CN112368260B

CN112368260B - Compound, liquid crystal composition and liquid crystal display element

Info

Publication number: CN112368260B
Application number: CN201980041349.0A
Authority: CN
Inventors: 矢野智広; 近藤史尚; 佐郷弘毅
Original assignee: JNC Corp; JNC Petrochemical Corp
Current assignee: JNC Corp; JNC Petrochemical Corp
Priority date: 2018-07-04
Filing date: 2019-06-12
Publication date: 2024-02-20
Anticipated expiration: 2039-06-12
Also published as: CN112368260A; WO2020008826A1; JPWO2020008826A1; TW202006124A

Abstract

The invention provides a compound, a liquid crystal composition and a liquid crystal display elementIt has at least one of high chemical stability, high ability to orient liquid crystal molecules horizontally, high orientation property in a wide range of addition concentration, proper reactivity, and high solubility in a liquid crystal composition. The present invention provides a compound of formula (1) below. In the formula (1), a and b are independently 0, 1 or 2, and 0.ltoreq.a+b.ltoreq.3, ring A ¹ Ring A ² Ring A ³ Ring A ⁴ Independently, for example, 1, 4-cyclohexylene, Z ¹ 、Z ² 、Z ³ 、Z ⁴ Z is as follows ⁵ Independently a single bond or an alkylene group of 1 to 10 carbon atoms, etc., sp ¹ Sp and Sp ² Independently a single bond or an alkylene group of 1 to 10 carbon atoms, etc., P ¹ P ² Independently a specific polymerizable group.

Description

Compound, liquid crystal composition and liquid crystal display element

Technical Field

The invention relates to a compound, a liquid crystal composition and a liquid crystal display element. More particularly, the present invention relates to a polar compound having excellent polymerizability of a light absorbing structure in one molecule, a liquid crystal composition containing the compound and having positive or negative dielectric anisotropy, and a liquid crystal display element containing the composition.

Background

In the liquid crystal display element, modes based on the operation mode of liquid crystal molecules are classified into Phase Change (PC), twisted Nematic (TN), super twisted nematic (super twisted nematic, STN), electrically controlled birefringence (electrically controlled birefringence, ECB), optically compensated bend (optically compensated bend, OCB), in-plane switching (IPS), vertical alignment (vertical alignment, VA), fringe field switching (fringe field switching, FFS), field-induced photo-reactive alignment (FPA), and the like. The driving modes based on the elements are classified into Passive Matrix (PM) and Active Matrix (AM). PM is classified into static type (static), multiplex type (multiplex) and the like, and AM is classified into thin film transistor (thin film transistor, TFT), metal-insulator-metal (metal insulator metal, MIM) and the like. TFTs are classified as amorphous silicon (amorphous silicon) and polysilicon (polycrystal silicon). The latter is classified into a high temperature type and a low temperature type according to the manufacturing steps. The classification based on the light source is a reflection type using natural light, a transmission type using 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 two characteristics is summarized in table 1 below. The properties of the composition are further described 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 preferable upper limit temperature of the nematic phase is about 70 ℃ or higher, and the preferable lower limit temperature of the nematic phase is about-10 ℃ or lower. The viscosity of the composition is related to the response time of the element. In order to display a moving image by an element, the response time is preferably short. Ideally less than 1 millisecond of response time. Thus, the viscosity of the composition is preferably small. More preferably, the viscosity at low temperature is small.

TABLE 1 Properties of compositions and AM elements

1) The time for injecting the composition into the liquid crystal display element can be shortened

The optical anisotropy of the composition is related to the contrast of the element. Depending on the mode of the element, it is necessary that the optical anisotropy is large or small, that is, the optical anisotropy is appropriate. The product (Δn×d) of the optical anisotropy (Δn) of the composition and the cell gap (d) of the element is designed to maximize the contrast. The appropriate value of the product depends on the type of operation mode. In elements of TN-like mode, the value is about 0.45. Mu.m. In VA mode elements, the values are in the range of about 0.30 μm to about 0.40 μm, and in IPS mode or FFS mode elements, the values are in the range of about 0.20 μm to about 0.30 μm. In these cases, a composition having large optical anisotropy is preferable for an element having a small cell gap. The large dielectric anisotropy in the composition contributes to a low threshold voltage, small power consumption and large contrast in the element. Thus, a large positive or negative dielectric anisotropy is preferable. The large specific resistance in the composition contributes to a large voltage holding ratio and a large contrast ratio in the element. Therefore, a composition having a large specific resistance not only at room temperature but also at a temperature close to the upper limit temperature of the nematic phase in the initial stage is preferable. It is preferable that the composition has a large specific resistance after a long period of use not only at room temperature but also at a temperature close to the upper limit temperature of the nematic phase. The stability of the composition to ultraviolet light and heat is related to the lifetime of the element. When the stability is high, the lifetime of the element is long. Such characteristics are preferable for AM elements used in liquid crystal projectors, liquid crystal televisions, and the like.

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

A composition having positive or negative dielectric anisotropy is used in an AM element in which a polymer is stably oriented (polymer sustained alignment, PSA). In a liquid crystal display element of polymer stable alignment (polymer sustained alignment, PSA), 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. Then, the composition is irradiated with ultraviolet rays while applying a voltage between the substrates of the element. The polymerizable compound is polymerized to form a network of polymers in the composition. In the composition, the orientation of liquid crystal molecules can be controlled by the polymer, and thus the response time of the element is shortened, and the afterimage of the image is improved. Elements having a pattern such as TN, ECB, OCB, IPS, VA, FFS, FPA may expect such effects from a polymer.

The following methods are reported: instead of an alignment film such as polyimide, a low molecular compound having a cinnamate group, a low molecular compound having a polyvinyl cinnamate (polyvinyl cinnamate), a chalcone structure, a low molecular compound having an azobenzene structure, or a dendrimer is used to control alignment of liquid crystal (patent document 1, patent document 2, or patent document 3). In the method of patent document 1, patent document 2 or patent document 3, first, the low molecular compound or polymer is dissolved as an additive in a liquid crystal composition. Then, a thin film containing the low molecular compound or polymer is formed on the substrate by phase-separating 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 polymer is dimerized or isomerized by the linear polarization, its molecules are aligned in a certain direction. In the method, a device of a horizontal alignment mode such as IPS or FFS and a device of a vertical alignment mode such as VA can be manufactured by selecting a type of a low molecular compound or a polymer. In the method, it is important that the low molecular compound or 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 upon returning to room temperature. However, it is difficult to ensure compatibility of the low molecular compound or polymer with the liquid crystal composition.

As a compound capable of horizontally aligning liquid crystal molecules, a compound (S-1) (see [ 2] of paragraph 0034 of the specification) has been described in patent document 2, and a compound (S-2) (see [14] of P176 of the specification) has been described in patent document 3. However, these compounds require high-energy light irradiation in order to orient the liquid crystal molecules horizontally with sufficient orientation, and there is a concern that the production time increases due to long-time light irradiation or damage to the liquid crystal occurs due to the increase, and improvement is desired.

Prior art literature

Patent literature

Patent document 1: international publication No. 2015/146369

Patent document 2: international publication No. 2017/057162

Patent document 3: international publication No. 2017/102068

Disclosure of Invention

Problems to be solved by the invention

The first object of the present invention is to provide a compound which has at least one of high chemical stability, high ability to orient liquid crystal molecules horizontally, high orientation in a wide concentration range to be added, proper reactivity, and high solubility in a liquid crystal composition, and which is expected to have a high voltage holding ratio when used in a liquid crystal display element. The second object is to provide a liquid crystal composition containing the compound and satisfying at least one of the characteristics of high upper limit temperature of a nematic phase, low lower limit temperature of a nematic phase, low viscosity, proper optical anisotropy, large positive or negative dielectric anisotropy, large specific resistance, high stability to ultraviolet light, high stability to heat, large elastic constant and the like. A third object is to provide a liquid crystal display element comprising the composition, wherein when a polar compound is formed into a film in the element by irradiating the composition with ultraviolet light, the film has at least one of the characteristics of proper hardness, low permeability of a contact component, high weather resistance, and proper volume resistance, and the liquid crystal display element has at least one of the characteristics of a wide usable element temperature range, short response time, high voltage holding ratio, low threshold voltage, large contrast, and long lifetime.

Technical means for solving the problems

The present inventors have found that the compound represented by the following formula (1) can solve the above-mentioned problems, and have completed the present invention.

(the explanation of the marks in the formula will be described later)

ADVANTAGEOUS EFFECTS OF INVENTION

The first advantage of the present invention is to provide a compound which has at least one of high chemical stability, high ability to orient liquid crystal molecules horizontally, high orientation in a wide range of addition concentration, proper reactivity, and high solubility in a liquid crystal composition, and which is expected to have a large voltage holding ratio when used in a liquid crystal display element. A second advantage is to provide a liquid crystal composition containing the compound and satisfying at least one of the characteristics of high upper limit temperature of a nematic phase, low lower limit temperature of a nematic phase, low viscosity, proper optical anisotropy, large positive or negative dielectric anisotropy, large specific resistance, high stability to ultraviolet light, high stability to heat, large elastic constant, and the like. A third advantage is to provide a liquid crystal display element comprising the composition, which has at least one of characteristics of proper hardness, low permeability of contact components, high weather resistance, proper volume resistance value, and at least one of characteristics of a wide usable element temperature range, short response time, high voltage holding ratio, low threshold voltage, large contrast, long lifetime when a polar compound is formed into a film in the element by irradiating ultraviolet rays to the composition. By using the liquid crystal composition containing the compound of the present invention, a step of forming an alignment film is not required, and thus a liquid crystal display element with reduced manufacturing cost can be obtained.

Detailed Description

The usage of the terms in the specification is as follows. The terms "liquid crystal composition" and "liquid crystal display element" are sometimes abbreviated as "composition" and "element", respectively. The term "liquid crystal display element" refers to a liquid crystal display panel and a liquid crystal display module. The "liquid crystalline compound" is a general term for a compound having a liquid crystal phase such as a nematic phase and a smectic phase, and a compound which is mixed into a composition for the purpose of adjusting characteristics such as a temperature range, viscosity, and dielectric anisotropy of the nematic phase, although not having the 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. The "polymerizable compound" is a compound added for the purpose of forming a polymer in the composition. The "polar compound" helps alignment of liquid crystal molecules by the interaction of polar groups with the substrate surface.

The liquid crystal composition is prepared by mixing a plurality of liquid crystalline compounds. The proportion (content) of the liquid crystalline compound is expressed as a weight percentage (wt%) based on the weight of the liquid crystal composition. Additives such as 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 are optionally added to the liquid crystal composition. The proportion (amount) of the additive is expressed as a weight percentage (wt%) based on the weight of the liquid crystal composition, as in the proportion of the liquid crystal compound. Weight parts per million (ppm) are also sometimes used. The proportions of the polymerization initiator and the polymerization inhibitor are expressed by weight of the polymerizable compound.

The compound represented by the formula (1) may be referred to simply as "compound (1)". The compound (1) is one compound, a mixture of two compounds, or a mixture of three or more compounds represented by the formula (1). The rule is also applicable to at least one compound selected from the group of compounds represented by formula (2), and the like. B surrounded by hexagons ¹ 、C ¹ Marks such as F and the like are respectively connected with the ring B ¹ Ring C ¹ Ring F, etc. Hexagonal represents a six-membered ring such as a cyclohexane ring or a benzene ring or a condensed ring such as a naphthalene ring. The diagonal lines intersecting the hexagons represent any hydrogen channels-Sp on the ring ¹ -P ¹ And the like. e and the like indicate the number of substituted groups. When the subscript is 0, no such substitution is present.

By incorporating end groups R ¹¹ The notation of (c) is used in multi-component compounds. Of these compounds, any two R ¹¹ The two groups represented may be the same or may be different. For example, there is R of the compound (2) ¹¹ R of compound (3) is ethyl ¹¹ In the case of ethyl. Also R of the compound (2) ¹¹ R of compound (3) is ethyl ¹¹ In the case of propyl. The rules also apply to other end group, ring, bond group, etc. notations. In formula (8), when i is 2, two rings D are present ¹ . In the compound, two rings D ¹ The two groups represented may be the same or may be different. The rule also applies to any two rings D when i is greater than 2 ¹ . The rules also apply to other rings, bond groups, and the like.

The expression "at least one of" A' "means that the number of" A "is arbitrary. In the expression "at least one of the" a "groups may be substituted with the" B ", the positions of the" a "groups may be arbitrary when the number of the" a "groups is one, and the positions of the" a "groups may be selected without limitation when the number of the" a "groups is two or more. The rules also apply to the expression "at least one 'a' is substituted by 'B'. The expression "at least one a may be substituted with B, C or D" is meant to include at least one a substituted with B, at least one a substituted with C, and at least one a substituted with D, thereby including at least two substituted cases of a plurality of a's B, C, D. For example at least one-CH ₂ - (or-CH) ₂ CH ₂ (-) alkyl which may be substituted by-O- (or-ch=ch-) includes alkyl, alkenyl, alkoxy, alkoxyalkyl, alkoxyalkenyl, alkenyloxyalkyl. Furthermore, two consecutive-CH ₂ -O-substitution to-O-is less preferred. In alkyl groups or the like, methyl groups Base moiety (-CH) ₂ -CH of H) ₂ The case of-O-substitution to-O-H is also less preferred.

Halogen means fluorine, chlorine, bromine or iodine. Preferred halogens are fluorine or chlorine. Further preferred halogen is fluorine. The alkyl group is linear or branched and does not include a cyclic alkyl group. In general, linear alkyl groups are preferred over branched alkyl groups. These are also the same for terminal groups such as alkoxy groups and alkenyl groups. Regarding the steric configuration related to 1, 4-cyclohexylene, the trans configuration is superior to the cis configuration in order to raise the upper temperature of the nematic phase. 2-fluoro-1, 4-phenylene means the following two divalent groups. In the chemical formula, fluorine can be left (L) or right (R). The rules also apply to asymmetric divalent radicals such as tetrahydropyran-2, 5-diyl which are generated by removal of two hydrogens from the ring.

The present invention includes the following items and the like.

[1] A compound represented by formula (1).

