component having a specified chemical structure and two specific liq. crystal components different in dielectic anisotropy into the same. SOLUTION: This compsn. contains a liq. crystal component (A) comprising at least one compd. selected from among compds. represented by the formula [wherein R<11> is 1-10C linear alkyl, alkoxy, or 2-10C linear alkenyl; X<11> and X<12> are each R<11> , H, F, Cl, -CF3 , -OCF3 , or -CN; Y<11> to Y<14> are each H or F; Z<11> and Z<12> are each a single bond, -COO-, -C≡C-, -C2 H4 -, or -C4 H8 -; Z<13> is -O(CH2 )k2 -, -(CH2 )k3 O-, or -(CH2 )k4 -; k2-k4 are each 1-5; k1 is 0 or 1; and ring A<11> is 1,4-phenylene or trans-1,4-cyclohexylene], 10-99 wt.% liq. crystal component (B) comprising a compd. having a dielectric anisotropy of +2 or higher. and 0-70 wt.% liq. crystal component (C) comprising a compd. having a dielectric anisotropy of from -2 to +2, the sum of components B and C being 75-99.9 wt.%.

Description

DETAILED DESCRIPTION OF THE INVENTION

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a nematic liquid crystal composition useful as an electro-optical display material and a liquid crystal display using the same.

2. Description of the Related Art A typical liquid crystal display element is a TN-LCD.
(Twisted nematic liquid crystal display element)
It is used in watches, calculators, electronic organizers, pocket computers, word processors, personal computers and the like. On the other hand, with the increase in processing information of OA equipment, Scheffer et al. [SID '85 Digest, p.120 1985
Year], Kinukawa et al. [SID '86 Digest, p.122 1986] developed STN (Super Twisted Nematic) -LCD, which can be used for mobile terminals, electronic organizers, pocket computers, word processors, personal computers, or monitors. It has begun to spread widely to displays for high information processing such as displays. Recently, the active addressing drive system [Pro
c.12th IDRC p.503 1992] and multi-line addressing drive method [SID'92 Digest, p.232 1992]
Has been proposed. In addition, in order to achieve a brighter display and a higher contrast ratio, a new reflective color liquid crystal display system using the birefringence of liquid crystal and a retardation plate instead of the color filter layer [Technical Report of the Institute of Television Engineers of Japan
vol.14 No10.p.51 1990], and a liquid crystal display device having a reflective surface with a small parabolic surface on the substrate electrode side has been proposed. As a liquid crystal material suitable for this, it is necessary to comprehensively optimize individual physical properties such as birefringence, elastic constant, dielectric anisotropy, wider nematic temperature, and chemical stability. Still, proposals for new liquid crystal compounds or liquid crystal compositions are still required. Furthermore, because of its excellent display quality, active matrix type liquid crystal display devices have been put on the market for portable terminals, liquid crystal televisions, projectors, computers and the like. In the active matrix display method, a TFT (thin film transistor) or a metal insulator metal (MIM) is used for each pixel, and a high voltage holding ratio is emphasized in this method. In order to obtain a wider viewing angle characteristic, IP
Super TFT combined with S mode [Asia Display
'95 Digest, p. 707 1995] was proposed by Kondo et al. (Hereinafter, these active matrix display type liquid crystal display elements are collectively referred to as TFT-LCD.) To cope with such a display element, a new liquid crystal compound or liquid crystal composition such as that disclosed in 3129
No. 49, Japanese Patent Publication No. 5-501735, and the like have been proposed. A liquid crystal display device in which liquid crystal droplets are dispersed in a polymer is a bright and high-contrast liquid crystal device that does not require a polarizing plate or alignment treatment.
1, Japanese Patent No. 4,350,047, Japanese Patent Publication No. 61-502128, and Japanese Patent Application Laid-Open No. 62-2231. (Hereinafter, these liquid crystal display elements are collectively referred to as PDLC.) These optimize the individual refractive index of the liquid crystal material and the refractive index of the polymer,
There was a problem that a high voltage was required to obtain sufficient transparency. On the other hand, U.S. Pat. No. 5,30 is disclosed as a technology that enables low voltage driving, high contrast, and time division driving.
4,323, JP-A-1-198725,
A liquid crystal display device having a structure in which a liquid crystal material forms a continuous layer and a polymer substance is distributed in a three-dimensional network in the continuous layer is disclosed. (Hereafter, this liquid crystal display element is called PN-LCD
As a liquid crystal material for this purpose, European Patent No. 359,
No. 146 discloses a method for optimizing birefringence and dielectric anisotropy of a liquid crystal material, and JP-A-6-222320 discloses a technique for specifying an elastic constant of a liquid crystal material.
No. 573 discloses that a fluoro compound is used. However, there are problems such as high resistance value, excellent voltage holding ratio, low driving voltage, strong light scattering, high contrast ratio, fast response speed, and good temperature characteristics. New proposals are still being made.

The problem to be solved by the present invention is to improve the characteristics of the liquid crystal display element as described above, especially to reduce the change in display characteristics due to temperature. Specifically, it is to improve the temperature change of the drive voltage. More specifically, as a liquid crystal material that improves the temperature change of the driving voltage, for example, the following general formula (a-1)
~ (A-3)

Embedded image (Wherein, R represents an alkyl group or an alkoxy group). According to the present invention, the above-mentioned problems are further made preferable. Since this effect can be obtained even when a small amount of the compound represented by the general formula (I-1) according to the present invention is used, it can be obtained with almost no change in the physical properties of the liquid crystal material as a base. The present invention also provides a TN-LCD having improved electro-optical properties, using the liquid crystal composition as a constituent material.
It is to provide a liquid crystal display device such as STN-LCD, TFT-LCD or PN-LCD, PDLC and the like.

The present invention has been made in order to solve the above problems. The liquid crystal composition has a general formula (I-1)

Embedded image(Where R¹¹Is a linear alkyl having 1 to 10 carbon atoms
Group, alkoxy group or linear alkyl having 2 to 10 carbon atoms
X represents a phenyl group;¹¹, X¹²Are each independently the number of carbon atoms
1 to 10 linear alkyl groups, alkoxy groups, carbon atoms
A linear alkenyl group of the number 2 to 10, a hydrogen atom, a fluorine atom
Child, chlorine atom, -CF_Three, -OCF_ThreeOr -CN, Y
¹¹~ Y¹⁴Each independently represents a hydrogen atom or a fluorine atom
Then Z¹¹, Z¹²Are each independently a single bond, -COO-, -C
≡C-, -C_TwoH_Four-Or-C_FourH₈-Represents Z ¹³Is -O (C
H_Two)_k2-,-(CH_Two)_k3O- or-(CH_Two)_k4-Represents k2 ~
k4 represents an integer of 1 to 5; k1 represents 0 or 1;
¹¹Is 1,4-phenyl which may be substituted by a fluorine atom
Eneylene group, trans-1,4-cyclohexylene group
Represents the hydrogen atom of the cyclohexane ring in each compound
(H) may be replaced by a deuterium atom (D). )
A liquid crystal component comprising one or more compounds represented by
A compound containing A and having a dielectric anisotropy of +2 or more
Liquid crystal component B comprising 10 to 99.9% by weight,
Liquid crystal component comprising a compound having a dielectric anisotropy of ~ 2
C in an amount of 0 to 70% by weight, and the liquid crystal component B and the liquid crystal component
Characterized in that the total amount of C is 75 to 99.9% by weight.
Nematic liquid crystal composition. 2. The liquid crystal component A is represented by R in general formula (I-1).¹¹But
Ethyl, propyl, butyl, vinyl or buteni
And / or X¹¹, X¹²Are both
A compound represented by a nitrogen atom, and / or Y¹¹, Y¹²Is
A compound represented by a fluorine atom, and / or Z¹¹, Z¹²
Is a single bond, and / or Z¹³But -O
(CH_Two)_k2A compound represented by-and / or k2 is represented by 1
Characterized by containing 30 to 100% by weight of the compound to be prepared
2. The nematic liquid crystal composition according to the above 1, wherein 3. The liquid crystal component B has a general formula (II-1) to (II-4)

