CN113710652B

CN113710652B - Compound, liquid crystal composition and liquid crystal display element

Info

Publication number: CN113710652B
Application number: CN202080029849.5A
Authority: CN
Inventors: 矢野智広; 荻田和寛
Original assignee: JNC Corp; JNC Petrochemical Corp
Current assignee: JNC Corp; JNC Petrochemical Corp
Priority date: 2019-04-25
Filing date: 2020-03-02
Publication date: 2024-06-21
Anticipated expiration: 2040-03-02
Also published as: JPWO2020217710A1; CN113710652A; WO2020217710A1; TW202039802A; JP7505487B2

Abstract

The present invention provides a compound, a liquid crystal composition and a liquid crystal display element, which have at least one of the characteristics of high chemical stability, high ability to horizontally orient liquid crystal molecules, high orientation in a wide concentration range, proper reactivity, high solubility in the liquid crystal composition, and the like. 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+.a+b+.3, ring A ¹, ring A ², ring A ³ and ring A ⁴ are independently, for example, 1, 4-cyclohexylene, Z ¹、Z²、Z³、Z⁴ and Z ⁵ are independently a single bond or an alkylene group having 1 to 10 carbon atoms or the like, sp ¹ and Sp ² are independently a single bond or an alkylene group having 1 to 10 carbon atoms or the like, and P ¹ and P ² are 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 specifically, the present invention relates to a polymerizable polar compound having a thioester (-COS-, -SCO-) or a thiocinnamate (-ch= CHCOS-, -scoch=ch-) in the 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 modes of liquid crystal molecules are classified into phase transition (PHASE CHANGE, PC), twisted nematic (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 (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 a static type (static), a multiplexing type (multiplex), etc., and AM is classified into a thin film transistor (thin film transistor, TFT), a metal-insulator-metal (metal insulator metal, MIM), etc. The TFT is classified into 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 in 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 with polymer stabilized orientation (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 modes such as TN, ECB, OCB, IPS, VA, FFS, FPA may expect such effects from the 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 the 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. But 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-term light irradiation or the liquid crystal is damaged due to the increase in the production time, 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)

The invention provides a liquid crystal composition, which contains at least one of the compounds.

The invention provides a liquid crystal display element, which contains the liquid crystal composition.

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. Symbols B ¹、C¹, F, etc. surrounded by hexagons correspond to the rings B ¹, C ¹, F, etc., respectively. 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 indicate that any hydrogen on the ring may be substituted with-Sp ¹-P¹ or the like. e and the like indicate the number of substituted groups. When the subscript is 0, no such substitution is present.

The notation of the end group R ¹¹ is used in multi-component compounds. In these compounds, any two groups represented by R ¹¹ may be the same or may be different. For example, R ¹¹ of the compound (2) is ethyl, and R ¹¹ of the compound (3) is ethyl. There are also cases where R ¹¹ of the compound (2) is ethyl and R ¹¹ of the compound (3) is propyl. The rules also apply to other end group, ring, bond group, etc. notations. In formula (8), when i is 2, two rings D ¹ are present. In the compounds, the two groups represented by the two rings D ¹ may be the same or may be different. The rule also applies to any two rings D ¹ when i is greater than 2. 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 of-CH ₂ - (or- (CH ₂)₂) -in the form of a powder in the alkyl group which may be substituted by-O- (or-ch=ch-), comprising alkyl, alkenyl, alkoxy, alkoxyalkyl, alkoxyalkenyl, alkenyloxyalkyl, two consecutive-CH ₂ -substituted by-O-) in the case of-O-, alkyl group and the like, in the case of being-O-, of the less preferred alkyl groups and the like.

Halogen means fluorine, chlorine, bromine or iodine. Preferred halogens are fluorine or chlorine. A particularly 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 and ring A ⁴ are 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-dioxan-2, 5-diyl, pyrimidine-2, 5-diyl, pyridine-2, 5-diyl, fluorene-2, 7-diyl, phenanthrene-2, 7-diyl, anthracene-2, 6-diyl, perhydrocyclopenta [ a ] phenanthrene-3, 17-diyl, or 2,3,4,7,8,9,10,11,12,13,14,15,16,17-tetradecahydrocyclopenta [ a ] phenanthrene-3, 17-diyl, at least one of which is 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, or an alkylene of 2 to 11 carbon atoms of which may be substituted with at least one of 4 to ²-P², chloro-498,

When a is 2, the two rings a ¹ may be different, and when b is 2, the two rings a ⁴ may be different;

Z ¹、Z²、Z³、Z⁴ and Z ⁵ are independently a single bond or an alkylene group having 1 to 10 carbon atoms, in which alkylene group, at least one of the-CH ₂ -groups may be substituted by-O-, -S-, -CO-, -COO-, -OCO-or-OCOO-, at least one- (CH ₂)₂ -may be substituted by-CH=CH-or-C.ident.C) -of these radicals, wherein at least one of Z ²、Z³ or Z ⁴ is-COS-, -SCO-, -CH= CHCOS-, -SCOCH=CH-, in Z ²、Z³ or Z ⁴ -COS-and-OCO-or-SCO-and-COO-, are not present at the same time, when a is 2, two Z ¹ may be different, when b is 2, two Z ⁵ may be different;

Sp ¹ and Sp ² are independently a single bond or an alkylene group having 1 to 10 carbon atoms, among which alkylene groups, at least one of the groups-CH ₂ -may be replaced by-O-, -CO-, -COO-, -OCO-or-OCOO-substitution, at least one- (CH ₂)₂) -can be used-CH=CH-or-C≡C-substitution, of these radicals, at least one hydrogen may be substituted by fluorine or chlorine,

In the case where there are a plurality of Sp ¹ or Sp ², each may be different;

P ¹ and P ² are independently a group represented by any one of the formulae (1 b) to (1 h), and may be different when a plurality of P ¹ or P ² are present;

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

M ¹、M²、M³ and M ⁴ are independently hydrogen, fluorine, chlorine, alkyl of 1 to 5 carbon atoms, or at least one alkyl of 1 to 5 carbon atoms in which hydrogen is substituted by fluorine or chlorine, X ¹ is O or S;

r ² is hydrogen, fluorine, chlorine or C1-5 alkyl, wherein at least one hydrogen may be substituted by fluorine or chlorine and at least one-CH ₂ -may be substituted by-O-;

R ³、R⁴、R⁵、R⁶ and R ⁷ are independently hydrogen or alkyl of 1 to 15 carbon atoms, of said alkyl groups, at least one-CH ₂ -may be substituted by-O-or-S-, at least one- (CH ₂)₂) -can be used-CH=CH-or-C≡C-substitution, of these groups, at least one hydrogen may be substituted with fluorine or chlorine.