In the formula (1), the components are as follows,

a and b are independently 0, 1 or 2, and 0.ltoreq.a+b.ltoreq.3,

ring A ¹ Ring A ² Ring A ³ Ring A ⁴ Is independently 1, 4-cyclohexylene, 1, 4-cyclohexenylene, 1, 4-phenylene, 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, 2,3,4,7,8,9,10,11,12,13,14,15,16,17-tetradecanocyclopenta [ a ]]Phenanthrene-3, 17-diyl, the group represented by (A-1) or the group represented by (A-2), wherein at least one hydrogen in these rings may be substituted by fluorine, chlorine, an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, carbonAlkoxy of 1 to 11, alkenyloxy of 2 to 11 carbon atoms, -Sp ¹ -P ¹ or-Sp ² -P ² Substituted, in which at least one hydrogen may be substituted by fluorine or chlorine, and when a is 2, two rings A ¹ Can be different, when b is 2, two rings A ⁴ May be different, in (A-2), c is 2,3 or 4. Wherein ring A ¹ Ring A ² Ring A ³ Or ring A ⁴ At least one of them is naphthalene-2, 6-diyl, phenanthrene-2, 7-diyl, a group represented by (A-1) or a group represented by (A-2);

Z ¹ 、Z ² 、Z ³ 、Z ⁴ z is as follows ⁵ Independently a single bond or an alkylene group of 1 to 10 carbon atoms, of which at least one-CH ₂ -can be substituted by-O-, -CO-, -COO-, -OCO-or-OCOO-, at least one- (CH) ₂ ) ₂ -may be substituted by-ch=ch-or-c≡c-, in which groups at least one hydrogen may be substituted by halogen. Wherein Z is ² 、Z ³ Or Z is ⁴ At least one of them is-COO-, -OCO-, -CH=CHCOO-, -OCOCH=CH-, -CH=CH-, -CH=CHCO-, or-COCH=CH-, when a is 2, two Z ¹ Can be different, when b is 2, two Z ⁵ May be different;

Sp ¹ sp and Sp ² Independently a single bond or an alkylene group of 1 to 10 carbon atoms, of which at least one-CH ₂ -can be substituted by-O-, -CO-, -COO-, -OCO-or-OCOO-, at least one- (CH) ₂ ) ₂ -may be substituted by-ch=ch-or-c≡c-, in which groups at least one hydrogen may be substituted by halogen, in the presence of multiple Sp's within the structure ¹ Or Sp ² May be different from each other;

P ¹ p ² Independently of the group represented by any one of the formulae (1 b) to (1 h), based on the presence of a plurality of P's within the structure ¹ Or P ² May be different from each other;

in the formulas (1 b) to (1 h),

M ¹ 、M ² 、M ³ m and M ⁴ Independently hydrogen, halogen, alkyl of 1 to 5 carbon atoms or alkyl of 1 to 5 carbon atoms with at least one hydrogen substituted with halogen;

R ² is hydrogen, halogen, alkyl of 1 to 5 carbon atoms, at least one hydrogen of which may be substituted by halogen, at least one-CH ₂ -may be substituted by-O-;

R ³ 、R ⁴ 、R ⁵ 、R ⁶ r is R ⁷ Independently hydrogen or C1-15 alkyl, at least one of said alkyl groups being-CH ₂ -may be substituted by-O-or-S-, at least one- (CH) ₂ ) ₂ -may be substituted by-ch=ch-or-c≡c-, in which groups at least one hydrogen may be substituted by halogen.

[2] The compound according to [1], wherein in the formula (1),

a and b are independently 0, 1 or 2, and 0+.a+b+.2;

Ring A ¹ Ring A ² Ring A ³ Ring A ⁴ Is independently 1, 4-cyclohexylene, 1, 4-cyclohexenylene, 1, 4-phenylene, 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, 2,3,4,7,8,9,10,11,12,13,14,15,16,17-tetradecanocyclopenta [ a ]]Phenanthrene-3, 17-diyl, the group represented by (A-1) or the group represented by (A-2), wherein at least one hydrogen in these rings 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, an alkenyloxy group having 2 to 11 carbon atoms, -Sp ¹ -P ¹ or-Sp ² -P ² Substituted, in which at least one hydrogen may be substituted by fluorine or chlorine, and when a is 2, two rings A ¹ Can be different, when b is 2, two rings A ⁴ May be different, in (A-2), c is 2,3 or 4. Wherein ring A ¹ Ring and ringA ² Ring A ³ Or ring A ⁴ At least one of them is naphthalene-2, 6-diyl, phenanthrene-2, 7-diyl, a group represented by (A-1) or a group represented by (A-2);

Z ¹ 、Z ² 、Z ³ 、Z ⁴ z is as follows ⁵ Independently a single bond, - (CH) ₂ ) ₂ -、-CH＝CH-、-C≡C-、-COO-、-OCO-、-CF ₂ O-、-OCF ₂ -、-CH ₂ O-、-OCH ₂ -, -cf=cf-, -ch=chcoo-, -ococh=ch-, -ch=chco-, or-coch=ch-, wherein Z ² 、Z ³ Or Z is ⁴ At least one of them is-COO-, -OCO-, -CH=CHCOO-, -OCOCH=CH-, -CH=CH-, -CH=CHCO-, or-COCH=CH-, when a is 2, two Z ¹ Can be different, two Z ⁵ May be different;

Sp ¹ sp and Sp ² Independently a single bond or an alkylene group of 1 to 10 carbon atoms, of which at least one-CH ₂ -may be substituted by-O-, -COO-or-OCO-, at least one- (CH) ₂ ) ₂ -can be substituted by-ch=ch-, in which at least one hydrogen can be substituted by fluorine or chlorine, in the presence of a plurality of Sp's within the structure ¹ Or Sp ² May be different from each other;

in the formulas (1 b) to (1 h),

[3] The compound according to [1] or [2], which is represented by any one of the formulas (1-1) to (1-3).

In the formulae (1-1) to (1-3),

ring A ¹ Ring A ² Ring A ³ Ring A ⁴ Independently 1, 4-cyclohexylene, 1, 4-phenylene, naphthalene-2, 6-diyl, pyrimidine-2, 5-diyl, pyridine-2, 5-diyl, fluorene-2, 7-diyl, phenanthrene-2, 7-diyl, anthracene-2, 6-diyl, the group represented by (A-1) or the group represented by (A-2), wherein at least one hydrogen in these rings may be substituted by fluorine, chlorine, alkyl having 1 to 12 carbon atoms, alkenyl having 2 to 12 carbon atoms, alkoxy having 1 to 11 carbon atoms, alkenyloxy having 2 to 11 carbon atoms, -Sp ¹ -P ¹ or-Sp ² -P ² Substituted, in which at least one hydrogen may be substituted by fluorine or chlorine, and when a is 2, two rings A ¹ Can be different, when b is 2, two rings A ⁴ May be different, in (A-2), c is 2, 3 or 4. Wherein ring A ¹ Ring A ² Ring A ³ Or ring A ⁴ At least one of them is naphthalene-2, 6-diyl, phenanthrene-2, 7-diyl, a group represented by (A-1) or a group represented by (A-2);

Z ² 、Z ³ z is as follows ⁴ Independently and separatelyIs a single bond, - (CH) ₂ ) ₂ -、-CH＝CH-、-C≡C-、-COO-、-OCO-、-CF ₂ O-、-OCF ₂ -、-CH ₂ O-、-OCH ₂ -, -cf=cf-, -ch=chcoo-, -ococh=ch-, -ch=chco-, or-coch=ch-, wherein Z ² 、Z ³ Z is as follows ⁴ At least one of them is-COO-, -OCO-, -CH=CHCOO-, -OCOCH=CH-, -CH=CH-, -CH=CHCO-, or-COCH=CH-;

Sp ¹ Sp and Sp ² Independently a single bond or an alkylene group of 1 to 10 carbon atoms, of which at least one-CH ₂ -may be substituted by-O-, -COO-, -OCOO-or-OCO-, at least one- (CH) ₂ ) ₂ -can be substituted by-ch=ch-, in which at least one hydrogen can be substituted by fluorine or chlorine, in the presence of a plurality of Sp's within the structure ¹ Or Sp ² May be different from each other;

in the formulas (1 b) to (1 h),

[4] The compound according to [3], wherein in the formula (1-1), the formula (1-2) and the formula (1-3),

ring A ¹ Ring A ² Ring A ³ Ring A ⁴ Independently 1, 4-cyclohexylene, 1, 4-phenylene, naphthalene-2, 6-diyl, fluorene-2, 7-diyl, phenanthrene-2, 7-diyl, the group represented by (A-1) or the group represented by (A-2), wherein at least one hydrogen in these rings may be substituted by fluorine, chlorine, alkyl of 1 to 12 carbon atoms, alkenyl of 2 to 12 carbon atoms, alkoxy of 1 to 11 carbon atoms, alkenyloxy of 2 to 11 carbon atoms, -Sp ¹ -P ¹ or-Sp ² -P ² In the substitution (A-2), c is 2, 3 or 4. Wherein ring A ¹ Ring A ² Ring A ³ Or ring A ⁴ At least one of them is naphthalene-2, 6-diyl, phenanthrene-2, 7-diyl, a group represented by (A-1) or a group represented by (A-2);

Z ² 、Z ³ z is as follows ⁴ Independently a single bond, - (CH) ₂ ) ₂ -, -CH=CH-, -C≡C-, -COO-, -OCO-, -CH=CHCOO-, -OCOCH=CH-, -CH=CHCO-, or-COCH=CH-, wherein Z ² 、Z ³ Z is as follows ⁴ At least one of them is-COO-, -OCO-, -CH=CHCOO-, -OCOCH=CH-, -CH=CH-, -CH=CHCO-, or-COCH=CH-;

Sp ¹ sp and Sp ² Independently a single bond or an alkylene group of 1 to 10 carbon atoms, of which at least one-CH ₂ -may be substituted by-O-, -COO-, -OCOO-or-OCO-, at least one- (CH) ₂ ) ₂ -can be substituted by-ch=ch-with multiple Sp's present in the structure ¹ Or Sp ² May be different from each other;

P ¹ p ² Independently of the group represented by any one of the formula (1 b), the formula (1 c), the formula (1 d) or the formula (1 e), based on the presence of a plurality of P's within the structure ¹ Or P ² May be different from each other;

in the formulas (1 b) to (1 e),

R ² is hydrogen, halogen or C1-5 alkyl, wherein at least one hydrogen may be substituted by halogen, at least one-CH ₂ -may be substituted by-O-;

R ³ 、R ⁴ 、R ⁵ r is R ⁶ Independently hydrogen or C1-15 alkyl, at least one of said alkyl groups being-CH ₂ -may be substituted by-O-or-S-, at least one- (CH) ₂ ) ₂ -may be substituted by-ch=ch-or-c≡c-, in which groups at least one hydrogen may be substituted by halogen.

[5] The compound according to [3], wherein in the formula (1-1), the formula (1-2) and the formula (1-3),

ring A ¹ Ring A ² Ring A ³ Ring A ⁴ Independently 1, 4-cyclohexylene, 1, 4-phenylene, naphthalene-2, 6-diyl, fluorene-2, 7-diyl, phenanthrene-2, 7-diyl, the group represented by (A-1) or the group represented by (A-2), wherein at least one hydrogen in these rings may be substituted by fluorine, chlorine, methyl or ethyl, and wherein c is 2, 3 or 4. Wherein ring A ¹ Ring A ² Ring A ³ Or ring A ⁴ At least one of them is naphthalene-2, 6-diyl, phenanthrene-2, 7-diyl, a group represented by (A-1) or a group represented by (A-2);

P ¹ p ² Independently is a group represented by formula (1 b-1), formula (1 b-2), formula (1 b-3), formula (1 b-4), formula (1 b-5), formula (1 c-1), formula (1 d-2) or formula (1 e-1).

[6]According to [3 ]]The compound, wherein Z is a compound represented by the formula (1-1), the formula (1-2) or the formula (1-3) ² 、Z ³ Or Z is ⁴ Either of them is-COO-or-OCO-.

[7] The compound according to any one of [1] to [6], which is represented by the formula (1-A).

P ¹ -Sp ¹ -Y-Sp ² -P ² (1-A)

P ¹ P ² Independently a group represented by formula (1 b-1), formula (1 b-2), formula (1 b-3), formula (1 b-4), formula (1 b-5), formula (1 c-1), formula (1 d-2) or formula (1 e-1);

Sp ¹ sp and Sp ² Independently a single bond or an alkylene group of 1 to 10 carbon atoms, of which at least one-CH ₂ -may be substituted by-O-, -COO-, -OCOO-or-OCO-, at least one- (CH) ₂ ) ₂ -may be substituted with-ch=ch-;

y is a group represented by any one of (MES-1-01) to (MES-1-10), and at least one hydrogen in these groups may be substituted with fluorine, chlorine, methyl or ethyl.

[8]According to [7]]The compound, wherein Sp is the compound represented by the formula (1-A) ¹ Sp and Sp ² Independently an alkylene group of 1 to 10 carbon atoms, at least one of the alkylene groups-CH ₂ -may be substituted by-O-, -COO-, -OCOO-or-OCO-, at least one- (CH) ₂ ) ₂ -may be substituted with-ch=ch-.

[9] A liquid crystal composition containing at least one of the compounds according to any one of [1] to [8 ].

[10] The liquid crystal composition according to [9], which further contains at least one compound selected from the group of compounds represented by the formulas (2) to (4).

In the formulas (2) to (4),

R ¹¹ r is R ¹² Independently is an alkyl group of 1 to 10 carbon atoms or an alkenyl group of 2 to 10 carbon atoms, at least one of which-CH ₂ -may be substituted by-O-, at least one hydrogen may be substituted by fluorine;

ring B ¹ Ring B ² Ring B ³ Ring B ⁴ Independently 1, 4-cyclohexylene, 1, 4-phenylene, 2-fluoro-1, 4-phenylene, 2, 5-difluoro-1, 4-phenylene or pyrimidine-2, 5-diyl;

Z ¹¹ 、Z ¹² z is as follows ¹³ Independently a single bond, -CH ₂ CH ₂ -, -CH=CH-, -C≡C-, or-COO-.

[11] The liquid crystal composition according to [9] or [10], which further contains at least one compound selected from the group of compounds represented by the formulas (5) to (7).

In the formulas (5) to (7),

R ¹³ is an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms, at least one of the alkyl and alkenyl groups being-CH ₂ -may be substituted by-O-, at least one hydrogen may be substituted by fluorine;

X ¹¹ is fluorine, chlorine, -OCF ₃ 、-OCHF ₂ 、-CF ₃ 、-CHF ₂ 、-CH ₂ F、-OCF ₂ CHF ₂ or-OCF ₂ CHFCF ₃ ；

Ring C ¹ Ring C ² Ring C ³ Independently 1, 4-cyclohexylene, 1, 4-phenylene, which may be substituted with at least one hydrogen by fluorine, tetrahydropyran-2, 5-diyl, 1, 3-dioxane-2, 5-diyl or pyrimidine-2, 5-diyl;

Z ¹⁴ 、Z ¹⁵ z is as follows ¹⁶ Independently a single bond, -CH ₂ CH ₂ -、-CH＝CH-、-C≡C-、-COO-、-CF ₂ O-、-OCF ₂ -、-CH ₂ O-, -cf=cf-, -ch=cf-, or- (CH) ₂ ) ₄ -；

L ¹¹ L and L ¹² Independently hydrogen or fluorine.

[12] The liquid crystal composition according to any one of [9] to [11], which further contains at least one compound of the compounds represented by the formula (8).

In the formula (8), the amino acid sequence of the compound,

R ¹⁴ is an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms, at least one of the alkyl and alkenyl groups being-CH ₂ -may be substituted by-O-, at least one hydrogen may be substituted by fluorine;

X ¹² is-C.ident.N or-C.ident.C-C.ident.N;

ring D ¹ 1, 4-cyclohexylene, 1, 4-phenylene, tetrahydropyran-2, 5-diyl, 1, 3-dioxane-2, 5-diyl or pyrimidine-2, 5-diyl, at least one hydrogen of which may be substituted by fluorine;

Z ¹⁷ is a single bond, -CH ₂ CH ₂ -、-C≡C-、-COO-、-CF ₂ O-、-OCF ₂ -or-CH ₂ O-；

L ¹³ L and L ¹⁴ Independently hydrogen or fluorine;

i is 1, 2, 3 or 4.

[13] The liquid crystal composition according to any one of [9] to [12], which further contains at least one compound selected from the group of compounds represented by formulas (9) to (15).

In the formulas (9) to (15),

R ¹⁵ r is R ¹⁶ Independently is an alkyl group of 1 to 10 carbon atoms or an alkenyl group of 2 to 10 carbon atoms, at least one of which-CH ₂ -may be substituted by-O-, at least one hydrogen may be substituted by fluorine;

R ¹⁷ is hydrogen, fluorine, C1-10 alkyl or C2-10 alkenyl, at least one of which is-CH ₂ -may be substituted by-O-, at least one hydrogen may be substituted by fluorine;

ring E ¹ Ring E ² Ring E ³ Ring E ⁴ Independently 1, 4-cyclohexylene, 1, 4-cyclohexenylene, 1, 4-phenylene, which may be fluorine substituted for at least one hydrogen, tetrahydropyran-2, 5-diyl or decahydronaphthalene-2, 6-diyl;

ring E ⁵ Ring E ⁶ Independently 1, 4-cyclohexylene, 1, 4-cyclohexenylene, 1, 4-phenylene, tetrahydropyran-2, 5-diyl or decahydronaphthalene-2, 6-diyl;

Z ¹⁸ 、Z ¹⁹ 、Z ²⁰ z is as follows ²¹ Independently a single bond, -CH ₂ CH ₂ -、-COO-、-CH ₂ O-、-OCF ₂ -or-OCF ₂ CH ₂ CH ₂ -；

L ¹⁵ L and L ¹⁶ Independently fluorine or chlorine;

S ¹¹ is hydrogen or methyl;

x is-CHF-or-CF ₂ -；

j. k, m, n, p, q, r and s are independently 0 or 1, the sum of k, m, n and p is 1 or 2, the sum of q, r and s is 0, 1, 2 or 3, and t is 1, 2 or 3.

