CN110546558A

CN110546558A - liquid crystal display element, liquid crystal composition and compound

Info

Publication number: CN110546558A
Application number: CN201880026399.7A
Authority: CN
Inventors: 平井吉治; 荻田和寛; 近藤史尚; 远藤浩史
Original assignee: JNC Corp; Chisso Petrochemical Corp
Current assignee: JNC Corp; JNC Petrochemical Corp
Priority date: 2017-06-28
Filing date: 2018-06-20
Publication date: 2019-12-06
Also published as: TW201905183A; WO2019004021A1; JPWO2019004021A1

Abstract

The invention provides a liquid crystal composition which uses an orientation control layer forming monomer without coloring to control the orientation of liquid crystal molecules of a liquid crystal display element without an orientation film, and the orientation control layer forming monomer without coloring shows good compatibility. A liquid crystal display element and a liquid crystal composition using a liquid crystal composition containing an alignment control layer forming monomer having a vinylidene group in a partial structure and having positive dielectric anisotropy are used.

Description

Liquid crystal display element, liquid crystal composition and compound

Technical Field

The present invention relates to a liquid crystal display element containing a liquid crystal composition having positive dielectric anisotropy, a liquid crystal composition, and a compound. In particular, the present invention relates to a liquid crystal display element using a liquid crystal composition containing an alignment control layer forming monomer having a vinylidene group in a partial structure, and capable of achieving alignment of liquid crystal molecules by the action of the compound.

Background

In a liquid crystal display device, the operation modes based on liquid crystal molecules are classified into Phase Change (PC), Twisted Nematic (TN), Super Twisted Nematic (STN), Electrically Controlled Birefringence (ECB), Optically Compensated Bend (OCB), in-plane switching (IPS), Vertical Alignment (VA), Fringe Field Switching (FFS), field-induced photo-reactive alignment (FPA), and the like. The driving methods of the elements are classified into Passive Matrix (PM) and Active Matrix (AM). The PM is classified into a static type (static), a multiplexing type (multiplex), etc., and the AM is classified into a Thin Film Transistor (TFT), a Metal Insulator Metal (MIM), etc. TFTs are classified into amorphous silicon (amorphous silicon) and polycrystalline silicon (polysilicon). The latter is classified into a high temperature type and a low temperature type according to the manufacturing steps. The light sources are classified into a reflection type using natural light, a transmission type using a backlight, and a semi-transmission type using both natural light and backlight.

the liquid crystal display element contains a liquid crystal composition having a nematic phase. The composition has suitable properties. By improving the characteristics of the composition, an AM element having good characteristics can be obtained. The correlation between the properties of both is summarized in the following Table 1. The properties of the composition are further illustrated based on commercially available AM elements. The temperature range of the nematic phase is associated with the temperature range in which the element can be used. The upper limit temperature of the nematic phase is preferably about 70 ℃ or higher, and the lower limit temperature of the nematic phase is preferably about-10 ℃ or lower. The viscosity of the composition correlates to the response time of the element. In order to display a moving image (moving image) with an element, the response time is preferably short. Ideally shorter than 1 millisecond of response time. Therefore, it is preferable that the viscosity of the composition is small. Further, it is preferable that the viscosity at low temperature is low.

[ Table 1]

TABLE 1 Properties of the compositions and AM elements

The optical anisotropy of the composition correlates with the contrast ratio of the element. Depending on the mode of the element, a large optical anisotropy or a small optical anisotropy, that is, an appropriate optical anisotropy is required. The product (Δ n × d) of the optical anisotropy (Δ n) of the composition and the cell gap (d) of the element is designed to maximize the contrast ratio. The value of the appropriate product depends on the type of operation mode. The value is in the range of about 0.30 μm to about 0.40 μm in a VA mode element, and in the range of about 0.20 μm to about 0.30 μm in an IPS mode or FFS mode element. In these cases, a composition having a large optical anisotropy is preferable for an element having a small cell gap. The large dielectric anisotropy of the composition contributes to a low threshold voltage, small power consumption and a large contrast ratio of the element. Therefore, a large dielectric anisotropy is preferable. The large specific resistance of the composition contributes to a large voltage holding ratio and a large contrast ratio of the element. Therefore, a composition having a large specific resistance in the initial stage is preferable. Preferred are compositions having a large specific resistance after a long period of use. The stability of the composition to ultraviolet light and heat correlates with the lifetime of the element. When the stability is high, the life of the element is long. Such characteristics are preferable for AM elements used for liquid crystal monitors, liquid crystal televisions, and the like.

A composition having positive dielectric anisotropy is used for an AM element having a TN mode. A composition having negative dielectric anisotropy is used for an AM element having a VA mode. A composition having positive or negative dielectric anisotropy is used for an AM element having an IPS mode or an FFS mode.

in a Polymer Sustained Alignment (PSA) type liquid crystal display element, a liquid crystal composition containing a polymer is used. First, a composition to which a small amount of a polymerizable compound is added is injected into an element. Next, the composition was irradiated with ultraviolet rays while applying a voltage between the substrates of the element. The polymerizable compound is polymerized to form a network structure of a polymer in the composition. In the composition, the polymer can be used to control the orientation of the liquid crystal molecules, so that the response time of the element is shortened and the afterimage of the image is improved. Such effects of the polymer can be expected in devices having modes such as TN, ECB, OCB, IPS, VA, FFS, and FPA.

In the IPS mode, FFS mode, and ECB mode, when no voltage is applied to the liquid crystal molecules, the liquid crystal molecules need to be aligned in a direction substantially horizontal to the main surface of the substrate. In order to control the alignment of the liquid crystal molecules, an alignment film such as polyimide has been used. In recent years, the liquid crystal panel has been made narrower in frame width, and the adhesion strength is weak due to a narrower adhesion width between the alignment film and the sealant, and the liquid crystal panel may be peeled from the interface between the alignment film and the sealant. In order to prevent such a problem, a method has been proposed in which a conventional alignment film such as polyimide is not used (patent documents 1 to 3).

The following methods are reported: instead of an alignment film such as polyimide, a low molecular compound having a cinnamate group, polyvinyl cinnamate, a low molecular compound having a chalcone structure, a low molecular compound having an azobenzene structure, or a dendrimer is used to control the alignment of liquid crystals (patent document 1). In the method of patent document 1, first, the low-molecular compound or the polymer is dissolved in the liquid crystal composition as an additive. Next, a thin film containing the low-molecular compound or the polymer is formed on the substrate by phase separation of the additive. Finally, the substrate is irradiated with linearly polarized light at a temperature higher than the upper limit temperature of the liquid crystal composition. When a low-molecular compound or a polymer is dimerized or isomerized by the linear polarization, its molecules are aligned in a fixed direction. In the above method, a horizontally aligned mode element such as IPS or FFS and a vertically aligned mode element such as VA can be produced by selecting the kind of the low molecular compound or the polymer. In the method, it is important that the low-molecular compound or the polymer is easily dissolved at a temperature higher than the upper limit temperature of the liquid crystal composition, and the compound is easily phase-separated from the liquid crystal composition when the temperature is returned to room temperature. Among them, it is difficult to ensure compatibility of a low-molecular compound or polymer with a liquid crystal composition.

In the methods of patent documents 2 and 3, a dendritic polymer having azobenzene as a partial structure is dissolved in a liquid crystal composition as an additive. Next, a thin film of the compound is formed on the substrate by allowing the compound to undergo phase separation. At this time, the liquid crystal composition is aligned vertically with respect to the substrate. Next, the substrate is irradiated with linearly polarized light without heating. When the dendrimer is dimerized or isomerized by the linear polarization, its molecules are aligned in a horizontal direction with respect to the substrate. Elements in a horizontal alignment mode such as IPS or FFS can be manufactured. In the above method, too, in order to facilitate dissolution and phase separation of the dendritic polymer, it is necessary to appropriately combine the dendritic polymer and the liquid crystal composition. In the case of using a dendritic polymer having azobenzene as a partial structure, there is a problem of coloring derived from azobenzene.

Patent document 4 discloses a polymer dispersed liquid crystal optical element including a polymer resin obtained by photopolymerization of a (meth) acrylate compound having a stilbene skeleton and a chiral nematic liquid crystal. The liquid crystal optical element herein is to reduce the driving voltage and the retardation. The polymer dispersed liquid crystal optical element is different from the present invention in configuration because it is a polymer dispersed liquid crystal optical element which contains a chiral nematic liquid crystal as an essential component, and which is in a transparent state or a selective reflection state when no voltage is applied, and which is in a scattering state when a voltage is applied. Further, there is no suggestion or description that the (meth) acrylate compound having a stilbene skeleton causes horizontal alignment of the liquid crystalline compound by polarized light irradiation.

Documents of the prior art

Patent document

Patent document 1: international publication No. 2015/146369

Patent document 2: japanese patent laid-open No. 2015-64465

Patent document 3: japanese patent laid-open No. 2015-125151

Patent document 4: japanese patent laid-open No. Hei 08-92561

disclosure of Invention

problems to be solved by the invention

the present invention addresses the problem of providing a liquid crystal display element that does not require a conventional alignment film formed of polyimide or the like or a step of forming the alignment film, by using a liquid crystal composition containing an alignment control layer-forming monomer. Further, an alignment control layer forming monomer which exhibits good compatibility with a liquid crystal composition and is free from coloration is provided to realize a liquid crystal display element having excellent transmittance characteristics and contrast ratio.

Means for solving the problems

the present invention uses a liquid crystal display element, a liquid crystal composition, and a compound, which utilize a liquid crystal composition that contains an alignment control layer forming monomer having a vinylidene group in a partial structure and has positive dielectric anisotropy.

ADVANTAGEOUS EFFECTS OF INVENTION

According to the present invention, a liquid crystal display element which is less likely to be peeled even in a narrow frame can be manufactured by using a liquid crystal composition containing an alignment control layer-forming monomer.

Further, by using an alignment control layer-forming monomer which is excellent in solubility in a liquid crystal composition and is free from coloration, a liquid crystal display element excellent in transmittance characteristics and contrast ratio can be realized.

Further, the step of forming the alignment film is not required in the production of the liquid crystal display element, and the production cost of the liquid crystal display element can be reduced.

Detailed Description

the terms used in the present specification are used as follows. The terms "liquid crystal composition" and "liquid crystal display element" may be simply referred to as "composition" and "element", respectively. The term "liquid crystal display element" is a generic term for liquid crystal display panels and liquid crystal display modules. The "liquid crystalline compound" is a general term for compounds having a liquid crystal phase such as a nematic phase or a smectic phase, and compounds which are mixed in the composition for the purpose of adjusting the characteristics such as the temperature range, viscosity, and dielectric anisotropy of the nematic phase, although they do not have a liquid crystal phase. The compound has a six-membered ring such as 1, 4-cyclohexylene or 1, 4-phenylene, and its molecular structure is rod-like (rod like). The "polymerizable compound" is a compound added for the purpose of forming a polymer in the composition. The liquid crystalline compound having an alkenyl group is not polymerizable in its meaning.

the liquid crystal composition is prepared by mixing a plurality of liquid crystalline compounds. Additives such as optically active compounds, antioxidants, ultraviolet absorbers, pigments, antifoaming agents, polymerizable compounds, polymerization initiators, polymerization inhibitors, and polar compounds are added to the composition as required. Even in the case where an additive is added, the proportion of the liquid crystalline compound is represented by a weight percentage (wt%) based on the weight of the liquid crystal composition containing no additive. The proportion of the additive is represented by a weight percentage (parts by weight) based on the weight of the liquid crystal composition containing no additive. That is, the ratio of the liquid crystalline compound or the additive is calculated based on the total weight of the liquid crystalline compound. Parts per million (ppm) by weight are sometimes used. The proportion of the polymerization initiator is exceptionally represented on the basis of the weight of the polymerizable compound.

The "upper limit temperature of the nematic phase" may be simply referred to as "upper limit temperature". The "lower limit temperature of the nematic phase" may be simply referred to as "lower limit temperature". The "large specific resistance" means that the composition has a large specific resistance in an initial stage and also has a large specific resistance after long-term use. The "large voltage holding ratio" means that the device has a large voltage holding ratio not only at room temperature but also at a temperature close to the upper limit temperature in the initial stage, and also has a large voltage holding ratio not only at room temperature but also at a temperature close to the upper limit temperature after long-term use. In order to investigate the characteristics of a composition or an element, a time-dependent change test is sometimes used. The expression "increase in dielectric anisotropy" means that the value increases positively in a composition having positive dielectric anisotropy, and increases negatively in a composition having negative dielectric anisotropy.

The compound represented by the formula (1) may be simply referred to as "compound (1)". At least one compound selected from the group of compounds represented by formula (1) may be abbreviated as "compound (1)". The "compound (1)" means one compound, a mixture of two compounds, or a mixture of three or more compounds represented by the formula (1). The same applies to the compounds represented by the other formulae. The expression "at least one 'a'" means that the number of 'a's is arbitrary. The expression "at least one 'a' may be substituted with 'B' means that the position of 'a' is arbitrary when the number of 'a' is one, and the position thereof may be selected without limitation when the number of 'a' is two or more. The rules also apply to the expression "at least one 'a' is substituted with 'B'.

The expression "at least one-CH 2-may be substituted by-O-is used in the present specification. In that case, -CH2-CH2-CH 2-can be converted to-O-CH 2-O-by substitution of the noncontiguous-CH 2-with-O-. However, the adjacent-CH 2-is not substituted by-O-. This is because-O-CH 2- (peroxide) is formed in the substitution. That is, the expression refers to both "one-CH 2-may be substituted with-O-and" at least two non-adjacent-CH 2-may be substituted with-O-. The rule applies not only to the case of substitution to-O-, but also to the case of substitution to a divalent group such as-CH ═ CH-or-COO-.