[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 and ring a ⁴ are 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, or 2,3,4,7,8,9,10,11,12,13,14,15,16,17-tetradecanoic cyclopenta [ a ] phenanthrene-3, 17-diyl, wherein at least one hydrogen may be substituted with fluorine, chlorine, an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an alkoxy group having 1 to 11 carbon atoms, an alkylene group having 2 to 11 carbon atoms, or an alkylene group having 24 to 11 carbon atoms, or with at least one of the same or two of Sp-122 b, and, when the two may be different ring a, or more than one of the ring a, 52 b and/or a, 52, can be substituted with at least one of the ring a;

Z ¹、Z²、Z³、Z⁴ and Z ⁵ are independently a single bond 、-(CH₂)₂-、-C≡C-、-C≡C-C≡C-、-COO-、-OCO-、-CF₂O-、-OCF₂-、-CH₂O-、-OCH₂-、-CF＝CF-、-CH＝CHCOO-、-OCOCH＝CH-、-CH＝CH-、-CH＝CHCO-、-COCH＝CH-、-COS-、-SCO-、-CH＝CHCOS- or-SCOCH=CH-, wherein at least one of Z ²、Z³ or Z ⁴ is-COS-, -SCO-, -CH= CHCOS-or-SCOCH=CH-, and in Z ²、Z³ or Z ⁴, -COS-and-OCO-or-SCO-and-COO-are not present at the same time;

When a is 2, two Z ¹ may be different and two Z ⁵ may be different;

Sp ¹ and Sp ² are independently a single bond or an alkylene group having 1 to 10 carbon atoms, of the alkylene groups, the alkylene groups are those, at least one of the-CH ₂ -groups may be substituted by-O-, -COO-or-OCO-, at least one- (CH ₂)₂ -may be substituted by-ch=ch-, and of these groups at least one hydrogen may be substituted by fluorine or chlorine, which may be different in the presence of a plurality of Sp ¹ or Sp ², respectively;

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 and ring A ⁴ are 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 or anthracene-2, 6-diyl, at least one hydrogen of which rings may be substituted by fluorine, chlorine, alkyl of 1to 12 carbon atoms, alkenyl of 2 to 12 carbon atoms, alkoxy of 1to 11 carbon atoms, alkenyloxy of 2 to 11 carbon atoms, -Sp ¹-P¹ or-Sp ²-P², at least one hydrogen of which groups may be substituted by fluorine or chlorine, two rings A ¹ may be different when a is 2, and two rings A ⁴ may be different when b is 2;

Z ²、Z³ and Z ⁴ are independently a single bond 、-(CH₂)₂-、-C≡C-、-C≡C-C≡C-、-COO-、-OCO-、-CF₂O-、-OCF₂-、-CH₂O-、-OCH₂-、-CF＝CF-、-CH＝CHCOO-、-OCOCH＝CH-、-CH＝CH-、-CH＝CHCO-、-COCH＝CH-、-COS-、-SCO-、-CH＝CHCOS- or-SCOCH=CH-, wherein at least one of Z ²、Z³ or Z ⁴ is-COS-, -SCO-, -CH= CHCOS-or-SCOCH=CH-, and in Z ²、Z³ or Z ⁴, -COS-and-OCO-or-SCO-and-COO-are not present at the same time;

Sp ¹ and Sp ² are independently a single bond or an alkylene group having 1 to 10 carbon atoms, among which alkylene groups, at least one of-CH ₂ -may be replaced by-O-, -COO-, -OCOO-or-OCO-substitution, at least one- (CH ₂)₂ -may be substituted by-ch=ch-, and of these groups at least one hydrogen may be substituted by fluorine or chlorine, which may be different in the presence of a plurality of Sp ¹ or Sp ², respectively;

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

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

Ring A ¹, ring A ², ring A ³ and ring A ⁴ are independently 1, 4-cyclohexylene, 1, 4-phenylene, naphthalene-2, 6-diyl, fluorene-2, 7-diyl, or phenanthrene-2, 7-diyl, in which rings at least one hydrogen is 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-P¹ or-Sp ²-P²;

Z ²、Z³ and Z ⁴ are independently a single bond 、-(CH₂)₂-、-C≡C-C≡C-、-C≡C-、-COO-、-OCO-、-CH＝CHCOO-、-OCOCH＝CH-、-CH＝CH-、-CH＝CHCO-、-COCH＝CH-、-COS-、-SCO-、-CH＝CHCOS- or-SCOCH=CH-, wherein at least one of Z ²、Z³ or Z ⁴ is-COS-, -SCO-, -CH= CHCOS-or-SCOCH=CH-, and in Z ²、Z³ or Z ⁴, -COS-and-OCO-or-SCO-and-COO-are not present at the same time;

Sp ¹ and Sp ² are independently a single bond or an alkylene group having 1 to 10 carbon atoms, among which alkylene groups, at least one of-CH ₂ -may be replaced by-O-, -COO-, -OCOO-or-OCO-substitution, at least one- (CH ₂)₂ -may be substituted by-ch=ch-, and in the case where there are multiple Sp ¹ or Sp ², respectively, may be different;

P ¹ and P ² are independently a group represented by any one of formula (1 b), formula (1 c), formula (1 d) or formula (1 e), and may be different in the case where there are a plurality of P ¹ or P ²;

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

R ³、R⁴、R⁵ and R ⁶ are independently hydrogen or alkyl of 1 to 15 carbon atoms, of said alkyl groups, at least one-CH ₂ -may be substituted by-O-or-S-, at least one- (CH ₂)₂) -can be used-CH=CH-or-C≡C-substitution, of these groups, at least one hydrogen may be substituted with fluorine or chlorine.

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

Ring a ¹, ring a ², ring a ³ and ring a ⁴ are independently 1, 4-cyclohexylene, 1, 4-phenylene, naphthalene-2, 6-diyl, fluorene-2, 7-diyl, or phenanthrene-2, 7-diyl, at least one hydrogen in these rings being substituted by fluorine, chlorine, methyl or ethyl;

P ¹ and P ² are 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), and X ²、X³、X⁴、X⁵ and X ⁶ are independently O or S.

[6] The compound according to [3], wherein any one of Z ²、Z³ or Z ⁴ in the compounds represented by the formulas (1-1) to (1-3) is-COS-or-SCO-.

[7] The compound according to any one of [1] to [6], which is represented by any one of the following formulas.

/>

P ¹ and P ² are 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), and X ²、X³、X⁴、X⁵ and X ⁶ are independently O or S;

Sp ¹ and Sp ² are independently a single bond or an alkylene group having 1 to 10 carbon atoms, among which alkylene groups, at least one-CH ₂ -may be substituted with-O-, -COO-, -OCOO-or-OCO-, at least one- (CH ₂)₂ -may be substituted with-ch=ch-;

In partial structures other than P ¹、P²、Sp¹ and Sp ², at least one hydrogen may be substituted with fluorine, chlorine, methyl or ethyl.