[14] The liquid crystal composition according to any one of [9] to [13], which contains at least one polymerizable compound of the compound represented by the formula (16).

In the formula (16), the amino acid sequence of the compound,

Ring F 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, in which rings at least one hydrogen may be substituted with halogen, alkyl of 1 to 12 carbon atoms or alkyl of 1 to 12 carbon atoms with at least one hydrogen substituted with halogen;

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 hydrogen may be substituted by halogen, alkyl of 1 to 12 carbon atoms, alkoxy of 1 to 12 carbon atoms or at least one hydrogen is substituted by halogen;

Z ²² z is as follows ²³ Independently a single bond or an alkylene group of 1 to 10 carbon atoms, of which at least one-CH ₂ -can be substituted by-O-, -CO-, -COO-or-OCO-, at least one-CH ₂ CH ₂ Can be modified by-ch=ch-, -C (CH ₃ )＝CH-、-CH＝C(CH ₃ ) -or-C (CH) ₃ )＝C(CH ₃ ) -substitution, of which at least one hydrogen may be substituted by fluorine or chlorine;

P ¹¹ 、P ¹² p ¹³ Independently selected from the group consisting of formula (P-1) through formula (P-5)A polymerizable group in the group of groups represented;

M ¹¹ 、M ¹² m and M ¹³ Independently hydrogen, fluorine, an alkyl group of 1 to 5 carbon atoms, or an alkyl group of 1 to 5 carbon atoms in which at least one hydrogen is substituted with fluorine or chlorine;

Sp ¹¹ 、Sp ¹² sp and Sp ¹³ Independently a single bond or an alkylene group of 1 to 10 carbon atoms, of which at least one-CH ₂ -can be substituted by-O-, -COO-, -OCO-or-OCOO-, at least one-CH ₂ CH ₂ -may be substituted by-ch=ch-or-c≡c-, in which groups at least one hydrogen may be substituted by fluorine or chlorine;

u is 0, 1 or 2;

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

[15] The liquid crystal composition according to any one of [9] to [14], which contains at least one polymerizable compound selected from the group of compounds represented by the formulas (16-1) to (16-27).

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In the formulae (16-1) to (16-27),

P ¹¹ 、P ¹² p ¹³ Independently a polymerizable group selected from the group consisting of groups represented by the formulas (P-1) to (P-3), where M ¹¹ 、M ¹² M and M ¹³ Independently hydrogen, fluorine, carbon number 1 to 5An alkyl group or an alkyl group having 1 to 5 carbon atoms, at least one hydrogen of which is substituted with halogen;

Sp ¹¹ 、Sp ¹² sp and Sp ¹³ Independently a single bond or an alkylene group of 1 to 10 carbon atoms, of which at least one-CH ₂ -can be substituted by-O-, -COO-, -OCO-or-OCOO-, at least one-CH ₂ CH ₂ -may be substituted by-ch=ch-or-c≡c-, in which groups at least one hydrogen may be substituted by fluorine or chlorine.

[16] The liquid crystal composition according to any one of [9] to [15], further comprising at least one of a polymerizable compound other than the compounds represented by the formulas (1) and (16), a polymerization initiator, a polymerization inhibitor, an optically active compound, an antioxidant, an ultraviolet absorber, a light stabilizer, a heat stabilizer and a defoaming agent.

[17] A liquid crystal display element containing the liquid crystal composition according to any one of [9] to [16 ].

The present invention also includes the following items. (a) The liquid crystal composition further contains at least two additives, such as a polymerizable compound, a polymerization initiator, a polymerization inhibitor, an optically active compound, an antioxidant, an ultraviolet absorber, a light stabilizer, a heat stabilizer, and a defoaming agent. (b) A polymerizable composition is prepared by adding a polymerizable compound different from the compound (1) or the compound (16) to the liquid crystal composition. (c) A polymerizable composition is prepared by adding a compound (1) and a compound (16) to the liquid crystal composition. (d) A liquid crystal composite is prepared by polymerizing a polymerizable composition. (e) A polymer-stabilized aligned element comprising said liquid crystal composite. (f) A polymer-stabilized alignment element is produced by using a polymerizable composition prepared by adding a compound (1) and a compound (16) and a polymerizable compound different from the compound (1) or the compound (16) to the liquid crystal composition.

The form of the compound (1), the synthesis of the compound (1), the liquid crystal composition and the liquid crystal display element will be described in order.

1. Morphology of Compound (1)

The compound (1) according to the embodiment of the present invention is a polar compound having a mesogen (mesogen) site including at least one excellent light-absorbing structure and a polymerizable group. The compound (1) has a structure such as phenanthrene, naphthalene, or tolane in a molecule, and thus has high light absorption characteristics and a characteristic of absorbing light in a relatively long wavelength region, and exhibits sufficient characteristics when irradiated with light of a short time or low energy as compared with a compound in which these structures are not present.

One of the uses of the compound (1) is an additive for a liquid crystal composition used in a liquid crystal display element. The compound (1) is added for the purpose of horizontally controlling the orientation of liquid crystal molecules. Such an additive is preferably chemically stable under the conditions of sealing the element, has high solubility in a liquid crystal composition, and has a large voltage holding ratio when used in a liquid crystal display element. The compound (1) satisfies such characteristics to a large extent.

Preferred examples of the compound (1) are described. R in Compound (1) ¹ 、Z ¹ ～Z ⁵ 、A ¹ ～A ⁴ 、Sp ¹ 、Sp ² 、P ¹ 、P ² Preferred examples of a and b are also applicable to the lower formula of the compound (1). In the compound (1), the characteristics can be arbitrarily adjusted by appropriately combining the kinds of these groups. Because there is no large difference in the nature of the compounds, compound (1) may contain a greater amount than natural abundance ² H (deuterium), ¹³ C equivalent element.

Ring A ¹ Ring A ² Ring A ³ Ring A ⁴ Independently 1, 4-cyclohexylene, 1, 4-cyclohexenylene, 1, 4-phenylene, naphthalene-2, 6-diyl, decalin-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, 2,3,4,7,8,9,10,11,12,13,14,15,16,17-tetradecanocyclopenta [ a ]]Phenanthrene-3, 17-diyl, the group represented by (A-1) or the group represented by (A-2), wherein at least one hydrogen in these rings 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, an alkenyloxy group having 2 to 11 carbon atoms, -Sp ¹ -P ¹ or-Sp ² -P ² Substituted, in which at least one hydrogen may be substituted by fluorine or chlorine, and when a is 2, two rings A ¹ Can be different, when b is 2, two rings A ⁴ May be different, in (A-2), c is 2,3 or 4. Wherein ring A ¹ Ring A ² Ring A ³ Or ring A ⁴ At least one of them is naphthalene-2, 6-diyl, phenanthrene-2, 7-diyl, a group represented by (A-1) or a group represented by (A-2);

preferred ring A ¹ Ring A ² Ring A ³ Ring A ⁴ Is independently 1, 4-cyclohexylene, 1, 4-phenylene, 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, perhydrocyclopenta [ a ] ]Phenanthrene-3, 17-diyl, 2,3,4,7,8,9,10,11,12,13,14,15,16,17-tetradecanocyclopenta [ a ]]Phenanthrene-3, 17-diyl, the group represented by (A-1) or the group represented by (A-2), preferably c is 1 or 2, and in these rings, 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 these groups, at least one hydrogen may be substituted by fluorine or chlorine. Further preferred are 1, 4-cyclohexylene, 1, 4-phenylene and perhydrocyclopenta [ a ]]Phenanthrene-3, 17-diyl or 2,3,4,7,8,9,10,11,12,13,14,15,16,17-tetradecanocyclopenta [ a ]]Phenanthrene-3, 17-diyl, in which ring at least one hydrogen is optionally substituted by fluorine or alkyl having 1 to 5 carbon atoms. Particularly preferred are 1, 4-cyclohexylene, 1, 4-phenylene or perhydrocyclopenta [ a ]]Phenanthrene-3, 17-diyl, in which ring at least one hydrogen is substituted by fluorine, methyl or ethyl.

Z ¹ 、Z ² 、Z ³ 、Z ⁴ Z is as follows ⁵ Independently a single bond or an alkylene group of 1 to 10 carbon atoms, of which at least one-CH ₂ -can be substituted by-O-, -CO-, -COO-, -OCO-or-OCOO-, at least one- (CH) ₂ ) ₂ -may be substituted by-ch=ch-or-c≡c-, in which groups at least one hydrogen may be substituted by halogen. Wherein Z is ² 、Z ³ Or Z is ⁴ At least one of them is any one of-COO-, -OCO-, -CH=CHCOO-, -OCOCH=CH-, -CH=CH-, -CH=CHCO-, -COCH=CH-, and when a is 2, two Z's are the same as each other ¹ Can be different, two Z ⁵ May be different.

Preferred Z ¹ 、Z ² 、Z ³ 、Z ⁴ Z is as follows ⁵ Independently a single bond, - (CH) ₂ ) ₂ -、-CH＝CH-、-C≡C-、-COO-、-OCO-、-CF ₂ O-、-OCF ₂ -、-CH ₂ O-、-OCH ₂ -or-cf=cf-. Further preferably a single bond, - (CH) ₂ ) ₂ -or-ch=ch-. Particularly preferred is a single bond.

Sp ¹ Sp and Sp ² Independently a single bond or an alkylene group of 1 to 10 carbon atoms, of which at least one-CH ₂ -can be substituted by-O-, -CO-, -COO-, -OCO-or-OCOO-, at least one- (CH) ₂ ) ₂ -may be substituted by-ch=ch-or-c≡c-, in which groups at least one hydrogen may be substituted by halogen.

Preferred Sp ¹ Sp and Sp ² Independently a single bond, an alkylene group of 1 to 6 carbon atoms, a-CH ₂ -an alkylene group of 1 to 6 carbon atoms substituted by-O-or-OCOO-. Further preferred is an alkylene group having 1 to 6 carbon atoms or-OCOO-.

P ¹ P ² Independently is a group represented by any one of the formulae (1 b) to (1 h).

Preferred P ¹ P ² Independently a group represented by any one of (1 b), (1 c), (1 d) and (1 e).

Preferred M ¹ 、M ² 、M ³ M and M ⁴ Independently hydrogen, fluorine, methyl, ethyl or trifluoromethyl. Further preferably hydrogen.

R ² Is hydrogen, halogen or C1-5 alkyl, wherein at least one hydrogen may be substituted by halogen, at least one-CH ₂ -may be substituted by-O-.

Preferred R ² Is hydrogen, fluorine, methyl, ethyl, methoxymethyl or trifluoromethyl. Further preferably hydrogen.

R ³ 、R ⁴ 、R ⁵ 、R ⁶ R is R ⁷ Independently hydrogen or a linear, branched or cyclic alkyl group of 1 to 15 carbon atoms, of which at least one-CH ₂ -may be substituted by-O-or-S-, at least one- (CH) ₂ ) ₂ -may be substituted by-ch=ch-or-c≡c-, in which groups at least one hydrogen may be substituted by halogen.

Preferred R ³ 、R ⁴ 、R ⁵ 、R ⁶ R is R ⁷ Independently hydrogen, a linear alkyl group having 1 to 10 carbon atoms, a linear alkenyl group having 2 to 10 carbon atoms, a linear alkoxy group having 1 to 10 carbon atoms, or a cyclic alkyl group having 3 to 6 carbon atoms. Further preferred are hydrogen, a linear alkyl group having 2 to 6 carbon atoms, a linear alkenyl group having 2 to 6 carbon atoms, a linear alkoxy group having 1 to 5 carbon atoms, and a cyclic alkyl group having 4 to 6 carbon atoms.

Further preferred groups are groups represented by formula (1 b-1), formula (1 b-2), formula (1 b-3), formula (1 b-4), formula (1 b-5), formula (1 c-1), formula (1 d-2) or formula (1 e-1).

In the formulae (1 b) to (1 h), M ¹ M and M ² Independently hydrogen, halogen, C1-5 alkyl or at least one hydrogen substituted by halogenAlkyl groups having 1 to 5 carbon atoms.

a and b are independently 0, 1 or 2, preferably 0+.a+b+.2.

Preferred examples of the compound (1) are the formulae (1-1) to (1-3).

In the formulae (1-1) to (1-3),

in these rings, at least one hydrogen may be substituted by fluorine, chlorine, alkyl of 1 to 12 carbon atoms, alkenyl of 2 to 12 carbon atoms, alkoxy of 1 to 11 carbon atoms, alkenyloxy of 2 to 11 carbon atoms, -Sp ¹ -P ¹ or-Sp ² -P ² Substitution, of which at least one hydrogen may be substituted by fluorine or chlorine;

Z ² 、Z ³ z is as follows ⁴ Independently a single bond, - (CH) ₂ ) ₂ -、-CH＝CH-、-C≡C-、-COO-、-OCO-、-CF ₂ O-、-OCF ₂ -、-CH ₂ O-、-OCH ₂ -, -cf=cf-, -ch=chcoo-, -ococh=ch-, -ch=chco-, or-coch=ch-, wherein Z ² 、Z ³ Z is as follows ⁴ At least one of them is-COO-, -OCO-, -CH=CHCOO-, -OCOCH=CH-, -CH=CH-, -CH=CHCO-, or-COCH=CH-;

in the formulas (1 b) to (1 h),

In the compound represented by the formula (1-1), the formula (1-2) or the formula (1-3), Z ² 、Z ³ Or Z is ⁴ Any of (3)Preferably, the latter is-COO-or-OCO-.

In the compound represented by the formula (1-1), the formula (1-2) or the formula (1-3), Z ² 、Z ³ Or Z is ⁴ Preferably, -ch=chcoo-, -ococh=ch-, -ch=ch-, -ch=chco-, or-coch=ch-.

The compound (1) is preferably a compound represented by the formula (1-A).

P ¹ -Sp ¹ -Y-Sp ² -P ² (1-A)

Specific examples of the compound (1) will be described in examples to be described later.

The formula (2) to formula (15) show constituent compounds of the liquid crystal composition. The compounds (2) to (4) have small dielectric anisotropy. The compounds (5) to (7) have positive and large dielectric anisotropy. The compound (8) has a cyano group and thus has positive and larger dielectric anisotropy. The compounds (9) to (16) have negative and large dielectric anisotropy. Specific examples of these compounds will be described later.

Of the compounds (16),P ¹¹ 、P ¹² p ¹³ Independently is a polymerizable group.

Preferred P ¹¹ 、P ¹² P ¹³ Is a polymerizable group selected from the group of groups represented by the formulas (P-1) to (P-5). Further preferably P ¹¹ 、P ¹² P ¹³ Is a group (P-1), a group (P-2) or a group (P-3). Particularly preferred radicals (P-1) are-OCO-ch=ch ₂ or-OCO-C (CH) ₃ )＝CH ₂ . The wavy lines of the groups (P-1) to (P-5) represent the sites where bonding is performed.

Radicals (P-1) to (P-5), M ¹¹ 、M ¹² M and M ¹³ Independently hydrogen, fluorine, an alkyl group of 1 to 5 carbon atoms or an alkyl group of 1 to 5 carbon atoms in which at least one hydrogen is substituted with halogen.