In the chemical formula of the component compound, the symbol of the terminal group R1 is used for a plurality of compounds. In these compounds, any two groups represented by R1 may be the same or different. For example, R1 in the compound (1-1) is ethyl, and R1 in the compound (1-2) is ethyl. There are also cases where R1 of compound (1-1) is ethyl and R1 of compound (1-2) is propyl. The rules also apply to the notation of other end groups and the like. In formula (1), when the subscript 'a' is 2, there are two rings a. In the compounds, the two rings represented by the two rings a may be the same or may also be different. Where subscript 'a' is greater than 2, the rules also apply to any two rings a. The rules also apply to Z1, Ring D, etc. tokens.

The symbols A, B, C, D and the like surrounded by hexagons correspond to the rings such as ring a, ring B, ring C, ring D, and the like, respectively, and represent the rings such as a six-membered ring, a condensed ring, and the like. In the formula (4), the diagonal lines crossing one side of the hexagon indicate that an arbitrary hydrogen on the ring may be substituted with a group such as-Sp 1-P1. The subscripts of 'e' etc. indicate the number of substituted groups. When subscript 'e' is 0 (zero), there is no such substitution. When the subscript 'e' is 2 or more, there are a plurality of-Sp 1-P1 on ring F3. The groups represented by-Sp 1-P1 may be the same or different.

2-fluoro-1, 4-phenylene refers to the following two divalent radicals. In the chemical formula, fluorine can be towards left (L) or right (R). The rules also apply to unsymmetrical divalent radicals such as tetrahydropyran-2, 5-diyl that are generated by removing two hydrogens from the ring. The rules also apply to divalent bonding groups such as carbonyloxy (-COO-or-OCO-).

The alkyl group of the liquid crystalline compound is linear or branched and does not contain a cyclic alkyl group. Straight chain alkyls are preferred over branched alkyls. These cases are also the same for terminal groups such as alkoxy groups and alkenyl groups. In order to increase the upper limit temperature, the steric configuration associated with the 1, 4-cyclohexylene group is a trans configuration rather than a cis configuration.

the present invention is as follows.

Item 1 is a liquid crystal display element in which a liquid crystal layer is sandwiched between a pair of substrates which are arranged to face each other and bonded to each other with a sealant interposed therebetween,

An alignment control layer that controls alignment of liquid crystal molecules is provided between the pair of substrates and the liquid crystal layer, the liquid crystal layer having positive dielectric anisotropy,

in the liquid crystal display element, the alignment control layer includes a polymer formed by polymerizing an alignment control layer forming monomer by sandwiching a liquid crystal composition containing at least one compound selected from the group of compounds represented by formulae (a) to (D) as a first additive and the alignment control layer forming monomer and a liquid crystal compound between the pair of substrates.

in the formulae (A) to (D), P10, P20, P30 and P40 are independently a group selected from the group consisting of the groups represented by the formulae (Q-1) to (Q-5);

In the formulae (Q-1) to (Q-5), M10, M20, and M30 are independently hydrogen, fluorine, an alkyl group having 1 to 5 carbon atoms, or an alkyl group having 1 to 5 carbon atoms in which at least one hydrogen is substituted with fluorine or chlorine;

Sp10, Sp20, and Sp40 are independently a single bond or an alkylene group having 1 to 12 carbon atoms, at least one hydrogen of which may be substituted by fluorine, chlorine or formula (Q-6), at least one-CH 2-may be substituted by-O-, -CO-, -COO-, or-OCO-, and at least one-CH 2CH 2-may be substituted by-CH ═ CH-;

Sp30 is independently a single bond or an alkylene group having 1 to 12 carbon atoms, at least one hydrogen of which may be substituted by fluorine, chlorine or a group of formula (Q-6), at least one-CH 2-may be substituted by-O-, -CO-, -COO-, or-OCO-;

in the formula (Q-6), M10, M20 and M30 are independently hydrogen, fluorine, an alkyl group having 1 to 5 carbon atoms, or an alkyl group having 1 to 5 carbon atoms in which at least one hydrogen is substituted with fluorine or chlorine;

Sp41 is independently a single bond or an alkylene group having 1 to 12 carbon atoms, at least one hydrogen of which may be substituted by fluorine or chlorine, at least one-CH 2-may be substituted by-O-, -CO-, -COO-, or-OCO-;

ring a10 and ring a20 are independently phenyl, 4-biphenyl, 1-naphthyl, 2-naphthyl, pyrimidin-2-yl, pyrimidin-5-yl, pyridin-2-yl, pyridin-5-yl, fluoren-2-yl, fluoren-3-yl, phenanthren-2-yl, or anthracen-2-yl, in which at least one hydrogen may be substituted with fluorine, chlorine, an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an alkoxy group having 1 to 11 carbon atoms, or an alkenyloxy group having 2 to 11 carbon atoms, and in which at least one hydrogen may be substituted with fluorine or chlorine;

Ring A11, ring A21, ring A12, ring A22, and ring A30 are independently 1, 4-cyclohexylene, 1, 4-cyclohexenylene, 1, 4-phenylene, 4' -biphenylene, naphthalene-2, 6-diyl, decahydronaphthalene-2, 6-diyl, 1,2,3, 4-tetrahydronaphthalene-2, 6-diyl, tetrahydropyran-2, 5-diyl, 1, 3-dioxane-2, 5-diyl, pyrimidine-2, 5-diyl, pyridine-2, 5-diyl, fluorene-2, 7-diyl, phenanthrene-2, 7-diyl, anthracene-2, 6-diyl, perhydrocyclopenta [ a ] phenanthrene-3, 17-diyl, or 2,3,4,7,8,9,10,11,12,13,14,15,16, 17-tetradecahydrocyclopenta [ a ] phenanthrene-3, 17-diyl in which adjacent bonds are-CH ═ CH-, -CR10 ═ CR20-, -CO-CH ═ CH-, -CH ═ CH-CO-, -OCO-CH ═ CH-, or-CH ═ CH-COO-, and when R10 and R20 are independently hydrogen, fluorine, a cyano group, an alkyl group having 1 to 10 carbon atoms, or an alkyl group having 1 to 10 carbon atoms in which at least one hydrogen is substituted with fluorine, 1, 4-phenylene, 4' -biphenylene, naphthalene-2, 6-diyl, pyrimidine-2, 5-diyl, pyridine-2, 5-diyl, fluorene-2, 7-diyl, phenanthrene-2, 7-diyl, or anthracene-2, 6-diyl in which at least one hydrogen may be substituted by fluorine, chlorine, an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an alkoxy group having 1 to 11 carbon atoms, or an alkenyloxy group having 2 to 11 carbon atoms, and in which at least one hydrogen may be substituted by fluorine or chlorine;

ring A40 is 1, 4-cyclohexylene, 1, 4-cyclohexenylene, 1, 4-phenylene, 4' -biphenylene, naphthalene-2, 6-diyl, decahydronaphthalene-2, 6-diyl, 1,2,3, 4-tetrahydronaphthalene-2, 6-diyl, tetrahydropyran-2, 5-diyl, 1, 3-dioxane-2, 5-diyl, pyrimidine-2, 5-diyl, pyridine-2, 5-diyl, fluorene-2, 7-diyl, phenanthrene-2, 7-diyl, anthracene-2, 6-diyl, perhydrocyclopenta [ a ] phenanthrene-3, 17-diyl, or 2,3,4,7,8,9,10,11,12,13,14,15,16, 17-tetradecahydrocyclopenta [ a ] phenanthrene-3, 17-diyl, when the adjacent bond is-CH-, -CO-CH-, -CH-CO-, -OCO-CH-, or-CH-COO-, is 1, 4-phenylene, 4' -biphenylene, naphthalene-2, 6-diyl, pyrimidine-2, 5-diyl, pyridine-2, 5-diyl, fluorene-2, 7-diyl, phenanthrene-2, 7-diyl or anthracene-2, 6-diyl, in these rings, at least one hydrogen may be substituted with P20-Sp20-, fluorine, chlorine, an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an alkoxy group having 1 to 11 carbon atoms, or an alkenyloxy group having 2 to 11 carbon atoms, and in these groups, at least one hydrogen may be substituted with fluorine or chlorine;

Z10 is independently-CH-, -CR10 ═ CR20-, -CO-CH ═ CH-, -CH ═ CH-CO-, -OCO-CH ═ CH-, or-CH ═ CH-COO-; r10 and R20 are independently hydrogen, fluorine, cyano, alkyl of 1 to 10 carbon atoms, or alkyl of 1 to 10 carbon atoms with at least one hydrogen substituted for fluorine;

Z11 is independently a single bond or an alkylene group having 1 to 6 carbon atoms, of which alkylene group at least one-CH 2-may be substituted by-O-, -CO-, -COO-, -OCO-, or-OCOO-, and at least one- (CH2) 2-may be substituted by-CH ═ CH-or-C ≡ C-, and of these groups, at least one hydrogen may be substituted by fluorine or chlorine;

Z20 and Z21 are independently a single bond, an alkylene group having 1 to 6 carbon atoms, or an alkenylene group having 2 to 6 carbon atoms, at least one of which is an alkenylene group having 2 to 6 carbon atoms. At least one of these alkylene groups and alkenylene groups, at least one of which-CH 2-may be substituted with-O-, -CO-, -COO-, -OCO-, or-OCOO-, and at least one of the other- (CH2) 2-may be substituted with-CH ═ CH-or-C.ident.C-, and of these groups, at least one hydrogen may be substituted with fluorine or chlorine;

k10 and n10 are independently integers from 0 to 3, and the sum of k10 and n10 is an integer from 1 to 6;

n20 is 1 or 2;

n30 is 1 or 2.

Item 2. the liquid crystal display element according to item 1, wherein the alignment control layer-forming monomer in the liquid crystal composition is represented by formula (A-1), formula (A-2), formula (B), formula (C-1), or formula (D-1).

in the formula (A-1), the formula (A-2), the formula (B), the formula (C-1) and the formula (D-1),

P10, P20, P30, P40, P50 and P60 are independently a group selected from the group represented by the formula (Q-1);

In the formula (Q-1), M10, M20 and M30 are independently hydrogen, fluorine, methyl or alkyl with 1 to 5 carbon atoms, wherein at least one hydrogen is replaced by fluorine;

Sp10, Sp20, and Sp40 are independently a single bond or an alkylene group having 1 to 12 carbon atoms, at least one hydrogen of which may be substituted by fluorine or by the formula (Q-6), at least one-CH 2-may be substituted by-O-, -CO-, -COO-, or-OCO-, and at least one-CH 2CH 2-may be substituted by-CH ═ CH-;

In the formula (Q-6), M10, M20 and M30 are independently hydrogen, fluorine, methyl or alkyl with 1 to 5 carbon atoms, wherein at least one hydrogen is replaced by fluorine;

Sp50 and Sp60 are independently C2-12 alkylene groups, at least one hydrogen of which may be substituted by fluorine, chlorine or a group of formula (Q-6), at least one-CH 2-group may be substituted by-O-, -CO-, -COO-, or-OCO-;

r10 and R20 are independently hydrogen, fluorine, cyano, alkyl of 1 to 10 carbon atoms, or alkyl of 1 to 10 carbon atoms with at least one hydrogen substituted for fluorine;

R30, R40, R41 and R50 are independently hydrogen, fluorine, chlorine, alkyl of 1 to 10 carbon atoms, or alkyl of 1 to 10 carbon atoms with at least one hydrogen substituted with fluorine;

k10 and n10 are independently 0,1, or 2, the sum of k10 and n10 is 2,3, or 4;

ring a11 and ring a21 are independently 1, 4-phenylene, or naphthalene-2, 6-diyl, in which at least one hydrogen may be substituted by fluorine, chlorine, an alkyl group having 1 to 12 carbon atoms, or an alkyl group having 1 to 12 carbon atoms in which at least one hydrogen is substituted by fluorine;

Z11 is a single bond, ethylene, methyleneoxy, -COO-, -OCO-, -OCOO-, or-CH ═ CH-COO-;

Z12 is-CO-, or-OCO-;

k10 and n10 are independently integers from 0 to 3, and the sum of k10 and n10 is an integer from 1 to 4;

n20 is 1 or 2;

n30 is 1 or 2;

Z20 and Z21 are independently a single bond, -CO-CH-, -CH-CO-, -OCO-CH-, -CH-COO-, or-CH-, but are not simultaneously single bonds.

Item 3. the liquid crystal display element according to item 2, wherein the alignment control layer forming monomer in the liquid crystal composition is formula (A-1), formula (A-2), or formula (B), and P10, P20, P30, P40, P50, and P60 are independently a group selected from the group represented by formula (Q-1);

In formula (Q-1), M10, M20, and M30 are independently hydrogen, fluorine, methyl, or trifluoromethyl;

Sp10 and Sp20 are independently a single bond or an alkylene group having 1 to 12 carbon atoms, at least one hydrogen of which may be substituted by fluorine or by the formula (Q-6), at least one-CH 2-may be substituted by-O-, -CO-, -COO-, or-OCO-;

Sp30 is a single bond or an alkylene group having 1 to 12 carbon atoms, at least one hydrogen of which may be substituted by fluorine, at least one-CH 2-may be substituted by-O-, -CO-, -COO-, or-OCO-;

sp40 is a single bond;

r30, R40 and R50 are independently hydrogen, fluorine, chlorine, alkyl of 1 to 10 carbon atoms, or alkyl of 1 to 10 carbon atoms with at least one hydrogen substituted with fluorine;

ring a11 and ring a21 are independently 1, 4-phenylene, or naphthalene-2, 6-diyl, in which at least one hydrogen may be substituted by fluorine, methyl, ethyl, or trifluoromethyl;

Z11 is a single bond, -COO-or-OCO-;

z12 is-CO-, or-OCO-;

n20 is 1 or 2;

n30 is 1 or 2.

Item 4. the liquid crystal display element according to any one of item 1 to item 3, wherein a ratio of the alignment control layer forming monomer in the liquid crystal composition is in a range of 0.1 parts by weight to 10 parts by weight based on the total amount of the liquid crystalline compound.

