CN112368260A

CN112368260A - Compound, liquid crystal composition and liquid crystal display element

Info

Publication number: CN112368260A
Application number: CN201980041349.0A
Authority: CN
Inventors: 矢野智広; 近藤史尚; 佐郷弘毅
Original assignee: JNC Corp; JNC Petrochemical Corp
Current assignee: JNC Corp; JNC Petrochemical Corp
Priority date: 2018-07-04
Filing date: 2019-06-12
Publication date: 2021-02-12
Anticipated expiration: 2039-06-12
Also published as: JPWO2020008826A1; TW202006124A; WO2020008826A1; CN112368260B

Abstract

The present invention provides a compound having at least one of high chemical stability, high ability to horizontally align liquid crystal molecules, high alignment properties in a wide additive concentration range, appropriate reactivity, and high solubility in a liquid crystal composition. The present invention provides a compound of the following formula (1). In formula (1), a and b are independently 0,1 or 2, and 0 ≦ a + b ≦ 3, ring A¹Ring A²Ring A³And ring A⁴Independently of one another are, for example, 1, 4-cyclohexylene, Z¹、Z²、Z³、Z⁴And Z⁵Independently a single bond or alkylene group having 1 to 10 carbon atoms, etc., Sp¹And Sp²Independently a single bond or alkylene group of 1 to 10 carbon atoms, etc., P¹And P²Independently a specific polymerizable group.

Description

Compound, liquid crystal composition and liquid crystal display element

Technical Field

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

Background

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

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

TABLE 1 Properties of the 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 correlates with the contrast of the element. Depending on the mode of the element, the optical anisotropy needs to be large or small, that is, the optical anisotropy needs to be appropriate. The product (Δ n × d) of the optical anisotropy (Δ n) of the composition and the cell gap (d) of the element is designed to maximize the contrast. The appropriate value of the product depends on the kind of the operation mode. In a cell of the TN or the like mode, the value is about 0.45. mu.m. In the VA mode element, the value is in the range of about 0.30 μm to about 0.40 μm, and in the IPS mode or FFS mode element, the value is in the range of about 0.20 μm to about 0.30 μm. In these cases, a composition having a 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. A large specific resistance in the composition contributes to a large voltage holding ratio and a large contrast in the element. Thus, 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. Preferred is 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 after long-term use. The stability of the composition to ultraviolet light and heat correlates with the lifetime of the component. When the stability is high, the life 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 for an AM element having a TN mode. A composition having negative dielectric anisotropy is used for an AM element having a VA mode. A composition having positive or negative dielectric anisotropy is used for an AM element having an IPS mode or an FFS mode.

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

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

As a compound capable of horizontally aligning liquid crystal molecules in a liquid crystal display element having no alignment film, a compound (S-1) has been described in patent document 2 (paragraph 2 of paragraph 0034 in the specification), and a compound (S-2) (compound [14] of P176 in the specification) has been described in patent document 3. However, these compounds require high-energy light irradiation to align the liquid crystal molecules at a sufficient level of alignment properties, and there is a concern that the production time increases due to long-time light irradiation or the liquid crystal is damaged due to the increase, and thus improvement is desired.

Documents of the prior art

Patent document

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

A first object of the present invention is to provide a compound which has at least one of high chemical stability, high ability to horizontally align liquid crystal molecules, high alignment properties in a wide additive concentration range, appropriate 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 device. A second object is to provide a liquid crystal composition which contains the above-mentioned compound and satisfies at least one of characteristics such as a high upper limit temperature of a nematic phase, a low lower limit temperature of the nematic phase, a low viscosity, an appropriate optical anisotropy, a large positive or negative dielectric anisotropy, a large specific resistance, a high stability against ultraviolet light, a high stability against heat, and a large elastic constant. 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 an element by irradiating the composition with ultraviolet rays, the film has at least one of properties of appropriate hardness, low permeability of a contact component, high weather resistance, and appropriate volume resistance, and the liquid crystal display element has at least one of properties of a wide temperature range in which the element can be used, a short response time, a high voltage holding ratio, a low threshold voltage, a large contrast, and a long lifetime.

Means for solving the problems

The present inventors have found that the above problems can be solved by a compound represented by the following formula (1), and have completed the present invention.