In order to increase the reactivity, M is preferably ¹¹ 、M ¹² M and M ¹³ Is hydrogen or methyl. Further preferably M ¹¹ Methyl group, and preferably M ¹² M and M ¹³ Is hydrogen.

Preferred Sp ¹¹ 、Sp ¹² Sp and Sp ¹³ Is a single bond.

Ring F 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, at least one hydrogen of which may be substituted by halogen, alkyl of 1 to 12 carbon atoms, alkoxy of 1 to 12 carbon atoms or alkyl of 1 to 12 carbon atoms substituted by halogen.

Preferred ring F and ring I are phenyl groups. 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 hydrogen may be substituted by halogen, alkyl of 1 to 12 carbon atoms, alkoxy of 1 to 12 carbon atoms or at least one hydrogen substituted by halogen. Particularly preferred ring G is 1, 4-phenylene or 2-fluoro-1, 4-phenylene.

Z ²² Z is as follows ²³ Independently a single bond or an alkylene group of 1 to 10 carbon atoms, of which at least one-CH ₂ -can be substituted by-O-, -CO-, -COO-or-OCO-, at least one-CH ₂ CH ₂ Can be modified by-ch=ch-, -C (CH ₃ )＝CH-、-CH＝C(CH ₃ ) -or-C (CH) ₃ )＝C(CH ₃ ) -substitution, in which at least one hydrogen may be substituted by fluorine or chlorine.

Preferred Z ²² Z is as follows ²³ Is a single bond, -CH ₂ CH ₂ -、-CH ₂ O-、-OCH ₂ -, -COO-or-OCO-. Further preferably Z ²² Z is as follows ²³ Is a single bond.

u is 0, 1 or 2.

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

2. Synthesis of Compound (1)

The synthesis of the compound (1) will be described. The compound (1) can be synthesized by appropriately combining the methods of organic synthetic chemistry. The compounds not described for the synthesis were synthesized by the methods described in books such as "organic synthesis (Organic Syntheses)" (John Wiley father and son publishing company (John Wiley & Sons, inc.), "organic reaction (Organic Reactions)" (John Wiley father and son, inc.), "comprehensive organic synthesis (Comprehensive Organic Synthesis)" (Pegman Press (Pergamon Press)) "," New laboratory chemistry lecture (Paddy) ", and the like.

2-1. Bonding group Z ¹ A bond group Z ² A bond group Z ³ A bond group Z ⁴ Bonding group Z ⁵ Is generated by (a)

Examples of the method for producing the bond group in the compound (1) are described in the following schemes. In the process, MSG ¹ (or MSG) ² ) Is a monovalent organic group having at least one ring. Multiple MSGs ¹ (or MSG) ² ) The monovalent organic groups represented may be the same or may be different. The compounds (1A) to (1J) correspond to the compound (1) or an intermediate of the compound (1).

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(I) Single bond formation

The compound (1A) is synthesized by reacting the arylboronic acid (21) with the compound (22) in the presence of a carbonate salt and a tetrakis (triphenylphosphine) palladium catalyst. The compound (1A) can also be synthesized as follows: compound (23) is reacted with n-butyllithium, followed by zinc chloride, and then reacted with compound (22) in the presence of bis (triphenylphosphine) palladium dichloride catalyst.

(II) -COO-and-OCO-formation

The compound (23) is reacted with n-butyllithium, followed by reaction with carbon dioxide to obtain a carboxylic acid (24). The carboxylic acid (24) and phenol (25) derived from the compound (21) are dehydrated in the presence of 1,3-Dicyclohexylcarbodiimide (DCC) and 4-dimethylaminopyridine (4-dimethylamino pyridine, DMAP) to synthesize the compound (1B) having-COO-. Compounds having-OCO-are also synthesized using the method.

(III)-CF ₂ O-and-OCF ₂ -generation of

Compound (26) is obtained by sulfiding compound (1B) with lawsen reagent. Complexing with hydrogen fluoride pyridineFluorination of Compound (26) with N-bromosuccinimide (NBS) to give the compound having-CF ₂ O-compound (1C). Reference is made to "chemical flash report (chem. Lett.)" of m. black star (m.kuroboshi) et al, 1992, 827. Compound (1C) can also be synthesized by fluorinating compound (26) with (diethylamino) sulfur trifluoride (DAST) sulphur trifluoride. Refer to "journal of organic chemistry (j. Org. Chem.)" in 1990, page 55 768, of w.h. banel (w.h. bunnelle) et al. with-OCF ₂ The compounds are also synthesized using the method.

Formation of (IV) -ch=ch

Compound (22) was reacted with N-butyllithium, followed by N, N-dimethylformamide (N, N-Dimethyl Formamide, DMF) to obtain aldehyde (27). The phosphonium salt (28) is reacted with potassium t-butoxide to produce phosphoylide, and the phosphoylide is reacted with aldehyde (27) to synthesize compound (1D). The cis form is formed by the reaction conditions, and thus, the cis form is isomerized to the trans form by a known method, if necessary.

(V)-CH ₂ CH ₂ -generation of

Compound (1E) is synthesized by hydrogenating compound (1D) in the presence of a palladium carbon catalyst.

Production of (VI) -C.ident.C-)

Compound (23) is reacted with 2-methyl-3-butyn-2-ol in the presence of a catalyst comprising palladium dichloride and copper iodide, and then deprotected under basic conditions to give compound (29). Compound (29) and compound (22) are reacted in the presence of a catalyst comprising bis (triphenylphosphine) palladium dichloride and a copper halide to synthesize compound (1F).

(VII)-CH ₂ O-and-OCH ₂ -generation of

Compound (30) is obtained by reducing compound (27) with sodium borohydride. Bromination thereof with hydrobromic acid gives compound (31). Compound (1G) is synthesized by reacting compound (25) with compound (31) in the presence of potassium carbonate. having-OCH ₂ The compounds are also synthesized using the method.

Formation of (VIII) -cf=cf

Compound (32) is obtained by treating compound (23) with n-butyllithium and then reacting tetrafluoroethylene. Compound (1H) is synthesized by treating compound (22) with n-butyllithium and then reacting with compound (32).

Formation of (VIV) -ch=chco-and-coch=ch

Compound (1I) is synthesized by aldolisation of compound (40) with compound (27) in the presence of NaOH.

Formation of (X) -ch=chcoo-and-ococh=ch-

Compound (1J) is synthesized by dehydrating cinnamic acid (41) and compound (25) in the presence of 1, 3-Dicyclohexylcarbodiimide (DCC) and 4-Dimethylaminopyridine (DMAP).

2-2 Ring A ¹ Ring A ² Ring A ³ Ring A ⁴ Is generated by (a)

The initiating materials are widely commercially available or known in the synthesis process for the rings such as 1, 4-cyclohexylene, 1, 4-cyclohexenylene, 1, 4-phenylene, 2-fluoro-1, 4-phenylene, 2-methyl-1, 4-phenylene, 2-ethyl-1, 4-phenylene, naphthalene-2, 6-diyl, decalin-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, perhydrocyclopenta [ a ] phenanthrene-3, 17-diyl, 2,3,4,7,8,9,10,11,12,13,14,15,16,17-tetradecano [ a ] phenanthrene-3, 17-diyl. The group represented by (A-1) and the group represented by (A-2) can be synthesized with reference to the production of-C.ident.C-.

2-3 linker Sp ¹ Or a linking group Sp ² Polymerizable group P ¹ Or a polymerizable group P ² Is generated by (a)

Polymerizable group P ¹ Or a polymerizable group P ² Preferred examples of (a) are acryloyloxy (1 b), maleimide (1 c), itaconate (1 d), vinyl ester (1 e), oxetanyl (1 g) or ethyleneoxy (1 h).

Synthesis of the polymerizable group through the linking group Sp ¹ Or a linking group Sp ² Examples of the method of bonding the ring-bonded compound are as follows. First, the linking group Sp is shown ¹ Or a linking group Sp ² Is an example of a single bond.

(1) Synthesis of Compounds that are Single bonds

Sp ¹ Or Sp ² The synthesis of compounds that are single bonds is described in the schemes below. In the process, MSG ¹ Is a monovalent organic group having at least one ring. The compounds (1S) to (1Z) correspond to the compound (1). In the case of acrylate derivatives as the polymerizable group, the polymerization reaction is carried out by using the corresponding acrylic acid and HO-MSG ¹ Is synthesized by esterification. Ethyleneoxy is obtained by HO-MSG ¹ Etherification with vinyl bromide. The oxetanyl group is synthesized by oxidation of the terminal double bond. Maleimido groups are synthesized by the reaction of an amino group with maleic anhydride. Itaconate is prepared from itaconic acid and HO-MSG ¹ Is synthesized by esterification. Vinyl ester is prepared from vinyl acetate and HOOC-MSG ¹ Is synthesized by transesterification.

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The linking group Sp is described above ¹ Or a linking group Sp ² Synthesis of a Compound which is a single bond. Methods for generating other linkers can refer to the bond group Z ¹ A bond group Z ² A bond group Z ³ A bond group Z ⁴ Bonding group Z ⁵ Is synthesized by the synthesis method.

2-4. Synthesis examples

Examples of the method for synthesizing the compound (1) are as follows. Of these compounds, MES is a mesogen having at least one ring. P (P) ¹ 、M ¹ 、M ² 、Sp ¹ Sp and Sp ² Is defined as described.

The compound (51A) and the compound (51B) are commercially available or can be synthesized by a usual organic synthesis method using a Mesogen (MES) having an appropriate ring structure as an initiating substance.

In the synthesis of MES and Sp ¹ In the case of a compound having an ether bond, the compound (53A) can be obtained by etherifying the compound (51A) with a base such as the compound (52) and potassium hydroxide as an initiating substance. In addition, in the synthesis of MES and Sp ¹ In the case of a compound having a single bond, the compound (53B) can be obtained by performing a cross-coupling reaction using the compound (52), a metal catalyst such as palladium, and a base with the compound (51B) as an initiating substance. The compound (53A) or the compound (53B) may be derived as needed from a compound (54A) or a compound (54B) in which a protecting group such as Trimethylsilyl (TMS) or Tetrahydropyranyl (THP) acts.

Thereafter, the compound (57A) or the compound (57B) is obtained by etherification of the compound (53A), the compound (53B), the compound (54A) or the compound (54B) again in the presence of a base such as the compound (55) and potassium hydroxide.

In this case, when the protecting group is allowed to act in the early stage, the protecting group is removed by a deprotection reaction.

P ² The compound (1A) which is a group represented by the formula (1 b-3) can be synthesized from the compound (57) by the following method. From the compound (57), an esterification reaction is performed in the presence of the compound (58), DCC, and DMAP, whereby the compound (1A) can be derived.

3. Liquid crystal composition

The liquid crystal composition of the embodiment of the present invention contains the compound (1) as the component a. The compound (1) can contribute to control of the orientation of liquid crystal molecules by interacting with the substrate of the element in a non-covalent bonding manner. The composition preferably contains the compound (1) as the component a, and further contains a liquid crystalline compound selected from the group consisting of the component B, the component C, the component D, and the component E shown below. Component B is compounds (2) to (4). Component C is compounds (5) to (7). Component D is compound (8). Component E is compounds (9) to (16). The composition may also contain other liquid crystalline compounds different from the compounds (2) to (16). In preparing the composition, it is preferable to select component B, component C, component D, and component E in consideration of the magnitude of positive or negative dielectric anisotropy, and the like. The composition of the components is suitably selected to have a high upper temperature limit, a low lower temperature limit, a small viscosity, a suitable optical anisotropy (i.e., a large optical anisotropy or a small optical anisotropy), a large positive or negative dielectric anisotropy, a large specific resistance, stability to heat or ultraviolet rays, and a suitable elastic constant (i.e., a large elastic constant or a small elastic constant).

In order to maintain high stability against ultraviolet rays, the preferable proportion of the compound (1) is usually about 0.01% by weight or more based on the weight of the liquid crystal composition, and in order to dissolve in the liquid crystal composition, the preferable proportion of the compound (1) is usually about 10% by weight or less. Further preferred proportions are in the range of about 0.1% to about 5% by weight, based on the weight of the liquid crystal composition. The most preferred proportion is in the range of about 0.5% to about 3% by weight based on the weight of the liquid crystal composition.

Component B is a compound having alkyl groups or the like at both end groups. Preferable examples of the component B include compounds (2-1) to (2-11), compounds (3-1) to (3-19) and compounds (4-1) to (4-7). In the compound of component B, R ¹¹ R is R ¹² Independently is an alkyl group of 1 to 10 carbon atoms or an alkenyl group of 2 to 10 carbon atoms, at least one of which is-CH ₂ -may be substituted by-O-and at least one hydrogen may be substituted by fluorine.

The component B is a compound close to neutral because of its small absolute value of dielectric anisotropy. The compound (2) is effective mainly in reducing viscosity or adjusting optical anisotropy. The compound (3) and the compound (4) have an effect of expanding the temperature range of the nematic phase by increasing the upper limit temperature or an effect of adjusting the optical anisotropy.

As the content of component B increases, the dielectric anisotropy of the composition becomes smaller, but the viscosity becomes smaller. Therefore, the content is more preferable as long as the required value of the threshold voltage of the element is satisfied. In the case of preparing a composition for modes such as IPS and VA, the content of component B is preferably 30% by weight or more, and more preferably 40% by weight or more, based on the weight of the liquid crystal composition.

The component C is compounds (5) to (7) having a halogen or fluorine-containing group at the right end. Preferable examples of the component C include compounds (5-1) to (5-16), compounds (6-1) to (6-120), and compounds (7-1) to (7-63). In the compound of component C, R ¹³ Is an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms, at least one of the alkyl and alkenyl groups being-CH ₂ -may be substituted by-O-, at least one hydrogen may be substituted by fluorine; x is X ¹¹ Is fluorine, chlorine, -OCF ₃ 、-OCHF ₂ 、-CF ₃ 、-CHF ₂ 、-CH ₂ F、-OCF ₂ CHF ₂ or-OCF ₂ CHFCF ₃ 。

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The component C has positive dielectric anisotropy and excellent stability to heat, light and the like, and thus can be used for producing a composition for a pattern such as IPS, FFS, OCB. The content of the component C is suitably in the range of 1 to 99% by weight, preferably in the range of 10 to 97% by weight, and more preferably in the range of 40 to 95% by weight, based on the weight of the liquid crystal composition. In the case of adding the component C to the composition having negative dielectric anisotropy, the content of the component C is preferably 30% by weight or less based on the weight of the liquid crystal composition. By adding component C, the elastic constant of the composition can be adjusted, and the voltage-transmittance curve of the element can be adjusted.

Component D is a compound (8) having a-C.ident.N or-C.ident.C-C.ident.N right-hand end group. Preferable examples of the component D include the compounds (8-1) to (8-64). In the compound of component D, R ¹⁴ Is an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms, at least one of the alkyl and alkenyl groups being-CH ₂ -may be substituted by-O-, at least one hydrogen may be substituted by fluorine; x is X ¹² is-C.ident.N or-C.ident.C-C.ident.N.

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Since the dielectric anisotropy of component D is positive and its value is large, it is mainly used for preparing a composition for TN or the like. By adding the component D, the dielectric anisotropy of the composition can be increased. The component D has an effect of expanding the temperature range of the liquid crystal phase, adjusting the viscosity, or adjusting the optical anisotropy. Component D is also useful for adjusting the voltage-transmittance curve of the element.

In the case of preparing a composition for TN or the like mode, the content of component D is suitably in the range of 1 to 99% by weight, preferably in the range of 10 to 97% by weight, and more preferably in the range of 40 to 95% by weight, based on the weight of the liquid crystal composition. In the case of adding the component D to the composition having negative dielectric anisotropy, the content of the component D is preferably 30% by weight or less based on the weight of the liquid crystal composition. By adding component D, the elastic constant of the composition can be adjusted, and the voltage-transmittance curve of the element can be adjusted.