Item 5. the liquid crystal display element according to any one of item 1 to item 4, which contains at least one compound selected from the group of compounds represented by formula (1) as a first component.

in the formula (1), R1 is alkyl with 1 to 12 carbon atoms, alkoxy with 1 to 12 carbon atoms or alkenyl with 2 to 12 carbon atoms; ring a is 1, 4-cyclohexylene, 1, 4-phenylene, 2-fluoro-1, 4-phenylene, 2, 3-difluoro-1, 4-phenylene, 2, 6-difluoro-1, 4-phenylene, pyrimidine-2, 5-diyl, 1, 3-dioxane-2, 5-diyl, or tetrahydropyran-2, 5-diyl; z1 is a single bond, ethylene, carbonyloxy, -CH ═ CF-, -CF ═ CF-, difluoromethyleneoxy, -CH ═ CF-CF2O-, or-CF ═ CF-CF 2O-; x1 and X2 are independently hydrogen or fluorine; y1 is fluorine, chlorine, an alkyl group of carbon number 1 to 12 wherein at least one hydrogen is substituted by fluorine or chlorine, an alkoxy group of carbon number 1 to 12 wherein at least one hydrogen is substituted by fluorine or chlorine, or an alkenyloxy group of carbon number 2 to 12 wherein at least one hydrogen is substituted by fluorine or chlorine; a is 1,2,3, or 4.

item 6. the liquid crystal display element according to any one of items 1 to 5, which contains at least one compound selected from the group of compounds represented by formulae (1-1) to (1-39) as a first component.

in the formulae (1-1) to (1-39), R1 is an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or an alkenyl group having 2 to 12 carbon atoms.

Item 7 the liquid crystal display element according to item 5 or item 6, wherein a proportion of the first component in the liquid crystal composition is in a range of 10% by weight to 85% by weight.

The liquid crystal display element according to any one of claims 1 to 7, which contains at least one compound selected from the group of compounds represented by formula (2) as a second component.

In the formula (2), R2 and R3 are independently an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, or an alkenyl group having 2 to 12 carbon atoms in which at least one hydrogen is substituted with fluorine or chlorine; ring B and ring C are independently 1, 4-cyclohexylene, 1, 4-phenylene, 2-fluoro-1, 4-phenylene, or 2, 5-difluoro-1, 4-phenylene; z2 is a single bond, ethylene, or carbonyloxy; b is 1,2, or 3.

The liquid crystal display element according to any one of claims 1 to 8, which contains at least one compound selected from the group of compounds represented by formulae (2-1) to (2-13) as a second component.

in the formulae (2-1) to (2-13), R2 and R3 are independently an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, or an alkenyl group having 2 to 12 carbon atoms in which at least one hydrogen is substituted with fluorine or chlorine.

Item 10 the liquid crystal display element according to item 8 or item 9, wherein a proportion of the second component in the liquid crystal composition is in a range of 10% by weight to 85% by weight.

The liquid crystal display element according to any one of items 1 to 10, which contains at least one compound selected from the group of compounds represented by formula (3) as a third component.

in the formula (3), R4 and R5 are independently alkyl having 1 to 12 carbon atoms, alkoxy having 1 to 12 carbon atoms, alkenyl having 2 to 12 carbon atoms, or alkenyloxy having 2 to 12 carbon atoms; ring D and ring F are independently 1, 4-cyclohexylene, 1, 4-cyclohexenylene, tetrahydropyran-2, 5-diyl, 1, 4-phenylene in which at least one hydrogen is substituted by fluorine or chlorine, naphthalene-2, 6-diyl in which at least one hydrogen is substituted by fluorine or chlorine, chroman-2, 6-diyl, or chroman-2, 6-diyl in which at least one hydrogen is substituted by fluorine or chlorine; ring E is 2, 3-difluoro-1, 4-phenylene, 2-chloro-3-fluoro-1, 4-phenylene, 2, 3-difluoro-5-methyl-1, 4-phenylene, 3,4, 5-trifluoronaphthalene-2, 6-diyl, or 7, 8-difluorochroman-2, 6-diyl; z3 and Z4 are independently a single bond, ethylene, carbonyloxy, or methyleneoxy; c is 1,2 or 3, d is 0 or 1; the sum of c and d is 3 or less.

Item 12. the liquid crystal display element according to any one of items 1 to 11, which contains at least one compound selected from the group of compounds represented by formulae (3-1) to (3-22) as a third component.

in the formulae (3-1) to (3-22), R4 and R5 are independently an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, or an alkenyloxy group having 2 to 12 carbon atoms.

Item 13 the liquid crystal display element according to item 11 or item 12, wherein a proportion of the third component is in a range of 3% by weight to 25% by weight.

item 14. the liquid crystal display element according to any one of item 1 to item 13, wherein the liquid crystal composition further contains at least one compound selected from the group of polymerizable compounds represented by formula (4) as a second additive.

In formula (4), ring F3 and ring I are independently cyclohexyl, cyclohexenyl, phenyl, 1-naphthyl, 2-naphthyl, tetrahydropyran-2-yl, 1, 3-dioxan-2-yl, pyrimidin-2-yl, or pyridin-2-yl, and in these rings, at least one hydrogen may be substituted with fluorine, chlorine, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or an alkyl group having 1 to 12 carbon atoms in which at least one hydrogen is substituted with fluorine or chlorine; ring G is 1, 4-cyclohexylene, 1, 4-cyclohexenylene, 1, 4-phenylene, naphthalene-1, 2-diyl, naphthalene-1, 3-diyl, naphthalene-1, 4-diyl, naphthalene-1, 5-diyl, naphthalene-1, 6-diyl, naphthalene-1, 7-diyl, naphthalene-1, 8-diyl, naphthalene-2, 3-diyl, naphthalene-2, 6-diyl, naphthalene-2, 7-diyl, tetrahydropyran-2, 5-diyl, 1, 3-dioxane-2, 5-diyl, pyrimidine-2, 5-diyl, or pyridine-2, 5-diyl, and in these rings, at least one of them is substituted with fluorine, chlorine, an alkyl group having 1 to 12 carbon atoms, An alkoxy group having 1 to 12 carbon atoms, or an alkyl group having 1 to 12 carbon atoms in which at least one hydrogen is substituted with fluorine or chlorine; z6 and Z7 are independently a single bond or an alkylene group having 1 to 10 carbon atoms, in which alkylene group at least one-CH 2-may be substituted by-O-, -CO-, -COO-, or-OCO-, and at least one-CH 2CH 2-may be substituted by-CH-, -C (CH3) ═ CH-, -CH ═ C (CH3) -, or-C (CH3) ═ C (CH3) -, and of which groups at least one hydrogen may be substituted by fluorine or chlorine; p1, P2, and P3 are polymerizable groups; sp1, Sp2, and Sp3 are independently a single bond or an alkylene group having 1 to 10 carbon atoms, in which at least one-CH 2-group may be substituted by-O-, -COO-, -OCO-, or-OCOO-, and at least one-CH 2CH 2-group may be substituted by-CH ═ CH-or-C ≡ C-, and among these groups, at least one hydrogen may be substituted by fluorine or chlorine; h is 0,1, or 2; e. f, and g are independently 0,1, 2,3, or 4, and the sum of e, f, and g is 1 or more.

The liquid crystal display element according to the item 14, wherein in the formula (4) in the liquid crystal composition, P1, P2, and P3 are independently a group selected from the group of polymerizable groups represented by the formulae (P-1) to (P-5).

in the formulae (P-1) to (P-5), M1, M2, and M3 are independently hydrogen, fluorine, an alkyl group having 1 to 5 carbon atoms, or an alkyl group having 1 to 5 carbon atoms in which at least one hydrogen is substituted with fluorine or chlorine.

Item 16. the liquid crystal display element according to any one of items 1 to 15, which contains at least one compound selected from the group of polymerizable compounds represented by formulae (4-1) to (4-27) as a second additive in the liquid crystal composition.

In the formulae (4-1) to (4-27), P4, P5 and P6 are independently a group selected from the group of polymerizable groups represented by the formulae (P-1) to (P-3),

Here, M1, M2, and M3 are independently hydrogen, fluorine, an alkyl group having 1 to 5 carbon atoms, or an alkyl group having 1 to 5 carbon atoms in which at least one hydrogen is substituted with fluorine or chlorine; sp1, Sp2 and Sp3 are independently a single bond or an alkylene group having 1 to 10 carbon atoms, in which at least one-CH 2-group may be substituted by-O-, -COO-, -OCO-, or-OCOO-, and at least one-CH 2CH 2-group may be substituted by-CH ═ CH-or-C ≡ C-, and among these groups, at least one hydrogen may be substituted by fluorine or chlorine.

the liquid crystal display element according to any one of items 14 to 16, wherein a ratio of the second additive in the liquid crystal composition is in a range of 0.03 parts by weight to 10 parts by weight based on the total amount of the liquid crystalline compound.

Item 18 the liquid crystal display element according to any one of items 1 to 17, wherein an upper limit temperature of the nematic phase is 70 ℃ or more, an optical anisotropy at a wavelength of 589nm (measured at 25 ℃) is 0.07 or more, and a dielectric anisotropy at a frequency of 1kHz (measured at 25 ℃) is 2 or more.

Item 19. a liquid crystal display element having the liquid crystal composition in the liquid crystal display element according to any one of items 1 to 18 and an electrode between a pair of substrates, and an alignment control layer forming monomer in the liquid crystal composition is reacted by irradiating linearly polarized light at or above an upper limit temperature of a nematic phase.

Item 20 the liquid crystal display element according to any one of items 1 to 19, wherein an operation mode of the liquid crystal display element is an IPS mode, a VA mode, an FFS mode, or an FPA mode, and a driving mode of the liquid crystal display element is an active matrix mode.

Item 21 the liquid crystal display element according to any one of items 1 to 19, wherein an operation mode of the liquid crystal display element is an IPS mode or an FFS mode, and a driving method of the liquid crystal display element is an active matrix method.

Item 22. a polymer stable alignment type liquid crystal display element, which contains the liquid crystal composition in the liquid crystal display element according to any one of items 1 to 17, and in which a polymerizable compound is polymerized.

Item 23. use of a liquid crystal composition in the liquid crystal display element according to any one of items 1 to 17, in a liquid crystal display element.

item 24. use of a liquid crystal composition in the liquid crystal display element according to any one of items 1 to 17, in a polymer stable alignment type liquid crystal display element.

the compound of item 25, which is represented by the formula (A-2).

In the formula (A-2), P50 and P60 are independently a group selected from the group consisting of the groups represented by the formula (Q-1);

Sp50 and Sp60 are independently an alkylene group having 1 to 12 carbon atoms, at least one hydrogen of which may be substituted by fluorine or by the formula (Q-6), at least one-CH 2-may be substituted by-O-, -CO-, -COO-, or-OCO-;

Z12 is-CO-, or-OCO-;

r50 is independently hydrogen, fluorine, alkyl of carbon number 1 to 10, or alkyl of carbon number 1 to 10 with at least one hydrogen substituted for fluorine;

k10 and n10 are independently integers from 0 to 3, and the sum of k10 and n10 is an integer from 1 to 4.

Item 26. use of a compound according to item 25 as a monomer for forming an alignment control layer.

an item 27. a liquid crystal composition in the liquid crystal display element according to any one of items 1 to 17.

The present invention also includes the following items. (a) The composition further contains at least one additive selected from the group consisting of an optically active compound, an antioxidant, an ultraviolet absorber, a pigment, an antifoaming agent, a polymerizable compound, a polymerization initiator, a polymerization inhibitor, and a polar compound. (b) An AM element comprising the composition. (c) An AM element of Polymer Stable Alignment (PSA) type, comprising the composition, which further comprises a polymerizable compound. (d) An AM element of Polymer Stable Alignment (PSA) type, which contains the composition, and in which a polymerizable compound is polymerized. (e) An element comprising the composition and having a pattern of PC, TN, STN, ECB, OCB, IPS, VA, FFS, or FPA. (f) A permeable element comprising the composition. (g) Use of the composition as a composition having a nematic phase. (h) Use as an optically active composition by adding an optically active compound to said composition.

the alignment control layer-forming monomer contained in the liquid crystal composition used in the liquid crystal display element of the present invention will be described. The alignment control layer-forming monomer is a compound that absorbs polarized light and causes a reaction such as dimerization or isomerization, and in the present invention, compounds represented by formula (A), formula (A-1), formula (A-2), formula (B), formula (C-1), formula (D) and formula (D-1) are used.

In the formula (A), the formula (A-1), the formula (A-2), the formula (B), the formula (C-1), the formula (D) and the formula (D-1),

p10, P20, P30, P40, P50 and P60 are independently a group selected from the group consisting of the groups represented by the formulae (Q-1) to (Q-5),

in the formulae (Q-1) to (Q-5), M10, M20, and M30 are independently hydrogen, fluorine, an alkyl group having 1 to 5 carbon atoms, or an alkyl group having 1 to 5 carbon atoms in which at least one hydrogen is substituted with fluorine or chlorine.

Preferably of formula (Q-1), M10, M20, and M30 are independently hydrogen, fluorine, methyl, or an alkyl group of 1 to 5 carbon atoms wherein at least one hydrogen is substituted with fluorine. More preferred M10, M20, and M30 are independently hydrogen, fluoro, methyl, or trifluoromethyl.

sp10, Sp20 and Sp40 are independently a single bond or an alkylene group having 1 to 12 carbon atoms, at least one hydrogen of which may be substituted by fluorine, chlorine or a group of formula (Q-6), and at least one-CH 2-may be substituted by-O-, -CO-, -COO-, or-OCO-.

Preferably a single bond or an alkylene group having 1 to 12 carbon atoms, at least one hydrogen of which may be substituted with fluorine, and at least one-CH 2-may be substituted with-O-, -CO-, -COO-, or-OCO-.

more preferably Sp40 is a single bond.