Embedded image (Wherein, R ^{21 to} R ²⁴ each independently represent 2 to 10 carbon atoms.
Linear alkyl group, alkenyl group or C _s H _{2s + 1} -O-
Represents C _t H _2t, s and t are each independently an integer of 1 to 5, X ²¹ to X ²⁴ are each independently a fluorine atom, a chlorine _{atom, -OCF 3, -OCHF 2, -CF} 3 Or -CN, Y
^{21 to} Y ²⁸ each independently represent a hydrogen atom or a fluorine atom, W ^{21 to} W ²⁴ each independently represent a hydrogen atom or a fluorine atom, Z ^{21 to} Z ²³ each independently represent a single bond, -COO -,
Represents —C ₂ H ₄ — or —C ₄ H ₈ —, and Z ²¹ is also —C≡C— or
—CH ＝ CH—, Z ²⁴ and Z ²⁵ each independently represent a single bond, —COO—, —C≡C— or —CF ＝ CF—, and ring A ²¹ represents a cyclohexane ring or benzene. Represents a ring,
m ^{1 to} m ⁴ each independently represent 0 or 1, and m ³ + m ⁴ represents 0
Or 1, and the hydrogen atom (H) of the cyclohexane ring in each compound may be substituted with a deuterium atom (D). 3. The nematic liquid crystal composition according to the above 1 or 2, further comprising a compound selected from the group of compounds represented by (1). 4. The liquid crystal component B is represented by the general formulas (II-1) to (II-4)
And / or a compound wherein R ^{21 to} R ²⁴ are an alkyl group or an alkenyl group having 2 to 5 carbon atoms, and / or a compound wherein X ^{21 to} X ²⁴ are a fluorine atom, a chlorine atom, —OCF ₃ or —CN. Or Z ²¹ in the compound of the general formula (II-1),
Z ²² is a single bond, a compound represented by —COO—, —C ₂ H ₄ — or —C ₄ H ₈ —, and / or Z ²⁴ in the compound of the general formula (II-2) is a single bond, —COO— Or a compound represented by -C-C- and / or a compound represented by formula (II-3) wherein Z ²⁵ contains a single bond or a compound represented by -C≡C- in an amount of 10 to 100% by weight. 4. The nematic liquid crystal composition according to the above 3, which is characterized in that: 5. The liquid crystal component C has a general formula (III-1) to (III-4)

Embedded image (Wherein, R ^{31 to} R ³⁴ each independently represent a linear alkyl group or alkenyl group having 2 to 7 carbon atoms, and R ^{35 to} R ³⁸
Are each independently a linear alkyl group having 1 to 7 carbon atoms,
Alkoxy group, a linear alkenyl group having 2 to 7 carbon atoms, represents alkenyloxy group or _{C u H 2u + 1 -O-} C v H 2v, u and v the each independently an integer of 1 to 5 Represents Y ³¹
Represents a hydrogen atom, a fluorine atom or —CH ₃ , and Y ³² and Y
³³ each independently represent a hydrogen atom or a fluorine atom, Z ³¹
To Z ³⁴ each independently represents a single _{bond, -COO -, - C 2 H} 4 - or
Represents —C ₄ H ₈ —, and Z ³¹ also represents —C≡C— or —CH ＝ CH—.
Wherein Z ³⁵ is a single bond, -C≡C-, -COO-,
-CH = NN-CH- or -CF = CF-; rings A ³¹ and A ³² each independently represent a cyclohexane ring or a cyclohexene ring; rings A ³³ and A ³⁴ each independently represent a cyclohexane ring Or n represents a benzene ring, n ^{1 to} n ⁵ each independently represent an integer of 0 or 1, n ⁴ + n ⁵ is 0 or 1, and a hydrogen atom (H) in a cyclohexane ring in each compound is a deuterium atom. (D) may be substituted. 5. The nematic liquid crystal composition according to the above 1, 2, 3 or 4, comprising a compound selected from the group of compounds represented by the formula: 6. The liquid crystal component C is a compound of the above general formula (III-1), wherein R ³¹ represents a straight-chain alkyl group or alkenyl group having 2 to 5 carbon atoms, and R ³⁵ represents a straight-chain alkyl group or alkenyl group having 1 to 5 carbon atoms. It represents linear alkyl group, an alkoxy group, a linear alkenyl group having 2 to 7 carbon atoms, an alkenyloxy group, ring a ³¹
Represents a cyclohexane ring, and when m ¹ is 0, a compound in which Z ³² is a single bond or —COO—, and / or m ¹ is 1
In the case of the above, the compound in which Z ³¹ and Z ³² are represented by a single bond is
6. The nematic liquid crystal composition according to the above item 5, wherein the composition contains 00% by weight. 7. It said liquid crystal component C, in said compound of general formula (III-2), R ³² represents a linear alkyl group or an alkenyl group having 2 to 5 carbon atoms, R ³⁶ is 1 to 5 carbon atoms directly chain alkyl group, an alkoxy group, a linear alkenyl group having 2 to 7 carbon atoms, represents alkenyloxy group, a case ring a ³² is a cyclohexane ring or cyclohexene ring of m ² is 0, bond Z ³³ is a single , -COO- or -C ₂ H ₄ - a compound represented by, and / or m ² is 1 when the ring a ³² is a cyclohexane ring, Z ³³ is a single bond or -C ₂ H ₄ - is represented by 7. The nematic liquid crystal composition according to the above item 5 or 6, wherein the composition contains 10 to 100% by weight of the compound. 8. The liquid crystal component C contains 10 to 100% by weight of a compound represented by the formula (III-3), wherein Z ³⁵ is represented by -C≡C-, -CH = NN = CH-. 8. The nematic liquid crystal composition according to the above item 5, 6 or 7, wherein 9. The liquid crystal composition is a compound having a core structure having four six-membered rings, and one or two or more compounds having a liquid crystal phase-isotropic liquid phase transition temperature of 100 ° C. or higher. 9. The nematic liquid crystal composition as described in any one of the above items 1 to 8, which comprises: 10. The liquid crystal composition has a dielectric anisotropy of 4 to 30, a birefringence of 0.08 to 0.33, and a temperature of 60C to 1C.
A nematic phase-isotropic liquid phase transition temperature of 80 ° C.,
10. The nematic liquid crystal composition according to any one of the above items 1 to 9, wherein the composition has a crystalline phase, a smectic phase or a glass phase-nematic phase transition temperature of -200 ° C to 0 ° C. 11. The liquid crystal composition has an induced helical pitch of 0.5 to 1
11. The nematic liquid crystal composition according to any one of the above 1 to 10, further comprising a compound having an optically active group having a thickness of 000 μm. 12. 12. An active matrix, twisted nematic or super twisted nematic liquid crystal display device using the nematic liquid crystal composition according to the above item 11. 13. 12. A light-scattering type liquid crystal display device having a dimming layer containing the liquid crystal composition according to any one of 1 to 11 and a transparent solid substance. 14． 14. The light-scattering liquid crystal display according to the above 13, wherein the liquid crystal composition forms a continuous layer, and the transparent solid substance is a light control layer in which a uniform three-dimensional network structure is formed in the continuous layer. apparatus. Was found as a means for solving the above-mentioned problem.

BEST MODE FOR CARRYING OUT THE INVENTION According to the present invention, the liquid crystal composition has the general formula (I-1)

Embedded image (Wherein, R ¹¹ represents a linear alkyl group having 1 to 10 carbon atoms, an alkoxy group or a linear alkenyl group having 2 to 10 carbon atoms, and X ¹¹ and X ¹² each independently represent a carbon atom. A linear alkyl group having 1 to 10 carbon atoms, an alkoxy group, a linear alkenyl group having 2 to 10 carbon atoms, a hydrogen atom (hereinafter represented by H), a fluorine atom (hereinafter represented by F), a chlorine atom (hereinafter Cl) ), -CF ₃ , -OCF ₃ or -CN;
^{11 to} Y ¹⁴ each independently represent a hydrogen atom or a fluorine atom; Z ¹¹ and Z ¹² each independently represent a single bond, -COO-, -C
Represents —C—, —C ₂ H ₄ — or —C ₄ H ₈ —, and Z ¹³ represents —O (C
_{H 2) k2 -, - (} CH 2) k3 O- or - (CH _{2) k4} - represents, K2～
k4 represents an integer of 1 to 5; k1 represents 0 or 1;
¹¹ represents a 1,4-phenylene group and a trans-1,4-cyclohexylene group which may be substituted by a fluorine atom (hereinafter, represented by F), and the hydrogen atom (H) of the cyclohexane ring in each compound is a heavy atom. It may be substituted by a hydrogen atom (D). ), Containing 10 to 99.9% by weight of a liquid crystal component B composed of a compound having a dielectric anisotropy of +2 or more. A liquid crystal component C comprising a compound having a dielectric anisotropy of 2 to +2 is contained in an amount of 0 to 70% by weight, and the total sum of the liquid crystal component B and the liquid crystal component C is 75 to 99.9% by weight. A nematic liquid crystal composition is provided. The liquid crystal component B according to the present invention has the general formulas (II-1) to (II-4)