Component E is compounds (9) to (16). These compounds have a phenylene group substituted with two halogens at the lateral position (lateral position) as 2, 3-difluoro-1, 4-phenylene group.

Preferable examples of the component E include compounds (9-1) to (9-8), compounds (10-1) to (10-17), compounds (11-1), compounds (12-1) to (12-3), compounds (13-1) to (13-11), compounds (14-1) to (14-3), compounds (15-1) to (15-3) and compounds (16-1) to (16-3). In the compound of the component E, R ¹⁵ R is R ¹⁶ Independently is an alkyl group of 1 to 10 carbon atoms or an alkenyl group of 2 to 10 carbon atoms, at least one of which-CH ₂ -may be substituted by-O-, at least one hydrogen may be substituted by fluorine; r is R ¹⁷ Is hydrogen, fluorine, C1-10 alkyl or C2-10 alkenyl, at least one of which is-CH ₂ -may be substituted by-O-and at least one hydrogen may be substituted by fluorine.

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The dielectric anisotropy of component E is negative and large. Component E can be used in the case of preparing a composition for a model such as IPS, VA, PSA. As the content of the component E increases, the dielectric anisotropy of the composition becomes negative and increases, but the viscosity becomes large. Therefore, the content is preferably small as long as the required value of the threshold voltage of the element is satisfied. When considering that the dielectric anisotropy is about-5, the content of the component E is preferably 40% by weight or more based on the weight of the liquid crystal composition in order to perform sufficient voltage driving.

In component E, the compound (9) is a bicyclic compound, and therefore is effective mainly in reducing viscosity, adjusting optical anisotropy, or increasing dielectric anisotropy. Since the compound (10) and the compound (11) are tricyclic compounds, there is an effect of increasing the upper limit temperature, increasing the optical anisotropy, or increasing the dielectric anisotropy. The compounds (12) to (16) have an effect of increasing dielectric anisotropy.

In the case of preparing a composition for a mode such as IPS, VA, PSA, the content of the component E is preferably 40% by weight or more, and more preferably in the range of 50% by weight to 95% by weight, based on the weight of the liquid crystal composition. In the case of adding the component E to the composition having positive dielectric anisotropy, the content of the component E is preferably 30% by weight or less based on the weight of the liquid crystal composition. By adding component E, the elastic constant of the composition can be adjusted, and the voltage-transmittance curve of the element can be adjusted.

By appropriately combining the above-described component B, component C, component D, and component E, a liquid crystal composition satisfying at least one of the following characteristics can be prepared: high upper limit temperature, low lower limit temperature, low viscosity, proper optical anisotropy, large positive or negative dielectric anisotropy, large specific resistance, high stability to ultraviolet light, high stability to heat, large elastic constant and the like. If necessary, a liquid crystalline compound different from the components B, C, D and E may be added.

The liquid crystal composition is prepared by a known method. For example, the constituent compounds are mixed and then dissolved in each other by heating. Additives may also be added to the composition according to the use. Examples of the additives are polymerizable compounds other than the formula (1) and the formula (16), polymerization initiators, polymerization inhibitors, optically active compounds, antioxidants, ultraviolet absorbers, light stabilizers, heat stabilizers, antifoaming agents, and the like. Such additives are well known to those of ordinary skill in the art and are described in the literature.

The polymerizable compound is added for the purpose of forming a polymer in the liquid crystal composition. Ultraviolet light is irradiated in a state where a voltage is applied between the electrodes, and the polymerizable compound and the compound (1) are copolymerized, whereby a polymer is formed in the liquid crystal composition. At this time, the compound (1) is immobilized in a state in which the polar group interacts with the substrate surface of the glass (or metal oxide) in a non-covalent bonding manner. Thereby, the ability to control the alignment of liquid crystal molecules is further improved, and the compound (1) does not leak out into the liquid crystal composition. In addition, since an appropriate pretilt angle is also obtained on the substrate surface of glass (or metal oxide), a liquid crystal display element having a reduced response time and a high voltage holding ratio can be obtained.

Preferable examples of the polymerizable compound are acrylic acid esters, methacrylic acid esters, vinyl compounds, ethyleneoxy compounds, propenyl ethers, epoxy compounds (oxetanes ) and vinyl ketones. Further preferable examples are compounds having at least one acryloyloxy group and compounds having at least one methacryloyloxy group. Further, preferable examples include compounds having both an acryloyloxy group and a methacryloyloxy group.

Further preferable examples of the polymerizable compounds are compounds (M-1) to (M-17). Compounds (M-1) to (M-17), R ²⁵ To R ³¹ Independently hydrogen or methyl; s, v and x are independently 0 or 1; t and u are independently integers from 1 to 10; l (L) ²¹ To L ²⁶ Independently hydrogen or fluorine, L ²⁷ L and L ²⁸ Independently hydrogen, fluorine or methyl.

The polymerizable compound can be rapidly polymerized by adding a polymerization initiator. By optimizing the reaction temperature, the amount of the remaining polymerizable compound can be reduced. Examples of photo-radical polymerization initiators are TPO, 1173 and 4265 in Darocure series of Basf company and 184, 369, 500, 651, 784, 819, 907, 1300, 1700, 1800, 1850 and 2959 in Irgacure series.

Additional examples of photo radical polymerization initiators are 4-methoxyphenyl-2, 4-bis (trichloromethyl) triazine, 2- (4-butoxystyryl) -5-trichloromethyl-1, 3, 4-oxadiazole, 9-phenylacridine, 9, 10-benzophenoxazine, benzophenone/Mitstone mixtures, hexaarylbisimidazole/mercaptobenzimidazole mixtures, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, benzyldimethyl ketal, 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholinopropane-1-one, 2, 4-diethylxanthone/p-dimethylaminobenzoate mixtures, benzophenone/methyltriethanolamine mixtures.

After adding a photo radical polymerization initiator to the liquid crystal composition, ultraviolet rays are irradiated in a state where an electric field is applied, whereby polymerization can be performed. However, unreacted polymerization initiator or decomposition products of the polymerization initiator may cause display defects such as image retention in the element. In order to prevent this, photopolymerization may be performed without adding a polymerization initiator. The preferred wavelength of the irradiated light is in the range of 150nm to 500 nm. Further, the wavelength is preferably in the range of 250nm to 450nm, and the most preferred wavelength is in the range of 300nm to 400 nm.

When the compound (1) having an ester bond group, a cinnamic acid ester bond, a chalcone skeleton or a stilbene skeleton is mixed into the composition, the main effects of the compound (1) as the component a on the characteristics of the composition are as follows. The compound (1) is arranged in a certain direction at a molecular level upon fries rearrangement, photodimerization or cis-trans isomerization of double bonds by polarization. Thus, the film made of the polar compound orients liquid crystal molecules in the same manner as an alignment film such as polyimide.

In the case of the compound (1) having an aromatic ester and having a polymerizable group, the aromatic ester site is photodegradation by irradiation with ultraviolet light, whereby radicals are formed and photofries rearrangement is generated.

In the photofries rearrangement, photodecomposition of the aromatic ester moiety occurs when the polarization direction of polarized ultraviolet light and the long axis direction of the aromatic ester moiety are in the same direction. After photodecomposition, rebinding proceeds and hydroxyl groups are generated intramolecularly by tautomerization. The hydroxyl groups are thought to cause interaction at the substrate interface, and the polar compound is thought to have anisotropy and be easily adsorbed on the substrate interface side. Further, since the compound (1) has a polymerizable group, the compound (1) reacts in the direction of polarized light by polymerization and is fixed without losing its directionality. The properties can be used to prepare films capable of orienting liquid crystal molecules. For the preparation of the film, the irradiated ultraviolet rays are suitably linearly polarized. First, the compound (1) as a polar compound is added to the liquid crystal composition in a range of 0.1 to 10 wt%, and the composition is heated to dissolve the polar compound. The composition is injected into an element without an orientation film. Then, the linear polarization is irradiated while heating the element, whereby the polar compound undergoes photofries rearrangement and is polymerized.

The polar compounds rearranged by photofries are arranged in a certain direction, and the film formed after polymerization has the function of a liquid crystal alignment film.

In storing the polymerizable compound, a polymerization inhibitor may be added to prevent polymerization. The polymerizable compound is usually added to the composition in a state in which the polymerization inhibitor is not removed. Examples of the polymerization inhibitor are hydroquinone, hydroquinone derivatives such as methyl hydroquinone, 4-tert-butyl catechol, 4-methoxyphenol, phenothiazine, etc.

The optically active compound exerts an effect of preventing reverse twist by imparting a desired twist angle by inducing a helical structure in liquid crystal molecules. By adding an optically active compound, the helical pitch can be adjusted. For the purpose of adjusting the temperature dependency of the spiral pitch, two or more optically active compounds may be added. Preferable examples of the optically active compound include the following compounds (Op-1) to (Op-18). In the compound (Op-18), the ring J is 1, 4-cyclohexylene or 1, 4-phenylene, R ²⁸ Is an alkyl group having 1 to 10 carbon atoms.

In order to maintain a large voltage holding ratio, the antioxidant is effective. Preferred examples of the antioxidant include: the following compound (AO-1) and compound (AO-2); yanjia (IRGANOX) 415, yanjia (IRGANOX) 565, yanjia (IRGANOX) 1010, yanjia (IRGANOX) 1035, yanjia (IRGANOX) 3114, and yanjia (IRGANOX) 1098 (trade name: BASF). In order to prevent the lowering of the upper limit temperature, the ultraviolet absorber is effective. Preferred examples of the ultraviolet absorber are benzophenone derivatives, benzoate derivatives, triazole derivatives, and the like. Specific examples include: the following compound (AO-3) and compound (AO-4); a Di Nun (TINUVIN) 329, a Di Nun (TINUVIN) P, a Di Nun (TINUVIN) 326, a Di Nun (TINUVIN) 234, a Di Nun (TINUVIN) 213, a Di Nun (TINUVIN) 400, a Di Nun (TINUVIN) 328, and a Di Nun (TINUVIN) 99-2 (trade name: basf Co.); and 1,4-Diazabicyclo [2.2.2] octane (1, 4-Diazabicyclo [2.2.2] octane; triethylenedimine, DABCO).

In order to maintain a large voltage holding ratio, a light stabilizer such as an amine having steric hindrance is preferable. Preferred examples of the light stabilizer include: the following compound (AO-5) and compound (AO-6); di Nun 144, di Nun 765 and Di Nun 770DF (trade name: basf). In order to maintain a large voltage holding ratio, the heat stabilizer is also effective, and preferred examples thereof include gorgeous (IRGAFOS) 168 (trade name: basf (BASF)). To prevent foaming, defoamers are effective. Preferred examples of the antifoaming agent are simethicone, methyl phenyl silicone oil and the like.

In the compound (AO-1), R ⁴⁰ Alkyl of 1 to 20 carbon atoms, alkoxy of 1 to 20 carbon atoms, -COOR ⁴¹ or-CH ₂ CH ₂ COOR ⁴¹ Here, R is ⁴¹ Is an alkyl group having 1 to 20 carbon atoms. In the compound (AO-2) and the compound (AO-5), R ⁴² Is an alkyl group having 1 to 20 carbon atoms. In the compound (AO-5), R ⁴³ Is hydrogen, methyl or O ^· (oxygen radical), ring G is 1, 4-cyclohexylene or 1, 4-phenylene, and z is 1, 2 or 3.

4. Liquid crystal display element

The liquid crystal composition can be used for a liquid crystal display element which has an operation mode of PC, TN, STN, OCB, PSA or the like and is driven in an active matrix manner. The composition can also be used in liquid crystal display elements having an operation mode of PC, TN, STN, OCB, VA, IPS or the like and driven in a passive matrix manner. These elements are also applicable to any of the types of reflective, transmissive, and semi-transmissive.

The composition can also be used for a nematic curvilinear alignment phase (nematic curvilinear aligned phase, NCAP) element prepared by microencapsulating nematic liquid crystal, a polymer dispersed liquid crystal display element (polymer dispersed liquid crystal display, PDLCD) prepared by forming a three-dimensional network polymer in liquid crystal, and a polymer network liquid crystal display element (polymer network liquid crystal display, PNLCD). When the amount of the polymerizable compound added is about 10 wt% or less based on the weight of the liquid crystal composition, a PSA-mode liquid crystal display element can be produced. The preferred proportion of the polymerizable compound is in the range of about 0.1% by weight to about 2% by weight based on the weight of the liquid crystal composition. Further preferred proportions are in the range of about 0.2% to about 1.0% by weight, based on the weight of the liquid crystal composition. The PSA mode elements may be driven in a driving manner such as active matrix, passive matrix, or the like. Such a device can be applied to any of a reflective type, a transmissive type, and a semi-transmissive type. By increasing the amount of the polymerizable compound to be added, a polymer dispersion (polymer dispersed) mode element can be produced.

In the polymer-stabilized alignment element, the polymer contained in the composition aligns liquid crystal molecules. The compound (1) as a polar compound assists alignment of liquid crystal molecules. That is, the compound (1) may be used instead of the alignment film. An example of a method of manufacturing such a device is as follows.

An element having two substrates called an array substrate and a color filter substrate is prepared. The substrate has no alignment film. At least one of the substrates has an electrode layer. The liquid crystal compound is mixed to prepare a liquid crystal composition. A polymerizable compound and a compound (1) as a polar compound are added to the composition. Additives may be further added as needed. The composition is injected into the component. The element is irradiated with light. Preferably ultraviolet light. The polymerizable compound is polymerized by light irradiation. A composition comprising a polymer is produced by the polymerization, thereby producing an element having a PSA mode.

A method of manufacturing the element is described. The first step is to add the compound (1) as a polar compound to the liquid crystal composition and to heat the composition at a temperature higher than the upper limit temperature to dissolve it. The second step is to inject the composition into a liquid crystal display element. The third step is to irradiate polarized ultraviolet rays at a temperature at which the liquid crystal composition is warmed to above the upper limit temperature. Compound (1) as a polar compound is polymerized at the same time as any one of photofries rearrangement, photodimerization, and cis-trans isomerization of a double bond is generated by linear polarization. The polymer of the compound (1) is formed as a thin film on a substrate and fixed. The polymer is aligned in a certain direction at a molecular level, and thus the film has a function as a liquid crystal alignment film. A liquid crystal display element without an alignment film such as polyimide can be manufactured by the method.

In the above procedure, the compound (1) as a polar compound is biased to exist on the substrate because the polar group interacts with the substrate surface. The compound (1) aligns liquid crystal molecules by irradiation of polarized ultraviolet rays, and the polymerizable compound is polymerized by ultraviolet rays, so that a polymer maintaining the alignment is produced. By the effect of the polymer, the orientation of the liquid crystal molecules is more stabilized, and thus the response time of the element is shortened. The afterimage of an image is a defective operation of liquid crystal molecules, and thus the afterimage is also improved by the effect of the polymer. In particular, since the compound (1) according to the embodiment of the present invention is a polymerizable polar compound, the liquid crystal molecules are aligned and copolymerized with other polymerizable compounds. Thus, the polar compound does not leak into the liquid crystal composition, and a liquid crystal display element having a large voltage holding ratio can be obtained.

Examples

The present invention will be further described in detail with reference to examples (including examples of synthesis and examples of use of elements). The present invention is not limited by these examples. The present invention includes a mixture of the composition of use example 1 and the composition of use example 2. The present invention also includes a mixture prepared by mixing at least two of the compositions of the use cases.