[8] The compound according to [7], wherein among the compounds represented by the formulae (1-1-1) to (1-1-7), the formulae (1-2-1) to (1-2-14), the formulae (1-3-1) or the formulae (1-3-2), sp ¹ and Sp ² are independently an alkylene group having 1 to 10 carbon atoms, among 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-.

[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 and R ¹² are independently C1-10 alkyl or C2-10 alkenyl, at least one of which-CH ₂ -may be substituted by-O-and at least one of which may be substituted by fluorine;

Ring B ¹, ring B ², ring B ³, and ring B ⁴ are 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、Z¹² and Z ¹³ are independently a single bond, - (CH ₂)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 C1-10 alkyl or C2-10 alkenyl, at least one of which-CH ₂ -may be substituted by-O-and at least one of which may be substituted by fluorine;

X ¹¹ is fluorine, chlorine, -OCF ₃、-OCHF₂、-CF₃、-CHF₂、-CH₂F、-OCF₂CHF₂ or-OCF ₂CHFCF₃;

Ring C ¹, ring C ², and ring C ³ are independently 1, 4-cyclohexylene, 1, 4-phenylene in which at least one hydrogen may be substituted by fluorine, tetrahydropyran-2, 5-diyl, 1, 3-dioxane-2, 5-diyl, or pyrimidine-2, 5-diyl;

Z ¹⁴、Z¹⁵ and Z ¹⁶ are independently a single bond 、-(CH₂)₂-、-CH＝CH-、-C≡C-、-COO-、-CF₂O-、-OCF₂-、-CH₂O-、-CF＝CF-、-CH＝CF- or- (CH ₂)₄ -;

l ¹¹ and L ¹² are independently hydrogen or fluorine.

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

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

R ¹⁴ is C1-10 alkyl or C2-10 alkenyl, at least one of which-CH ₂ -may be substituted by-O-and at least one of which may be substituted by fluorine;

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

Ring D ¹ is independently 1, 4-cyclohexylene, 1, 4-phenylene, which may be substituted with fluorine for at least one hydrogen, tetrahydropyran-2, 5-diyl, 1, 3-dioxane-2, 5-diyl or pyrimidine-2, 5-diyl;

Z ¹⁷ is independently a single bond, - (CH ₂)₂-、-C≡C-、-COO-、-CF₂O-、-OCF₂ -or-CH ₂ O-;

L ¹³ and L ¹⁴ are 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 and R ¹⁶ are independently C1-10 alkyl or C2-10 alkenyl, at least one of which-CH ₂ -may be substituted by-O-and at least one of which may be substituted by fluorine;

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

Ring E ¹, ring E ², ring E ³, and ring E ⁴ are independently 1, 4-cyclohexylene, 1, 4-cyclohexenylene, 1, 4-phenylene in which at least one hydrogen may be fluoro-substituted, tetrahydropyran-2, 5-diyl, or decahydronaphthalene-2, 6-diyl;

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

Z ¹⁸、Z¹⁹、Z²⁰ and Z ²¹ are independently a single bond, - (CH ₂)₂-、-COO-、-CH₂O-、-OCF₂ -or-OCF ₂CH₂CH₂ -;

L ¹⁵ and L ¹⁶ are 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 selected from the group of compounds represented by 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, at least one hydrogen of which may be substituted with fluorine, chlorine, an alkyl group of 1 to 12 carbon atoms, or an alkyl group of 1 to 12 carbon atoms, at least one hydrogen of which is substituted with fluorine or chlorine;

Ring G is 1, 4-cyclohexylene, 1, 4-cyclohexenylene, 1, 4-phenylene, naphthalene-1, 2-diyl, naphthalene-1, 3-diyl, naphthalene-1, 4-diyl, naphthalene-1, 5-diyl, naphthalene-1, 6-diyl, naphthalene-1, 7-diyl, naphthalene-1, 8-diyl, naphthalene-2, 3-diyl, naphthalene-2, 6-diyl, naphthalene-2, 7-diyl, tetrahydropyran-2, 5-diyl, 1, 3-dioxane-2, 5-diyl, pyrimidine-2, 5-diyl or pyridine-2, 5-diyl, and in these rings, at least one hydrogen may be substituted by fluorine, chlorine, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or at least one hydrogen may be substituted by fluorine or chlorine;

Z ²² and Z ²³ are independently a single bond or an alkylene group having 1 to 10 carbon atoms, in which alkylene group, at least one of-CH ₂ -may be replaced by-O-, -CO-, -COO-or-OCO-substitution, at least one- (CH ₂)₂ -may be substituted by-ch=ch-, -C (CH ₃)＝CH-、-CH＝C(CH₃) -or-C (CH ₃)＝C(CH₃) -and at least one hydrogen of these groups may be substituted by fluorine or chlorine;

P ¹¹、P¹² and P ¹³ are independently a polymerizable group selected from the group of groups represented by the formulas (P-1) to (P-5);

M ¹¹、M¹² and M ¹³ are independently hydrogen, fluorine, an alkyl group of 1 to 5 carbon atoms, or at least one alkyl group of 1 to 5 carbon atoms in which hydrogen is substituted with fluorine or chlorine;

Sp ¹¹、Sp¹² and Sp ¹³ are independently a single bond or an alkylene group having 1 to 10 carbon atoms, among which alkylene groups, at least one of-CH ₂ -may be replaced by-O-, -COO-, -OCO-or-OCOO-substitution, at least one- (CH ₂)₂ -may be substituted by-ch=ch-or-c≡c-, of which 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、P¹² and P ¹³ are independently a polymerizable group selected from the group of groups represented by formulas (P-1) to (P-3), where M ¹¹、M¹² and M ¹³ are independently hydrogen, fluorine, an alkyl group of 1 to 5 carbon atoms, or at least one alkyl group of 1 to 5 carbon atoms in which hydrogen is substituted with fluorine or chlorine;

Sp ¹¹、Sp¹² and Sp ¹³ are independently a single bond or an alkylene group having 1 to 10 carbon atoms, among which alkylene groups, at least one of-CH ₂ -may be replaced by-O-, -COO-, -OCO-or-OCOO-substitution, at least one- (CH ₂)₂) -can be used-CH=CH-or-C≡C-substitution, of these groups, at least one hydrogen may be substituted with 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) of the embodiment of the present invention is a polar compound having at least one thioester (-COS-, -SCO-) or thiocinnamate (-ch= CHCOS-, -scoch=ch-) as a bonding group and having a polymerizable group. The compound (1) has a high light absorption property and a property of absorbing light in a relatively long wavelength region by having a structure such as thioester (-COS-, -SCO-) or thiocinnamate (-ch= CHCOS-, -scoch=ch-) in the molecule, and exhibits sufficient properties when irradiated with light of a short time or a 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. The preferable examples of R¹、Z¹～Z⁵、A¹～A⁴、Sp¹、Sp²、P¹、P²、a and b in the compound (1) are also applicable to the lower formulae 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 more ² H (deuterium), ¹³ C equivalent elements than the amount of natural abundance.