Sp30 is independently a single bond or an alkylene group having 1 to 12 carbon atoms, at least one hydrogen of which may be substituted by fluorine, chlorine or a group of formula (Q-6), and at least one-CH 2-may be substituted by-O-, -CO-, -COO-, or-OCO-. Preferably a single bond or an alkylene group having 1 to 12 carbon atoms, at least one hydrogen of which may be substituted with fluorine, and at least one-CH 2-may be substituted with-O-, -CO-, -COO-, or-OCO-.

In the formula (Q-6), M10, M20 and M30 are independently hydrogen, fluorine, an alkyl group having 1 to 5 carbon atoms, or an alkyl group having 1 to 5 carbon atoms in which at least one hydrogen is substituted with fluorine or chlorine.

sp41 is independently a single bond or an alkylene group having 1 to 12 carbon atoms, at least one hydrogen of which may be substituted by fluorine or chlorine, and at least one-CH 2-may be substituted by-O-, -CO-, -COO-, or-OCO-.

Sp50 and Sp60 are independently an alkylene group having 1 to 12 carbon atoms, at least one hydrogen of which may be substituted by fluorine, chlorine or a group of formula (Q-6), and at least one-CH 2-may be substituted by-O-, -CO-, -COO-, or-OCO-. Preferably an alkylene group having 2 to 12 carbon atoms, at least one hydrogen of which may be substituted by fluorine, chlorine or the formula (Q-6), and at least one-CH 2-may be substituted by-O-, -CO-, -COO-, or-OCO-.

ring a10 and ring a20 are independently phenyl, 4-biphenyl, 1-naphthyl, 2-naphthyl, pyrimidin-2-yl, pyrimidin-5-yl, pyridin-2-yl, pyridin-5-yl, fluoren-2-yl, fluoren-3-yl, phenanthren-2-yl, or anthracen-2-yl, in which at least one hydrogen may be substituted with fluorine, chlorine, an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an alkoxy group having 1 to 11 carbon atoms, or an alkenyloxy group having 2 to 11 carbon atoms, and in which at least one hydrogen may be substituted with fluorine or chlorine.

Ring A11, ring A21, ring A12, ring A22, and ring A30 are independently 1, 4-cyclohexylene, 1, 4-cyclohexenylene, 1, 4-phenylene, 4' -biphenylene, naphthalene-2, 6-diyl, decahydronaphthalene-2, 6-diyl, 1,2,3, 4-tetrahydronaphthalene-2, 6-diyl, tetrahydropyran-2, 5-diyl, 1, 3-dioxane-2, 5-diyl, pyrimidine-2, 5-diyl, pyridine-2, 5-diyl, fluorene-2, 7-diyl, phenanthrene-2, 7-diyl, anthracene-2, 6-diyl, perhydrocyclopenta [ a ] phenanthrene-3, 17-diyl, or 2,3,4,7,8,9,10,11,12,13,14,15,16, 17-tetradecahydrocyclopenta [ a ] phenanthrene-3, 17-diyl in which adjacent bonds are-CH ═ CH-, -CR10 ═ CR20-, -CO-CH ═ CH-, -CH ═ CH-CO-, -OCO-CH ═ CH-, or-CH ═ CH-COO-, and when R10 and R20 are independently hydrogen, fluorine, a cyano group, an alkyl group having 1 to 10 carbon atoms, or an alkyl group having 1 to 10 carbon atoms in which at least one hydrogen is substituted with fluorine, 1, 4-phenylene, 4' -biphenylene, naphthalene-2, 6-diyl, pyrimidine-2, 5-diyl, pyridine-2, 5-diyl, fluorene-2, 7-diyl, phenanthrene-2, 7-diyl, anthracene-2, 6-diyl, in which at least one hydrogen may be substituted by fluorine, chlorine, an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an alkoxy group having 1 to 11 carbon atoms, or an alkenyloxy group having 2 to 11 carbon atoms, and in which at least one hydrogen may be substituted by fluorine or chlorine.

Ring A40 is 1, 4-cyclohexylene, 1, 4-cyclohexenylene, 1, 4-phenylene, 4' -biphenylene, naphthalene-2, 6-diyl, decahydronaphthalene-2, 6-diyl, 1,2,3, 4-tetrahydronaphthalene-2, 6-diyl, tetrahydropyran-2, 5-diyl, 1, 3-dioxane-2, 5-diyl, pyrimidine-2, 5-diyl, pyridine-2, 5-diyl, fluorene-2, 7-diyl, phenanthrene-2, 7-diyl, anthracene-2, 6-diyl, perhydrocyclopenta [ a ] phenanthrene-3, 17-diyl, or 2,3,4,7,8,9,10,11,12,13,14,15,16, 17-tetradecahydrocyclopenta [ a ] phenanthrene-3, 17-diyl, when the adjacent bond is-CH-, -CO-CH-, -CH-CO-, -OCO-CH-, or-CH-COO-, is 1, 4-phenylene, 4' -biphenylene, naphthalene-2, 6-diyl, pyrimidine-2, 5-diyl, pyridine-2, 5-diyl, fluorene-2, 7-diyl, phenanthrene-2, 7-diyl, anthracene-2, 6-diyl, in these rings, at least one hydrogen may be substituted with P20-Sp20-, fluorine, chlorine, an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an alkoxy group having 1 to 11 carbon atoms, or an alkenyloxy group having 2 to 11 carbon atoms, and in these groups, at least one hydrogen may be substituted with fluorine or chlorine.

Ring a11 and ring a21 are independently 1, 4-phenylene, naphthalene-2, 6-diyl, in which at least one hydrogen may be substituted by fluorine, chlorine, an alkyl group having 1 to 12 carbon atoms, or an alkyl group having 1 to 12 carbon atoms in which at least one hydrogen is substituted by fluorine.

z10 is independently-CH-, -CR 10-CR 20-, -CO-CH-, -CH-CO-, -OCO-CH-, or-CH-COO-, R10 and R20 are independently hydrogen, fluorine, cyano, alkyl having 1 to 10 carbon atoms, or alkyl having 1 to 10 carbon atoms in which at least one hydrogen is substituted with fluorine.

Z11 is independently a single bond or an alkylene group having 1 to 6 carbon atoms, in which at least one of-CH 2-may be substituted by-O-, -CO-, -COO-, -OCO-, or-OCOO-, and at least one of- (CH2) 2-may be substituted by-CH ═ CH-or-C ≡ C-, and of these groups, at least one hydrogen may be substituted by fluorine or chlorine.

preferably a single bond, ethylene, methyleneoxy, -COO-, -OCO-, or-OCOO-, and more preferably a single bond, -COO-or-OCO-.

Z12 is-CO-, or-OCO-.

Z20 and Z21 are independently a single bond, an alkylene group having 1 to 6 carbon atoms, or an alkenylene group having 2 to 6 carbon atoms, at least one of which is an alkenylene group having 2 to 6 carbon atoms. At least one of these alkylene groups and alkenylene groups may be substituted with-O-, -CO-, -COO-, -OCO-, or-OCOO-, and at least one other group- (CH2) 2-may be substituted with-CH-or-C.ident.C-, and among these groups, at least one hydrogen may be substituted with fluorine or chlorine.

Preferably a single bond, -CO-CH-, -CH-CO-, -OCO-CH-, -CH-COO-, or-CH-, but not simultaneously a single bond.

R30, R40, R41 and R50 are independently hydrogen, fluorine, chlorine, an alkyl group having 1 to 10 carbon atoms, or an alkyl group having 1 to 10 carbon atoms wherein at least one hydrogen is substituted with fluorine.

k10 and n10 are independently integers from 0 to 3, the sum of k10 and n10 is an integer from 1 to 6, preferably the sum of k10 and n10 is an integer from 1 to 4.

n20 is 1 or 2.

n30 is 1 or 2.

It is considered that the alignment control layer-forming monomer having a vinylidene group generates formation of a cyclobutane ring by photoisomerization or dimerization from a trans form to a cis form by irradiation with ultraviolet light. The properties can be used to prepare films capable of orienting liquid crystal molecules.

For the production of the film, the ultraviolet rays irradiated are suitably linearly polarized light.

First, an alignment control layer forming monomer is added to a liquid crystal composition in a range of 0.1 to 10% by weight, and the composition is heated in order to dissolve the alignment control layer forming monomer. The composition was injected into the element having no alignment film. Next, the device is irradiated with linearly polarized light while being heated to a temperature equal to or higher than the upper limit temperature of the nematic phase, thereby promoting photoisomerization or dimerization of the monomers forming the alignment control layer. The photoisomerized compound or dimerized compound is aligned in a fixed orientation. Photopolymerization also occurs, forming a thin film on the substrate. The formed film functions as a liquid crystal alignment film.

The composition used in the present invention is described in the following order. First, the composition is explained. Second, the main characteristics of the component compounds and the main effects of the compounds on the composition or element will be described. Third, the combination of the components in the composition, the preferred proportions of the components, and their basis are described. Fourth, preferred embodiments of the component compounds will be described. Fifth, preferred component compounds are shown. Sixth, additives that can be added to the composition will be described. Seventh, a method for synthesizing the component compound will be explained. Eighth, the use of the composition is explained. Ninth, a method of manufacturing the element is explained.

First, the composition is explained. The composition contains a plurality of liquid crystalline compounds. The composition may also contain additives. The additive is an optically active compound, an antioxidant, an ultraviolet absorber, a pigment, an antifoaming agent, a polymerizable compound, a polymerization initiator, a polymerization inhibitor, a polar compound, or the like. From the viewpoint of the liquid crystalline compound, the compositions are classified into composition a and composition B. The composition a may further contain other liquid crystalline compounds in addition to the liquid crystalline compound selected from the compounds (1) and (2). The "other liquid crystalline compound" is a liquid crystalline compound different from the compound (1) and the compound (2). Such compounds are mixed in the composition for the purpose of further adjusting the properties.

The composition B substantially contains only a liquid crystalline compound selected from the compound (1) and the compound (2). The term "substantially" means that the composition may contain additives but does not contain other liquid crystalline compounds. The amount of ingredients of composition B is small compared to composition a. From the viewpoint of cost reduction, composition B is superior to composition a. From the viewpoint that the characteristics can be further adjusted by mixing other liquid crystalline compounds, the composition a is superior to the composition B.

Second, the main characteristics of the component compounds and the main effects of the compounds on the composition or element will be described. The main properties of the component compounds based on the effects of the present invention are summarized in Table 2. In the notation of Table 2, L means large or high, M means moderate, and S means small or low. The symbol L, M, S is a classification based on qualitative comparison between component compounds, and the symbol 0 (zero) means that the dielectric anisotropy is extremely small.

[ Table 2]

TABLE 2 characterization of the Compounds

compound (I)	Compound (1)	Compound (2)
			upper limit temperature	M～L	S～L
Viscosity of the oil	M～L	S～M
			Optical anisotropy	M～L	S～L
dielectric anisotropy	M～L¹⁾	0
			specific resistance	L	L

1) the value of the dielectric anisotropy is positive, and the symbol indicates the magnitude of the absolute value

When the component compounds are mixed in the composition, the main effects of the component compounds on the properties of the composition are as follows. The orientation control layer forming monomer is a first additive. The alignment control layer-forming monomers are aligned in a fixed direction at a molecular level when dimerized or isomerized by polarization. Therefore, the film prepared from the alignment control layer-forming monomer aligns liquid crystal molecules in the same manner as an alignment film such as polyimide. The compound (1) as the first component improves the dielectric anisotropy. The compound (2) as the second component lowers the viscosity or raises the upper limit temperature. The compound (3) as the third component increases the dielectric constant in the short axis direction. The compound (4) as the second additive provides a polymer by polymerization, which shortens the response time of the element and improves the afterimage of the image.

third, the combination of the components in the composition, the preferred proportions of the components, and their basis are described. Preferred combinations of components in the composition are the first component + the first additive, the first component + the second component + the first additive, the first component + the third component + the first additive, or the first component + the second component + the third component + the first additive. A further preferred combination is the first component + the second component + the first additive. A second additive may be further added to these combinations.

The preferred ratio of the alignment control layer forming monomer as the first additive is about 0.1 parts by weight or more based on the total amount of the liquid crystalline compound in order to align the liquid crystal molecules, and the preferred ratio of the alignment control layer forming monomer as the first additive is about 10 parts by weight or less in order to prevent display defects of the device. Even more preferred ratios range from about 0.3 parts by weight to about 6 parts by weight. A particularly preferred ratio is in the range of about 0.5 parts by weight to about 4 parts by weight.

the preferable proportion of the first component is about 10% by weight or more for improving the dielectric anisotropy, and about 85% by weight or less for lowering the lower limit temperature or lowering the viscosity. Even more preferred is a ratio in the range of about 15 wt% to about 80 wt%. A particularly preferred ratio is in the range of about 20% to about 75% by weight.

the preferable proportion of the second component is about 10% by weight or more in order to increase the upper limit temperature or to reduce the viscosity, and about 85% by weight or less in order to increase the dielectric anisotropy. Even more preferred is a ratio in the range of about 15 wt% to about 80 wt%. A particularly preferred ratio is in the range of about 20% to about 75% by weight.

the preferable proportion of the third component is about 3 wt% or more in order to increase the dielectric constant in the short axis direction, and about 25 wt% or less in order to lower the lower limit temperature. Even more preferred is a ratio in the range of about 5 wt% to about 20 wt%. A particularly preferred ratio is in the range of about 5% to about 15% by weight.

The second additive may also be added to the composition for the purpose of being suitable for a polymer-stabilized oriented element. The preferable proportion of the additive is about 0.03 parts by weight or more based on the total amount of the liquid crystalline compound in order to align liquid crystal molecules, and about 10 parts by weight or less in order to prevent display defects of the element. Even more preferred ratios range from about 0.1 parts by weight to about 2 parts by weight. A particularly preferred ratio is in the range of about 0.2 parts by weight to about 1.0 parts by weight.