(the description of the symbols in the formula will be described later)

ADVANTAGEOUS EFFECTS OF INVENTION

A first advantage of the present invention is to provide a compound which has at least one of high chemical stability, high ability to horizontally align liquid crystal molecules, high alignment properties in a wide additive concentration range, appropriate 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 device. A second advantage is to provide a liquid crystal composition which contains the compound and satisfies at least one of characteristics such as a high upper limit temperature of a nematic phase, a low lower limit temperature of the nematic phase, a low viscosity, an appropriate optical anisotropy, a large positive or negative dielectric anisotropy, a large specific resistance, a high stability to ultraviolet light, a high stability to heat, and a large elastic constant. A third advantage is to provide a liquid crystal display element comprising the composition, which has at least one of characteristics of appropriate hardness, low permeability of contact components, high weather resistance, and appropriate volume resistance value when a polar compound is formed into a film in the element by irradiating the composition with ultraviolet rays, and which has at least one of characteristics of a wide temperature range in which the element can be used, a short response time, a high voltage holding ratio, a low threshold voltage, a large contrast, and a long lifetime. 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" may be simply referred to as "composition" and "element", respectively. The term "liquid crystal display element" is a generic term for liquid crystal display panels and liquid crystal display modules. The "liquid crystalline compound" is a general term for compounds having a liquid crystal phase such as a nematic phase or a smectic phase, and compounds which are mixed in the composition for the purpose of adjusting the characteristics such as the temperature range, viscosity, and dielectric anisotropy of the nematic phase, although they do not have a liquid crystal phase. The compound has a six-membered ring such as 1, 4-cyclohexylene or 1, 4-phenylene, and its molecular structure is rod-like (rod like). The "polymerizable compound" is a compound added for the purpose of forming a polymer in the composition. The "polar compound" helps the liquid crystal molecules align by the interaction of the 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 optically active compounds, antioxidants, ultraviolet absorbers, pigments, antifoaming agents, polymerizable compounds, polymerization initiators, polymerization inhibitors, and polar compounds may be added to the liquid crystal composition as required. The proportion (addition 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 crystalline compound. Parts per million (ppm) by weight are also sometimes used. The proportions of the polymerization initiator and the polymerization inhibitor are exceptionally expressed on the basis of the weight of the polymerizable compound.

The compound represented by the formula (1) may be simply referred to as "compound (1)". The compound (1) refers to one compound, a mixture of two compounds, or a mixture of three or more compounds represented by the formula (1). The rule also applies to at least one compound selected from the group of compounds represented by formula (2), and the like. B surrounded by hexagon¹、C¹F, etc. with ring B¹Ring C¹Ring F, etc. The hexagon 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 across the hexagon indicate that any hydrogen on the ring can pass through-Sp¹-P¹And the like. Subscripts such as e indicate the number of substituted groups. When the subscript is 0, there is no such substitution.

The terminal group R¹¹Are used in a multi-component compound. In these compounds, any two R¹¹The two radicals indicated may be identical or may also be different. For example, R of the compound (2)¹¹Is ethyl, R of the compound (3)¹¹In the case of ethyl. Also R of the compound (2)¹¹Is ethyl, R of the compound (3)¹¹In the case of propyl. The rules apply to other end groups, rings, bonding groups, etc. In the formula (8), when i is 2, there are two rings D¹. In the compounds, two rings D¹The two radicals indicated may be identical or may also be different. The rule also applies to any two rings D where i is greater than 2¹. The rules apply to other ring, bond base, etc. notations.

The expression "at least one 'a' means that the number of 'a's is arbitrary. The expression "at least one of a's may be substituted with a ' B ', and when the number of ' a's is one, the position of ' a ' is arbitrary, and when the number of ' a's is two or more, the position of ' a ' may be selected without limitation. The rules also apply to the expression "at least one 'a' is substituted with 'B'. The expression "at least one A may be substituted by B, C or DRefers to the case comprising at least one a substituted with B, at least one a substituted with C, and at least one a substituted with D, thereby comprising the case of a plurality of at least two a substitutions with B, C, D. For example at least one-CH₂- (or-CH)₂CH₂-) alkyl groups which may be substituted with-O- (or-CH ═ CH-) include alkyl, alkenyl, alkoxy, alkoxyalkyl, alkoxyalkenyl, alkenyloxyalkyl. Further, two-CH in succession₂The case of substitution of-O-to-O-is not preferred. Alkyl, etc., methyl moiety (-CH)₂-CH of- (O-H)₂The case where the-O-is substituted with-O-H is also not preferable.

Halogen means fluorine, chlorine, bromine or iodine. Preferred halogens are fluorine or chlorine. Further preferred halogen is fluorine. The alkyl group is linear or branched and does not include a cyclic alkyl group. Generally, a straight-chain alkyl group is preferred to a branched alkyl group. The same applies to terminal groups such as alkoxy groups and alkenyl groups. Regarding the steric configuration related to the 1, 4-cyclohexylene group, the trans configuration is preferable to the cis configuration in order to increase the upper limit temperature of the nematic phase. 2-fluoro-1, 4-phenylene refers to the following two divalent radicals. In the formula, fluorine may be either to the left (L) or to the right (R). The rules also apply to unsymmetrical divalent radicals such as tetrahydropyran-2, 5-diyl that are generated by removing two hydrogens from the ring.

The present invention includes the following items, etc.