Ring a ¹, ring a ², ring a ³ and ring a ⁴ are 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-tetradecahydrocyclopenta [ a ] phenanthrene-3, 17-diyl, wherein at least one hydrogen may be substituted with fluorine, chlorine, an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an alkoxy group having 1 to 11 carbon atoms, an alkylene group having 2 to 11 carbon atoms, an oxygen having Sp of 2 to 11, or with one or two of the same carbon numbers Sp-32 to Sp-24 and/or two of the same groups may be substituted with respect to 52 b, 5262.

Preferred rings A ¹, A ², A ³ and A ⁴ are 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, perhydrocyclopenta [ a ] phenanthrene-3, 17-diyl, 2,3,4,7,8,9,10,11,12,13,14,15,16,17-tetradecahydrocyclopenta [ a ] phenanthrene-3, 17-diyl, preferably c is 1 or 2, in which 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, in which at least one hydrogen may be substituted by fluorine or chlorine. Particular preference is given to 1, 4-cyclohexylene, 1, 4-phenylene, perhydrocyclopenta [ a ] phenanthrene-3, 17-diyl or 2,3,4,7,8,9,10,11,12,13,14,15,16,17-tetradecylcyclopenta [ a ] phenanthrene-3, 17-diyl, in which rings at least one hydrogen may be substituted by fluorine or alkyl having 1 to 5 carbon atoms. Particular preference is given to 1, 4-cyclohexylene, 1, 4-phenylene or perhydrocyclopenta [ a ] phenanthrene-3, 17-diyl, in which rings at least one hydrogen is substituted by fluorine, methyl or ethyl.

Z ¹、Z²、Z³、Z⁴ and Z ⁵ are independently single bond 、-(CH₂)₂-、-C≡C-、-C≡C-C≡C-、-COO-、-OCO-、-CF₂O-、-OCF₂-、-CH₂O-、-OCH₂-、-CF＝CF-、-CH＝CHCOO-、-OCOCH＝CH-、-CH＝CH-、-CH＝CHCO-、-COCH＝CH-、-COS-、-SCO-、-CH＝CHCOS- or-scoch=ch-, wherein at least one of Z ²、Z³ or Z ⁴ is-COS-, -SCO-, -ch= CHCOS-or-scoch=ch-, when a is 2, two Z ¹ may be different, and two Z ⁵ may be different.

Preferred Z ¹、Z²、Z³、Z⁴ and Z ⁵ are independently a single bond 、-(CH₂)₂-、-CH＝CH-、-C≡C-、-COO-、-OCO-、-CF₂O-、-OCF₂-、-CH₂O-、-OCH₂-、-CF＝CF-、-COS-、-SCO-、-CH＝CHCOS- or-scoch=ch-. Particularly preferred are single bonds, - (CH ₂)₂ -, -CH=CH-, -COS-, -SCO-, -CH= CHCOS-, or-SCOCH=CH-. Particularly preferred are single bonds, -COS-, -SCO-, -CH= CHCOS-, or-SCOCH=CH-.

Sp ¹ and Sp ² are independently a single bond or an alkylene group having 1 to 10 carbon atoms, among which alkylene groups, at least one of the groups-CH ₂ -may be replaced by-O-, -CO-, -COO-, -OCO-or-OCOO-substitution, at least one- (CH ₂)₂) -can be used-CH=CH-or-C≡C-substitution, of these groups, at least one hydrogen may be substituted with fluorine or chlorine.

Preferred Sp ¹ and Sp ² are independently a single bond, an alkylene group of 1 to 6 carbon atoms, a-CH ₂ -O-substituted alkylene group of 1 to 6 carbon atoms or-OCOO-. Alkylene groups having 1 to 6 carbon atoms or-OCOO-are particularly preferred.

P ¹ and P ² are independently a group represented by any one of the formulae (1 b) to (1 h).

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

Preferred M ¹、M²、M³ and M ⁴ are independently hydrogen, fluorine, methyl, ethyl or trifluoromethyl. Hydrogen is particularly preferred.

R ² is hydrogen, fluorine, chlorine or C1-5 alkyl, at least one of which may be substituted by fluorine or chlorine and at least one of which may be substituted by-O-CH ₂ -.

Preferred R ² is hydrogen, fluoro, methyl, ethyl, methoxymethyl or trifluoromethyl. Hydrogen is particularly preferred.

R ³、R⁴、R⁵、R⁶ and R ⁷ are independently hydrogen or a linear, branched or cyclic alkyl group having 1 to 15 carbon atoms, of said alkyl groups, at least one-CH ₂ -may be substituted by-O-or-S-, at least one- (CH ₂)₂) -can be used-CH=CH-or-C≡C-substitution, of these groups, at least one hydrogen may be substituted with fluorine or chlorine.

R ³、R⁴、R⁵、R⁶ and R ⁷ are preferably 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. Particularly 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.

X ¹ is O or S.

Particularly 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 and M ² are independently hydrogen, fluorine, chlorine, an alkyl group having 1 to 5 carbon atoms, or an alkyl group having 1 to 5 carbon atoms in which at least one hydrogen is substituted with fluorine or chlorine, and X ²、X³、X⁴、X⁵ and X ⁶ are independently O or S.

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),

Ring a ¹, ring a ², ring a ³ and ring a ⁴ are 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, at least one hydrogen of which may be substituted by fluorine, chlorine, alkyl of 1to 12 carbon atoms, alkenyl of 2 to 12 carbon atoms, alkoxy of 1to 11 carbon atoms, alkenyloxy of 2 to 11 carbon atoms, -Sp ¹-P¹ or-Sp ²-P², at least one hydrogen of which may be substituted by fluorine or chlorine, two rings a ¹ may be different when a is 2, and two rings a ⁴ may be different when b is 2;

In these rings, at least one hydrogen may be substituted with fluorine, chlorine, an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an alkoxy group having 1 to 11 carbon atoms, an alkenyloxy group having 2 to 11 carbon atoms, -Sp ¹-P¹, or-Sp ²-P², and at least one hydrogen of these groups may be substituted with fluorine or chlorine;

Z ²、Z³ and Z ⁴ are independently single bond 、-(CH₂)₂-、-C≡C-、-C≡C-C≡C-、-COO-、-OCO-、-CF₂O-、-OCF₂-、-CH₂O-、-OCH₂-、-CF＝CF-、-CH＝CHCOO-、-OCOCH＝CH-、-CH＝CH-、-CH＝CHCO-、-COCH＝CH-、-COS-、-SCO-、-CH＝CHCOS- or-scoch=ch-, wherein at least one of Z ²、Z³ or Z ⁴ is-COS-, -SCO-, -ch= CHCOS-or-scoch=ch-;

Sp ¹ and Sp ² are independently a single bond or an alkylene group having 1 to 10 carbon atoms, among which alkylene groups, at least one of-CH ₂ -may be replaced by-O-, -COO-, -OCOO-or-OCO-substitution, at least one- (CH ₂)₂ -may be substituted by-ch=ch-, and at least one hydrogen of these groups may be substituted by fluorine or chlorine, and may be different in the case where a plurality of Sp ¹ or Sp ² are present within the structure;

P ¹ and P ² are independently a group represented by any one of the formulas (1 b) to (1 h), and may be different when a plurality of P ¹ or P ² are present in the structure;

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), either Z ²、Z³ or Z ⁴ is preferably-COS-or-SCO-.