Fourth, preferred embodiments of the component compounds will be described. In the formulae (1), (2) and (3), R1 is an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms or an alkenyl group having 2 to 12 carbon atoms. In order to improve stability against ultraviolet light or heat, R1 is preferably an alkyl group having 1 to 12 carbon atoms. R2 and R3 are independently an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, or an alkenyl group having 2 to 12 carbon atoms in which at least one hydrogen is substituted with fluorine or chlorine. In order to reduce viscosity, R2 or R3 is preferably an alkenyl group having 2 to 12 carbon atoms, and R2 or R3 is preferably an alkyl group having 1 to 12 carbon atoms in order to improve stability to ultraviolet light or heat. R4 and R5 are independently an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, or an alkenyloxy group having 2 to 12 carbon atoms. In order to improve stability against ultraviolet light or heat, R4 or R5 is preferably an alkyl group having 1 to 12 carbon atoms, and R4 or R5 is preferably an alkoxy group having 1 to 12 carbon atoms in order to improve dielectric constant in the short axis direction.

Preferred alkyl groups are methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, or octyl. Further preferred alkyl groups for reducing the viscosity are methyl, ethyl, propyl, butyl, or pentyl groups.

Preferred alkoxy groups are methoxy, ethoxy, propoxy, butoxy, pentoxy, hexoxy, or heptoxy. Further preferred alkoxy groups for reducing the viscosity are methoxy or ethoxy.

Preferred alkenyl groups are vinyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, or 5-hexenyl. Further preferable alkenyl groups for reducing the viscosity are vinyl, 1-propenyl, 3-butenyl, or 3-pentenyl. The preferred steric configuration of-CH ═ CH-in these alkenyl groups depends on the position of the double bond. For reasons of viscosity reduction and the like, the trans configuration is preferred among alkenyl groups such as 1-propenyl, 1-butenyl, 1-pentenyl, 1-hexenyl, 3-pentenyl, 3-hexenyl. Among alkenyl groups such as 2-butenyl, 2-pentenyl, 2-hexenyl, the cis configuration is preferred. Among these alkenyl groups, a straight-chain alkenyl group is preferable to a branched alkenyl group.

Preferred alkenyloxy groups are vinyloxy, allyloxy, 3-butenyloxy, 3-pentenyloxy, or 4-pentenyloxy. Further preferred alkenyloxy groups for reducing the viscosity are allyloxy or 3-butenyloxy.

Preferred examples of alkyl groups in which at least one hydrogen is substituted by fluorine or chlorine are fluoromethyl, 2-fluoroethyl, 3-fluoropropyl, 4-fluorobutyl, 5-fluoropentyl, 6-fluorohexyl, 7-fluoroheptyl or 8-fluorooctyl. Further preferable examples are 2-fluoroethyl, 3-fluoropropyl, 4-fluorobutyl and 5-fluoropentyl for improving the dielectric anisotropy.

Preferred examples of alkenyl groups in which at least one hydrogen is substituted by fluorine or chlorine are 2, 2-difluorovinyl, 3-difluoro-2-propenyl, 4-difluoro-3-butenyl, 5-difluoro-4-pentenyl, or 6, 6-difluoro-5-hexenyl. Further preferable examples for lowering the viscosity are 2, 2-difluorovinyl group or 4, 4-difluoro-3-butenyl group.

Ring a is 1, 4-cyclohexylene, 1, 4-phenylene, 2-fluoro-1, 4-phenylene, 2, 3-difluoro-1, 4-phenylene, 2, 6-difluoro-1, 4-phenylene, pyrimidine-2, 5-diyl, 1, 3-dioxane-2, 5-diyl, or tetrahydropyran-2, 5-diyl. In order to improve the optical anisotropy, ring A is preferably 1, 4-phenylene or 2-fluoro-1, 4-phenylene. Tetrahydropyran-2, 5-diyl as

Preferably, it is

Ring B and ring C are independently 1, 4-cyclohexylene, 1, 4-phenylene, 2-fluoro-1, 4-phenylene, or 2, 5-difluoro-1, 4-phenylene. The ring B or the ring C is preferably a1, 4-cyclohexylene group for lowering the viscosity, or a1, 4-phenylene group for improving the optical anisotropy. Ring D and ring F are independently 1, 4-cyclohexylene, 1, 4-cyclohexenylene, tetrahydropyran-2, 5-diyl, 1, 4-phenylene in which at least one hydrogen is substituted by fluorine or chlorine, naphthalene-2, 6-diyl in which at least one hydrogen is substituted by fluorine or chlorine, chroman-2, 6-diyl in which at least one hydrogen is substituted by fluorine or chlorine, or chroman-2, 6-diyl in which at least one hydrogen is substituted by fluorine or chlorine. The ring D or F is preferably a1, 4-cyclohexylene group for lowering the viscosity, a tetrahydropyran-2, 5-diyl group for increasing the dielectric constant in the short axis direction, and a1, 4-phenylene group for increasing the optical anisotropy. Ring E is 2, 3-difluoro-1, 4-phenylene, 2-chloro-3-fluoro-1, 4-phenylene, 2, 3-difluoro-5-methyl-1, 4-phenylene, 3,4, 5-trifluoronaphthalene-2, 6-diyl, or 7, 8-difluorochroman-2, 6-diyl. In order to increase the dielectric constant in the short axis direction, the preferred ring E is 2, 3-difluoro-1, 4-phenylene.

Z1 is a single bond, ethylene, carbonyloxy, or difluoromethyleneoxy. In order to reduce the viscosity, Z1 is preferably a single bond, and in order to improve the dielectric anisotropy, Z1 is preferably difluoromethyleneoxy. Z2 is a single bond, ethylene, or carbonyloxy. To reduce viscosity, preferably Z2 is a single bond. Z3 and Z4 are independently a single bond, ethylene, carbonyloxy, or methyleneoxy. In order to lower the viscosity, preferably Z3 or Z4 is a single bond, and in order to increase the dielectric constant in the short axis direction, preferably Z3 or Z4 is a methyleneoxy group.

X1 and X2 are independently hydrogen or fluorine. For improving the dielectric anisotropy, X1 or X2 is preferably fluorine.

y1 is fluorine, chlorine, an alkyl group of carbon number 1 to 12 wherein at least one hydrogen is substituted by fluorine or chlorine, an alkoxy group of carbon number 1 to 12 wherein at least one hydrogen is substituted by fluorine or chlorine, or an alkenyloxy group of carbon number 2 to 12 wherein at least one hydrogen is substituted by fluorine or chlorine. For lowering the lower temperature, preferably Y1 is fluorine.

a preferred example of an alkyl group in which at least one hydrogen is substituted by fluorine or chlorine is trifluoromethyl. A preferred example of an alkoxy group wherein at least one hydrogen is substituted by fluorine or chlorine is trifluoromethoxy. A preferred example of an alkenyloxy group substituted by at least one hydrogen with fluorine or chlorine is trifluorovinyloxy.

a is 1,2,3, or 4. In order to lower the lower limit temperature, a is preferably 2, and in order to improve the dielectric anisotropy, a is preferably 3. b is 1,2, or 3. For lowering the viscosity, b is preferably 1, and for raising the upper limit temperature, b is preferably 2 or 3. c is 1,2 or 3, d is 0 or 1, and the sum of c and d is 3 or less. For lowering the viscosity, c is preferably 1, and for raising the upper limit temperature, c is preferably 2 or 3. For lowering the viscosity, d is preferably 0, and for lowering the lower limit temperature, d is preferably 1.

in formula (4), P1, P2, and P3 are independently a polymerizable group. Preferred P1, P2, or P3 is a polymerizable group selected from the group of groups represented by the formulae (P-1) to (P-5). Further preferably, P1, P2 or P3 is a group represented by the formula (P-1), the formula (P-2) or the formula (P-3). Particularly preferred P1, P2 or P3 is a group represented by the formula (P-1) or the formula (P-2). Most preferably, P1, P2, or P3 is a group represented by the formula (P-1). A preferred group represented by formula (P-1) is-OCO-CH ═ CH2 or-OCO-C (CH3) ═ CH 2. The wavy lines of the formulae (P-1) to (P-5) indicate the sites to which the bonds are bonded.

In the formulae (P-1) to (P-5), M1, M2, and M3 are independently hydrogen, fluorine, an alkyl group having 1 to 5 carbon atoms, or an alkyl group having 1 to 5 carbon atoms in which at least one hydrogen is substituted with fluorine or chlorine. For enhanced reactivity, preferably M1, M2, or M3 is hydrogen or methyl. Further preferably M1 is hydrogen or methyl, further preferably M2 or M3 is hydrogen.

Sp1, Sp2, and Sp3 are independently a single bond or an alkylene group having 1 to 10 carbon atoms, in which at least one-CH 2-group may be substituted with-O-, -COO-, -OCO-, or-OCOO-, and at least one-CH 2-CH 2-group may be substituted with-CH ═ CH-or-C ≡ C-, and among these groups, at least one hydrogen may be substituted with fluorine or chlorine. Preferred Sp1, Sp2, or Sp3 is a single bond, -CH2-CH2-, -CH2O-, -OCH2-, -COO-, -OCO-, -CO-CH-, or-CH-CO-. Further preferably, Sp1, Sp2 or Sp3 is a single bond.

Ring F3 and ring I are independently cyclohexyl, cyclohexenyl, phenyl, 1-naphthyl, 2-naphthyl, tetrahydropyran-2-yl, 1, 3-dioxan-2-yl, pyrimidin-2-yl, or pyridin-2-yl, and in these rings, at least one hydrogen may be substituted with fluorine, chlorine, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or an alkyl group having 1 to 12 carbon atoms in which at least one hydrogen is substituted with fluorine or chlorine. Preferred ring F3 or ring I is phenyl. Ring G is 1, 4-cyclohexylene, 1, 4-cyclohexenylene, 1, 4-phenylene, naphthalene-1, 2-diyl, naphthalene-1, 3-diyl, naphthalene-1, 4-diyl, naphthalene-1, 5-diyl, naphthalene-1, 6-diyl, naphthalene-1, 7-diyl, naphthalene-1, 8-diyl, naphthalene-2, 3-diyl, naphthalene-2, 6-diyl, naphthalene-2, 7-diyl, tetrahydropyran-2, 5-diyl, 1, 3-dioxane-2, 5-diyl, pyrimidine-2, 5-diyl, or pyridine-2, 5-diyl, and in these rings, at least one of them is substituted with fluorine, chlorine, an alkyl group having 1 to 12 carbon atoms, An alkoxy group having 1 to 12 carbon atoms, or an alkyl group having 1 to 12 carbon atoms in which at least one hydrogen is substituted with fluorine or chlorine. Preferred ring G is 1, 4-phenylene or 2-fluoro-1, 4-phenylene.

z6 and Z7 are independently a single bond or an alkylene group having 1 to 10 carbon atoms, in which at least one-CH 2-may be substituted by-O-, -CO-, -COO-, or-OCO-, and at least one-CH 2-CH 2-may be substituted by-CH-, -C (CH3) ═ CH-, -CH ═ C (CH3) -, or-C (CH3) ═ C (CH3) -, and of these groups, at least one hydrogen may be substituted by fluorine or chlorine. Preferred Z6 or Z7 is a single bond, -CH2-CH2-, -CH2O-, -OCH2-, -COO-, or-OCO-. Further preferably, Z6 or Z7 is a single bond.

h is 0,1, or 2. Preferably h is 0 or 1. e. f, and g are independently 0,1, 2,3, or 4, and the sum of e, f, and g is 1 or more. Preferably e, f, or g is 1 or 2.

Fifth, preferred component compounds are shown. Preferred alignment control layer-forming monomers will be described. The orientation control layer-forming monomer preferably has at least two or more polymerizable groups. In the case where there is one polymerizable group, the orientation control layer obtained after polymerization is a flexible film, and therefore the orientation control layer is likely to be deformed in a temperature environment in which the liquid crystal display element is driven, and the orientation control force is likely to be reduced. It is considered that when the polymerizable group has at least two or more polymerizable groups, the crosslinking density of the orientation control layer obtained after polymerization increases to form a strong film, and therefore, it is considered that the orientation control layer is less likely to be deformed even in a high-temperature environment. The site where dimerization or isomerization is caused by polarization is a vinylidene group. The compound having a chalcone structure or cinnamate structure containing a vinylidene group is preferable because the same effect can be obtained. In order to control the solubility in the liquid crystalline compound, a spacer may be introduced between the polymerizable group and the central structure in order to improve the compatibility with the terminal chain of the liquid crystalline compound. The spacer is preferably linear or branched. The length of the spacer is preferably 2 or more carbon atoms. Two or more alignment control layers may be used in combination as a monomer. Specifically exemplified is a preferred orientation control layer-forming monomer. Are compounds (A-1-1) to (A-1-8), compounds (A-A-1) to (A-A-15), compounds (A-2-1) to (A-2-12), compounds (B-1-1) to (B-1-17), compounds (C-1-1) to (C-1-10) and compounds (D-1-1) to (D-1-9). N in the compounds (A-1-4) to (A-1-7), the compounds (A-A-5), the compounds (A-A-7), the compounds (A-2-1) to (A-2-2), the compounds (A-2-7) to (A-2-12) is independently 2 to 12. Among the compounds (A-2-1) to (A-2-2) and (A-2-7) to (A-2-12), n is more preferably 2 to 10 from the viewpoint of improving compatibility with a liquid crystalline compound.

As preferred orientation control layer-forming monomers having a cinnamate structure in addition to the above, there can be mentioned compounds (I-1) to (I-34) described in paragraphs 0029 to 0033 of Japanese patent laid-open No. 2011-202168, compounds (I-36) to (I-39), compounds (I-1) to (I-52) described in paragraphs 0031 to 0042 of Japanese patent laid-open No. 2010-285499, compounds (I-56) to (I-59), and compounds (I-60) to (I-62).