Embedded image (Wherein, R ^{21 to} R ²⁴ each independently represent 2 to 10 carbon atoms.
Linear alkyl group, alkenyl group or C _s H _{2s + 1} -O-
C _t H _2t , s and t each independently represent an integer of 1 to 5, and X ^{21 to} X ²⁴ each independently represent a fluorine atom (hereinafter F
Represent), chlorine atom (hereinafter referred to as Cl), - OCF _3, -O
CHF _2, represents -CF ₃ or -CN, Y ²¹ ~Y ^{2 8} each independently represent a hydrogen atom or a fluorine atom, W ²¹ to ^W-24 is (expressed as follows H) each independently hydrogen atom or Z ^{21 to} Z ²³ each independently represent a single bond, —COO—, —C ₂ H ₄ — or —C ₄ H ₈ —, and Z ²¹ also represents —C ≡C— or —CH ＝ CH—, Z ²⁴ ,
Z ²⁵ is each independently a single bond, -COO-, -C≡C- or-
CF = CF-, ring A ²¹ represents a cyclohexane ring or a benzene ring, m ^{1 to} m ⁴ each independently represent 0 or 1, m ³ + m ⁴ represents 0 or 1, and cyclohexane in each compound is represented by A hydrogen atom (H) in the ring may be substituted with a deuterium atom (D). ) Can be contained. The liquid crystal component C
Has the general formulas (III-1) to (III-4)

Embedded image(Where R³¹~ R³⁴Each independently has 2 to 7 carbon atoms
Represents a linear alkyl group or an alkenyl group,³⁵~ R³⁸
Are each independently a linear alkyl group having 1 to 7 carbon atoms,
Alkoxy group, linear alkenyl having 2 to 7 carbon atoms
Group, alkenyloxy group or C_uH_{2u + 1}-OC_vH_2vThe table
U and v each independently represent an integer of 1 to 5,³¹
Represents a hydrogen atom (hereinafter referred to as H) and a fluorine atom (hereinafter referred to as F)
) Or -CH_ThreeAnd Y³²And Y³³Are each independently water
Elemental atom (hereinafter referred to as H) or fluorine atom (hereinafter referred to as F)
) And Z³¹~ Z³⁴Are each independently a single bond, -CO
O-, -C_TwoH_Four-Or-C_FourH₈-Represents Z³¹Is also -C≡C
-Or -CH = CH-;³⁵Is a single bond, -C
≡C-, -COO-, -CH = NN-CH- or -CF = C
F- represents a ring A³¹, A³²Are each independently cyclohexa
Ring A or cyclohexene ring;³³, A³⁴Are each
Independently represents a cyclohexane ring or a benzene ring;¹
~ N^FiveEach independently represents an integer of 0 or 1, and n^Four+ N^Five
Is 0 or 1, and the cyclohexane ring in each compound is
Is replaced with a deuterium atom (D)
May be. A compound selected from the group of compounds represented by)
Can be contained. Furthermore, the present invention
Matrix using a liquid crystal composition
Isted nematic or super twisted
De nematic liquid crystal display device, or the above liquid crystal composition
Scattering with light modulating layer containing objects and transparent solid substances
A liquid crystal display device is provided. An example of the present invention is described below.
Will be explained. The liquid crystal composition of the present invention has the general formula (I-1)
The liquid crystal component A comprising the compound represented by
Have. The compound represented by the general formula (I-1) is bent
It is characterized by its molecular structure. With this structural feature
When the liquid crystal component A is mixed with the liquid crystal composition, the elastic constant K₁₁
To reduce the driving voltage.
X¹², Y¹², Y¹⁴Is a polar group such as F, the molecular long axis direction
Tend to increase dielectric anisotropy,
The effect of reducing the pressure is increased. In addition, liquid crystal
Component A increases the temperature dependence of dielectric anisotropy,
It tends to be close to the temperature dependence of the sex constant. This allows
(Elastic constant / dielectric anisotropy)^1/2Temperature change
And the temperature dependence of the drive voltage can be reduced.
It has the feature of The liquid crystal composition of the present invention
Containing a liquid crystal component A comprising a compound of the general formula (I-1),
Liquid crystal component comprising a compound having two or more dielectric anisotropies
B containing 10 to 99.9% by weight and a dielectric constant of -2 to +2
A liquid crystal component C composed of a compound having anisotropy has a weight of 0 to 70
% And the sum of the liquid crystal component B and the liquid crystal component C is 75%.
効果 99.9% by weight has this effect
I found something. The liquid crystal component A is the above liquid crystal
When the components B and C are mixed with the liquid crystal material,
Low solid phase or smectic-nematic phase transition temperature
Lowering the temperature or increasing the storage time at low temperatures.
The indicated temperature range can be made wider. Such a view
From the viewpoint, the compounds represented by the general formulas (I-2) to (I-9)
A more preferred form of R¹¹Is ethyl group, propyl group
Compounds represented by butyl, vinyl or butenyl groups and
Or X¹¹, X¹²Is a compound represented by F and or Y¹¹,
Y¹²Is a compound represented by F and / or Z¹¹~ Z¹²Is a single bond
And / or Z ¹³Is -O (CH_Two)_k2-Represented
And / or compounds wherein k2 is 1 are preferred.
And more specifically represented by the general formulas (I-2) to (I-9)
Compounds are preferable, and the liquid crystal component A contains at least one compound
Nematic containing 30 to 100% by weight of the above compounds
Liquid crystal compositions are preferred. In addition, each compound is distilled, column
Remove impurities using purification, recrystallization, etc.
What was manufactured was used.

Embedded image

Embedded image One or more compounds of the general formula (I-1) can be contained as the liquid crystal component A, but the effect described above can be obtained even with one compound. The liquid crystal composition of the present invention containing the liquid crystal component A containing at least one kind of the compound represented by the general formula (I-1) includes TN-LCD, ST
A liquid crystal display device such as an N-LCD, a TFT-LCD, a PDLC, and a PN-LCD is made to have improved electro-optical characteristics, and has a more favorable temperature dependency particularly at a wide low temperature. The liquid crystal composition of the present invention contains, in addition to the liquid crystal component A, a liquid crystal component B containing one or more compounds having a dielectric anisotropy of +2 or more. The liquid crystal compound having a dielectric anisotropy larger than 2 described in the present invention has the following significance. The chemical structure of the liquid crystal compound is rod-shaped, and the central part is one to four.
Has a core structure having six six-membered rings, the six-membered ring located at both ends in the central portion long axis direction has a terminal group substituted at a position corresponding to the liquid crystal molecule long axis direction, and at both ends At least one of the terminal groups present is a polar group, that is, for example,-
CN, -OCN, -NCS, -F, -Cl, -NO 2, -CF 3,
The compound is -OCF ₃ or -OCHF ₂ . Thereby, the optical anisotropy of the liquid crystal layer can be set to a predetermined value,
It can be electrically driven, and the operating temperature range can be widened. As the liquid crystal component B, at least one compound having a dielectric anisotropy of +2 or more is required, and
Five ranges are preferred. Further, the dielectric anisotropy is +8 to +
It is preferable to appropriately select from among the compounds of 13, the compounds of +14 to +18, and the compounds of +18 or more, so that a predetermined driving voltage and response characteristics can be obtained. in this case,
It is preferable to mix at most 10 or less compounds having a dielectric anisotropy of +8 to +13, and +14 to +18.
It is preferable that at most 8 compounds be mixed in a range of at most 8, and that compounds of +18 or more are mixed at most 10 or less. Use of the liquid crystal component B as described above gives a more favorable effect to the temperature characteristics of the display characteristics. More specifically, it is preferable that the temperature dependency such as the driving voltage, the contrast relating to the steepness, and the response is more preferable. As the liquid crystal component B of the present invention, general formula (II)
It is preferable to contain 10 to 100% by weight of a compound selected from the compounds represented by -1) to (II-4). More preferred forms of the compounds represented by the general formulas (II-1) to (II-4) are compounds in which R ^{21 to} R ²⁴ are represented by an alkyl group or alkenyl group having 2 to 7 carbon atoms, and / or X ^{21 to} X ²⁴
Is preferably selected from compounds represented by F, Cl, —OCF ₃ , or —CN and contains at least one or more compounds. Further, in the general formula (II-2), Z ²⁴ is a single bond, a compound represented by —COO— or —C≡C—, and in the general formula (II-3), Z ²⁵ is represented by —C≡C—. It is preferable to contain a compound. Particularly preferred and more specific compounds represented by formulas (II-1) to (II-4) include compounds represented by formulas (II-1a) to (II-
4d) is shown below. In addition, each compound was used after removing impurities by a method such as distillation, column purification, recrystallization, etc. and sufficiently purified. The liquid crystal component B containing these compounds has a feature of being well mixed with the liquid crystal component A, which is an essential component, and is particularly useful for adjusting the drive voltage according to the purpose and improving its temperature dependence or response. is there. In particular, the general formulas (II-1a) to (II-1h) and the general formulas (II-2a) to (II-4d)
Is excellent in this effect, and this effect can be obtained even with a small content of 1 to 25%.