In the compound represented by the formula (1-1), the formula (1-2) or the formula (1-3), either Z ²、Z³ or Z ⁴ is preferably-ch= CHCOS-or-scoch=ch-.

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

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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.

In the compound (16), P ¹¹、P¹² and P ¹³ are independently a polymerizable group.

Preferred P ¹¹、P¹² and P ¹³ are polymerizable groups selected from the group consisting of groups represented by the formulas (P-1) to (P-5). Particularly preferred P ¹¹、P¹² and P ¹³ are the radical (P-1), the radical (P-2) or the radical (P-3). Particularly preferred groups (P-1) are-OCO-CH=CH ₂ or-OCO-C (CH ₃)＝CH₂. The wavy line of groups (P-1) to (P-5) indicates the site of bonding.

In the groups (P-1) to (P-5), M ¹¹、M¹² and M ¹³ are independently hydrogen, fluorine, an alkyl group having 1 to 5 carbon atoms, or an alkyl group having 1 to 5 carbon atoms in which at least one hydrogen is substituted with fluorine or chlorine.

In order to increase the reactivity, M ¹¹、M¹² and M ¹³ are preferably hydrogen or methyl. Particularly preferred M ¹¹ is methyl, and particularly preferred M ¹² and M ¹³ are hydrogen.

Preferably Sp ¹¹、Sp¹² and Sp ¹³ are single bonds.

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 with fluorine, chlorine, an alkyl group of 1 to 12 carbon atoms, an alkoxy group of 1 to 12 carbon atoms, or at least one hydrogen of which is substituted with fluorine or chlorine-substituted alkyl group of 1 to 12 carbon atoms.

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 fluorine, chlorine, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or at least one hydrogen may be substituted by fluorine or chlorine. Particularly preferred ring G is 1, 4-phenylene or 2-fluoro-1, 4-phenylene.

Z ²² and Z ²³ are independently a single bond or an alkylene group having 1 to 10 carbon atoms, in which alkylene group, at least one of-CH ₂ -may be replaced by-O-, -CO-, -COO-or-OCO-substitution, at least one- (CH ₂)₂ -may be substituted by-ch=ch-, -C (CH ₃)＝CH-、-CH＝C(CH₃) -or-C (CH ₃)＝C(CH₃) -and at least one hydrogen in these groups may be substituted by fluorine or chlorine.

Preferred Z ²² and Z ²³ are single bonds, - (CH ₂)₂-、-CH₂O-、-OCH₂ -, -COO-or-OCO-. Particularly preferred Z ²² and Z ²³ are single bonds.

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. Compounds not described for synthesis are synthesized by the methods described in books such as "organic Synthesis (Organic Syntheses") (John Wiley father-son publishing Co., ltd. (John Wiley & Sons, inc.)), "organic reactions (Organic Reactions) (John Wiley father-son publishing Co., ltd. (John Wiley & Sons, inc.))," comprehensive organic Synthesis (Comprehensive Organic Synthesis) (Pergamon Press)), ", and" New laboratory chemistry lecture (Wash) ".

2-1 Generation of bond Z ¹, bond Z ², bond Z ³, bond Z ⁴, and bond Z ⁵

Examples of the method for producing the bond group in the compound (1) are described in the following schemes. In the scheme, MSG ¹ (or MSG ²) is a monovalent organic group having at least one ring. The monovalent organic groups represented by the multiple MSGs ¹ (or MSG ²) may be the same or may be different. The compounds (1A) to (1L) 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 (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.

Production of (III) -CF ₂ O-and-OCF ₂

Compound (26) is obtained by sulfiding compound (1B) with lawsen reagent. Compound (26) was fluorinated with N-bromosuccinimide (N-bromosuccinimide, NBS) to synthesize Compound (1C) having-CF ₂ O-. Reference is made to m. black star (m.kuroboshi et al, "chemical report (chem. Lett.))", 1992, 827. Compound (1C) can also be synthesized by fluorinating compound (26) with (diethylamino) sulfur trifluoride ((diethylamino) sulphur trifluoride, DAST). Refer to the journal of organic chemistry (J.Org.chem.) by W.H. Bannier et al, 1990, page 55 768. Compounds having-OCF ₂ -were also synthesized using the described methods.

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)₂) -generation

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).

Production of (VII) -CH ₂ O-and-OCH ₂

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. Compounds having-OCH ₂ -are also synthesized using the methods.

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).

(IX) -ch=chco-and-coch=ch-formation

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).

Formation of (XI) -ch= CHCOS-and-scoch=ch

Compound (1K) is synthesized by dehydrating cinnamic acid (41) and compound (26) in the presence of 1, 3-Dicyclohexylcarbodiimide (DCC) and 4-Dimethylaminopyridine (DMAP).

(XII) -COS-and-SCO-production

Compound (1L) is synthesized by dehydrating carboxylic acid (24) with compound (26) in the presence of 1, 3-Dicyclohexylcarbodiimide (DCC) and 4-Dimethylaminopyridine (DMAP).

2-2 Production of Ring A ¹, ring A ², ring A ³ and Ring A ⁴

The initiating materials are widely commercially available or known in the synthesis process, and the initiating materials are widely used 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.

2-3 Formation of the linking group Sp ¹ or the linking group Sp ² and the polymerizable group P ¹ or the polymerizable group P ²

Preferable examples of the polymerizable group P ¹ or the polymerizable group P ² are an acrylic ester (1 b), a maleimide (1 c), an itaconate (1 d), a vinyl ester (1 e), an oxetanyl group (1 g) or an ethyleneoxy group (1 h).

Examples of the method for synthesizing the compound in which the polymerizable group is bonded to the ring through the linking group Sp ¹ or the linking group Sp ² are as follows. First, an example in which the linking group Sp ¹ or the linking group Sp ² is a single bond is shown.