Preferred compound (1) is the compound (1-1) to the compound (1-39) described in the item 6. Of these compounds, it is preferable that at least one of the first components is a compound (1-4), a compound (1-12), a compound (1-14), a compound (1-15), a compound (1-17), a compound (1-18), a compound (1-23), a compound (1-24), a compound (1-27), a compound (1-29), or a compound (1-30). Preferably, at least two of the first components are a combination of the compounds (1-12) and (1-15), the compounds (1-14) and (1-27), the compounds (1-18) and (1-24), the compounds (1-18) and (1-29), the compounds (1-24) and (1-29), or the compounds (1-29) and (1-30).

preferred compound (2) is the compound (2-1) to the compound (2-13) described in the item 9. Of these compounds, at least one of the second components is preferably compound (2-1), compound (2-3), compound (2-5), compound (2-6), or compound (2-7). Preferably, at least two of the second components are a combination of the compound (2-1) and the compound (2-5), the compound (2-1) and the compound (2-6), the compound (2-1) and the compound (2-7), the compound (2-3) and the compound (2-5), the compound (2-3) and the compound (2-6), and the compound (2-3) and the compound (2-7).

preferred compound (3) is the compound (3-1) to the compound (3-22) described in the item 12. Of these compounds, it is preferable that at least one of the third components is compound (3-1), compound (3-3), compound (3-4), compound (3-6), compound (3-8), or compound (3-10). Preferably, at least two of the third components are a combination of the compound (3-1) and the compound (3-6), the compound (3-3) and the compound (3-10), the compound (3-4) and the compound (3-6), the compound (3-4) and the compound (3-8), or the compound (3-6) and the compound (3-10).

sixth, additives that can be added to the composition will be described. Such additives include optically active compounds, antioxidants, ultraviolet absorbers, pigments, antifoaming agents, polymerizable compounds, polymerization initiators, polymerization inhibitors, polar compounds, and the like. An optically active compound is added to the composition for the purpose of inducing a helical structure of liquid crystal molecules to impart a twist angle (torsion angle). Examples of such compounds are compounds (Op-1) to (Op-5). The preferable proportion of the optically active compound is about 5 parts by weight or less based on the total amount of the liquid crystalline compound. Even more preferred is a ratio in the range of about 0.01 to about 2 parts by weight.

in order to prevent a decrease in specific resistance caused by heating in the atmosphere or to maintain a large voltage holding ratio at room temperature and at a temperature close to the upper limit temperature even after the device is used for a long time, an antioxidant is added to the composition. Preferable examples of the antioxidant include a compound (G) wherein n is an integer of 1 to 9, and the like.

in the compound (G), n is preferably 1,3, 5, 7, or 9. Further, n is preferably 7. Since the compound (G) having n of 7 has low volatility, it is effective for maintaining a large voltage holding ratio not only at room temperature but also at a temperature close to the upper limit temperature after the device is used for a long time. In order to obtain the above effect, the preferable proportion of the antioxidant is about 50ppm or more, and in order not to lower the upper limit temperature or to raise the lower limit temperature, the preferable proportion of the antioxidant is about 600ppm or less. Even more preferred ratios range from about 100ppm to about 300 ppm.

Preferable examples of the ultraviolet absorber include benzophenone derivatives, benzoate derivatives, triazole derivatives and the like. Light stabilizers such as sterically hindered amines are also preferred. The preferable proportion of these absorbents or stabilizers is about 50ppm or more in order to obtain the effect, and about 10000ppm or less in order not to lower the upper limit temperature or not to raise the lower limit temperature. Even more preferred ratios range from about 100ppm to about 10000 ppm.

In order to be suitable for a guest-host (GH) mode element, a dichroic dye (dichromatic dye) such as an azo dye or an anthraquinone dye is added to the composition. The preferable proportion of the pigment ranges from about 0.01 parts by weight to about 10 parts by weight based on the total amount of the liquid crystalline compound. In order to prevent foaming, an antifoaming agent such as dimethylsilicone oil or methylphenylsilicone oil is added to the composition. The preferable ratio of the defoaming agent is about 1ppm or more in order to obtain the above effects, and about 1000ppm or less in order to prevent display failure. Even more preferred ratios range from about 1ppm to about 500 ppm.

Polymerizable compounds are used to adapt to polymer-stabilized alignment (PSA) type devices. The compounds (4) are suitable for this purpose. The compound (4) and a polymerizable compound different from the compound (4) may be added to the composition. Instead of the compound (4), a polymerizable compound different from the compound (4) may be added to the composition. Preferable examples of such polymerizable compounds are compounds such as acrylic acid esters, methacrylic acid esters, vinyl compounds, vinyloxy compounds, propenyl ethers, epoxy compounds (oxetane ) and vinyl ketones. Further preferable examples are derivatives of acrylic acid esters or methacrylic acid esters. By changing the kind of the compound (4) or by combining polymerizable compounds different from the compound (4) at an appropriate ratio, the reactivity of the polymerizable compounds or the pretilt angle of the liquid crystal molecules can be adjusted. By optimizing the pretilt angle, a short response time of the element can be achieved. Since the alignment of the liquid crystal molecules is stabilized, a large contrast ratio or a long lifetime can be achieved.

The compound (4) or a polymerizable compound such as an alignment control layer-forming monomer is polymerized by irradiation with ultraviolet rays. The polymerization may be carried out in the presence of an appropriate initiator such as a photopolymerization initiator. Suitable conditions, suitable types of initiators, and suitable amounts for carrying out the polymerization are known to those skilled in the art and are described in the literature. For example, ornirade (Omnirad)651 (registered trademark; IGM Resins), ornirade (Omnirad)184 (registered trademark; IGM Resins), or ornirade (Omnirad)1173 (registered trademark; IGM Resins) as photopolymerization initiators are suitable for radical polymerization. The preferable proportion of the photopolymerization initiator ranges from about 0.1 part by weight to about 5 parts by weight based on the total amount of the polymerizable compound. Still more preferred is a range of about 1 part by weight to about 3 parts by weight.

when storing the compound (4) or the polymerizable compound such as the alignment control layer-forming monomer, a polymerization inhibitor may be added to prevent polymerization. The polymerizable compound is usually added to the composition in a state where the polymerization inhibitor is not removed. Examples of the polymerization inhibitor are hydroquinone derivatives such as hydroquinone and methylhydroquinone, 4-t-butylcatechol, 4-methoxyphenol, phenothiazine and the like.

The polar compound is an organic compound having polarity. Here, no compound having an ionic bond is contained. Atoms such as oxygen, sulfur, and nitrogen are negatively charged and tend to have a partial negative charge. Carbon and hydrogen are neutral or tend to have a partial positive charge. Polarity arises because part of the charge is distributed unequally among the atoms of different species in the compound. For example, the polar compound has at least one of partial structures such as-OH, -COOH, -SH, -NH2, > NH, > N-.

Seventh, a method for synthesizing the component compound will be explained. These compounds can be synthesized using known methods. A synthesis method is exemplified. The compound (1-1) is synthesized by the method described in Japanese patent laid-open No. Hei 2-503441. The compound (2-5) is synthesized by the method described in Japanese patent laid-open No. 57-165328. The compound (3-18) is synthesized by the method described in Japanese patent laid-open No. Hei 7-101900. Antioxidants are commercially available. The compound of formula (5) wherein n is 1 is available from Sigma Aldrich Corporation. The compound (5) wherein n is 7, etc. is synthesized by the method described in the specification of U.S. Pat. No. 3660505. The orientation control layer-forming monomer having a vinylidene group is synthesized by the methods described in International publication No. 2013/077343, International publication No. 2002/048281, International publication No. 2015/004947, U.S. Pat. No. 2013-0277609, and Japanese patent laid-open publication No. 63-8361. An alignment control layer-forming monomer having an α -fluoroacrylate group is synthesized by the method described in Japanese patent laid-open No. 2005-112850.

Compounds not described in the synthesis method can be synthesized by the methods described in the following written description: organic Synthesis (Organic Synthesis), Inc. (John Wiley & Sons, Inc.), (Organic Reactions), Inc. (John Wiley & Sons, Inc.)), (Organic Synthesis), Integrated Circuit (Pergeman Press), New Experimental chemistry lecture (Bolus), etc. The compositions are prepared from the compounds obtained in the manner described, using known methods. For example, the component compounds are mixed and then dissolved in each other by heating.

Eighth, the use of the composition is explained. Most compositions have a lower temperature of about-10 ℃ or less, an upper temperature of about 70 ℃ or more, and an optical anisotropy in the range of about 0.07 to about 0.20. A composition having an optical anisotropy in the range of about 0.08 to about 0.25 may be prepared by controlling the ratio of component compounds, or by mixing other liquid crystalline compounds. Further, a composition having an optical anisotropy in a range of about 0.10 to about 0.30 may also be prepared by the method. The device containing the composition has a large voltage holding ratio. The composition is suitable for AM elements. The composition is particularly suitable for transmissive AM elements. The composition can be used as a composition having a nematic phase, and can be used as an optically active composition by adding an optically active compound.

The compositions are useful in AM elements. Further, the present invention can be applied to a PM element. The composition can be used for AM elements and PM elements with modes of PC, TN, STN, ECB, OCB, IPS, FFS, VA, FPA and the like. Particularly preferably, the AM device is used in an AM device having a VA mode, an OCB mode, an IPS mode, or an FFS mode. In an AM element having an IPS mode or an FFS mode, the arrangement of liquid crystal molecules may be parallel or may be perpendicular to a glass substrate when no voltage is applied. These elements may be reflective, transmissive or transflective. Preferably for use in transmissive devices. But also for amorphous silicon-TFT elements or polysilicon-TFT elements. The present invention can also be used for a Nematic Curvilinear Aligned Phase (NCAP) type element prepared by microencapsulating the composition, or a Polymer Dispersed (PD) type element in which a three-dimensional network polymer is formed in the composition.

Ninth, a method of manufacturing the element is explained. The first step is to add an alignment control layer-forming monomer to the liquid crystal composition and to heat and dissolve the composition at a temperature higher than the upper limit temperature. The second step is to inject the composition into a liquid crystal display element. In the above step, when the liquid crystal composition is heated and injected at a temperature higher than the upper limit temperature, the shear stress when the liquid crystal composition flows in the cell can be reduced, and the occurrence of alignment defects can be easily prevented. The third step is to irradiate the linearly polarized ultraviolet rays in a state where the liquid crystal composition is heated to a temperature higher than the upper limit temperature. The alignment control layer-forming monomer is polymerized while being dimerized or isomerized by linearly polarized ultraviolet rays. The preferred cumulative amount of linearly polarized ultraviolet light (J/cm2) reaching the element surface is 0.1J/cm 2-20J/cm 2. The cumulative light amount is preferably in the range of 0.1J/cm2 to 10J/cm2, and more preferably in the range of 0.1J/cm2 to 7J/cm 2. The cumulative light amount (J/cm2) can be obtained by the illuminance (unit: mW/cm2) of ultraviolet light x the irradiation time (unit: sec). The temperature conditions for the irradiation of linearly polarized ultraviolet rays are preferably set in the same manner as the heat treatment temperature. The time for the linearly polarized ultraviolet ray irradiation is calculated from the lamp illuminance, and therefore, from the viewpoint of production efficiency, it is preferable to perform the irradiation with the illuminance as high as possible. Since the polymer containing the alignment control layer forming monomer is arranged in a fixed direction at a molecular level and fixed on the substrate, the thin film functions as a liquid crystal alignment film. A liquid crystal display element having no alignment film such as polyimide can be manufactured by the method.

Examples

The present invention will be further described in detail by way of examples. The present invention is not limited by these examples. The invention comprises a mixture of the composition of example 1 and the composition of example 2. The invention also includes mixtures of at least two of the compositions of the examples. The synthesized compound is identified by Nuclear Magnetic Resonance (NMR) analysis or the like. The properties of the compounds, compositions and devices were measured by the methods described below.

NMR analysis: DRX-500 manufactured by Bruker BioSpin was used for the measurement. In the 1H-NMR measurement, a sample was dissolved in a deuterated solvent such as CDCl3, and the measurement was carried out under conditions of 500MHz at room temperature and 16 cumulative times. Tetramethylsilane was used as an internal standard. The 19F-NMR measurement was carried out by accumulating 24 times using CFCl3 as an internal standard. In the description of nmr spectra, s is a singlet (singlet), d is a doublet (doublt), t is a triplet (triplet), q is a quartet (quatet), quin is a quintet (quintet), sex is a sextant (sextet), m is a multiplet (multiplex), and br is a broad (broad).

Gas chromatographic analysis: for the measurement, a GC-14B gas chromatograph manufactured by Shimadzu corporation was used. The carrier gas was helium (2 mL/min). The sample vaporizer was set at 280 ℃ and the detector (flame ionization detector, FID) was set at 300 ℃. For separation of component compounds, a capillary column DB-1 (length 30m, inner diameter 0.32mm, film thickness 0.25 μm; fixing liquid phase is dimethylpolysiloxane; non-polar) manufactured by Agilent Technologies Inc. was used. After the column was held at 200 ℃ for 2 minutes, the temperature was raised to 280 ℃ at a rate of 5 ℃/min. After preparing the sample into an acetone solution (0.1 wt%), 1. mu.L thereof was injected into the sample vaporization chamber. The record is a chromatograph module (Chromatopac) model C-R5A manufactured by Shimadzu corporation or an equivalent thereof. The obtained gas chromatogram showed the retention time of the peak and the area of the peak corresponding to the component compound.

As a solvent for diluting the sample, chloroform, hexane, etc. can be used. To separate the constituent compounds, the following capillary column may be used. HP-1 (length 30m, inner diameter 0.32mm, film thickness 0.25 μm) manufactured by Agilent Technologies Inc., Rtx-1 (length 30m, inner diameter 0.32mm, film thickness 0.25 μm) manufactured by Rasteck Corporation, BP-1 (length 30m, inner diameter 0.32mm, film thickness 0.25 μm) manufactured by Australian SGE International Pty.Ltd. For the purpose of preventing overlapping of compound peaks, capillary columns manufactured by Shimadzu corporation CBP1-M50-025 (length 50M, inner diameter 0.25mm, film thickness 0.25 μ M) were used.