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

In the formula (1), the reaction mixture is,

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

ring A¹Ring A²Ring A³And ring A⁴Independently 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 ] s]Phenanthrene-3, 17-diyl, 2,3,4,7,8,9,10,11,12,13,14,15,16, 17-tetradecahydrocyclopenta [ a ]]Phenanthrene-3, 17-diyl group, (A-1) or (A-2), wherein at least one hydrogen in the ring may be 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, -Sp¹-P¹or-Sp²-P²In which at least one hydrogen may be substituted by fluorine or chlorine, and when a is 2, two rings A¹Can be different, when b is 2, two rings A⁴In (A-2), c is 2,3 or 4. Wherein, ring A¹Ring A²Ring A³Or ring A⁴At least one of which is naphthalene-2, 6-diyl, phenanthrene-2, 7-diyl, a group represented by (A-1) or a group represented by (A-2);

Z¹、Z²、Z³、Z⁴and Z⁵Independently a single bond or an alkylene group having 1 to 10 carbon atoms, in which at least one-CH group₂At least one- (CH) which may be substituted by-O-, -CO-, -COO-, -OCO-or-OCOO-₂)₂-may be substituted by-CH-or-C ≡ C-, of which groups at least one hydrogen may be substituted by halogen. Wherein Z is²、Z³Or Z⁴At least one of which is-COO-, -OCO-, -CH ═ CHCOO-, -OCOCH ═ CH-, -CH ═ CHCO-or-COCH ═ CH-, and when a is 2, two Z's are present¹Can be different, when b is 2, two Z' s⁵May be different;

Sp¹and Sp²Independently a single bond or an alkylene group having 1 to 10 carbon atoms, in which at least one-CH group₂At least one- (CH) which may be substituted by-O-, -CO-, -COO-, -OCO-or-OCOO-₂)₂-may be substituted by-CH ═ CH-or-C ≡ C-, at least one of these groups may be substituted by halogen, and there may be more Sp's in the structure¹Or Sp²In the case of (2), each may be different;

P¹and P²Independently a group represented by any one of the formulae (1b) to (1h) in the structure, in which a plurality of P's are present¹Or P²In the case of (2), each may be different;

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

M¹、M²、M³and M⁴Independently hydrogen, halogen, alkyl of carbon number 1 to 5 or alkyl of carbon number 1 to 5 with at least one hydrogen substituted with halogen;

R²is hydrogen, halogen, alkyl of carbon number 1 to 5, at least one hydrogen of the alkyl being substituted by halogen, at least one-CH₂-may be substituted by-O-;

R³、R⁴、R⁵、R⁶and R⁷Independently hydrogen or an alkyl group of 1 to 15 carbon atoms, in which at least one-CH group₂-may be substituted by-O-or-S-, at least one- (CH)₂)₂-may be substituted by-CH-or-C ≡ C-, of which groups at least one hydrogen may be substituted by halogen.

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

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

ring A¹Ring A²Ring A³And ring A⁴Independently 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 ] group]Phenanthrene-3, 17-diyl, 2,3,4,7,8,9,10,11,12,13,14,15,16, 17-tetradecahydrocyclopenta [ a ]]Phenanthrene-3, 17A diradical group, a group represented by (A-1) or a group represented by (A-2), wherein at least one hydrogen atom in the ring may be 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, -Sp¹-P¹or-Sp²-P²In which at least one hydrogen may be substituted by fluorine or chlorine, and when a is 2, two rings A¹Can be different, when b is 2, two rings A⁴In (A-2), c is 2,3 or 4. Wherein, ring A¹Ring A²Ring A³Or ring A⁴At least one of which is naphthalene-2, 6-diyl, phenanthrene-2, 7-diyl, a group represented by (A-1) or a group represented by (A-2);

Z¹、Z²、Z³、Z⁴and Z⁵Independently a single bond, - (CH)₂)₂-、-CH＝CH-、-C≡C-、-COO-、-OCO-、-CF₂O-、-OCF₂-、-CH₂O-、-OCH₂-, -CF ═ CF-, -CH ═ CHCOO-, -OCOCH ═ CH-, -CH ═ CHCO-, or-COCH ═ CH-, wherein Z is²、Z³Or Z⁴At least one of which is-COO-, -OCO-, -CH ═ CHCOO-, -OCOCH ═ CH-, -CH ═ CHCO-or-COCH ═ CH-, and when a is 2, two Z's are present¹Can be different by two Z⁵May be different;

Sp¹and Sp²Independently a single bond or an alkylene group having 1 to 10 carbon atoms, in which at least one-CH group₂-may be substituted by-O-, -COO-or-OCO-, at least one- (CH)₂)₂-may be substituted by-CH ═ CH-, where at least one hydrogen may be substituted by fluorine or chlorine, and where a plurality of Sp's are present in the structure¹Or Sp²In the case of (2), each may be different;