1. Examples of Compound (1)

Compound (1) was synthesized by the procedure shown in example 1 and the like. Unless otherwise specified, the reaction is carried out under a nitrogen atmosphere. The synthesized compound is identified by nuclear magnetic resonance (Nuclear Magnetic Resonance, NMR) analysis or the like. The characteristics of the compound (1), the liquid crystalline compound, the composition and the element were measured by the following methods.

NMR analysis: DRX-500 manufactured by Bruker Biospin was used for the measurement. At the position of ¹ In the measurement of H-NMR, a sample was dissolved in CDCl ₃ The measurement was performed in an isotonic medium at room temperature under conditions of 500MHz and 16 times of cumulative number of times. Tetramethylsilane was used as an internal standard. At the position of ¹⁹ In the determination by F-NMR, CFCl was used ₃ As an internal standard, measurement was performed 24 times in total. Nuclear magnetismIn the description of resonance spectra, s denotes a single peak, d denotes a double peak, t denotes a triple peak, q denotes a quadruple peak, quin denotes a quintuple, sex denotes a hexa-double peak, m denotes a multiple peak, and br denotes a broad peak.

Gas chromatography analysis: for measurement, a GC-2010 type gas chromatograph manufactured by Shimadzu corporation was used. The column was a capillary column DB-1 (length 60m, inner diameter 0.25mm, film thickness 0.25 μm) manufactured by Agilent technologies Co., ltd (Agilent Technologies Inc.). Helium (1 ml/min) was used as carrier gas. The temperature of the sample vaporization chamber was set to 300 ℃, and the temperature of the detector (flame ionization detector (flame ionization detector, FID)) portion was set to 300 ℃. The sample was dissolved in acetone and prepared as a 1 wt% solution, and 1. Mu.l of the obtained solution was injected into the sample vaporization chamber. The recorder uses a GC dissolution (GC Solution) system manufactured by shimadzu corporation, or the like.

High performance liquid chromatography (High Performance Liquid Chromatography, HPLC) analysis: for the measurement, prominence (LC-20 AD; SPD-20A) manufactured by Shimadzu corporation was used. The column was YMC-Pack (YMC-Pack) ODS-A (150 mm in length, 4.6mm in inside diameter, 5 μm in particle diameter) manufactured by Vitamics (YMC). The solution is obtained by mixing acetonitrile with water. As the detector, an Ultraviolet (UV) detector, a Refractive Index (RI) detector, a CORONA (CORONA) detector, and the like are suitably used. In the case of using a UV detector, the detection wavelength was set to 254nm. The sample was dissolved in acetonitrile and prepared as a 0.1 wt% solution, and 1. Mu.L of the solution was introduced into the sample chamber. As a recorder, a C-R7A reinforced plate (C-R7A plus) manufactured by Shimadzu corporation was used.

Ultraviolet visible light spectrometry: for the measurement, french code Sibirh (PharmaSpec) UV-1700 manufactured by Shimadzu corporation was used. The detection wavelength was set to 190nm to 700nm. The sample was dissolved in acetonitrile and prepared as a solution of 0.01mmol/L, and was placed in a quartz cell (optical path length 1 cm) for measurement.

Measuring a sample: the compound itself was used as a sample when the phase structure and the transition temperature (clearing point, melting point, polymerization initiation temperature, etc.) were measured.

The measuring method comprises the following steps: the characteristics were measured by the following method. Most of these methods are those described in the JEITA standard (JEITA. ED-2521B) which is examined and formulated by the society of electronic information technology and technology (Japan Electronics and Information Technology Industries Association, JEITA), or those modified. In the TN element used for measurement, a Thin Film Transistor (TFT) was not mounted.

(1) Phase structure

The sample was placed on a hot plate (hot stage) of FP-52 type, manufactured by Mettler (Mettler) having a melting point measuring device of a polarization microscope. The sample was heated at a rate of 3 ℃/min, and the phase state and its change were observed with a polarization microscope to determine the type of phase.

(2) Transition temperature (. Degree. C.)

For measurement, a scanning calorimeter, a Diamond DSC system, manufactured by Perkin Elmer, or a high sensitivity differential scanning calorimeter, X-DSC7000, manufactured by SSI nanotechnology (SSI Nanotechnology) were used. The sample was cooled at a rate of 3 ℃/min, and the peak of the endothermic or exothermic peak associated with the phase change of the sample was obtained by extrapolation, and the transition temperature was determined. The melting point of the compound, polymerization initiation temperature, was also determined using the apparatus. The temperature at which the compound changes from a solid to a smectic phase, a nematic, or the like liquid crystal phase is sometimes referred to simply as the "lower limit temperature of the liquid crystal phase". The temperature at which a compound changes from a liquid crystal phase to a liquid is sometimes referred to simply as the "clearing point".

The crystals are denoted as C. In the case of distinguishing the kinds of crystals, e.g. C ₁ 、C ₂ That is shown. The smectic phase is denoted S and the nematic phase is denoted N. In the smectic phase, when the smectic A phase, the smectic B phase, the smectic C phase, or the smectic F phase are distinguished, they are denoted by S respectively _A 、S _B 、S _C Or S _F . The liquid (isotropic) is denoted as I. The transition temperature is expressed, for example, as "C50.0N 100.0I". It means that the temperature for the self-crystallization to the nematic phase is 50.0℃and that the self-crystallization is carried outThe temperature at which the nematic phase converts to a liquid is 100.0 ℃.

(3) Upper limit temperature of nematic phase (T _NI Or NI; DEG C)

The sample was placed on a hot plate equipped with a melting point measuring device of a polarization microscope, and heated at a rate of 1 ℃/min. The temperature at which a part of the sample was changed from a nematic phase to an isotropic liquid was measured. The upper limit temperature of the nematic phase is sometimes simply referred to as "upper limit temperature". When the sample is a mixture of the compound (1) and a mother liquid crystal, T is used as _NI Is represented by the notation of (c). When the sample is a mixture of the compound (1) and the compounds such as the component B, the component C, and the component D, the symbol of NI is used.

(4) Lower limit temperature of nematic phase (T _C ；℃)

After the samples having a nematic phase were kept in a freezer at 0 ℃, -10 ℃, -20 ℃, -30 ℃ and-40 ℃ for 10 days, a liquid crystal phase was observed. For example, T is determined when the sample maintains a nematic phase at-20℃and changes to a crystalline or smectic phase at-30 DEG C _C The temperature was set at-20 ℃. The lower limit temperature of the nematic phase is sometimes simply referred to as "lower limit temperature".

( 5) Viscosity (bulk viscosity); η; measured at 20 ℃; mPas )

For measurement, an E-type rotary viscometer manufactured by Tokyo counter Co., ltd was used.

( 6) Optical anisotropy (refractive index anisotropy; measured at 25 ℃; Δn )

The measurement was performed by an abbe refractometer having a polarizing plate attached to an eyepiece using light having a wavelength of 589 nm. After rubbing the surface of the main prism in one direction, a sample is dropped onto 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+.T) is measured when the direction of polarization is perpendicular to the direction of rubbing. The value of the optical anisotropy (Δn) is calculated from the equation Δn=n-n+..

(7) Specific resistance (ρ; measured at 25 ℃ C.; Ω cm)

1.0mL of the sample was poured into a container equipped with an electrode. A DC voltage (10V) was applied to the container, and a DC current was measured after 10 seconds. The specific resistance is calculated by the following equation. (specific resistance) = { (voltage) × (capacitance of container) }/{ (direct current) × (dielectric constant of vacuum) }.

The measurement method of the characteristics may be different between a sample having positive dielectric anisotropy and a sample having negative dielectric anisotropy. The measurement method in which the dielectric anisotropy is positive is described in the items (8 a) to (12 a). When the dielectric anisotropy is negative, the measurement method is described in the items (8 b) to (12 b).

( 8a) Viscosity (rotational viscosity; γ1; measured at 25 ℃; mPas )

Positive dielectric anisotropy: the measurement is based on the method described in "molecular crystal and liquid crystal (Molecular Crystals and Liquid Crystals)" (Vol. 259, 37 (1995)) by M.Nwell (M.Imai) et al. Samples were placed in a TN cell having a twist angle of 0 degrees and a gap (cell gap) between two glass substrates of 5. Mu.m. The voltage was applied to the element in a stepwise manner in units of 0.5V in the range of 16V to 19.5V. After 0.2 seconds of no voltage was applied, the voltage was repeatedly applied with only one rectangular wave (rectangular pulse; 0.2 seconds) and no voltage was applied (2 seconds). The peak current (peak current) and the peak time (peak time) of the transient current (transient current) generated by the application are measured. The value of the rotational viscosity was obtained from these measurement values and the calculation formula (8) on page 40 of the paper by m.to date well (m.imai et al). The value of the dielectric anisotropy necessary for the calculation is obtained by using an element for measuring the rotational viscosity and using the method described below.

( 8b) Viscosity (rotational viscosity; γ1; measured at 25 ℃; mPas )

Negative dielectric anisotropy: the measurement is based on the method described in "molecular crystal and liquid crystal (Molecular Crystals and Liquid Crystals)" (Vol. 259, 37 (1995)) by M.Nwell (M.Imai) et al. Samples were placed in VA elements having a gap (cell gap) of 20 μm between two glass substrates. The device is applied with a voltage in steps of 1 volt in a range of 39 volts to 50 volts. After 0.2 seconds of no voltage was applied, the voltage was repeatedly applied with only one rectangular wave (rectangular pulse; 0.2 seconds) and no voltage was applied (2 seconds). The peak current (peak current) and the peak time (peak time) of the transient current (transient current) generated by the application are measured. The value of the rotational viscosity was obtained from these measurement values and the calculation formula (8) on page 40 of the paper by m.to date well (m.imai et al). The dielectric anisotropy necessary for the calculation is a value measured using the term of dielectric anisotropy described below.

(9a) Dielectric anisotropy (Δε; measured at 25 ℃ C.)

Positive dielectric anisotropy: samples were placed in a TN cell having a gap (cell gap) between two glass substrates of 9 μm and a twist angle of 80 degrees. A sine wave (10V, 1 kHz) was applied to the element, and the dielectric constant (. Epsilon. Cndot.) of the liquid crystal molecules was measured in the long axis direction after 2 seconds. A sine wave (0.5V, 1 kHz) was applied to the element, and the dielectric constant (. Epsilon. DELTA.T.) of the liquid crystal molecules was measured in the short axis direction after 2 seconds. The value of dielectric anisotropy is calculated from the equation of Δε=ε - ε.

(9b) Dielectric anisotropy (Δε; measured at 25 ℃ C.)

Negative dielectric anisotropy: the value of dielectric anisotropy is calculated from the equation of Δε=ε - ε. The dielectric constant (. Epsilon. T) was measured as follows.

1) Determination of dielectric constant (ε): a well-cleaned glass substrate was coated with a solution of octadecyltriethoxysilane (0.16 mL) in ethanol (20 mL). After the glass substrate was rotated by a rotator, the glass substrate was heated at 150℃for 1 hour. Samples were placed in VA devices having a gap (cell gap) of 4 μm between two glass substrates, and the devices were sealed with an adhesive cured by ultraviolet light. A sine wave (0.5V, 1 kHz) was applied to the element, and the dielectric constant (. Epsilon./V) of the liquid crystal molecules was measured in the long axis direction after 2 seconds.

2) Determination of dielectric constant (ε+.T): a polyimide solution was coated on the sufficiently cleaned glass substrate. After the glass substrate is fired, the resultant alignment film is subjected to a rubbing treatment. Samples were placed in a TN cell having a gap (cell gap) between two glass substrates of 9 μm and a twist angle of 80 degrees. A sine wave (0.5V, 1 kHz) was applied to the element, and the dielectric constant (. Epsilon. DELTA.T.) of the liquid crystal molecules was measured in the short axis direction after 2 seconds.

(10a) Spring constant (K; measured at 25 ℃ C.; pN)

Positive dielectric anisotropy: for the measurement, an LCR meter of the type HP4284A manufactured by Yokogawa-Hewlett Packard Co., ltd was used. Samples were placed in a horizontally oriented element having a gap (cell gap) of 20 μm between two glass substrates. The device was charged with 0 to 20 volts, and the capacitance and applied voltage were measured. The measured capacitance (C) and the value of the applied voltage (V) were fitted using the formulas (2.98) and (2.101) in "liquid crystal device handbook" (journal of the Japanese Industrial Co., ltd.) page 75, and K was obtained from the formula (2.99) ₁₁ K is as follows ₃₃ Is a value of (2). Then, in the formula (3.18) on page 171, K obtained before is used ₁₁ K is as follows ₃₃ To calculate K by the value of (2) ₂₂ . The elastic constant K is K obtained in this way ₁₁ 、K ₂₂ K is as follows ₃₃ Is represented by the average value of (a).

(10b) Spring constant (K) ₁₁ K is as follows ₃₃ The method comprises the steps of carrying out a first treatment on the surface of the Measured at 25 ℃; pN)

Negative dielectric anisotropy: an EC-1 type elastic constant measuring instrument manufactured by TOYO technology Co., ltd was used for the measurement. Samples were placed in vertically oriented elements having a gap (cell gap) of 20 μm between the two glass substrates. The device was charged with 20 to 0 volts, and the capacitance and applied voltage were measured. The value of the elastic constant was obtained from equation (2.100) by fitting the value of the electrostatic capacitance (C) and the applied voltage (V) using equations (2.98) and (2.101) in page 75 of "handbook of liquid crystal devices" (journal of the industry).

(11a) Threshold voltage (Vth; measured at 25 ℃ C.; V)

Positive dielectric anisotropy: an LCD5100 type luminance meter manufactured by tsukamurelku electronics corporation was used for the measurement. The light source is a halogen lamp. Samples were placed in a TN cell in a normally white mode (normally white mode) having a gap (cell gap) between two glass substrates of 0.45/. DELTA.n (. Mu.m) and a twist angle of 80 degrees. The voltage (32 Hz, rectangular wave) applied to the element was increased stepwise from 0V to 10V in units of 0.02V. At this time, the element is irradiated with light from the vertical direction, and the amount of light transmitted through the element is measured. A voltage-transmittance curve was produced in which the transmittance was 100% when the light amount was maximum and 0% when the light amount was minimum. The threshold voltage is expressed as the voltage at which the transmittance becomes 90%.

(11b) Threshold voltage (Vth; measured at 25 ℃ C.; V)

Negative dielectric anisotropy: an LCD5100 type luminance meter manufactured by tsukamurelku electronics corporation was used for the measurement. The light source is a halogen lamp. A sample was placed in a VA element having a gap (cell gap) between two glass substrates of 4 μm and a normally black mode (normally black mode) having an antiparallel rubbing direction, and the element was sealed with an adhesive cured by ultraviolet rays. The voltage applied to the element (60 Hz, rectangular wave) was increased stepwise from 0V to 20V 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 was produced in which the transmittance was 100% when the light amount was maximum and 0% when the light amount was minimum. The threshold voltage is expressed as a voltage at which the transmittance becomes 10%.

(12a) Response time (τ; measured at 25 ℃ C.; ms)

Positive dielectric anisotropy: an LCD5100 type luminance meter manufactured by tsukamurelku electronics corporation was used for the measurement. The light source is a halogen lamp. The Low pass filter (Low pass filter) is set to 5kHz. Samples were placed in a TN cell in a normally white mode (normally white mode) in which the interval (cell gap) between two glass substrates was 5.0 μm and the twist angle was 80 degrees. Rectangular waves (60 Hz, 5V, 0.5 seconds) were 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. When the light quantity reaches the maximum, the transmittance is regarded as 100%, and when the light quantity is minimum, the transmittance is regarded as 0%. The rise time (τr: rise time; millisecond) is the time required for the transmittance to change from 90% to 10%. The fall time (τf: fall time; millisecond) is the time required for the transmittance to change from 10% to 90%. The response time is expressed as the sum of the rise time and the fall time thus obtained.