(1) Synthesis of Compounds that are Single bonds

The synthesis of compounds wherein Sp ¹ or Sp ² is a single bond is described in the following schemes. In the scheme, MSG ¹ is a monovalent organic group having at least one ring. The compounds (1S) to (1X) correspond to the compound (1). In the case where the polymerizable group is an acrylate derivative, the polymerization is synthesized by esterifying the corresponding acrylic acid with HO-MSG ¹. The ethyleneoxy group is synthesized by etherification of HO-MSG ¹ 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. Itaconates are synthesized by esterification of the corresponding itaconic acid with HO-MSG ¹. Vinyl esters are synthesized by transesterification of vinyl acetate with HOOC-MSG ¹.

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The synthesis of compounds wherein the linking group Sp ¹ or the linking group Sp ² is a single bond is described above. Methods for forming other linkers can be synthesized with reference to the synthesis of linker Z ¹, linker Z ², linker Z ³, linker Z ⁴, and linker Z ⁵.

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. The definition of P ¹、M¹、M²、Sp¹ and Sp ² are the same 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 case of synthesizing a compound in which MES and Sp ¹ are linked by an ether bond, the compound (53A) can be obtained by etherifying the compound (51A) as an initiating substance with a base such as the compound (52) and potassium hydroxide. In the case of synthesizing a compound in which MES and Sp ¹ are linked by 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 group (TRIMETHYLSILYL, TMS) or tetrahydropyranyl group (Tetrahydropyranyl, THP) acts.

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

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

The compound (1) in which P ² 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 (1Y) 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. Particularly 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 and R ¹² are independently an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms, at least one of which-CH ₂ -may be substituted with-O-and at least one of which may be substituted with 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, particularly preferably 40% by weight or more, based on the weight of the liquid crystal composition.

The component C is compounds (5) to (7) having fluorine, chlorine or fluorine-containing groups 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 (7-62). In the compound of the component C, R ¹³ is alkyl with 1 to 10 carbon atoms or alkenyl with 2 to 10 carbon atoms, wherein at least one of the alkyl and alkenyl groups is-CH ₂ -substituted by-O-and at least one hydrogen is substituted by fluorine; x ¹¹ is fluorine, chlorine, -OCF ₃、-OCHF₂、-CF₃、-CHF₂、-CH₂F、-OCF₂CHF₂ or-OCF ₂CHFCF₃.

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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 use in modes 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, particularly 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 the component D, R ¹⁴ is alkyl with 1 to 10 carbon atoms or alkenyl with 2 to 10 carbon atoms, wherein at least one of the alkyl and alkenyl groups is-CH ₂ -substituted by-O-and at least one hydrogen is substituted by fluorine; 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, particularly 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 fluorine or chlorine groups in the lateral position (lateral position) as in 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 and R ¹⁶ are independently alkyl with 1 to 10 carbon atoms or alkenyl with 2 to 10 carbon atoms, wherein at least one of the alkyl and alkenyl groups is-CH ₂ -substituted by-O-and at least one of the hydrogen is substituted by fluorine; r ¹⁷ is hydrogen, fluorine, C1-10 alkyl or C2-10 alkenyl, at least one of which-CH ₂ -may be substituted by-O-and at least one of which may be substituted by fluorine.

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The dielectric anisotropy of component E is negative and large. Component E may 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 modes such as IPS, VA, PSA, the content of the component E is preferably 40% by weight or more, particularly 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. Particularly preferred examples are compounds having at least one acryloyloxy group and compounds having at least one methacryloyloxy group. Particularly preferred examples also include compounds having both acryloyloxy and methacryloyloxy groups.

Particularly preferred examples of the polymerizable compounds are compounds (M-1) to (M-17). In the compounds (M-1) to (M-17), R ²⁵ to R ³¹ are independently hydrogen or methyl; s, v and x are independently 0 or 1; t and u are independently integers from 1 to 10; l ²¹ to L ²⁶ are independently hydrogen or fluorine, and L ²⁷ and L ²⁸ are 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-benzorphazine, benzophenone/Mitstone mixtures, hexaarylbisimidazole/mercaptobenzimidazole mixtures, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, benzyl dimethyl 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 defective display such as image retention on 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. Particularly preferred wavelengths are in the range 250nm to 450nm, most preferred wavelengths are in the range 300nm to 400 nm.

In the case where the compound (1) having a thioester (-COS-, -SCO-) or a thiocinnamate (-ch= CHCOS-, -scoch=ch-) as a bonding group 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 when fries rearrangement or photodimerization occurs 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 thioester and having a polymerizable group, the aromatic thioester moiety is photodegradation by irradiation with ultraviolet light, whereby a radical is formed and photofries rearrangement is generated.

In the photofries rearrangement, photodecomposition of the aromatic thioester moiety occurs when the polarization direction of the polarized ultraviolet light is in the same direction as the long axis direction of the aromatic thioester moiety. After photodecomposition, rebinding proceeds and thiol groups are generated intramolecularly by tautomerization. The thiol group is thought to cause interaction at the substrate interface, and thus the polar compound has anisotropy and is 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, and the like.

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, and 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 (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 is an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, -COOR ⁴¹ or-CH ₂CH₂COOR⁴¹, where R 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 PC, TN, STN, OCB, VA, IPS or the like modes of operation 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 is also useful for nematic curved alignment phase (nematic curvilinear ALIGNED PHASE, NCAP) elements produced by microencapsulation of nematic liquid crystals, polymer dispersed liquid crystal display elements (polymer dispersed liquid CRYSTAL DISPLAY, PDLCD) produced by formation of three-dimensional network macromolecules in liquid crystals, and polymer network liquid crystal display elements (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. Particularly 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. The compound (1) as a polar compound causes photofries rearrangement or photodimerization by linear polarization while also performing polymerization. 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. In ¹ H-NMR measurement, a sample is dissolved in a deuterated solvent such as CDCl ₃, and the measurement is performed at room temperature under conditions of 500MHz and the number of times of accumulation is 16 times. Tetramethylsilane was used as an internal standard. In ¹⁹ F-NMR measurements, CFCl ₃ was used as an internal standard and the measurements were performed 24 times in total. In the description of nuclear magnetic resonance spectroscopy, s refers to a single peak, d refers to a double peak, t refers to a triple peak, q refers to a quadruple peak, quin refers to a quintuple peak, sex refers to a hexa-doublet peak, m refers to a multiple peak, and br refers to 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 (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, pr Luo Mina S (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 (REFLECTIVE INDEX, RI) detector, a CORONA (CORONA) detector, or the like is 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, 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 has been 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 Diamond DSC system manufactured by Perkin Elmer (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 types of crystals, they are indicated as C ₁、C₂. 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 is distinguished, the smectic phase is denoted by S _A、S_B、S_C or S _F, respectively. The liquid (isotropic) is denoted as I. The transition temperature is expressed, for example, as "C50.0N 100.0I". It means that the temperature at which the self-crystallization turns into a nematic phase is 50.0℃and the temperature at which the self-nematic phase turns into a liquid is 100.0 ℃.