Embedded image

Embedded image

Embedded image

Embedded image(Where R^{twenty one}~ R^{twenty four}, X^{twenty one}~ X^{twenty four}, Y^{twenty one}~ Y²⁸, W^{twenty one}~ W
^{twenty four}Represents the same meaning as described above. A more preferable embodiment will be specifically described in detail. R^{twenty one}Is charcoal
An alkyl group having 2 to 5 element atoms or CH_Two= CH- (CH_Two)
_pCompounds which are alkenyl groups (p = 0, 2) are preferred.
Compounds of the general formulas (II-1a) and (II-1d) have this group
And the liquid crystal component B has an alkenyl group.
By incorporating at least one compound, the viscosity
And viscoelasticity can be reduced. Similarly, R^{twenty two}Charcoal
An alkyl group having 2 to 5 atoms, an alkenyl group described above.
Compounds represented by general formulas (II-2a), (II-2d) and
The compounds (II-2f) and (II-2g) may have this group.
preferable. X^{twenty one}~ X^{twenty four}Is F, Cl, -OCF_Three, -CN
It is preferable to use a lot of compounds, and fast response is important.
X^{twenty one}~ X^{twenty four}Is F, -OCF_ThreeThe general formula (II-1
a), (II-1d), (II-2a), (II-2c), (II-2d),
Compounds (II-2g) and (II-3a) are frequently used in liquid crystal component B
Is preferable, when a higher birefringence is required
Is X^{twenty two}~ X^{twenty four}Is Cl, -OCF_Three, -CN is a general formula (II
-2a) to (II-4d) to be frequently used in liquid crystal component B
Is preferable, and when a lower drive voltage is required, X^{twenty one}But
-Y in CN^{twenty one}Is H or F, the general formulas (II-1a) to (II-1a)
g) a compound of the formula X^{twenty two}Is F, Cl, -CN and Y^{twenty three}Is H or F
A compound of the general formulas (II-2a) to (II-2f),^{twenty three}But
Y in F, Cl, -CN^{twenty five}Is a general formula (II-3a) or
Compound of (II-3c), X^{twenty four}Is F, Cl, -CN and Y²⁷Is F
Compounds of general formulas (II-4a) to (II-4d)
It is preferable to frequently use B. In particular, active mat
Rix display, TFT-LCD, MIM-LCD, IPS mode
Combined super TFT and active matrix technology
Light-scattering type liquid crystal display device having (for example, a liquid crystal material and
Display device with a dimming layer containing a transparent solid substance)
Is X^{twenty one}~ X^{twenty four}It is preferable to frequently use a compound in which
Good. Fast response in general formulas (II-1) to (II-4)
When importance is placed on Y^{twenty one}~ Y²⁸Is H and / or W^{twenty one}~ W^{twenty four}
Can be used frequently, and the temperature of the driving voltage can be increased.
Y to improve degree dependency^{twenty one}~ Y²⁸Is F, W^{twenty one}~ W^{twenty four}
Is F, particularly preferably Y^{twenty one}, Y^{twenty three}, Y^{twenty five}, Y
²⁷, W^{twenty one}~ W^{twenty four}It is preferable to use a compound in which
Well, W in this^{twenty one}And W^{twenty two}If F is Y^{twenty four}Is H
By selecting a certain compound, the compatibility can be further improved and the general formula
W for (II-3)^{twenty three}And / or W^{twenty four}Is a compound wherein F is
If selected, the compatibility can be further improved. In general formula (II-1)
And Z ^{twenty one}And Z^{twenty two}One of them is preferably a single bond compound
In order to improve the responsiveness and compatibility at low temperature,
Compound and -COO-, -C_TwoH_Four-, -C_FourH₈-Combination of compounds
It is preferable to use the liquid crystal component B described above. Good birefringence
If it is required to be larger, the general formula (II-2)
Z in (II-3)^{twenty four}, Z^{twenty five}A compound of the formula -C≡C-, and
Or X in the general formula (II-4)^{twenty four}Liquid crystal of CN compound
It is preferred that the component B is frequently used. General formula (II-1),
M in (II-2) and (II-4)¹~ M^FourIs 0, and
M in general formulas (II-1) and (II-2)¹, M^TwoIs 1 compound
, M in general formula (II-4)^Three+ M^FourIs the compound of 1 and
Or the mixing ratio of the compound of general formula (II-3) with the liquid crystal component B
Can be selected from 0 to 100 to 100 in a timely manner
Higher nematic phase-isotropic liquid phase transition temperature
If necessary, m in general formulas (II-1) and (II-2)
¹, M^TwoIs 1, a compound of the general formula (II-3) and / or
M in the general formula (II-4)^Three+ M^FourFrequently use one compound
Preferably. Cyclo of general formulas (II-1) and (II-2)
Compound where hydrogen atom in hexane ring is replaced by deuterium atom
Can be used, but this compound is used in the liquid crystal composition.
Adjustment of elastic constant and adjustment of pretilt angle corresponding to alignment film
Compounds substituted with deuterium atoms because they are useful for
Is preferably contained in at least one kind. Above
The effect of the liquid crystal component B described above includes the effect of the liquid crystal component C described later.
It can be obtained even when the prevalence is very small.
For the purpose of particularly lowering the driving voltage, the liquid crystal component C
The content can be 10% by weight or less. This place
In this case, it is preferable to make the viscosity of the liquid crystal component C as low as possible.
More preferably, the drive voltage is hardly or slightly increased.
Stopping and an improvement in response speed can be obtained efficiently. For example,
This effect is achieved with liquid crystal component B when liquid crystal component C is small.
As a method for causing the odor, general formulas (II-1) to (II-4)
And X^{twenty one}~ X^{twenty four}Is F, Cl, -OCF_ThreeA compound or
Y ^{twenty one}~ Y^{twenty four}Wherein Z is F or Z^{twenty four}, Z^{twenty five}But -COO
-, -C≡C-, or m¹Of the compound where is 1
It is preferable to include any of these compounds in the liquid crystal component B.
No. In particular, in the general formulas (II-1) to (II-4), X^{twenty one}~
X^{twenty four}Is F, Cl, -OCF_Three, -CN, and / or Y^{twenty one}~ Y^{twenty three}
Is preferably F. The liquid crystal composition of the present invention,
In addition to the liquid crystal component A, which is an essential component, a dielectric constant of -2 to 2
A liquid crystal component C comprising a compound having anisotropy is at most 7
It is preferable to contain 0% by weight. Described in the present invention-
Preferred liquid crystal compounds having a dielectric anisotropy of 2 to 2
The following are shown. That is, the liquid crystal compound
Has a rod-like chemical structure with one to four hexagons in the center.
It has a core structure with a member ring, and both ends in the central part long axis direction
Is located in the position corresponding to the long axis direction of the liquid crystal molecule.
And has both terminal groups present at both ends.
Is a non-polar group, that is, for example, an alkyl group,
Coxy, alkoxyalkyl, alkenyl, al
A compound that is a kenyloxy group or an alkanoyloxy group
is there. The liquid crystal component C is composed of at least one kind and no more than 20 kinds.
Preferably, the composition is in the range of 2 or more and 12 or less
Is more preferable. As the liquid crystal component C of the present invention,
Selected from compounds represented by formulas (III-1) to (III-4)
Preferably contains 10 to 100% by weight of the compound
No. Particularly preferred represented by formulas (III-1) to (III-4)
Formulas (III-1a) to (III-4e)
Shown in The liquid crystal component C containing these compounds is generally
Mix well with liquid crystal component A containing the compound of formula (I)
Characteristic, useful for improving the nematic phase at low temperatures
It is for.