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

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

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

ring A¹Ring A²Ring A³And ring A⁴Independently 1, 4-cyclohexylene group, 1, 4-phenylene group, naphthalene-2, 6-diyl group, pyrimidine-2, 5-diyl group, pyridine-2, 5-diyl group, fluorene-2, 7-diyl group, phenanthrene-2, 7-diyl group, anthracene-2, 6-diyl group, group represented by (A-1) or group represented by (A-2), in which at least one hydrogen may be substituted by fluorine, chlorine, an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an alkoxy group having 1 to 11 carbon atoms, an alkenyloxy group having 2 to 11 carbon atoms, -Sp¹-P¹or-Sp²-P²In which at least one hydrogen may be substituted by fluorine or chlorine, and when a is 2, two rings A¹Can be different, when b is 2, two rings A⁴It may be different from that in (A-2),c is 2,3 or 4. Wherein, ring A¹Ring A²Ring A³Or ring A⁴At least one of which is naphthalene-2, 6-diyl, phenanthrene-2, 7-diyl, a group represented by (A-1) or a group represented by (A-2);

Z²、Z³and Z⁴Independently a single bond, - (CH)₂)₂-、-CH＝CH-、-C≡C-、-COO-、-OCO-、-CF₂O-、-OCF₂-、-CH₂O-、-OCH₂-, -CF ═ CF-, -CH ═ CHCOO-, -OCOCH ═ CH-, -CH ═ CHCO-, or-COCH ═ CH-, wherein Z is²、Z³And Z⁴At least one of which is-COO-, -OCO-, -CH ═ CHCOO-, -OCOCH ═ CH-, -CH ═ CHCO-, or-COCH ═ CH-;

Sp¹and Sp²Independently a single bond or an alkylene group having 1 to 10 carbon atoms, in which at least one-CH group₂At least one- (CH) which may be substituted by-O-, -COO-, -OCOO-or-OCO-₂)₂-may be substituted by-CH ═ CH-, where at least one hydrogen may be substituted by fluorine or chlorine, and where a plurality of Sp's are present in the structure¹Or Sp²In the case of (2), each may be different;

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

R²is hydrogen, halogen, alkyl of 1 to 5 carbon atoms, orIn the alkyl, at least one hydrogen may be substituted by halogen, at least one-CH₂-may be substituted by-O-;

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

ring A¹Ring A²Ring A³And ring A⁴Independently 1, 4-cyclohexylene group, 1, 4-phenylene group, naphthalene-2, 6-diyl group, fluorene-2, 7-diyl group, phenanthrene-2, 7-diyl group, group represented by (A-1) or group represented by (A-2), and in these rings, at least one hydrogen may be 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, -Sp¹-P¹or-Sp²-P²In the substituent (A-2), c is 2,3 or 4. Wherein, ring A¹Ring A²Ring A³Or ring A⁴At least one of which is naphthalene-2, 6-diyl, phenanthrene-2, 7-diyl, a group represented by (A-1) or a group represented by (A-2);

Z²、Z³and Z⁴Independently a single bond, - (CH)₂)₂-, -CH ═ CH-, -C ≡ C-, -COO-, -OCO-, -CH ═ CHCOO-, -OCOCH ═ CH-, -CH ═ CHCO-, or-COCH ═ CH-, wherein Z is²、Z³And Z⁴At least one of which is-COO-, -OCO-, -CH ═ CHCOO-, -OCOCH ═ CH-, -CH ═ CHCO-, or-COCH ═ CH-;

Sp¹and Sp²Independently a single bond or an alkylene group having 1 to 10 carbon atoms, in which at least one-CH group₂At least one- (CH) which may be substituted by-O-, -COO-, -OCOO-or-OCO-₂)₂-may be substituted by-CH ═ CH-, where multiple Sp are present in the structure¹Or Sp²In the case of (2), each may be different;

P¹and P²Independently a group represented by any one of formula (1b), formula (1c), formula (1d) or formula (1e) in the presence of a plurality of P's in the structure¹Or P²In the case of (2), each may be different;

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

R²is hydrogen, halogen or alkyl of carbon number 1 to 5, in which at least one hydrogen may be substituted by halogen, at least one-CH₂-may be substituted by-O-;

R³、R⁴、R⁵and R⁶Independently hydrogen or an alkyl group of 1 to 15 carbon atoms, in which at least one-CH group₂-may be substituted by-O-or-S-, at least one- (CH)₂)₂-may be substituted by-CH-or-C ≡ C-, of which groups at least one hydrogen may be substituted by halogen.