( 3) The upper temperature limit of the 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 the mother liquid crystal, the sample is represented by a symbol of T _NI. 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) The lower temperature of the nematic phase (T _C; DEG 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, when the sample maintains a nematic phase at-20℃and changes to a crystalline or smectic phase at-30℃T _C is described as +.about.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 carried out by the method described in "Molecular Crystals and Liquid Crystals" (Molecular CRYSTALS AND Liquid Crystals) (Vol.259, 37 (1995)) of M.Jinwell (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) resulting from 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 carried out by the method described in "Molecular Crystals and Liquid Crystals" (Molecular CRYSTALS AND Liquid Crystals) (Vol.259, 37 (1995)) of M.Jinwell (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) resulting from 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 values of K ₁₁ and K ₃₃ were obtained from the formula (2.99) by fitting the measured values of the electrostatic capacitance (C) and the applied voltage (V) using the formulas (2.98) and (2.101) in page 75 of the handbook of liquid crystal devices (journal of journal industry). Then, in the formula (3.18) on page 171, K ₂₂ is calculated using the values of K ₁₁ and K ₃₃ obtained previously. The elastic constant K is represented by the average value of K ₁₁、K₂₂ and K ₃₃ thus obtained.

( 10B) Elastic constant (K ₁₁ and K ₃₃; 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 the equation (2.100) by fitting the value of the electrostatic capacitance (C) and the applied voltage (V) using the 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) in which the interval (cell gap) between two glass substrates was 0.45/. DELTA.n (. Mu.m) and the twist angle was 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. The element was applied with a voltage slightly exceeding the threshold voltage for 1 minute, and then irradiated with ultraviolet light of 23.5mW/cm ² for 8 minutes while applying a voltage of 5.6V. 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

Solmixes (solmix) (registered trademark) A-11 was a mixture of ethanol (85.5%), methanol (13.4%) and isopropanol (1.1%) obtained from the Japanese alcohol market (stock).

Synthesis example 1

Synthesis of Compound (No. 1)

First step

Compound (T-1) (10.00 g), compound (T-2) (17.01 g), DMAP (1.30 g) and methylene chloride (150 ml) were placed in a reactor, and cooled to 0 ℃. DCC (12.00 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=1:19) to give compound (T-3) (9.98 g; 41%). Further, the compound (T-2) can be obtained as a commercially available product (4- ([ 6- (acryloyloxy) hexyl ] oxy) benzoic acid) (4- ([ 6- (acryloyloxy) hexyl ] oxy) benzoic acid) from, for example, sigma-Aldrich.

A second step of

Compound (T-3) (5.00 g), compound (T-4) (2.68 g), copper iodide (0.21 g), pd (PPh ₃)₄ (0.4 g), tetrahydrofuran (Tetrahydrofuran, THF) (50 ml) and triethylamine (50 ml) were collected into a container and stirred under nitrogen for one night.

The NMR analysis values of the obtained compound (No. 1) were as follows.

¹ H-NMR: chemical shift δ(ppm;CDCl₃)：8.02(d,2H),7.59(d,2H),7.51(d,2H),7.50(d,2H),6.97(d,2H),6.92(d,2H),6.46(dd,1H),6.45(dd,1H),6.19(dd,1H),6.14(dd,1H),5.88(dd,1H),5.87(dd,1H),4.56(t,2H),4.27(t,2H),4.20(t,2H),4.07(t,2H),1.86(quint,2H),1.75(quint,2H),1.55(quint,2H),1.49(quint,2H).

The physical properties of the compound (No. 1) are as follows.

Transition temperature (DEG C): C83.1I polymerization temperature (C): 212.8

Synthesis example 2

Synthesis of Compound (No. 2)

First step

Compound (T-5) (0.50 g), compound (T-2) (1.47 g), DMAP (0.06 g) and methylene chloride (100 ml) were placed in a reactor, and cooled to 0 ℃. DCC (1.04 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. 2) (0.92 g; 52%) was obtained.

The NMR analysis values of the obtained compound (No. 2) were as follows.

¹ H-NMR: chemical shift δ(ppm;CDCl₃)：8.04(d,4H),7.71(d,4H),7.62(d,4H),6.98(d,4H),6.43(dd,2H),6.17(dd,2H),5.85(dd,2H),4.21(t,2H),4.07(t,2H),1.86(quint,4H),1.75(quint,4H),1.55(quint,4H),1.49(quint,4H).

The physical properties of the compound (No. 2) are as follows.

Transition temperature (DEG C): c124.8i polymerization temperature (°c): 127.7

Synthesis example 3

Synthesis of Compound (No. 617)

First step

Compound (T-6) (25.0 g) and THF (200 ml) were placed in a reactor and cooled to below-60 ℃. Sec-butyllithium (sec-BuLi) (1M hexane solution (1M hexane solution)) (75 ml) was added dropwise thereto while keeping the temperature below-60℃and then stirred for 1 hour. Sulfur (2.5 g) was added thereto, and after stirring for 30 minutes, the mixture was returned to room temperature, followed by stirring for 1 hour. To this was slowly added compound (T-7), and stirred for 1 hour. The reaction mixture was poured into water, and the aqueous layer was extracted with toluene. 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=3:10) to give compound (T-8) (14.9 g; 38%). Further, the compound (T-6) and the compound (T-7) 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-8) (16.4 g), pyridinium p-toluenesulfonate (Pyridinium Paratoluenesulfonate, PPTS) (4.1 g), THF (150 ml) and MeOH (150 ml) were collected into a vessel and stirred under nitrogen at 40℃for 4 hours. The reaction mixture was poured into water, extracted with ethyl acetate, 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) to obtain compound (T-9) (13.1 g; 89%).

Third step

Compound (T-9) (12.6 g), methacrylic acid (3.0 g), DMAP (0.99 g) and methylene chloride (250 ml) were placed in a reactor, and cooled to 0 ℃. DCC (7.19 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 give compound (T-10) (10.64 g; 71%).

Fourth step

The compound (T-10) (10.1 g), the compound (T-11) (3.2 g), copper iodide (0.35 g), pd (PPh ₃)₄ (1.08 g), THF (100 ml) and triethylamine (50 ml) were collected into a container and stirred under nitrogen overnight.

Fifth step

Compound (T-12) (6.72 g), compound (T-13) (1.37 g), DMAP (0.29 g) and methylene chloride (134 ml) were placed in a reactor, and cooled to 0 ℃. DCC (3.15 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=19:1) to give compound (No. 617) (6.93 g; 85%).

The NMR analysis values of the obtained compound (No. 617) are as follows.