Embedded image

Embedded image

Embedded image(Where R³¹~ R³⁸, Y³¹~ Y³³Is the same as above
Represent meaning. ) As the liquid crystal component C, general formulas (III-1) to
By containing the compound of (III-4), viscosity and viscoelasticity can be reduced.
Can be reduced and the specific resistance and voltage holding ratio are relatively high
It has the feature of The viscosity of the liquid crystal component C is as low as possible.
It is preferable that the viscosity is as low as possible.
cp or less, more preferably 30 cp or less, and 2
0 cp or less is more preferable, and 15 cp or less is particularly preferable.
No. As the liquid crystal component C, any of the general formulas (III-1) to (III-4)
More preferred compounds are represented by the general formulas (III-1a) to (III-3).
a), (III-3c) to (III-3g), (III-3i), (III-4
a), (III-4d) to (III-4e). Also, R³¹~ R
³⁴Is a linear alkyl group having 2 to 5 carbon atoms or CH _Two= C
H- (CH_Two)_q(q = 0, 2) a compound which is an alkenyl group
Liquid crystal component C containing at least one or more of
Effect can be obtained. More particularly, general formulas (III-1a), (II
Compounds of I-1d), (III-2a) and (III-3i), Y³¹Is hydrogen
Compounds of the general formulas (III-3c) to (III-3f),
Or R³⁸A compound of the general formula (III-4a), wherein
Can obtain this effect even if it is contained as small as 3 to 30%
Can be used to improve the response speed. For example, STN-LCD
Useful for Due to the effects described above, the liquid crystal component C contains
More preferred compounds to be possessed are those represented by the general formula (III-1)
In the compound, R³¹Is a linear alkyl having 2 to 5 carbon atoms
Represents a kill group or an alkenyl group,³⁵Has 1 to 1 carbon atoms
4, a linear alkyl group, an alkoxy group, an alkenyl group,
Represents an alkenyloxy group, and represents a ring A³¹Is the cyclohexane ring
And n¹Is 0, Z³²Is a single bond or -COO-
Yes, n¹If is 1, Z ³¹, Z³²Is represented by a single bond
A compound represented by the general formula (III-2):
³²Is a linear alkyl group or alkenyl having 2 to 5 carbon atoms
R³⁶Is a linear alkyl having 1 to 4 carbon atoms
Group, alkoxy group, alkenyl group, alkenyloxy group
And n^TwoIs 0, ring A³²Is cyclohexane ring
Is a cyclohexene ring; Z³³Is a single bond, -COO- or
Is -C_TwoH_Four-N^TwoIs 1, the ring A³²Is cyclohe
A xan ring, Z³³Is a single bond or -C_TwoH_Four-Represented by
Compound. Compound of general formula (III-3i) related to the present invention
For example, Japanese Patent Application Laid-Open No. 54-87688
Mentioned in the newsletter. However, Japanese Patent Application Laid-Open No. 54-87688
The composition disclosed in Japanese Patent Publication No.
Needed. Regarding response characteristics, for example, TN
-The response characteristic of LCD is less than 60msec, preferably 50msec
Or less, more preferably 40 msec or less, particularly preferably 3 msec or less.
0msec or less is currently required and needs improvement
You. The present invention has solved the above problems, and has been described in detail.
For example, due to finding each of the following measures
Things. (1) Excessive content of general formula (III-3i)
Do not use too much and keep it at 50% by weight or less. (2) Liquid crystal component
The compound constituting B is characterized by the content of general formula (III-3i)
If there are many, use 4 or more types. (3) Cyclohexa
Liquid crystal component B contains at least one compound having a ring
thing. In this case, the compound of the general formula (II-1) is more preferable.
Results were shown. (4) Formulas (II-2) and (II-3)
When the compound is used, the compound of the general formula (II-1) is used in combination
Showed particularly favorable results. (5) Liquid crystal component C
The constituent compound has a particularly high content of the general formula (III-3i).
If not, contain. (6) When the liquid crystal component B has the general formula (II)
-2), when the compound of (II-3) is contained, the liquid crystal component C
It was found that it is preferable to use even a small amount in combination. This place
In this case, the compounds of the general formulas (III-1) to (III-3) are more preferred.
It showed good results. The liquid crystal component C of the present invention has the general formula (II)
I-1), general formula (III-2), general formula (III-3), general formula (I
The compound represented by II-4) can be composed independently of each other.
Can be represented by the general formula (III-1) and / or (III-2)
Compound and represented by general formula (III-3) and / or general formula (III-4)
Compounds, especially Z³⁵Is -C≡C-, -CH = NN-CH
The liquid crystal composition can be obtained by using the compound represented by-
The birefringence of an object can be easily optimized according to the application.
Wear. Compounds of general formulas (III-1) and (III-2), examples
For example, compounds of general formulas (III-1a) to (III-2f) are frequently used
The birefringence can be reduced by
Reduction of color unevenness of display device, improvement of viewing angle characteristics, contrast
The increase in the ratio can be easily achieved. Also, the general formula
Compounds of (III-3), for example, of the general formulas (III-3a) to (III-3)
a compound of j) or a compound of general formula (III-4), for example
If the compounds of general formulas (III-4a) to (III-4e) are frequently used,
With this, the birefringence can be increased, and the liquid crystal layer
It is possible to manufacture a thin liquid crystal display element of 5 μm.
Wear. The liquid crystal composition of the present invention has a
If you want faster responsiveness,
be able to. If a medium drive voltage is intended,
The liquid crystal composition of the invention has a dielectric anisotropy in the range of 3 to 15.
And a viscosity at 20 ° C. of 8 to 20 c. p. In the range
Preferably. In this case, the viscosity of only the liquid crystal component C is
25c. p. The following is preferred, and 15c. p. Less than
Preferably 10c. p. The following are particularly preferred. And especially
When a low drive voltage is intended, the liquid crystal composition of the present invention is used.
Preferably has a dielectric anisotropy in the range of 15 to 30.
And the range of 18 to 28 is particularly preferred. Currently, TN-LCD,
The alignment film used for STN-LCD or TFT-LCD is
Liimide type is widely used, such as LX1400, SE
150, SE610, AL1051, AL3408, etc. are used. Orientation
Film specifications include liquid crystal display characteristics, display quality, reliability, and production.
Properties are closely related, and for liquid crystal materials, for example,
The tilt angle characteristics are important. The magnitude of the pretilt angle is
To obtain desired liquid crystal display characteristics and uniform orientation,
Need to adjust. For example, when the pretilt angle is large
Instability is likely to occur when alignment is small.
The measured characteristics will not be satisfied. The present inventors
Liquid crystal materials with larger and smaller tilt angles
Have been found to be sorted
The desired liquid crystal display characteristics and uniform orientation
To achieve from the fee. This technology is
It can be applied to light. For example, the liquid crystal component B has the general formula (II-
When 1) to (II-4) are contained, the results are as follows. Yo
The larger pretilt angle is R^{twenty one}Is an alkenyl group, X^{twenty one}But
F, Cl, -CN, Y^{twenty one}, Y^{twenty two}Is a compound of F and / or R^{twenty one}
Is an alkyl group, X^{twenty one}Is F, Cl, -CN, Z^{twenty two}But -C_TwoH_Four
-, -C_FourH₈-Obtained by increasing the content of the compound
And the smaller pretilt angle is R^{twenty one}Is an alkenyl group,
C_sH_{2s + 1}-OC_tH_2t, X^{twenty one}Is F, Y^{twenty one}Is F, Y^{twenty two}Is H
And / or Z^{twenty two}Increases the content of -COO- compounds
Obtained by making In general formulas (II-1) and (II-2)
Hydrogen atoms on the cyclohexane ring
Compound, depending on the substitution position, the pretilt
Enables a wide range of corner adjustments. Such an effect, for example,
To obtain a larger pretilt angle, the above-mentioned compound
From 10 to 40% by weight or the total amount of the liquid crystal composition.
Almost can be obtained by containing more than this.
The content of each liquid crystal component in the nematic liquid crystal composition of the present invention
The weight can be as follows. The liquid crystal component A is 0.1 to 2
In the range of 5% by weight, but in the range of 0.5 to 15% by weight.
Preferably, the range of 1 to 10% by weight is more preferable. liquid crystal
Component B is in the range of 10-99.9% by weight, but 25%.
To 90% by weight, preferably 25 to 80% by weight.
Enclosures are more preferred. The liquid crystal component C is at most 70% by weight.
But preferably in the range of 3 to 65% by weight.
More preferably in the range of 60 to 60% by weight, and more preferably 10 to 55% by weight.
Is more preferable. Compound represented by general formula (I-1)
The content of the substance is preferably 8% by weight or less by itself,
The above is preferably composed of two or more kinds, and the general formula (I-
2) Compounds represented by (I-9) with respect to liquid crystal component A
The content is in the range of 50 to 100% by weight,
A range of 100% by weight is preferred. General formulas (II-1) to (II
-4) or compounds represented by general formulas (II-1a) to (II-
The content of the compound represented by 4d) is 30% by weight or less by itself.
Is preferably lower, more preferably 25% by weight or less,
The upper part is preferably composed of two or more types.
The content ratio is in the range of 10 to 100% by weight,
It is preferably in the range of 50 to 100% by weight, and 75 to 100% by weight.
The range of the amount% is more preferable. General formulas (III-1) to (III-
The compound represented by 4) or the general formulas (III-1a) to (III
-4e) The content of the compound represented by 30% by weight alone
Or less, more preferably 25% by weight or less.
The above is preferably composed of two or more types.
Is in the range of 10 to 100% by weight.
Is preferably in the range of 50 to 100% by weight, and 75 to 10% by weight.
A range of 0% by weight is more preferred. Crystal phase or smectic
Phase transition temperature is preferably −10 ° C. or lower.
Below, more preferably −20 ° C. or lower, particularly preferably −3 ° C.
0 ° C. or less. Nematic phase-isotropic liquid phase transition temperature
Is at least 60 ° C, preferably at least 70 ° C, more preferably
Ranges from 80C to 130C. Liquid crystal composition of the present invention
Is required to have a dielectric anisotropy of 3 or more, and is in a range of 4 to 40.
Is preferable, and when high-speed response is important, the range of 4 to 16 is preferable.
17-30 if the enclosure requires a lower drive voltage
Is preferable. Small or medium birefringence
Is preferably in the range of 0.08 to 0.18, and larger
The birefringence is preferably in the range of 0.18 to 0.33. This
The characteristics of a nematic liquid crystal composition such as
Tricks, twisted nematic or soot
Used for per twisted nematic liquid crystal display
Useful for The nematic liquid crystal composition has a high speed
Useful for responsive TN-LCD and STN-LCD,
Birefringence between the liquid crystal layer and the retardation plate without using a filter layer
Useful for liquid crystal display devices capable of color display
It is a transparent and reflective liquid crystal display device.
Can be used. This liquid crystal display element has a transparent electrode
A substrate having a layer and at least one of which is transparent,
The molecules of the nematic liquid crystal composition are twisted between the substrates.
Direction, select from 30 ° to 360 ° according to the purpose
Can be selected in the range of 90 ° to 270 °.
Is preferably in the range of 45 ° to 135 ° or 180 °
It is particularly preferred to select within the range of -260 °. this
Therefore, the liquid crystal composition of the present invention has an induced helical pitch of 0.5
Contains a compound having an optically active group of up to 1000 μm
Can be done. Orientation provided on transparent electrode substrate
The pretilt angle obtained by the film ranges from 1 ° to 20 °.
It is preferable to select in a box, and the torsion angle is 30 ° to 10 °.
At 0 °, a pretilt angle of 1 ° to 4 ° is preferable,
2 ° to 6 ° pretilt angle is preferred for ° to 180 °
Pretilt of 3 to 12 degrees for 180 to 260 degrees
Angles are preferred, and between 260 ° and 360 °, between 6 ° and 20 °.
Pretilt angles are preferred. The liquid crystal composition of the present invention has the above
In addition to the compounds represented by the general formulas (I-1) to (III-4),
As a liquid crystal compound, to improve the properties of the liquid crystal composition
Recognized normal nematic liquid crystal, smectic liquid crystal,
A cholesteric liquid crystal or the like may be contained. example
For example, a compound having a core structure having four six-membered rings,
The compound has a liquid crystal phase-isotropic liquid phase transition temperature of 100 ° C. or lower.
Whether to contain one or more compounds having the above
it can. However, these compounds are used in large quantities
This means that the properties of the nematic liquid crystal composition are reduced.
Therefore, the amount of addition depends on the nematic liquid crystal composition to be obtained.
It is limited according to the characteristics. The present inventors have
The liquid crystal composition has at least one transparent electrode layer
Has a light control layer sandwiched between two transparent substrates,
Light scattering type in which optical layer contains liquid crystal material and transparent solid material
We have found that liquid crystal displays also have advantageous display characteristics.
I did. The present inventors have disclosed in JP-A-6-222320.
The relationship between the physical properties of the liquid crystal material and the display characteristics of the liquid crystal display
It has been shown that the relationship is represented by the following equation (VI).