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

ring A¹Ring A²Ring A³And ring A⁴Independently 1, 4-cyclohexylene, 1, 4-phenylene, naphthalene-2, 6-diyl, fluorene-2, 7-diyl, phenanthrene-2, 7-diyl, a group represented by (A-1) or a group represented by (A-2), wherein at least one hydrogen in these rings may be substituted with fluorine, chlorine, methyl or ethyl, and in (A-2), c is 2,3 or 4. Wherein, ring A¹Ring A²Ring A³Or ring A⁴At least one of which is naphthalene-2, 6-diyl, phenanthrene-2, 7-diyl, a group represented by (A-1) or a group represented by (A-2);

P¹and P²Independently a group represented by formula (1b-1), formula (1b-2), formula (1b-3), formula (1b-4), formula (1b-5), formula (1c-1), formula (1d-2) or formula (1 e-1).

[6]According to [3]The compound represented by the formula (1-1), the formula (1-2) or the formula (1-3), wherein Z is²、Z³Or Z⁴is-COO-or-OCO-.

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

P¹-Sp¹-Y-Sp²-P² (1-A)

P¹And P²Independently formula (1b-1), formula (1b-2), formula (1b-3), formula (1b-4), formula (1b-5), formula (1c-1), formula (I)A group represented by the formula (1d-1), the formula (1d-2) or the formula (1 e-1);

Sp¹and Sp²Independently a single bond or an alkylene group having 1 to 10 carbon atoms, in which at least one-CH group₂At least one- (CH) which may be substituted by-O-, -COO-, -OCOO-or-OCO-₂)₂-may be substituted by-CH ═ CH-;

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

[8]According to [7]The compound wherein Sp is present in the compound represented by the formula (1-A)¹And Sp²Independently an alkylene group having 1 to 10 carbon atoms, in which at least one-CH group₂At least one- (CH) which may be substituted by-O-, -COO-, -OCOO-or-OCO-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 formulae (2) to (4).

In the formulae (2) to (4),

R¹¹and R¹²Independently an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms, at least one-CH group being present in the alkyl group or the alkenyl group₂-may be substituted by-O-, at least one hydrogen may be substituted by fluorine;

ring B¹Ring B²Ring B³And ring B⁴Independently 1, 4-cyclohexylene, 1, 4-phenylene, 2-fluoro-1, 4-phenylene, 2, 5-difluoro-1, 4-phenylene or pyrimidin-2, 5-diyl;

Z¹¹、Z¹²and Z¹³Independently a single bond, -CH₂CH₂-, -CH-, -C.ident.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 formulae (5) to (7).

In the formulae (5) to (7),

R¹³is C1-10 alkyl or C2-10 alkenyl, at least one-CH in the alkyl and alkenyl₂-may be substituted by-O-, at least one hydrogen may be substituted by fluorine;

X¹¹is fluorine, chlorine, -OCF₃、-OCHF₂、-CF₃、-CHF₂、-CH₂F、-OCF₂CHF₂or-OCF₂CHFCF₃；

Ring C¹Ring C²And ring C³Independently 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;

Z¹⁴、Z¹⁵and Z¹⁶Independently a single bond, -CH₂CH₂-、-CH＝CH-、-C≡C-、-COO-、-CF₂O-、-OCF₂-、-CH₂O-, -CF-, -CH-CF-, or- (CH)₂)₄-；

L¹¹And L¹²Independently hydrogen or fluorine.

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

In the formula (8), the reaction mixture is,

R¹⁴is C1-10 alkyl or C2-10 alkenyl, at least one-CH in the alkyl and alkenyl₂-may be substituted by-O-, at least one hydrogen may be substituted by fluorine;

X¹²is-C.ident.N or-C.ident.C-C.ident.N;

ring D¹Is 1, 4-cyclohexylene, 1, 4-phenylene in which at least one hydrogen is substituted by fluorine, tetrahydropyran-2, 5-diyl, 1, 3-dioxane-2, 5-diyl or pyrimidine-2, 5-diyl;

Z¹⁷is a single bond, -CH₂CH₂-、-C≡C-、-COO-、-CF₂O-、-OCF₂-or-CH₂O-；

L¹³And L¹⁴Independently 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 formulae (9) to (15).

In the formulae (9) to (15),

R¹⁵and R¹⁶Independently an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms, at least one-CH group being present in the alkyl group or the alkenyl group₂-may be substituted by-O-, at least one hydrogen may be substituted by fluorine;

R¹⁷is hydrogen, fluorine, C1-10 alkyl or C2-10 alkenyl, at least one-CH in the alkyl and alkenyl₂-may be substituted by-O-, at least one hydrogen may be substituted by fluorine;

ring E¹Ring E²Ring E³And ring E⁴Independently 1, 4-cyclohexylene, 1, 4-cyclohexenylene, 1, 4-phenylene in which at least one hydrogen may be substituted by fluorine, tetrahydropyran-2, 5-diyl or decahydronaphthalene-2, 6-diyl;

ring E⁵And ring E⁶Independently is 1, 4-cyclohexylene, 1, 4-cyclohexyleneAlkenyl, 1, 4-phenylene, tetrahydropyran-2, 5-diyl or decahydronaphthalene-2, 6-diyl;