The ratio of the liquid crystalline compound contained in the composition can be calculated by the following method. The mixture of liquid crystalline compounds was detected by gas chromatography (FID). The area ratio of the peaks in the gas chromatogram corresponds to the ratio (weight ratio) of the liquid crystalline compound. When the capillary column described above is used, the correction coefficient of each liquid crystalline compound can be regarded as 1. Therefore, the ratio (% by weight) of the liquid crystalline compound can be calculated from the area ratio of the peak.

measurement of the sample: when the characteristics of the composition and the element were measured, the composition was used as a sample as it is. In order to measure the characteristics of the compound, a sample for measurement was prepared by mixing the compound (15 wt%) in a mother liquid crystal (85 wt%). From the values obtained by the measurement, the characteristic values of the compounds were calculated by extrapolation. (extrapolated value) { (measured value of sample) — 0.85 × (measured value of mother liquid crystal) }/0.15. When a smectic phase (or crystal) precipitates at 25 ℃ at the stated ratio, the ratio of the compound to the mother liquid crystal is set at 10% by weight: 90 wt%, 5 wt%: 95% by weight, 1% by weight: the order of 99 wt.% was changed. The values of the upper limit temperature, optical anisotropy, viscosity, and dielectric anisotropy relating to the compound were obtained by the above extrapolation method.

the following mother liquid crystal was used. The proportions of the component compounds are expressed in% by weight.

The determination method comprises the following steps: the characteristics were measured by the following methods. These methods are mostly described in JEITA standard (JEITA. ED-2521B) examined and established by the Japan electronic Information Technology Industries Association (hereinafter, JEITA), or modified. In the TN cell used for the measurement, a Thin Film Transistor (TFT) was not mounted.

(1) Upper limit temperature of nematic phase (NI;. degree. C.): the sample was placed on a hot plate of a melting point measuring apparatus equipped with a polarizing microscope, and heated at a rate of 1 ℃/min. The temperature at which a part of the sample changes from nematic phase to isotropic liquid was measured. The upper limit temperature of the nematic phase may be simply referred to as "upper limit temperature".

(2) Lower limit temperature of nematic phase (TC;): the nematic phase was observed after placing the sample in a glass bottle and keeping the bottle in a freezer at 0 ℃, -10 ℃, -20 ℃, -30 ℃ and-40 ℃ for 10 days. For example, when a sample is in a nematic phase at-20 ℃ and changes to a crystalline or smectic phase at-30 ℃, TC is described as < -20 ℃. The lower limit temperature of the nematic phase may be simply referred to as "lower limit temperature".

(3) viscosity (. eta.; measured at 20 ℃ C.; mPas): for the measurement, an E-type rotational viscometer manufactured by tokyo counter gmbh was used.

(4) Viscosity (rotational viscosity; γ 1; measured at 25 ℃; mPas): the measurement was carried out according to the method described in M.Imai et al, Molecular Crystals and Liquid Crystals (Molecular Crystals and Liquid Crystals), 259, page 37 (1995). A sample was placed in a TN cell having a twist angle of 0 DEG and a gap (cell gap) of 5 μm between two glass substrates. The element was applied with a voltage in 0.5V unit in a stepwise manner in a range of 16V to 19.5V. After 0.2 seconds of no voltage application, the application was repeated under the condition of applying only one square wave (square pulse; 0.2 seconds) and no voltage application (2 seconds). The peak current (peak current) and peak time (peak time) of the transient current (transient current) generated by the application are measured. The value of the rotational viscosity is obtained from these measured values and the calculation formula (8) described on page 40 of the paper by M. The value of the dielectric anisotropy required for the calculation is measured using an element for measuring the rotational viscosity and using the term (6).

(5) Optical anisotropy (refractive index anisotropy; Δ n; measured at 25 ℃): the measurement was performed using light having a wavelength of 589nm by an Abbe refractometer having a polarizing plate attached to an eyepiece lens. After rubbing the surface of the main prism in one direction, the sample was dropped on the main prism. The refractive index n/is measured when the direction of polarization is parallel to the direction of rubbing. The refractive index n ″) is measured when the direction of the polarized light is perpendicular to the direction of the friction. The value of the optical anisotropy is calculated from the formula Δ n ═ n/n ″.

(6) Dielectric anisotropy (. DELTA.. di-elect cons.; measured at 25 ℃): a sample was placed in a TN cell having a cell gap of 9 μm and a twist angle of 80 degrees between two glass substrates. A sine wave (10V, 1kHz) was applied to the cell, and the dielectric constant (. epsilon. /) in the long axis direction of the liquid crystal molecules was measured after 2 seconds. Sine wave (0.5V, 1kHz) was applied to the element, and the dielectric constant (∈ ∈ in the short axis direction of the liquid crystal molecules was measured after 2 seconds. The value of the dielectric anisotropy is calculated according to the formula Δ ∈/∈ j.

(7) Threshold voltage (Vth; measured at 25 ℃; V): a luminance meter model LCD5100 manufactured by tsukau electronics gmbh was used for the measurement. The light source is a halogen lamp. A sample was placed in a TN element of normal white mode (normal white mode) in which the gap between two glass substrates (cell gap) was 0.45/. DELTA.n (. mu.m) and the twist angle was 80 degrees. The voltage (32Hz, rectangular wave) applied to the element was increased stepwise from 0V to 10V in units of 0.02V. At this time, the element was irradiated with light from the vertical direction, and the amount of light transmitted through the element was measured. A voltage-transmittance curve is prepared in which the transmittance is 100% when the light amount reaches the maximum and the transmittance is 0% when the light amount is the minimum. The threshold voltage is represented by a voltage at which the transmittance reaches 90%.

(8) Voltage holding ratio (VHR-1; measured at 25;%): the TN element used for the measurement had a polyimide alignment film, and the interval (cell gap) between the two glass substrates was 5 μm. After the sample is placed in the element, the element is sealed with an adhesive cured with ultraviolet rays. The TN cell was charged by applying a pulse voltage (5V, 60 μ sec). The decayed voltage was measured by a high-speed voltmeter for 16.7 milliseconds, and the area a between the voltage curve and the horizontal axis in the unit period was determined. The area B is the area when not attenuated. The voltage holding ratio is expressed by a percentage of the area a to the area B.

(9) Voltage holding ratio (VHR-2; measured at 80;%): the voltage holding ratio was measured in the same procedure as described except that the measurement was performed at 80 ℃ instead of 25 ℃. The obtained value is represented by VHR-2.

(10) Voltage holding ratio (VHR-3; measured at 25;%): after irradiation with ultraviolet rays, the voltage holding ratio was measured, and stability against ultraviolet rays was evaluated. The TN cells used in the measurement had a polyimide alignment film and had a cell gap of 5 μm. The sample was injected into the cell and irradiated with light for 20 minutes. The light source was an ultra-high pressure mercury lamp USH-500D (manufactured by Ushio motor), and the spacing between the elements and the light source was 20 cm. In the measurement of VHR-3, the voltage decayed was measured during 16.7 milliseconds. Compositions with large VHR-3 have a large stability to UV light. VHR-3 is preferably 90% or more, more preferably 95% or more.

(11) Voltage holding ratio (VHR-4; measured at 25;%): after the TN cells impregnated with the samples were heated in a thermostatic bath at 80 ℃ for 500 hours, the voltage holding ratio was measured, and the stability against heat was evaluated. In the measurement of VHR-4, the voltage decayed was measured during 16.7 milliseconds. Compositions with large VHR-4 have a large stability to heat.

(12) response time (. tau.; measured at 25 ℃ C.; ms): a luminance meter model LCD5100 manufactured by tsukau electronics gmbh was used for the measurement. The light source is a halogen lamp. The Low-pass filter (Low-pass filter) is set to 5 kHz. A sample was placed in a TN cell of normal white mode (normal white mode) in which the gap between two glass substrates (cell gap) was 5.0 μm and the twist angle was 80 degrees. A square wave (60Hz, 5V, 0.5 sec) was applied to the element. At this time, the element was irradiated with light from the vertical direction, and the amount of light transmitted through the element was measured. The transmittance was regarded as 100% when the light amount reached the maximum, and 0% when the light amount was the minimum. The rise time (τ r: rise time; millisecond) is the time required for the transmittance to change from 90% to 10%. The fall time (τ f: fall time; millisecond) is the time required for the change from a transmittance of 10% to a transmittance of 90%. The response time is represented by the sum of the rise time and the fall time found in the above manner.

(13) Elastic constant (K; measured at 25 ℃ C.; pN): for the measurement, an LCR tester model HP4284A manufactured by Hewlett-Packard (Hewlett-Packard) GmbH was used. A sample was placed in a horizontally oriented cell having a spacing (cell gap) of 20 μm between two glass substrates. A charge of 0 to 20 volts was applied to the element, and the electrostatic capacitance and applied voltage were measured. Values of K11 and K33 were obtained from equation (2.99) by fitting the measured electrostatic capacitance (C) to the value of the applied voltage (V) using equations (2.98) and (2.101) on page 75 of the handbook of liquid crystal devices (japan industrial news). Next, K22 was calculated using the values of K11 and K33 obtained before in equation (3.18) on page 171 of the handbook of liquid crystal devices (japan industrial news). The elastic constant is represented by the average value of K11, K22, and K33 determined in the above manner.

(14) specific resistance (. rho.; measured at 25 ℃ C.;. omega. cm): 1.0mL of the sample was injected into a container equipped with an electrode. A DC voltage (10V) was applied to the vessel, and a DC current after 10 seconds was measured. The specific resistance is calculated according to the following equation. (specific resistance) { (voltage) × (capacitance of container) }/{ (direct current) × (dielectric constant of vacuum) }.

(15) Helical pitch (P; measured at room temperature; μm): the helical pitch is measured using the wedge method. Refer to "liquid Crystal Messaging" page 196 (2000 release, Wanshan). The sample was poured into a wedge-shaped cell, and after standing at room temperature for 2 hours, the interval of misorientation lines (d2-d1) was observed by a polarizing microscope (Nikon (Strand), trade name MM40/60 series). The pitch (P) of the helix is calculated from the following equation in which the angle of the wedge element is represented by θ. P is 2 × (d2-d1) × tan θ.

The compounds in the examples are represented by symbols based on the definitions of table 3 below. In Table 3, the configuration of the 1, 4-cyclohexylene group-related solid is trans configuration. The numbers in brackets after the symbol correspond to the numbers of the compounds. The symbol (-) indicates other liquid crystalline compounds. The proportion (percentage) of the liquid crystalline compound is a weight percentage (wt%) based on the weight of the liquid crystal composition. Finally, the values of the properties of the composition are summarized.

Expression of compounds using symbols

R-(A)-Z-......Z-(A)-R'

[ Table 3]

Embodiments of the elements

1. Raw materials

A composition to which an alignment control layer-forming monomer is added is injected into an element having no alignment film. After irradiation with linearly polarized ultraviolet rays, the alignment of the liquid crystal molecules in the cell was confirmed. First, the raw materials will be described. The raw materials are suitably selected from the group consisting of the compositions (M1) to (M20), and the orientation controlling layer-forming monomers are suitably selected from the group consisting of the compound (A-1-1), the compound (A-2-3), the compound (A-2-4), the compound (B-1), the compound (C-1-1), the compound (D-1-5), the compound (D-1-7) and the compound (D-1-8). The composition was as follows.

[ composition (M1) ]

NI＝79.8℃；Tc＜-30℃；Δn＝0.106；Δε＝8.5；Vth＝1.45V；η＝11.6mPa·s；γ1 ＝60.0mPa·s.

[ composition (M2) ]

NI＝71.2℃；Tc＜-20℃；Δn＝0.099；Δε＝6.1；Vth＝1.74V；η＝13.2mPa·s；γ1 ＝59.3mPa·s.

[ composition (M3) ]

NI＝78.5℃；Tc＜-20℃；Δn＝0.095；Δε＝3.4；Vth＝1.50V；η＝8.4mPa·s；γ1 ＝54.2mPa·s.

[ composition (M4) ]

NI＝90.3℃；Tc＜-20℃；Δn＝0.089；Δε＝5.5；Vth＝1.65V；η＝13.6mPa·s；γ1 ＝60.1mPa·s.

[ composition (M5) ]

NI＝78.3℃；Tc＜-20℃；Δn＝0.107；Δε＝7.0；Vth＝1.55V；η＝11.6mPa·s；γ1 ＝55.6mPa·s.

[ composition (M6) ]

NI＝80.4℃；Tc＜-20℃；Δn＝0.106；Δε＝5.8；Vth＝1.40V；η＝11.6mPa·s；γ1 ＝61.0mPa·s.

[ composition (M7) ]

NI＝78.4℃；Tc＜-20℃；Δn＝0.094；Δε＝5.6；Vth＝1.45V；η＝11.5mPa·s；γ1 ＝61.7mPa·s.

[ composition (M8) ]

NI＝80.0℃；Tc＜-20℃；Δn＝0.101；Δε＝4.6；Vth＝1.71V；η＝11.0mPa·s；γ1 ＝47.2mPa·s.

[ composition (M9) ]

NI＝78.6℃；Tc＜-20℃；Δn＝0.088；Δε＝5.6；Vth＝1.85V；η＝13.9mPa·s；γ1 ＝66.9mPa·s.

[ composition (M10) ]

NI＝82.9℃；Tc＜-20℃；Δn＝0.093；Δε＝6.9；Vth＝1.50V；η＝16.3mPa·s；γ1 ＝65.2mPa·s.

[ composition (M11) ]

NI＝79.6℃；Tc＜-20℃；Δn＝0.111；Δε＝4.7；Vth＝1.86V；η＝9.7mPa·s；γ1 ＝49.9mPa·s.