(Equation 1) Vth represents a threshold voltage, ¹ Kii and ² Kii represent elastic constants, ii represents 11, 22, or 33, Δε represents dielectric anisotropy, and <r> is a transparent solid. A represents the average gap distance at the material interface, A represents the anchoring energy of the transparent solid substance with respect to the liquid crystal molecules, and d represents the distance between the substrates having the transparent electrodes. This equation means that the regulating force exerted on the liquid crystal molecules by the transparent solid interface changes depending on the ratio between the elastic constant ¹ Kii and the anchoring energy A. In particular, the effect is larger than the actual average gap distance <r>. It shows that the driving voltage is effectively reduced by an amount of ¹ Kii / A, thus effectively reducing the driving voltage. This relationship can be applied to the present invention. More specifically, the following is preferable. By forming a transparent solid substance from a polymerizable composition containing a bifunctional monomer and a monofunctional monomer as a polymer-forming compound, a transparent solid substance is formed in the process of forming the transparent solid substance from the polymer-forming compound. It is considered that the shape of the conductive solid substance forms a more uniform structure, and the properties of the interface with the liquid crystal material can be manipulated. In the liquid crystal composition of the present invention, the liquid crystal component A composed of the compound of the general formula (I-1) characterized by a bent molecular structure has the effect of lowering the driving voltage by reducing the elastic constant ² Kii. Have. The liquid crystal component A is
This has the effect of increasing the temperature dependence of the dielectric anisotropy, canceling the temperature change of the dielectric anisotropy and the elastic constant ² Kii, and reducing the temperature dependence of the driving voltage. The liquid crystal material used in the present invention is also useful for display in which liquid crystal droplets in which a liquid crystal material is microencapsulated between two substrates having a transparent electrode layer are dispersed in a transparent solid substance. There is expected. The transparent solid substance formed between the substrates may be in the form of fibers or particles, or may be in the form of a film in which liquid crystal materials are dispersed in the form of droplets, but those having a three-dimensional network structure may be used. More preferred.
Also, the liquid crystal material preferably forms a continuous layer,
The formation of a disordered state of a liquid crystal material is important for forming an optical interface and causing light scattering. The average diameter of the shape of the three-dimensional network structure formed from such a transparent solid material is too large or too small compared to the wavelength of light. The range is preferably from 2 to 2 μm. Further, the thickness of the light control layer is preferably in the range of 2 to 30 μm, and particularly preferably in the range of 5 to 20 μm, depending on the purpose of use. The light-scattering type liquid crystal display of the present invention manufactured in this way achieves a drivability with less temperature dependence, thereby having characteristics required for, for example, an active matrix system. The liquid crystal display of the present invention is, for example, a projection display device or a direct-view type portable terminal display (Personal).
Digital Assistance).

EXAMPLES The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. Further, “%” in the compositions of the following examples means “% by weight”. The chemical stability of the composition was measured by placing 2 g of the liquid crystal composition in an ampoule tube, performing a process of purging with nitrogen after degassing in a vacuum, and performing a heating promotion test at 150 ° C. for 1 hour. The specific resistance or voltage holding ratio was measured. The characteristics measured in the examples are as follows. T _NI : Nematic phase-isotropic liquid phase transition temperature (° C.) T → _N : Solid phase or smectic phase-nematic phase transition temperature (° C.) Vth: Threshold value when a TN-LCD having a cell thickness of 6 μm is formed. Voltage (V) γ: ratio of saturation voltage (Vsat) to Vth Δε: dielectric anisotropy Δn: birefringence (Example 1)

Embedded image Was prepared, and various properties of the composition were measured. The results were as follows. T _NI : 98.7 ° C. T → _N : −70. ° C Vth: 0.92 Vγ: 1.20 Δε: 27.2 Δn: 0.137 A chiral substance “S-81” was added to this nematic liquid crystal composition.
1 "(manufactured by Merck) was added to prepare a mixed liquid crystal. On the other hand, an alignment film is formed by rubbing an organic film of “Sun Ever 610” (manufactured by Nissan Chemical Industries, Ltd.) on the opposing flat transparent electrode,
An STN-LCD display cell having a twist angle of 240 degrees was manufactured. The mixed liquid crystal was injected into this cell to construct a liquid crystal display, and the display characteristics were measured. As a result, a liquid crystal display device having a low driving voltage, a small temperature dependency of 0.1 mV / ° C., and exhibiting STN-LCD display characteristics excellent in high time division characteristics was obtained. The chiral substance is composed of a specific helical pitch P of the mixed liquid crystal due to the addition of the chiral substance and a cell thickness d of the display cell.
Was added so that Δn · d = 0.85 and d / P = 0.50. STN-LCD display characteristics at a twist angle of 240 degrees Vth: 0.98 Vγ: 1.017 Δ (Vth) / Δ (T): 0.1 mV / ° C (T = 5
(Range of -40 ° C.) In order to show the superiority of the present invention, a mixed liquid crystal (b-1) was prepared in which the liquid crystal component A contained in the nematic liquid crystal composition (2-1) was replaced with another compound. Specifically, the formula (I-
The compound of 8) is replaced by a compound of the formula (a-3) having an excellent effect of reducing driving voltage and improving its temperature dependency. The results were as follows.

Embedded image T _NI : 98.3 ° C. T → _N : 0. ° C Vth: 0.89 Vγ: 1.20 Δε: 27.2 Δn: 0.134 STN using the mixed liquid crystal (b-1) in the same manner as in the nematic liquid crystal composition (2-1). -LCD was manufactured. STN-LCD display characteristics with a twist angle of 240 degrees Vth: 0.99 V γ: 1.014 Δ (Vth) / Δ (T): 1.3 mV / ° C (T = 5
Comparing the characteristics, the liquid crystal composition of the present invention improves the T → _N and reduces the temperature dependence of the threshold voltage by 90% with a small amount of the liquid crystal component A of 4%. It became clear that there was. In general, a compound having a fluoro group has a higher threshold voltage than a compound having a cyano group. In the case of the present invention, since they were almost the same, it was shown that the liquid crystal component A was useful for reducing the driving voltage. (Example 2)