Z¹⁸、Z¹⁹、Z²⁰and Z²¹Independently a single bond, -CH₂CH₂-、-COO-、-CH₂O-、-OCF₂-or-OCF₂CH₂CH₂-；

L¹⁵And L¹⁶Independently fluorine or chlorine;

S¹¹is hydrogen or methyl;

x is-CHF-or-CF₂-；

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

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

In the formula (16), the compound represented by the formula,

ring F and ring I are independently cyclohexyl, cyclohexenyl, phenyl, 1-naphthyl, 2-naphthyl, tetrahydropyran-2-yl, 1, 3-dioxan-2-yl, pyrimidin-2-yl or pyridin-2-yl, in which ring at least one hydrogen may be substituted with halogen, alkyl of carbon number 1 to 12 or alkyl of carbon number 1 to 12 in which at least one hydrogen is substituted with halogen;

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

Z²²and Z²³Independently is a sheetA bond or an alkylene group having 1 to 10 carbon atoms, in which at least one-CH group₂-may be substituted by-O-, -CO-, -COO-or-OCO-, at least one-CH₂CH₂-may be via-CH ═ CH-, -C (CH)₃)＝CH-、-CH＝C(CH₃) -or-C (CH)₃)＝C(CH₃) -substitution, of which at least one hydrogen may be substituted by fluorine or chlorine;

P¹¹、P¹²and P¹³Independently a polymerizable group selected from the group of groups represented by the formulae (P-1) to (P-5);

M¹¹、M¹²and M¹³Independently hydrogen, fluorine, alkyl of carbon number 1 to 5, or alkyl of carbon number 1 to 5 wherein at least one hydrogen is substituted with fluorine or chlorine;

Sp¹¹、Sp¹²and Sp¹³Independently a single bond or an alkylene group having 1 to 10 carbon atoms, in which at least one-CH group₂At least one-CH which may be substituted by-O-, -COO-, -OCO-or-OCOO-)₂CH₂-may be substituted by-CH ═ CH-or-C ≡ C-, at least one of these groups being 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 formulae (16-1) to (16-27).

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

P¹¹、P¹²and P¹³Independently a polymerizable group selected from the group of groups represented by the formulae (P-1) to (P-3), wherein M is¹¹、M¹²And M¹³Independently hydrogen, fluorine, alkyl of carbon number 1 to 5 or alkyl of carbon number 1 to 5 wherein at least one hydrogen is substituted with a halogen;

Sp¹¹、Sp¹²and Sp¹³Independently a single bond or an alkylene group having 1 to 10 carbon atoms, in which at least one-CH group₂At least one-CH which may be substituted by-O-, -COO-, -OCO-or-OCOO-)₂CH₂-may be substituted by-CH ═ CH-or-C ≡ C-, at least one of these groups being substituted by fluorine or chlorine.

[16] The liquid crystal composition according to any one of [9] to [15], which further contains at least one of a polymerizable compound other than the compounds represented by the formulae (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 an antifoaming agent.

[17] A liquid crystal display element comprising 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 kinds of 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 an antifoaming agent. (b) A polymerizable composition prepared by adding a polymerizable compound different from the compound (1) or the compound (16) to the liquid crystal composition. (c) A polymerizable composition prepared by adding a compound (1) and a compound (16) to the liquid crystal composition. (d) A liquid crystal composite is produced by polymerizing a polymerizable composition. (e) A polymer-stabilized alignment type element comprising the liquid crystal composite. (f) A polymer stable alignment type element 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. Forms of Compound (1)

The compound (1) according to the embodiment of the present invention is a polar compound having a mesogen (mesogen) site having at least one excellent light absorption structure and a polymerizable group. The compound (1) has a structure such as phenanthrene, naphthalene, or tolane in the molecule, and thus has high light absorption characteristics and characteristics of absorbing light in a relatively long wavelength region, and exhibits sufficient characteristics when irradiated with light in a shorter time or at a lower energy than a compound having no such structure.

One of the uses of the compound (1) is as 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 in an element, has high solubility in a liquid crystal composition, and has a high 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) will be described. R in Compound (1)¹、Z¹～Z⁵、A¹～A⁴、Sp¹、Sp²、P¹、P²Preferred examples of a and b also apply to the lower formula of the compound (1). In the compound (1), the properties can be arbitrarily adjusted by appropriately combining the types of these groups. Since there is no large difference in the characteristics of the compounds, the compound (1) may contain a larger amount than the natural abundance²H (deuterium),¹³C is an isotope.