(12b) Response time (τ; measured at 25 ℃ C.; ms)

Negative dielectric anisotropy: an LCD5100 type luminance meter manufactured by tsukamurelku electronics corporation was used for the measurement. The light source is a halogen lamp. The Low pass filter (Low pass filter) is set to 5kHz. A sample was placed in a PVA element having a gap (cell gap) between two glass substrates of 3.2 μm and a normally black mode (normally black mode) in which the rubbing direction was antiparallel. The element was sealed with an adhesive that was cured with ultraviolet light. Applying a voltage slightly exceeding the threshold voltage to the element for 1 minute, and then applying a voltage of 5.6V while irradiating 23.5mW/cm ² Ultraviolet rays of (2) for 8 minutes. Rectangular waves (60 Hz, 10V, 0.5 seconds) were 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. When the light quantity reaches the maximum, the transmittance is regarded as 100%, and when the light quantity is minimum, the transmittance is regarded as 0%. The response time is expressed as the time (fall time; millisecond) required for the transmittance to change from 90% to 10%.

Raw materials

Sormix (registered trademark) a-11 is a mixture of ethanol (85.5%), methanol (13.4%) and isopropanol (1.1%) obtained from japan alcohol sales (stock).

Synthesis example 1

Synthesis of Compound (No. 81)

First step

Compound (T-1) (3.2 g), potassium carbonate (0.61 g), compound (T-2) (4.1 g) and DMF (100 ml) were put into a reactor and stirred at 60℃for 2 hours. The reaction mixture was poured into water, and the aqueous layer was extracted with ethyl acetate. The organic layer was washed with water and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (volume ratio, ethyl acetate: toluene=1:3) to give compound (T-3) (1.55 g; 33%). Further, the compound (T-1) and the compound (T-2) are known substances, and if they are known to those skilled in the art, the synthesis method can be easily obtained.

A second step of

Compound (T-3) (1.55 g), compound (T-4) (1.69 g), DMAP (0.12 g) and methylene chloride (100 ml) were placed in a reactor, and cooled to 0 ℃. DCC (1.14 g) was added thereto, allowed to return to room temperature and stirred for 12 hours. After insoluble matter was separated by filtration, the reaction mixture was poured into water, and the aqueous layer was extracted with methylene chloride. The organic layer was washed with water and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (volume ratio, ethyl acetate: toluene=1:4), and reprecipitated with heptane, whereby compound (No. 81) (2.34 g; 80%) was obtained. Further, the compound (T-4) is a known substance, and if it is a person of ordinary skill in the art, a synthesis method can be easily obtained.

The NMR analysis values of the obtained compound (No. 81) were as follows.

¹ H-NMR: chemical shift delta (ppm; CDCl) ₃ )：8.61(d,1H)、8.55(d,2H)、8.21(d,2H)、7.70(d,1H)、7.68(s,1H)、7.67(s,1H)、7.48(dd,1H)、7.31(dd,1H)、7.27(d,1H)、6.98(d,2H)、6.43(dd,1H)、6.42(dd,1H)、6.18(dd,1H)、6.13(dd,1H)、5.85(dd,1H)、5.84(dd,1H)、4.60(t,2H)、4.37(t,2H)、4.18(t,2H)、4.04(t,2H)、1.84(quint,2H)、1.72(quint,2H)、1.55(quint,2H)、1.46(quint,2H).

Physical properties of the compound (No. 81) are as follows.

Transition temperature (DEG C): c82.5i polymerization temperature (°c): 136.49

Synthesis example 2

Synthesis of Compound (No. 165)

First step

4-iodophenol (30.0 g), trimethylsilylacetylene (16.1 g), copper iodide (1.3 g), pd (PPh) ₃ ) ₂ Cl ₂ (1.91g) Tetrahydrofuran (THF) (200 ml) and triethylamine (200 ml) were collected into a container and stirred overnight under nitrogen. THF (200 ml), meOH (200 ml) and KF (15.8 g) were added thereto, and stirred under an air atmosphere overnight. The reaction mixture was poured into water, extracted with toluene, washed with water, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure to obtain a pale brown solid. The solid was prepared as a solution, and purified by silica gel column chromatography (volume ratio, ethyl acetate: toluene=1:4) to obtain compound (T-5) (12.7 g; 80%).

The two subsequent steps can be synthesized by using the compound (T-5) instead of the compound (T-1) and the compound (T-6) instead of the compound (T-2) in the first step and the second step of Synthesis example 1, and performing the same procedure. Further, the compound (T-6) is a known substance, and if it is a person of ordinary skill in the art, a synthesis method can be easily obtained.

The NMR analysis values of the obtained compound (No. 165) were as follows.

¹ H-NMR: chemical shift delta (ppm; CDCl) ₃ )：8.13(d,2H)、7.57(d,2H)、7.46(d,2H)、7.19(d,2H)、6.97(d,2H)、6.85(d,2H)、6.42(dd,1H)、6.41(dd,1H)、6.13(dd,1H)、6.11(dd,1H)、5.84(dd,1H)、5.82(dd,1H)、4.24(t,2H)、4.18(t,2H)、4.05(t,2H)、4.01(t,2H)、1.91(t,2H)、1.90(t,2H)、1.84(quint,2H)、1.73(quint,2H)、1.57(quint,2H)、1.48(quint,2H).

Physical properties of the compound (No. 165) are as follows.

Transition temperature (DEG C): c80.0i polymerization temperature (C): 230.8

Synthesis example 3

Synthesis of Compound (No. 148)

First step

Compound (T-5) (3 g), triethylamine (2.6 g) and methylene chloride (100 ml) were placed in a reactor, and cooled using an ice bath. To this was added dropwise acryloyl chloride (1.16 g), and the mixture was returned to room temperature and stirred overnight. The reaction mixture was filtered, and the filtrate was concentrated, and the residue was purified by silica gel chromatography (volume ratio, ethyl acetate: toluene=1:3) to obtain compound (T-7) (0.77 g; 21%).

A second step of

In the second step of Synthesis example 1, compound (No. 148) was synthesized by using Compound (T-7) in place of Compound (T-3) and performing the same operation.

The NMR analysis values of the obtained compound (No. 148) were as follows.

¹ H-NMR: chemical shift delta (ppm; CDCl) ₃ )：8.12(d,2H)、7.58(d,2H)、7.55(d,2H)、7.20(d,2H)、7.14(d,2H)、6.96(d,2H)、6.62(dd,1H)、6.41(dd,1H)、6.31(dd,1H)、6.13(dd,1H)、6.04(dd,1H)、5.82(dd,1H)、4.18(t,2H)、4.05(t,2H)、1.84(quint,2H)、1.73(quint,2H)、1.53(quint,2H)、1.48(quint,2H).

Physical properties of the compound (No. 148) are as follows.

Transition temperature (DEG C): c113.8i polymerization temperature (°c): 259.1

Synthesis example 4

Synthesis of Compound (No. 221)

First step

4-iodo-2-methylphenol (6 g), 1, 4-diacetylene benzene (1.53 g), copper iodide (0.12 g), pd (PPh) ₃ ) ₂ Cl ₂ (0.90 g), THF (50 ml) and triethylamine (50 ml) were collected into a container and stirred under nitrogen overnight. The reaction mixture was poured into water, extracted with toluene, washed with water, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure to obtain a pale brown solid. The solid was prepared as a solution and purified by silica gel column chromatography (volume ratio, ethyl acetate: toluene=1:3), the obtained was dissolved in MeOH(100 ml), THF (100 ml). KF (7.7 g) was added thereto, and stirred at room temperature overnight. The obtained material was concentrated and purified by silica gel column chromatography (volume ratio, ethyl acetate: toluene=1:4) to obtain compound (T-8) (2.95 g; 68%).

The two subsequent steps can be synthesized by using the compound (T-8) in place of the compound (T-1) in the first step and the second step of synthesis example 1, and performing the same operation.

The NMR analysis values of the obtained compound (No. 221) were as follows.

¹ H-NMR: chemical shift delta (ppm; CDCl) ₃ )：8.15(d,2H)、7.48(s,4H)、7.45(s,1H)、7.42(d,1H)、7.35(d,1H)、7.34(s,1H)、7.13(d,1H)、6.98(d,2H)、6.78(d,1H)、6.45(dd,1H)、6.40(dd,1H)、6.17(dd,1H)、6.13(dd,1H)、5.87(dd,1H)、5.82(dd,1H)、4.55(t,2H)、4.24(t,2H)、4.18(t,2H)、4.05(t,2H)、1.85(quint,2H)、1.73(quint,2H)、1.54(quint,2H)、1.47(quint,2H).

Physical properties of the compound (No. 221) are as follows.

Transition temperature (DEG C): C77.22N 95.28I polymerization temperature (. Degree.C.): 198.8

Synthesis example 5

Synthesis of Compound (No. 16)

In Synthesis example 1, compound (No. 16) was synthesized by using Compound (T-10) in place of Compound (T-1), compound (T-9) in place of Compound (T-4), and the same procedure was followed. Further, the compound (T-9) and the compound (T-10) are known substances, and if they are known to those skilled in the art, the synthesis method can be easily obtained.

The NMR analysis values of the obtained compound (No. 16) were as follows.

¹ H-NMR: chemical shift delta (ppm; CDCl) ₃ )：8.73(s,1H)、8.18(dd,1H)、7.90(d,1H)、7.82(d,1H)、7.53(d,2H)、7.46(s,1H)、7.43(dd,1H)、7.23(dd,1H)、7.22(d,1H)、7.19(s,1H)、7.00(d,2H)、6.46(dd,1H)、6.41(dd,1H)、6.19(dd,1H)、6.13(dd,1H)、5.87(dd,1H)、5.82(dd,1H)、4.55(t,2H)、4.27(t,2H)、4.19(t,2H)、4.13(t,2H)、1.90(quint,2H)、1.75(quint,2H)、1.58(quint,2H)、1.50(quint,2H).

Physical properties of the compound (No. 16) are as follows.

Transition temperature (DEG C): c96.8n154.3i polymerization temperature (°c): 176.8

Synthesis example 6

Synthesis of Compound (No. 158)

First step

4-iodophenol (30.0 g), potassium carbonate (38.0 g), compound (T-11) (17.0 g) and DMF (300 ml) were placed in a reactor and stirred at 100℃for 10 hours. The reaction mixture was poured into water, and the aqueous layer was extracted with ethyl acetate. The organic layer was washed with water and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (volume ratio, ethyl acetate: toluene=1:3) to give compound (T-12) (35.0 g; 97%).

A second step of

Compound (T-12) (35.0 g), trimethylsilylacetylene (15.6 g), copper iodide (2.5 g), pd (PPh) ₃ ) ₂ Cl ₂ (4.67 g) and triethylamine (200 ml) were collected into a container and stirred overnight. The reaction mixture was poured into water, extracted with toluene, washed with water, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure to obtain a pale brown solid. The solid was prepared as a solution, and purified by silica gel column chromatography (volume ratio, ethyl acetate: toluene=1:4), and the obtained was dissolved in a mixed solution of methanol (100 ml) and THF (100 ml). KF (7.7 g) was added thereto, and stirred at room temperature overnight. Concentrating the obtained product, and subjecting to silica gel column chromatography (volume ratio, bEthyl acid ester: toluene=1: 4) Purification was performed to obtain compound (T-13) (17.9 g; 83%).

Third step

Compound (T-13) (32.5 g), acrylic acid (20.0 g), DMAP (2.7 g) and methylene chloride (500 ml) were placed in a reactor, and cooled to 0 ℃. DCC (48.1 g) was added thereto, allowed to return to room temperature and stirred for 12 hours. After insoluble matter was separated by filtration, the reaction mixture was poured into water, and the aqueous layer was extracted with methylene chloride. The organic layer was washed with water and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (toluene) to obtain compound (T-14) (45 g; 93%).

Fourth step

Compound (T-14) (24.0 g), trimethylsilylacetylene (54.5 g), copper iodide (2.11 g), pd (PPh) ₃ ) ₂ Cl ₂ (3.89 g), THF (200 ml) and triethylamine (200 ml) were collected into a container and stirred under oxygen overnight. The reaction mixture was poured into water, extracted with toluene, washed with water, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure to obtain a pale brown solid. The solid was prepared as a solution, and purified by silica gel column chromatography (volume ratio, ethyl acetate: toluene=1:4), and the obtained was dissolved in a mixed solution of methanol (100 ml) and THF (100 ml). KF (7.7 g) was added thereto, and stirred at room temperature overnight. The obtained material was concentrated and purified by silica gel column chromatography (volume ratio, ethyl acetate: toluene=1:4) to obtain compound (T-15) (12.6 g; 66%).

Fifth step

4-iodo-2-methylphenol (50.0 g), compound (T-16) (65.5 g), DMAP (5.2 g) and methylene chloride (1000 ml) were placed in a reactor, and cooled to 0 ℃. DCC (46.2 g) was added thereto, allowed to return to room temperature and stirred for 12 hours. After insoluble matter was separated by filtration, the reaction mixture was poured into water, and the aqueous layer was extracted with methylene chloride. The organic layer was washed with water and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (volume ratio, ethyl acetate: toluene=1:9) to give compound (T-17) (86 g; 79%).

Sixth step

Compound (T-17) (4.9 g), compound (T-15) (2.2 g), copper iodide (0.05 g), pd (PPh) ₃ ) ₂ Cl ₂ (0.18 g), THF (200 ml) and triethylamine (200 ml) were collected into a container and stirred overnight. The reaction mixture was poured into water, extracted with toluene, washed with water, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure to obtain a pale brown solid. The solid was prepared as a solution, and purified by silica gel column chromatography (volume ratio, ethyl acetate: toluene=1:9) to obtain compound (No. 158) (21 g; 64.5%).

The NMR analysis values of the obtained compound (No. 158) were as follows.

¹ H-NMR: chemical shift delta (ppm; CDCl) ₃ )：8.13(d,2H)、7.49(d,2H)、7.44(s,1H)、7.40(d,1H)、7.11(d,1H)、6.98(d,2H)、6.88(d,2H)、6.43(dd,2H)、6.15(dd,2H)、5.85(dd,2H)、4.52(t,2H)、4.23(t,2H)、4.18(t,2H)、4.05(t,2H)、2.21(s,3H)、1.84(quint,2H)、1.73(quint,2H)、1.55(quint,2H)、1.47(quint,2H).

Physical properties of the compound (No. 158) are as follows.

Transition temperature (DEG C): C77.9N82.5I polymerization temperature (. Degree.C.): 231.86

The following compounds (No. 1) to (No. 224) can be synthesized according to the synthesis methods described in the synthesis examples.

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2. Use case of element

The compounds in the examples of use are denoted by symbols based on the definition of table 2 below. In Table 2, the steric configuration associated with 1, 4-cyclohexylene is the trans configuration. The numbering in brackets following the notation corresponds to the numbering of the compounds. The symbol of (-) refers to 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 characteristic values of the liquid crystal composition are summarized.

Table 2 expression of compounds using markers

R-(A ₁ )-Z ₁ -·····-Z _n -(A _n )-R’

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1. Raw materials

The composition to which the polar compound was added was injected into the element having no alignment film. After the irradiation of the linearly polarized light, the alignment of the liquid crystal molecules in the element was confirmed. First, the raw materials will be described. The starting material is suitably selected from the group consisting of compositions such as composition (M1) to composition (M41), and polar compounds such as compound (No. 1) to compound (No. 224). The composition is as follows.

[ composition (M1) ]

NI＝73.2℃；Tc<-20℃；Δn＝0.113；Δε＝-4.0；Vth＝2.18V；η＝22.6mPa·s.

[ composition (M2) ]

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NI＝82.8℃；Tc<-30℃；Δn＝0.118；Δε＝-4.4；Vth＝2.13V；η＝22.5mPa·s.

[ composition (M3) ]

NI＝78.1℃；Tc<-30℃；Δn＝0.107；Δε＝-3.2；Vth＝2.02V；η＝15.9mPa·s.