Embedded image Was prepared, and various properties of the composition were measured. The results were as follows. _{T NI: 99.1 ℃ Vth: 2.02} V △ ε: 7.1 △ n: 0.169 chiral substance "S-81 in the nematic liquid crystal composition
1 "(manufactured by Merck) was added to prepare a mixed liquid crystal. On the other hand, an alignment film is formed by rubbing an organic film of “Sun Ever 610” (manufactured by Nissan Chemical Industries, Ltd.) on the opposing flat transparent electrode,
An STN-LCD display cell having a twist angle of 240 degrees was manufactured. The mixed liquid crystal was injected into this cell to construct a liquid crystal display, and the display characteristics were measured. As a result, a liquid crystal display device having a low driving voltage, a small temperature dependency of 0.1 mV / ° C., and exhibiting STN-LCD display characteristics excellent in high time division characteristics was obtained. The chiral substance is composed of a specific helical pitch P of the mixed liquid crystal due to the addition of the chiral substance and a cell thickness d of the display cell.
Was added so that Δn · d = 0.85 and d / P = 0.50. STN-LCD display characteristics with a twist angle of 240 degrees Vth: 2.30 Vγ: 1.04 Δ (Vth) / Δ (T): 1.3 mV / ° C (T = 5
Response range (τr = τd): 17.1 msec (static drive) 85.0 msec (1/240 duty drive) In order to show the superiority of the present invention, the nematic liquid crystal composition (2-2) Liquid crystal (b-
2) was prepared, and an STN-LCD using the mixed liquid crystal (b-2) was prepared in the same manner as in the nematic liquid crystal composition (2-2). STN-LCD display characteristics with a twist angle of 240 degrees Vth: 2.65 Vγ: 1.04 Δ (Vth) / Δ (T): 3.3 mV / ° C. (T = 5
Comparison of the characteristics revealed that the liquid crystal composition of the present invention reduced the temperature dependence of the threshold voltage by 60% by 7% of the liquid crystal component A. The liquid crystal component A
Has been shown to be useful for reducing the drive voltage. These effects were also obtained in the nematic liquid crystal composition of the present invention in which the compounds of formulas (I-2) to (I-7) and (I-9) were added to the mixed liquid crystal (b-2) at 7%. . (Example 3)

Embedded image A nematic liquid crystal composition (2-3) was prepared, and various characteristics of the composition were measured. The results were as follows. T _NI : 93.0 ° C. T → _N : −20. ° C Vth: 1.94 Vγ: 1.13 Δε: 8.5 Δn: 0.239 Specific resistance before test: 9.0 × 10 ¹¹ Ω · c
m Specific resistance after heating acceleration test: 6.4 × 10 ¹¹ Ω · c
m Voltage holding ratio before test: 98.8% Voltage holding ratio after heating acceleration test: 98.2% This nematic liquid crystal composition is described in the literature “High-speed liquid crystal technology”.
(P. 63, published by CMC Co., Ltd.), which shows a value close to the limit value of 1.12 which is the limit value of the optical steepness of the liquid crystal display. It can be understood that it is useful for driving. Using this nematic liquid crystal composition, a TN-LCD having a cell thickness d of 2.1 μm was constructed and its display characteristics were measured. As a result, the threshold voltage was 1.7.
A liquid crystal display device having a response speed of 9 V and a response speed of 2.1 msec was obtained. Since the nematic liquid crystal composition has a high specific resistance and a high voltage holding ratio after the heating acceleration test, it can be understood that the composition is thermally stable. Further, a new nematic liquid crystal composition of the present invention using this composition as a basic constituent material was prepared, and an active matrix liquid crystal display device using the same was prepared. Was confirmed. Furthermore, in the same manner, another nematic liquid crystal composition of the present invention using this composition as a basic constituent material was prepared, and a twisted nematic and a super twisted nematic liquid crystal display device were prepared. It was confirmed that the product was excellent without flicker. (Example 4)

Embedded image Was prepared, and various properties of the composition were measured. The results were as follows. T _NI : 75.6 ° C. T → _N : −40. ° C Vth: 1.74 Vγ: 1.15 Δε: 8.2 Δn: 0.215 (Example 5)

Embedded image Was prepared, and various properties of the composition were measured. The results were as follows. _TNI : 65.1 ° C T → _N : −70. ° C Vth: 1.22 Vγ: 1.13 Δε: 14.5 Δn: 0.18 This nematic liquid crystal composition is described in the literature “High-speed liquid crystal technology”.
(P. 63, published by CMC Co., Ltd.), which shows a value close to the limit value of 1.12 which is the limit value of the optical steepness of the liquid crystal display. It can be understood that it is useful for driving. (Example 6)

Embedded image A nematic liquid crystal composition (2-6) was prepared, and various properties of the composition were measured. The results were as follows. T _NI : 74.3 ° C. T → _N : −40. ° C Vth: 1.61 Vγ: 1.13 Δε: 10.7 Δn: 0.107 This nematic liquid crystal composition has a high response speed at low temperatures, and is described in the literature “High-speed liquid crystal technology” (page 63, ( (Published by CMC Co., Ltd.), which is close to the limit value of 1.12 which is the limit value of the optical steepness of the liquid crystal display. Therefore, this liquid crystal composition is useful for high time division driving. I can understand. (Example 7)

Embedded image A nematic liquid crystal composition (2-7) was prepared, and various properties of the composition were measured. The results were as follows. T _NI : 90.6 ° C. T → _N : −70. ° C Vth: 1.09 V γ: 1.30 Δε: 8.7 Δn: 0.098 Specific resistance before test: 4.3 × 10 ¹² Ω ·
cm Specific resistance after heating acceleration test: 9.9 × 10 ¹¹ Ω ·
cm Voltage holding ratio before the test: 99.2% Voltage holding ratio after the heating acceleration test: 98.8% This nematic liquid crystal composition has high specific resistance and voltage holding ratio after the heating acceleration test, so that it is stable to heat. I understand that there is. Further, a new nematic liquid crystal composition of the present invention using this composition as a basic constituent material was prepared, and an active matrix liquid crystal display device using the same was prepared. Was confirmed. Furthermore, in the same manner, another nematic liquid crystal composition of the present invention using this composition as a basic constituent material was prepared, and a twisted nematic and a super twisted nematic liquid crystal display device were prepared. It was confirmed that the product was excellent without flicker. (Example 8) A light-scattering type liquid crystal display using the liquid crystal compositions of (2-3) and (2-4) will be described in more detail below.
However, the invention is not limited to these examples. 80% of the liquid crystal composition as a liquid crystal material,
13.86% of “HX-220” (manufactured by Nippon Kayaku) and 5.9 of lauryl acrylate as polymer-forming compounds.
4%, 2-hydroxy-2-methyl- as a polymerization initiator
1-phenylpropan-1-one was mixed at a ratio of 0.2% to prepare a light control layer forming material in a uniform solution. This light modulating layer forming material was placed in a 50 × 50 mm empty cell manufactured using two ITO electrode glass substrates with spacers having an average particle diameter of 10 μm interposed between the uniform solution and the transition temperature of the solution.
Vacuum was injected under high temperature. This is passed at a speed of 3.5 m / min under a metal halide lamp (80 W / cm2) while maintaining the temperature at 3 ° C. higher than the transition temperature of the homogeneous solution, and irradiated with ultraviolet rays having an energy equivalent to 500 mJ / cm2. Then, the polymer-forming compound was cured to obtain a liquid crystal device having a light control layer composed of a liquid crystal material and a transparent solid substance. When the cross section of the cured product formed between the substrates of the obtained liquid crystal device was observed using a scanning electron microscope, a transparent solid substance having a three-dimensional network structure composed of a polymer was recognized. The characteristics of the obtained light-scattering type liquid crystal display are wider than the conventional light-scattering type liquid crystal device. It has characteristics and is useful for a display device such as a decorative display plate such as an advertising board, a clock, or a projection display device. In particular, when the liquid crystal composition of (2-3) was used, it was useful for active use, and when the liquid crystal composition of (2-4) was used, it was useful for improving the response at low temperatures. . Example 9 The temperature characteristics of the liquid crystal display devices manufactured in Examples 3 to 8 were measured in detail. The results showed that all of them improved the temperature dependence of the driving voltage. In particular, the improvement effect at −10 to 40 ° C. was a reduction of 40 to 90%.

Nematic liquid compositions of the present invention exhibits the general formula (I-1) liquid crystal component A consisting of compounds represented by as essential components, when mixed in the liquid crystal composition, to reduce the elastic constant K ₁₁ Has the effect of lowering the drive voltage. Also, by increasing the temperature dependence of the dielectric anisotropy, the temperature dependence of the driving voltage can be reduced. Therefore, the nematic liquid crystal composition of the present invention,
It can be used for an active matrix type, twisted nematic or super twisted nematic liquid crystal display device. Further, it is possible to provide a liquid crystal display element which performs color display by the birefringence of the liquid crystal layer and the retardation plate. Furthermore, a useful device can be provided for a light scattering type liquid crystal display having a light control layer containing a liquid crystal material and a transparent solid substance.