Ring A¹Ring A²Ring A³And ring A⁴Independently 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 ] group]Phenanthrene-3, 17-diyl, 2,3,4,7,8,9,10,11,12,13,14,15,16, 17-tetradecahydrocyclopenta [ a ]]Phenanthrene-3, 17-diyl group, (A-1) or (A-2), wherein at least one hydrogen in the ring may be 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, -Sp¹-P¹or-Sp²-P²In which at least one hydrogen may be substituted by fluorine or chlorine, and when a is 2, two rings A¹Can be different, when b is 2, two rings A⁴In (A-2), c is 2,3 or 4. Wherein, ring A¹Ring A²Ring A³Or ring A⁴At least one of which is naphthalene-2, 6-diyl, phenanthrene-2, 7-diyl, a group represented by (A-1) or a group represented by (A-2);

preferred ring A¹Ring A²Ring A³And ring A⁴Independently 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, perhydrocyclopenta [ a ] o [ 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 group, group represented by (A-1) or group represented by (A-2)In the above groups, c is preferably 1 or 2, at least one hydrogen in the ring may be substituted by fluorine, chlorine, an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an alkoxy group having 1 to 11 carbon atoms or an alkenyloxy group having 2 to 11 carbon atoms, and at least one hydrogen in these groups may be substituted by fluorine or chlorine. Further preferred are 1, 4-cyclohexylene, 1, 4-phenylene and perhydrocyclopenta [ a ]]Phenanthrene-3, 17-diyl or 2,3,4,7,8,9,10,11,12,13,14,15,16, 17-tetradecylcyclopenta [ a [ ]]Phenanthrene-3, 17-diyl, in which at least one hydrogen may be substituted by fluorine or an alkyl group having 1 to 5 carbon atoms. Particularly preferably 1, 4-cyclohexylene, 1, 4-phenylene or perhydrocyclopenta [ a ]]Phenanthrene-3, 17-diyl, in which rings at least one hydrogen may be substituted by fluorine, methyl or ethyl.

Z¹、Z²、Z³、Z⁴And Z⁵Independently a single bond or an alkylene group having 1 to 10 carbon atoms, in which at least one-CH group₂At least one- (CH) which may be substituted by-O-, -CO-, -COO-, -OCO-or-OCOO-₂)₂-may be substituted by-CH-or-C ≡ C-, of which groups at least one hydrogen may be substituted by halogen. Wherein Z is²、Z³Or Z⁴At least one of which is-COO-, -OCO-, -CH ═ CHCOO-, -OCOCH ═ CH-, -CH ═ CHCO-, -COCH ═ CH-, and when a is 2, two Z are present¹Can be different by two Z⁵May be different.

Preferred Z¹、Z²、Z³、Z⁴And Z⁵Independently a single bond, - (CH)₂)₂-、-CH＝CH-、-C≡C-、-COO-、-OCO-、-CF₂O-、-OCF₂-、-CH₂O-、-OCH₂-or-CF ═ CF-. Further preferably a single bond, - (CH)₂)₂-or-CH ═ CH-. Particularly preferred is a single bond.

Sp¹And Sp²Independently a single bond or an alkylene group having 1 to 10 carbon atoms, in which at least one-CH group₂At least one- (CH) which may be substituted by-O-, -CO-, -COO-, -OCO-or-OCOO-₂)₂-may be substituted by-CH-or-C ≡ C-, of which groups at least one hydrogen may be substituted by halogen.

It is preferable thatSp¹And Sp²Independently a single bond, an alkylene group having 1 to 6 carbon atoms, or a-CH₂-C1-6 alkylene substituted with-O-or-OCOO-. More preferably an alkylene group having 1 to 6 carbon atoms or-OCOO-.

P¹And P²Independently represents a group represented by any one of the formulae (1b) to (1 h).

Preferred P¹And P²Independently a group represented by any one of (1b), (1c), (1d) and (1 e).

Preferred M¹、M²、M³And M⁴Independently hydrogen, fluoro, methyl, ethyl or trifluoromethyl. More preferably hydrogen.

R²Is hydrogen, halogen or alkyl of carbon number 1 to 5, in which at least one hydrogen may be substituted by halogen, at least one-CH₂-may be substituted by-O-.

Preferred R²Is hydrogen, fluorine, methyl, ethyl, methoxymethyl or trifluoromethyl. More preferably hydrogen.

R³、R⁴、R⁵、R⁶And R⁷Independently hydrogen or a linear, branched or cyclic alkyl group having 1 to 15 carbon atoms, wherein at least one-CH group is present in the alkyl group₂-may be substituted by-O-or-S-, at least one- (CH)₂)₂-may be substituted by-CH-or-C ≡ C-, of which groups at least one hydrogen may be substituted by halogen.

Preferred R³、R⁴、R⁵、R⁶And R⁷Independently hydrogen, a linear alkyl group having 1 to 10 carbon atoms, a linear alkenyl group having 2 to 10 carbon atoms, a linear alkoxy group having 1 to 10 carbon atoms, or a cyclic alkyl group having 3 to 6 carbon atoms. Further preferred is 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 or a cyclic alkyl group having 4 to 6 carbon atoms.