[ composition (M4) ]

NI＝88.5℃；Tc<-30℃；Δn＝0.108；Δε＝-3.8；Vth＝2.25V；η＝24.6mPa·s；VHR-1＝99.1％；VHR-2＝98.2％；VHR-3＝97.8％.

[ composition (M5) ]

NI＝81.1℃；Tc<-30℃；Δn＝0.119；Δε＝-4.5；Vth＝1.69V；η＝31.4mPa·s.

[ composition (M6) ]

NI＝98.8℃；Tc<-30℃；Δn＝0.111；Δε＝-3.2；Vth＝2.47V；η＝23.9mPa·s.

[ composition (M7) ]

NI＝77.5℃；Tc<-30℃；Δn＝0.084；Δε＝-2.6；Vth＝2.43V；η＝22.8mPa·s.

[ composition (M8) ]

NI＝70.6℃；Tc<-20℃；Δn＝0.129；Δε＝-4.3；Vth＝1.69V；η＝27.0mPa·s.

[ composition (M9) ]

NI＝93.0℃；Tc<-30℃；Δn＝0.123；Δε＝-4.0；Vth＝2.27V；η＝29.6mPa·s.

[ composition (M10) ]

NI＝87.6℃；Tc<-30℃；Δn＝0.126；Δε＝-4.5；Vth＝2.21V；η＝25.3mPa·s.

[ composition (M11) ]

NI＝93.0℃；Tc<-20℃；Δn＝0.124；Δε＝-4.5；Vth＝2.22V；η＝25.0mPa·s.

[ composition (M12) ]

NI＝76.4℃；Tc<-30℃；Δn＝0.104；Δε＝-3.2；Vth＝2.06V；η＝15.6mPa·s.

[ composition (M13) ]

NI＝78.3℃；Tc<-20℃；Δn＝0.103；Δε＝-3.2；Vth＝2.17V；η＝17.7mPa·s.

[ composition (M14) ]

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NI＝81.2℃；Tc<-20℃；Δn＝0.107；Δε＝-3.2；Vth＝2.11V；η＝15.5mPa·s.

[ composition (M15) ]

NI＝88.7℃；Tc<-30℃；Δn＝0.115；Δε＝-1.9；Vth＝2.82V；η＝17.3mPa·s.

[ composition (M16) ]

NI＝89.9℃；Tc<-20℃；Δn＝0.122；Δε＝-4.2；Vth＝2.16V；η＝23.4mPa·s.

[ composition (M17) ]

NI＝77.1℃；Tc<-20℃；Δn＝0.101；Δε＝-3.0；Vth＝2.04V；η＝13.9mPa·s.

[ composition (M18) ]

NI＝75.9℃；Tc<-20℃；Δn＝0.114；Δε＝-3.9；Vth＝2.20V；η＝24.7mPa·s.

[ composition (M19) ]

NI＝80.8℃；Tc<-20℃；Δn＝0.108；Δε＝-3.8；Vth＝2.02V；η＝19.8mPa·s.

[ composition (M20) ]

NI＝85.3℃；Tc<-20℃；Δn＝0.109；Δε＝-3.6；Vth＝2.06V；η＝20.9mPa·s.

[ composition (M21) ]

NI＝87.5℃；Tc<-20℃；Δn＝0.100；Δε＝-3.4；Vth＝2.25V；η＝16.6mPa·s.

[ composition (M22) ]

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

[ composition (M23) ]

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

[ composition (M24) ]

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

[ composition (M25) ]

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

[ composition (M26) ]

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

[ composition (M27) ]

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

[ composition (M28) ]

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

[ composition (M29) ]

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

[ composition (M30) ]

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

[ composition (M31) ]

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

[ composition (M32) ]

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

[ composition (M33) ]

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

[ composition (M34) ]

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

[ composition (M35) ]

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

[ composition (M36) ]

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NI＝77.6℃；Tc<-20℃；Δn＝0.109；Δε＝10.6；Vth＝1.34V；η＝22.6mPa·s；γ1＝92.4mPa·s.

[ composition (M37) ]

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

[ composition (M38) ]

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

[ composition (M39) ]

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[ composition (M40) ]

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

[ composition (M41) ]

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

2. Alignment of liquid crystal molecules

Use examples 1 to 7

(preparation of sample)

The compound (No. 148) as the first additive was added to the composition (M1) in a proportion of 0.1 wt%, 0.3 wt%, 0.5 wt%, 1.0 wt%, 3.0 wt%, 5.0 wt%, 10.0 wt%, and R as an antioxidant was added in a proportion of 150ppm ⁴⁰ A compound (AO-1) which is a n-heptyl group. After heating and stirring at 100 ℃, the temperature was returned to room temperature and left for one week, and as a result, crystals and the like were not deposited and dissolved completely.

(fabrication of element)

The mixture was injected into the IPS element without alignment film at 90 ℃ (upper limit temperature of nematic phase or higher). While heating the IPS element at 90 ℃, the element was irradiated with polarized ultraviolet rays having peaks at wavelengths of 313nm, 335nm, and 365nm for a certain period of time from the normal direction, whereby alignment treatment was performed, and irradiation was continued until alignment became good.

(irradiation conditions of polarized ultraviolet rays)

Illuminance at wavelength 313nm of 3mW/cm ² . The measurement was performed using UIT-150 and UVD-S313 manufactured by Ushio electric motors company.

As the ultraviolet irradiation lamp, use was made of USH-250BY manufactured BY Buddha Motor Co., ltd.

The exposure machine unit used ML-251A/B manufactured by oxtail (Ushio) Motor Co., ltd.

Polarized ultraviolet rays are formed using wire grid (wire grid) polarizing elements (profux UVT260A manufactured by Polatechno (strands)).

(method for confirming orientation)

The polarizing element is arranged in parallel to the polarizing axis of the linear polarization, and is provided on a polarizing microscope in which the polarizing element and the analyzer are arranged in a perpendicular manner, and the light is irradiated from below to observe the presence or absence of light leakage. When the light does not pass through the element, the orientation is determined to be "good". When light transmitted through the element is observed, it is determined that the orientation is "poor" and the irradiation is insufficient.

(evaluation of ease of orientation)

The irradiation time was changed from 1 minute to 60 minutes, and the orientation at each irradiation time was confirmed. The irradiation was ended at the time point when the orientation became good, respectively. The irradiation time until the alignment became good is summarized in table 3 below.

Use examples 8 to 42

Using the composition (M1), R as an antioxidant was added in a proportion of 150ppm ⁴⁰ The compound (AO-1) was n-heptyl, and the first additive was mixed in the proportions shown in Table 3 below. The procedure was carried out in the same manner as in use example 1. The irradiation time was measured in the same manner as in use example 1. The results are summarized in Table 3 below.

TABLE 3 Table 3

In usage examples 1 to 42, the compositions used were changed to M2 to M41, and the same operations were performed, respectively, with the result that: in either case, the irradiation time did not change much.

The composition from composition (M1) to composition (M41), the first additive of compound (No. 1) to compound (No. 224), and the like were appropriately selected, and the same operation was performed, with the result that: in either case, the irradiation time is 15 minutes or less.

Comparative examples 1 to 21

The irradiation time was evaluated by the same procedure as in the working example, except that the compound (A-1-1), the compound (S-1) described in patent document 3 and the compound (S-2) described in patent document 2 were mixed as the first additive into the composition (M1) in the proportions shown in Table 4 below. As a result, in any of the compounds, when the longest irradiation time in the use example was 10 minutes, no good orientation could be obtained, and it was confirmed that the irradiation time for the good orientation was 30 minutes or more, as compared with the compound according to the embodiment of the present invention. The same evaluation was performed using the compositions (M2) to (M41), and the results were all the same tendency as in the case of using the composition (M1).

TABLE 4 Table 4

In the use examples, although the kind and amount of the composition or the compound (1) as the polar compound were changed, no dissolution residue or precipitation was observed, and no light leakage of the element was observed in the irradiation for 15 minutes or less. The results represent: even if there is no alignment film such as polyimide in the element, alignment is good, and all liquid crystal molecules are aligned in a certain direction. On the other hand, in the comparative example, when the irradiation was performed for 30 minutes or less, light leakage from the element was observed, and the alignment was not good. Therefore, when the compound (1) according to the embodiment of the present invention is used, it is possible to reduce the shortening of the tact time and the damage of the mother liquid crystal due to light irradiation by using light irradiation for a short time or at a low energy. Further, when the liquid crystal composition according to the embodiment of the present invention is used, a liquid crystal display element having at least one of a wide usable element temperature range, a short response time, a high voltage holding ratio, a low threshold voltage, a large contrast ratio, and a long lifetime can be obtained. Further, a liquid crystal display element having a liquid crystal composition satisfying at least one of the characteristics of high upper limit temperature of a nematic phase, low lower limit temperature of a nematic phase, low viscosity, proper optical anisotropy, large negative dielectric anisotropy, large specific resistance, high stability to ultraviolet light, and high stability to heat can be obtained.

Industrial applicability

The liquid crystal composition of the embodiment of the present invention can be used in a liquid crystal monitor, a liquid crystal television, or the like.

Claims

1. A compound represented by formula (1-1) or formula (1-3);

in the formula (1-1) and the formula (1-3),

ring A ¹ Ring A ² Ring A ³ Ring A ⁴ Independently 1, 4-cyclohexylene, 1, 4-phenylene, naphthalene-2, 6-diyl, pyrimidine-2, 5-diyl, pyridine-2, 5-diyl, fluorene-2, 7-diyl, phenanthrene-2, 7-diyl, anthracene-2, 6-diyl, the group represented by (a-1), or the group represented by (a-2), at least one hydrogen in these rings being 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, at least one hydrogen in these groups being substituted by fluorine or chlorine, (a-2), c is 2, 3, or 4; wherein ring A ¹ Ring A ² Ring A ³ Or ring A ⁴ At least one of which is phenanthrene-2, 7-diyl, (A-1) or (A-2);

Sp ¹ sp and Sp ² Independently a single bond or an alkylene group of 1 to 10 carbon atoms, of which at least one-CH ₂ -may be substituted by-O-, -COO-, -OCOO-or-OCO-, at least one- (CH) ₂ ) ₂ -may be substituted by-ch=ch-, of which groups at least one hydrogen may be substituted by fluorine or chlorine;

P ¹ p ² Independently a group represented by any one of the formulae (1 b) to (1 h);

in the formulas (1 b) to (1 h),

2. The compound according to claim 1, wherein in the formula (1-1) and the formula (1-3),

ring A ¹ Ring A ² Ring A ³ Ring A ⁴ Independently 1, 4-cyclohexylene, 1, 4-phenylene, naphthalene-2, 6-diyl, fluorene-2, 7-diyl, phenanthrene-2, 7-diyl, the group represented by (a-1) or the group represented by (a-2), wherein at least one hydrogen in these rings 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, (a-2) wherein c is 2, 3 or 4; wherein ring A ¹ Ring A ² Ring A ³ Or ring A ⁴ At least one of which is phenanthrene-2, 7-diyl, (A-1) or (A-2);

P ¹ p ² Independently a group represented by any one of formula (1 b), formula (1 c), formula (1 d) or formula (1 e);

in the formulas (1 b) to (1 e),

M ¹ 、M ² 、M ³ m and M ⁴ Independently and separatelyIs hydrogen, halogen, alkyl of 1 to 5 carbon atoms or alkyl of 1 to 5 carbon atoms with at least one hydrogen substituted by halogen;

3. The compound according to claim 1, wherein in the formula (1-1) and the formula (1-3),

ring A ¹ Ring A ² Ring A ³ Ring A ⁴ Independently 1, 4-cyclohexylene, 1, 4-phenylene, naphthalene-2, 6-diyl, fluorene-2, 7-diyl, phenanthrene-2, 7-diyl, the group represented by (a-1) or the group represented by (a-2), wherein at least one hydrogen in these rings may be substituted by fluorine, chlorine, methyl or ethyl, and wherein c is 2, 3 or 4; wherein ring A ¹ Ring A ² Ring A ³ Or ring A ⁴ At least one of which is phenanthrene-2, 7-diyl, (A-1) or (A-2);

4. The compound according to claim 1, wherein Z in the compound represented by the formula (1-1) or the formula (1-3) ² 、Z ³ Or Z is ⁴ Either of them is-COO-or-OCO-.

5. A compound represented by the formula (1-a);

P ¹ —Sp ¹ -Y-Sp ² —P ² (1-A)

y is a group represented by any one of (MES-1-01) to (MES-1-06), in which at least one hydrogen may be substituted with fluorine, chlorine, methyl or ethyl;

6. the compound according to claim 5, wherein Sp is the compound represented by the formula (1-A) ¹ Sp and Sp ² Independently an alkylene group of 1 to 10 carbon atoms, at least one of the alkylene groups-CH ₂ -may be substituted by-O-, -COO-, -OCOO-or-OCO-, at least one- (CH) ₂ ) ₂ -may be substituted with-ch=ch-.

7. A liquid crystal composition containing at least one of the compounds according to any one of claims 1 to 6.

8. The liquid crystal composition according to claim 7, further comprising at least one compound selected from the group of compounds represented by formulas (2) to (4);

In the formulas (2) to (4),

9. The liquid crystal composition according to claim 7 or 8, further comprising at least one compound selected from the group of compounds represented by formulas (5) to (7);

in the formulas (5) to (7),

L ¹¹ L and L ¹² Independently hydrogen or fluorine.

10. The liquid crystal composition according to claim 7 or 8, further comprising at least one compound of the compounds represented by formula (8);

In the formula (8), the amino acid sequence of the compound,

X ¹² is-C.ident.N or-C.ident.C-C.ident.N;

ring D ¹ Is 1, 4-cyclohexylene, at least one hydrogen may be fluorinatedSubstituted 1, 4-phenylene, tetrahydropyran-2, 5-diyl, 1, 3-dioxane-2, 5-diyl or pyrimidine-2, 5-diyl;

L ¹³ L and L ¹⁴ Independently hydrogen or fluorine;

i is 1, 2, 3 or 4.

11. The liquid crystal composition according to claim 7 or 8, further comprising at least one compound selected from the group of compounds represented by formulas (9) to (15);

in the formulas (9) to (15),

L ¹⁵ L and L ¹⁶ Independently fluorine or chlorine;

S ¹¹ is hydrogen or methyl;

x is-CHF-or-CF ₂ -；

j. k, m, n, p, q, r and s are independently 0 or 1, the sum of k, m, n and p is 1 or 2, the sum of q, r and s is 0, 1,2 or 3, and t is 1,2 or 3.

12. The liquid crystal composition according to claim 7 or 8, which contains at least one polymerizable compound of the compound represented by formula (16);

in the formula (16), the amino acid sequence of the compound,

P ¹¹ 、P ¹² p ¹³ Independently a polymerizable group selected from the group of groups represented by the formulas (P-1) to (P-5);

u is 0, 1 or 2;

13. The liquid crystal composition according to claim 7 or 8, which contains at least one polymerizable compound selected from the group of compounds represented by formulas (16-1) to (16-27);

in the formulae (16-1) to (16-27),

P ¹¹ 、P ¹² p ¹³ Independently a polymerizable group selected from the group consisting of groups represented by the formulas (P-1) to (P-3), where M ¹¹ 、M ¹² M and M ¹³ Independently hydrogen, fluorine, an alkyl group of 1 to 5 carbon atoms or an alkyl group of 1 to 5 carbon atoms in which at least one hydrogen is substituted with halogen;

14. The liquid crystal composition according to claim 7 or 8, further comprising at least one of a polymerization initiator, a polymerization inhibitor, an optically active compound, an antioxidant, a light stabilizer, a heat stabilizer, and a defoaming agent.

15. A liquid crystal display element comprising the liquid crystal composition according to any one of claims 7 to 14.