Claims (14)

[Claims] 1. A liquid crystal composition represented by the general formula (I-1):(Where R¹¹Is a linear alkyl having 1 to 10 carbon atoms
Group, alkoxy group or linear alkyl having 2 to 10 carbon atoms
X represents a phenyl group;¹¹, X¹²Are each independently the number of carbon atoms
1 to 10 linear alkyl groups, alkoxy groups, carbon atoms
A linear alkenyl group of the number 2 to 10, a hydrogen atom, a fluorine atom
Child, chlorine atom, -CF_Three, -OCF_ThreeOr -CN, Y
¹¹~ Y¹⁴Each independently represents a hydrogen atom or a fluorine atom
Then Z¹¹, Z¹²Are each independently a single bond, -COO-, -C
≡C-, -C_TwoH_Four-Or-C_FourH₈-Represents Z ¹³Is -O (C
H_Two)_k2-,-(CH_Two)_k3O- or-(CH_Two)_k4-Represents k2 ~
k4 represents an integer of 1 to 5; k1 represents 0 or 1;
¹¹Is 1,4-phenyl which may be substituted by a fluorine atom
Eneylene group, trans-1,4-cyclohexylene group
Represents the hydrogen atom of the cyclohexane ring in each compound
(H) may be replaced by a deuterium atom (D). )
A liquid crystal component comprising one or more compounds represented by
A compound containing A and having a dielectric anisotropy of +2 or more
Liquid crystal component B comprising 10 to 99.9% by weight,
Liquid crystal component comprising a compound having a dielectric anisotropy of ~ 2
C in an amount of 0 to 70% by weight, and the liquid crystal component B and the liquid crystal component
Characterized in that the total amount of C is 75 to 99.9% by weight.
Nematic liquid crystal composition. 2. The liquid crystal component A is a compound in which R ¹¹ in the general formula (I-1) is an ethyl group, a propyl group, a butyl group, a vinyl group or a butenyl group, and / or X ¹¹ , X
A compound in which ¹² is both represented by a fluorine atom, and / or a compound in which both Y ¹¹ and Y ¹² are represented by a fluorine atom, and / or
Or a compound in which both Z ¹¹ and Z ¹² are represented by a single bond, and / or
_2. The nematic liquid crystal composition according to claim 1, wherein Z ¹³ contains 30 to 100% by weight of a compound represented by —O (CH ₂ ) _{k 2} — and / or a compound represented by _{k 2} of 1. Stuff. 3. The liquid crystal component B represented by the general formula (II-1):
(II-4) (Wherein, R ^{21 to} R ²⁴ each independently represent 2 to 10 carbon atoms.
Linear alkyl group, alkenyl group or C _s H _{2s + 1} -O-
Represents C _t H _2t, s and t are each independently an integer of 1 to 5, X ²¹ to X ²⁴ are each independently a fluorine atom, a chlorine _{atom, -OCF 3, -OCHF 2, -CF} 3 Or -CN, Y
^{21 to} Y ²⁸ each independently represent a hydrogen atom or a fluorine atom, W ^{21 to} W ²⁴ each independently represent a hydrogen atom or a fluorine atom, Z ^{21 to} Z ²³ each independently represent a single bond, -COO -,
Represents —C ₂ H ₄ — or —C ₄ H ₈ —, and Z ²¹ is also —C≡C— or
—CH ＝ CH—, Z ²⁴ and Z ²⁵ each independently represent a single bond, —COO—, —C≡C— or —CF ＝ CF—, and ring A ²¹ represents a cyclohexane ring or benzene. Represents a ring,
m ^{1 to} m ⁴ each independently represent 0 or 1, and m ³ + m ⁴ represents 0
Or 1, and the hydrogen atom (H) of the cyclohexane ring in each compound may be substituted with a deuterium atom (D). 3. The nematic liquid crystal composition according to claim 1, wherein the composition comprises a compound selected from the group consisting of compounds represented by the formula: 4. The liquid crystal component B according to the general formula (II-1)
Compounds in which R ^{21 to} R ²⁴ in (II-4) are an alkyl group or alkenyl group having 2 to 5 carbon atoms, and / or X
²¹ to X ²⁴ is a fluorine atom, a chlorine atom, -OCF ₃ or -CN
And / or Z ²¹ and Z ²² in the compound of the general formula (II-1) are a single bond, —COO—, —C ₂ H ₄ — or —C ₄
In the compound represented by H _8- and / or the compound of the general formula (II-2), Z ²⁴ is a single bond, a compound represented by —COO— or —C≡C—, and / or a compound represented by the general formula (II-3) ) Wherein the compound in which Z ²⁵ is a single bond or —C≡C—
The nematic liquid crystal composition according to claim 3, wherein the composition is contained in an amount of 00% by weight. 5. The liquid crystal component C represented by the general formula (III-1):
(III-4) (Wherein, R ^{31 to} R ³⁴ each independently represent a linear alkyl group or alkenyl group having 2 to 7 carbon atoms, and R ^{35 to} R ³⁸
Are each independently a linear alkyl group having 1 to 7 carbon atoms,
Alkoxy group, a linear alkenyl group having 2 to 7 carbon atoms, represents alkenyloxy group or _{C u H 2u + 1 -O-} C v H 2v, u and v the each independently an integer of 1 to 5 Represents Y ³¹
Represents a hydrogen atom, a fluorine atom or —CH ₃ , and Y ³² and Y
³³ each independently represent a hydrogen atom or a fluorine atom, Z ³¹
To Z ³⁴ each independently represents a single _{bond, -COO -, - C 2 H} 4 - or
Represents —C ₄ H ₈ —, and Z ³¹ also represents —C≡C— or —CH ＝ CH—.
Wherein Z ³⁵ is a single bond, -C≡C-, -COO-,
-CH = NN-CH- or -CF = CF-; rings A ³¹ and A ³² each independently represent a cyclohexane ring or a cyclohexene ring; rings A ³³ and A ³⁴ each independently represent a cyclohexane ring Or n represents a benzene ring, n ^{1 to} n ⁵ each independently represent an integer of 0 or 1, n ⁴ + n ⁵ is 0 or 1, and a hydrogen atom (H) in a cyclohexane ring in each compound is a deuterium atom. (D) may be substituted. 5. The nematic liquid crystal composition according to claim 1, wherein the composition comprises a compound selected from the group consisting of: 6. The liquid crystal component C according to the general formula (III-
In the compound of 1), R ³¹ represents a linear alkyl group or alkenyl group having 2 to 5 carbon atoms, and R ³⁵ represents a linear alkyl group having 1 to 5 carbon atoms, an alkoxy group, and 2 carbon atoms. And 7 represents a linear alkenyl group or an alkenyloxy group, a ring A ³¹ represents a cyclohexane ring, and when m ¹ is 0, a compound wherein Z ³² is represented by a single bond or —COO—, and / or
6. The nematic liquid crystal composition according to claim 5, wherein when m ¹ is 1, 10 to 100% by weight of a compound represented by Z ³¹ and Z ³² by a single bond is contained. 7. The liquid crystal component C according to the general formula (III-
In the compound of 2), R ³² represents a linear alkyl group or alkenyl group having 2 to 5 carbon atoms, and R ³⁶ represents a linear alkyl group having 1 to 5 carbon atoms, an alkoxy group, and 2 carbon atoms. to 7 straight chain alkenyl group, an alkenyloxy group, m ² is when the ring a ³² is a cyclohexane ring or a cyclohexene ring 0, Z ³³ is a single bond, -COO- or -
A compound represented by C ₂ H ₄ — and / or when m ² is 1, ring A ³² is a cyclohexane ring, and Z ³³ is a single bond or —C ₂
7. The nematic liquid crystal composition according to claim 5, wherein the compound represented by H _4- is contained in an amount of 10 to 100% by weight. 8. The liquid crystal component C having the general formula (III-
In the compound of 3), Z ³⁵ is -C≡C-, -CH = N-N
The nematic liquid crystal composition according to claim 5, 6 or 7, comprising 10 to 100% by weight of a compound represented by = CH-. 9. The liquid crystal composition according to claim 1, wherein the compound has a core structure having four six-membered rings, and the compound having a liquid crystal phase-isotropic liquid phase transition temperature of 100 ° C. or higher. 9. A composition comprising one or more species.
The nematic liquid crystal composition according to the above. 10. The liquid crystal composition has a dielectric anisotropy of 4 to 30, a birefringence of 0.08 to 0.33,
The nematic phase-isotropic liquid phase transition temperature of 60 ° C to 180 ° C, and the crystalline phase, smectic phase or glass phase-nematic phase transition temperature of -200 ° C to 0 ° C. 9. The nematic liquid crystal composition according to item 9. 11. The nematic liquid crystal composition according to claim 1, wherein the liquid crystal composition contains a compound having an optically active group having an induced helical pitch of 0.5 to 1000 μm. 12. An active matrix using the nematic liquid crystal composition according to claim 11, and a twisted liquid crystal.
Nematic or super twisted nematic liquid crystal display. 13. A light-scattering type liquid crystal display device having a dimming layer containing the liquid crystal composition according to claim 1 and a transparent solid substance. 14. The light control layer according to claim 13, wherein the liquid crystal composition forms a continuous layer, and the transparent solid substance forms a uniform three-dimensional network structure in the continuous layer. Light scattering type liquid crystal display device.