¹ H-NMR: chemical shift δ(ppm;CDCl₃)：7.87(s,1H),7.82(d,1H),7.55(d,1H),7.50(d,2H),7.39(d,2H),6.97(d,2H),6.92(d,2H),6.10(s,1H),5.78(dd,1H),5.55(t,1H),5.38(dd,1H),4.61(t,2H),4.28(t,2H),4.16(t,2H),4.00(t,2H),2.57(s,3H),1.95(s,3H),1.82(quint,2H),1.72(quint,2H),1.55(quint,2H),1.47(quint,2H).

Physical properties of the compound (No. 617) are as follows.

Transition temperature (DEG C): C72.25I polymerization temperature (C): 118.8

Synthesis example 4

Synthesis of Compound (No. 618)

In Synthesis example 3, compound (No. 618) was obtained by using Compound (T-14) in place of Compound (T-6) and Compound (T-15) in place of Compound (T-7). Further, the compound (T-14) can be easily synthesized by the synthesis of the reference compound (T-6). In addition, the compound (T-15) is a known substance.

The NMR analysis values of the obtained compound (No. 618) were as follows.

¹ H-NMR: chemical shift δ(ppm;CDCl₃)：8.15(d,2H),7.62(d,2H),7.51(d,2H),7.31(d,1H),7.05(s,1H),7.03(d,1H),6.92(d,2H),6.10(s,1H),5.67(dd,1H),5.55(t,1H),5.38(dd,1H),4.61(t,2H),4.28(t,2H),4.15(t,2H),2.90(t,2H),2.40(s,3H),1.95(s,3H),1.67(quint,2H),1.66(quint,2H),1.50(quint,2H),1.43(quint,2H).

Physical properties of the compound (No. 618) are as follows.

Transition temperature (DEG C): c59.74I polymerization temperature (°c): 154.6

According to the synthesis method described in the synthesis example, the following compounds may be synthesized as specific examples of the compound (1) in addition to the compounds shown in the synthesis example.

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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-(A₁)-Z₁-·····-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 (M1) to (M41) and the like, and compounds (1) to (618) and the like. The composition is as follows.

[ Composition (M1) ]

[ Composition (M2) ]

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[ Composition (M3) ]

[ Composition (M4) ]

[ Composition (M5) ]

[ Composition (M6) ]

[ Composition (M7) ]

[ Composition (M8) ]

[ Composition (M9) ]

[ Composition (M10) ]

[ Composition (M11) ]

[ Composition (M12) ]

[ Composition (M13) ]

[ Composition (M14) ]

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[ Composition (M15) ]

[ Composition (M16) ]

[ Composition (M17) ]

[ Composition (M18) ]

[ Composition (M19) ]

[ Composition (M20) ]

[ Composition (M21) ]

[ Composition (M22) ]

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[ Composition (M23) ]

[ Composition (M24) ]

[ Composition (M25) ]

[ Composition (M26) ]

[ Composition (M27) ]

[ Composition (M28) ]

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[ Composition (M29) ]

[ Composition (M30) ]

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[ Composition (M31) ]

[ Composition (M32) ]

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[ Composition (M33) ]

[ Composition (M34) ]

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[ Composition (M35) ]

[ Composition (M36) ]

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[ Composition (M37) ]

[ Composition (M38) ]

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[ Composition (M39) ]

[ Composition (M40) ]

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[ Composition (M41) ]

2. Alignment of liquid crystal molecules

Use examples 1 to 7

(Preparation of sample)

The compound (No. 1) as the compound (1) 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 the compound (AO-1) as the antioxidant R ⁴⁰ was added in a proportion of 150 ppm. After stirring at 100℃with heating, the temperature was returned to room temperature and left for one week, and as a result, these mixtures were completely dissolved without precipitation of crystals or the like.

(Fabrication of element)

These mixtures were injected into IPS elements without alignment films at 90 ℃. Since these mixtures show isotropic phases at 90 ℃, these mixtures are injected above and below the upper temperature limit of the nematic phase. 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)

The illuminance at a wavelength of 313nm was 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 a wire grid polarizer (ProFlux UVT a manufactured by Polatechno (strand)).

(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 28

Using the composition (M1), a compound (AO-1) wherein R ⁴⁰ as an antioxidant was n-heptyl was added in a proportion of 150ppm, and the compound (1) was mixed in a proportion 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. The mixtures of use examples 8 to 28 also show isotropic phases at 90 ℃.

TABLE 3 Table 3

In usage examples 1 to 28, 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), compound (1) from compound (No. 1) to compound (No. 618), and the same operations were carried out, resulting in: in either case, the irradiation time is 10 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 compound (1) into the composition (M1) in the proportions shown in Table 4 below. The mixtures of comparative examples 1 to 21 also show isotropic phase at 90 ℃.

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 10 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 any one of the formulae (1-1-3), (1-1-4), (1-2-1), (1-2-2), (1-2-7) to (1-2-10), (1-3-1) and (1-3-2);

in the formula (1-1-3), the formula (1-1-4), the formula (1-2-1), the formula (1-2-2), the formula (1-2-7) to the formula (1-2-10), the formula (1-3-1) and the formula (1-3-2),

P ¹ and P ² are independently a group represented by formula (1 b-1), formula (1 b-2) or formula (1 b-3), X ²、X³ and X ⁴ are O;

Sp ¹ and Sp ² are independently a single bond or an alkylene group of 1 to 10 carbon atoms, of which at least one-CH ₂ -may be-O-substituted;

In partial structures other than P ¹、P²、Sp¹ and Sp ², at least one hydrogen may be substituted with a methyl group.

2. A liquid crystal composition comprising at least one of the compounds according to claim 1.

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

In the formulas (2) to (4),

4. The liquid crystal composition according to claim 2 or 3, 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 and L ¹² are independently hydrogen or fluorine.

5. The liquid crystal composition according to claim 2 or 3, further comprising at least one compound selected from the group of 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;

L ¹³ and L ¹⁴ are independently hydrogen or fluorine;

i is 1,2, 3 or 4.

6. The liquid crystal composition according to claim 2 or 3, 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 and L ¹⁶ are independently fluorine or chlorine;

s ¹¹ is hydrogen or methyl;

X is-CHF-or-CF ₂ -;

7. The liquid crystal composition according to claim 2 or 3, which contains at least one polymerizable compound selected from the group of compounds represented by formula (16);

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

u is 0, 1 or 2;

8. The liquid crystal composition according to claim 2 or 3, 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),

9. The liquid crystal composition according to claim 2 or 3, further comprising at least one of a polymerizable compound other than the formula (1) and the formula (16), a polymerization initiator, a polymerization inhibitor, an optically active compound, an antioxidant, a light stabilizer, a heat stabilizer, and a defoaming agent.

10. A liquid crystal display element comprising the liquid crystal composition according to any one of claims 2 to 9.