[ composition (M12) ]

NI＝83.0℃；Tc＜-20℃；Δn＝0.086；Δε＝3.8；Vth＝1.94V；η＝7.5mPa·s；γ1 ＝51.5mPa·s.

[ composition (M13) ]

NI＝81.9℃；Tc＜-20℃；Δn＝0.109；Δε＝4.8；Vth＝1.75V；η＝13.3mPa·s；γ1 ＝57.4mPa·s.

[ composition (M14) ]

NI＝78.2℃；Tc＜-20℃；Δn＝0.101；Δε＝6.7；Vth＝1.45V；η＝17.8mPa·s；γ1 ＝67.8mPa·s.

[ composition (M15) ]

NI＝77.6℃；Tc＜-20℃；Δn＝0.109；Δε＝10.6；Vth＝1.34V；η＝22.6mPa·s；γ 1＝92.4mPa·s.

[ composition (M16) ]

NI＝85.2℃；Tc＜-20℃；Δn＝0.102；Δε＝4.1；γ1＝43.0mPa·s.

[ composition (M17) ]

NI＝85.8℃；Tc＜-20℃；Δn＝0.115；Δε＝4.2；γ1＝41.4mPa·s.

[ composition (M18) ]

[ composition (M19) ]

NI＝79.3℃；Tc＜-20℃；Δn＝0.099；Δε＝5.0；Vth＝1.64V；η＝10.4mPa·s；γ1 ＝44.7mPa·s.

[ composition (M20) ]

NI＝79.7℃；Tc＜-20℃；Δn＝0.091；Δε＝5.7；Vth＝1.83V；η＝14.9mPa·s；γ1 ＝69.3mPa·s.

the first additive is the following compound.

2. alignment of liquid crystal molecules

< polarizing exposure condition >

the intensity of Light was measured using a 250W ultrahigh-pressure mercury lamp (Multi-Light lamp manufactured by oxtail (Ushio) electric machinery Co., Ltd.) and a wire grid (wire grid) polarizer (ProFlux (UVT-260A) manufactured by Moxtek Co., Ltd.) at an intensity of 3mW/cm2 (illuminance at a wavelength of 313nm was measured using ultraviolet illuminometers UIT-150 and UVD-S313 manufactured by oxtail (Ushio) electric machinery Co., Ltd.).

Example 1

the orientation control layer-forming monomer (a-1-1) was added to the composition (M1) in a proportion of 0.3 part by weight based on the total amount of the composition (M1). The mixture was injected at 90 ℃ (upper temperature limit or higher) into IPS cells without alignment film. The IPS element was irradiated with linearly polarized ultraviolet rays (313nm, 5.0J/cm2) from the normal direction while heating the IPS element at 90 ℃ (upper limit temperature or higher) to obtain an element having an alignment control layer formed thereon. The irradiated ultraviolet rays pass through the polarizer, and become linearly polarized light. Next, the element on which the alignment control layer was formed was set on a polarization microscope to observe the alignment state of the liquid crystal. The polarizer and the analyzer of the polarizing microscope are arranged so that their transmission axes are orthogonal to each other. First, the element was set on the horizontal rotation stage of the polarization microscope so that the alignment direction of the liquid crystal molecules was parallel to the transmission axis of the polarizer of the polarization microscope, that is, so that the angle formed by the alignment direction of the liquid crystal molecules and the transmission axis of the polarizer of the polarization microscope became 0 degree. The lower side of the device, i.e., the polarizer side, was irradiated with light, and the presence or absence of light transmitted through the analyzer was observed. Since light transmitted through the analyzer was not observed, the orientation was judged to be "good". In the same observation, when light transmitted through the analyzer is observed, the orientation is determined to be "defective". Next, the element was rotated on a horizontal rotation stage of a polarization microscope, and the angle formed by the transmission axis of the polarizer of the polarization microscope and the alignment direction of the liquid crystal molecules was changed from 0 degrees. Confirming that: the intensity of light transmitted through the analyzer increases as the angle formed by the transmission axis of the polarizer of the polarization microscope and the alignment direction of the liquid crystal molecules increases, and becomes substantially maximum when the angle is 45 degrees. In the element obtained as described above, the liquid crystal molecules are aligned in a direction substantially horizontal to the main surface of the substrate of the element, and are determined as "horizontal alignment".

Examples 2 to 24

the alignment control layer forming monomers were added to the compositions (M1) to (M20) in the combinations of table 4. An element was produced in the same manner as in example 1 except that the injection temperature of the liquid crystal and the temperature at the time of polarization exposure were set to the temperatures described in table 4 using the mixture, and the presence or absence of light leakage was observed in the same manner as in example 1.

comparative example 1

An IPS device having no alignment film was injected by the same method as in example 1, except that no alignment control layer forming monomer was added to the composition (M1), and heated polarized light exposure treatment was performed. The presence or absence of light leakage was observed in the same manner as in example 1. The results of examples 1 to 24 and comparative example 1 are summarized in Table 4.

[ Table 4]

Alignment of liquid crystal molecules

Comparative example 2

The following alignment control layer-forming compound (R-1) having no polymerizable group but having a cinnamate structure was added to the composition (M1), injected into an IPS element having no alignment film by the same method as in example 1, and subjected to heat polarization exposure treatment. The alignment state of the liquid crystal was observed by the same method as in example 1. Regions where light did not pass through the analyzer were observed in the cell, while regions where light passed through the analyzer were also observed. The orientation was judged to be poor overall.

3. Compatibility of orientation control layer forming monomer with liquid crystal composition

The mixture of the liquid crystal composition and the alignment control layer-forming monomer obtained in the example and the mixture of the liquid crystal composition and the polymerizable compound obtained in the comparative example were evaluated for stability at room temperature. After mixing, the mixture was changed to an isotropic liquid at 100 ℃ and left to cool to 25 ℃. As a result of confirming whether or not precipitation occurred after a lapse of half a day at room temperature, precipitation was not confirmed in the mixtures of examples 1 to 24 and comparative example 1, and the compatibility of the alignment control layer-forming monomer was good.

As is clear from table 4, in examples 1 to 24, although the kind of the composition or the alignment control layer-forming monomer was changed, light leakage was not observed. The same tendency applies to the case where a plurality of alignment control layer forming monomers are used. The results show that the alignment was good and all the liquid crystal molecules were aligned in the fixed direction even without an alignment film such as polyimide in the device. On the other hand, in comparative example 1 containing no alignment control layer forming monomer, light leakage was observed. In addition, sufficient alignment properties cannot be obtained in an alignment control layer-forming compound having no polymerizable group.

From the above results, it is understood that a thin film formed from an alignment control layer-forming monomer having two or more polymerizable groups plays an important role in uniformizing the alignment of liquid crystal molecules. Further, it was found that the compatibility with the liquid crystal composition was also good.

The same effect can be expected also in the case of other alignment controlling layer-forming monomers (for example, the compound (A-2-1-1), the compound (A-2-2-1), the compound (A-2-3), the compound (A-2-4), the compound (D-1-7), the compound (D-1-8), the compound (A-A-4), the compound (A-A-13), the compound (A-A-14), and the compound (A-A-15)).

Therefore, when the liquid crystal composition of the present invention is used, a liquid crystal display element having characteristics such as a wide temperature range in which the element can be used, a short response time, a high voltage holding ratio, a low threshold voltage, a large contrast ratio, and a long life can be obtained.

further, a liquid crystal display element having a liquid crystal composition satisfying at least one of the characteristics of a high upper limit temperature of a nematic phase, a low lower limit temperature of the nematic phase, a low viscosity, an appropriate optical anisotropy, a large positive dielectric anisotropy, a large specific resistance, a high stability to ultraviolet light, and a high stability to heat can be obtained.

Industrial applicability

The liquid crystal composition of the present invention can be used in liquid crystal monitors, liquid crystal televisions, and the like.

Claims

1. a liquid crystal display element in which a liquid crystal layer is sandwiched between a pair of substrates which are arranged to face each other and bonded to each other with a sealant interposed therebetween,

In the liquid crystal display element, the alignment control layer includes a polymer formed by polymerizing an alignment control layer forming monomer by sandwiching a liquid crystal composition containing at least one compound selected from the group of compounds represented by formulae (A) to (D) as a first additive and the alignment control layer forming monomer and a liquid crystal compound between the pair of substrates,

z20 and Z21 are independently a single bond, an alkylene group having 1 to 6 carbon atoms, or an alkenylene group having 2 to 6 carbon atoms, at least one of which is an alkenylene group having 2 to 6 carbon atoms; at least one of these alkylene groups and alkenylene groups, at least one of which-CH 2-may be substituted with-O-, -CO-, -COO-, -OCO-, or-OCOO-, and at least one of the other- (CH2) 2-may be substituted with-CH ═ CH-or-C.ident.C-, and of these groups, at least one hydrogen may be substituted with fluorine or chlorine;

n20 is 1 or 2;

n30 is 1 or 2.

2. The liquid crystal display element according to claim 1, wherein the alignment control layer-forming monomer in the liquid crystal composition is represented by formula (A-1), formula (A-2), formula (B), formula (C-1), or formula (D-1),

z12 is-CO-, or-OCO-;

n20 is 1 or 2;

n30 is 1 or 2;

3. The liquid crystal display element according to claim 2, wherein the alignment control layer-forming monomer in the liquid crystal composition is represented by formula (a-1), formula (a-2), or formula (B), and P10, P20, P30, P40, P50, and P60 are independently a group selected from the group represented by formula (Q-1);

Sp40 is a single bond;

z11 is a single bond, -COO-or-OCO-;

Z12 is-CO-, or-OCO-;

n20 is 1 or 2;

n30 is 1 or 2.

4. the liquid crystal display element according to any one of claims 1 to 3, wherein a ratio of the alignment control layer forming monomer in the liquid crystal composition is in a range of 0.1 parts by weight to 10 parts by weight based on a total amount of the liquid crystalline compound.

5. The liquid crystal display element according to any one of claims 1 to 4, which contains at least one compound selected from the group of compounds represented by formula (1) as a first component,

6. the liquid crystal display element according to any one of claims 1 to 5, which contains at least one compound selected from the group of compounds represented by formulae (1-1) to (1-39) as a first component,

7. The liquid crystal display element according to claim 5 or 6, wherein a proportion of the first component in the liquid crystal composition is in a range of 10% by weight to 85% by weight.

8. The liquid crystal display element according to any one of claims 1 to 7, which contains at least one compound selected from the group of compounds represented by formula (2) as a second component,

9. The liquid crystal display element according to any one of claims 1 to 8, which contains at least one compound selected from the group of compounds represented by formulae (2-1) to (2-13) as a second component,

10. The liquid crystal display element according to claim 8 or 9, wherein a proportion of the second component in the liquid crystal composition is in a range of 10% by weight to 85% by weight.

11. the liquid crystal display element according to any one of claims 1 to 10, which contains at least one compound selected from the group of compounds represented by formula (3) as a third component,

12. the liquid crystal display element according to any one of claims 1 to 11, which contains at least one compound selected from the group of compounds represented by formulae (3-1) to (3-22) as a third component,

13. the liquid crystal display element according to claim 11 or 12, wherein a proportion of the third component is in a range of 3% by weight to 25% by weight.

14. The liquid crystal display element according to any one of claims 1 to 13, wherein the liquid crystal composition further contains at least one compound selected from the group of polymerizable compounds represented by formula (4) as a second additive,

15. The liquid crystal display element according to claim 14, wherein in formula (4) in the liquid crystal composition, P1, P2, and P3 are independently a group selected from the group of polymerizable groups represented by formulae (P-1) to (P-5),

16. the liquid crystal display element according to any one of claims 1 to 15, which contains at least one compound selected from the group of polymerizable compounds represented by formulae (4-1) to (4-27) as a second additive in the liquid crystal composition,

17. The liquid crystal display element according to any one of claims 14 to 16, wherein a ratio of the second additive in the liquid crystal composition is in a range of 0.03 parts by weight to 10 parts by weight based on the total amount of the liquid crystalline compound.

18. the liquid crystal display element according to any one of claims 1 to 17, wherein an upper limit temperature of a nematic phase is 70 ℃ or more, an optical anisotropy at a wavelength of 589nm (measured at 25 ℃) is 0.07 or more, and a dielectric anisotropy at a frequency of 1kHz (measured at 25 ℃) is 2 or more.

19. a liquid crystal display element having the liquid crystal composition in the liquid crystal display element according to any one of claims 1 to 18 and an electrode between a pair of substrates, wherein an alignment control layer forming monomer in the liquid crystal composition is reacted by irradiating linearly polarized ultraviolet rays at a temperature equal to or higher than an upper limit temperature of a nematic phase.

20. The liquid crystal display element according to any one of claims 1 to 19, wherein the liquid crystal display element operates in an in-plane switching mode, a vertical alignment mode, a fringe field switching mode, or an electric field induced photo-responsive alignment mode, and the liquid crystal display element is driven in an active matrix mode.

21. the liquid crystal display element according to any one of claims 1 to 19, wherein an operation mode of the liquid crystal display element is an in-plane switching mode or a fringe field switching mode, and a driving mode of the liquid crystal display element is an active matrix mode.

22. A polymer stable alignment type liquid crystal display element comprising the liquid crystal composition in the liquid crystal display element according to any one of claims 1 to 17, wherein a polymerizable compound in the liquid crystal composition is polymerized.

23. Use of a liquid crystal composition in a liquid crystal display element according to any one of claims 1 to 17 in a liquid crystal display element.

24. Use of a liquid crystal composition in a liquid crystal display element according to any one of claims 1 to 17 in a liquid crystal display element of a polymer stabilized alignment type.

25. A compound represented by the formula (A-2),

Z12 is-CO-, or-OCO-;

26. Use of a compound according to claim 25 as a monomer for forming an orientation control layer.

27. A liquid crystal composition in the liquid crystal display element according to any one of claims 1 to 17.