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

In the formulae (1b) to (1h), M¹And M²Independently hydrogen, halogen, alkyl of carbon number 1 to 5 or alkyl of carbon number 1 to 5 in which at least one hydrogen is substituted by halogen.

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 A¹Ring A²Ring A³And ring A⁴Independently 1, 4-cyclohexylene group, 1, 4-phenylene group, naphthalene-2, 6-diyl group, pyrimidine-2, 5-diyl group, pyridine-2, 5-diyl group, fluorene-2, 7-diyl group, phenanthrene-2, 7-diyl group, anthracene-2, 6-diyl group, group represented by (A-1) or group represented by (A-2), in which at least one hydrogen may be substituted by fluorine, chlorine, an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an alkoxy group having 1 to 11 carbon atoms, an alkenyloxy group having 2 to 11 carbon atoms, -Sp¹-P¹or-Sp²-P²In which at least one hydrogen may be substituted by fluorine or chlorine, and when a is 2, two rings A¹Can be different, when b is 2, two rings A⁴In (A-2), c is 2,3 or 4. Wherein, ring A¹Ring A²Ring A³Or ring A⁴At least one of which is naphthalene-2, 6-diyl, phenanthrene-2, 7-diyl, a group represented by (A-1) or a group represented by (A-2);

in the form of a ring of these types,at least one hydrogen atom may be fluorine, chlorine, alkyl group having 1 to 12 carbon atoms, alkenyl group having 2 to 12 carbon atoms, alkoxy group having 1 to 11 carbon atoms, alkenyloxy group having 2 to 11 carbon atoms, -Sp¹-P¹or-Sp²-P²In which at least one hydrogen may be substituted by fluorine or chlorine;

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

In the compound represented by the formula (1-1), the formula (1-2) or the formula (1-3), Z²、Z³Or Z⁴Either of them is preferably-COO-or-OCO-.

In addition, in the compound represented by the formula (1-1), the formula (1-2) or the formula (1-3), Z²、Z³Or Z⁴Any of these is preferably-CH ═ CHCOO-, -OCOCH ═ CH-, -CH ═ CHCO-, or-COCH ═ CH-.

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

P¹-Sp¹-Y-Sp²-P² (1-A)

P¹And P²Independently a group represented by formula (1b-1), formula (1b-2), formula (1b-3), formula (1b-4), formula (1b-5), formula (1c-1), formula (1d-2) or formula (1 e-1);

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

The formulas (2) to (15) show component 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. Since the compound (8) has a cyano group, it has positive and greater 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), P¹¹、P¹²And P¹³Independently a polymerizable group.

Preferred P¹¹、P¹²And P¹³Is a polymerizable group selected from the group of groups represented by the formulae (P-1) to (P-5). Further preferred is P¹¹、P¹²And P¹³Is a group (P-1), a group (P-2) or a group (P-3). A particularly preferred radical (P-1) is-OCO-CH ═ CH₂or-OCO-C (CH)₃)＝CH₂. The wavy lines from the group (P-1) to the group (P-5) indicate the sites where bonding is to take place.

In the groups (P-1) to (P-5), M¹¹、M¹²And M¹³Independently hydrogen, fluorine, alkyl of carbon number 1 to 5 or alkyl of carbon number 1 to 5 in which at least one hydrogen is substituted by a halogen.

For the purpose of enhancing reactivity, M is preferred¹¹、M¹²And M¹³Is hydrogen or methyl. Further preferred is M¹¹Is methyl, more preferably M¹²And M¹³Is hydrogen.

Preferred is Sp¹¹、Sp¹²And Sp¹³Is a single bond.

Ring F and ring I are independently cyclohexyl, cyclohexenyl, phenyl, 1-naphthyl, 2-naphthyl, tetrahydropyran-2-yl, 1, 3-dioxan-2-yl, pyrimidin-2-yl or pyridin-2-yl, in which ring at least one hydrogen may be substituted with halogen, alkyl of carbon number 1 to 12, alkoxy of carbon number 1 to 12 or alkyl of carbon number 1 to 12 in which at least one hydrogen is substituted with halogen.

Preferred rings F and I are phenyl. Ring G is 1, 4-cyclohexylene, 1, 4-cyclohexenylene, 1, 4-phenylene, naphthalene-1, 2-diyl, naphthalene-1, 3-diyl, naphthalene-1, 4-diyl, naphthalene-1, 5-diyl, naphthalene-1, 6-diyl, naphthalene-1, 7-diyl, naphthalene-1, 8-diyl, naphthalene-2, 3-diyl, naphthalene-2, 6-diyl, naphthalene-2, 7-diyl, tetrahydropyran-2, 5-diyl, 1, 3-dioxane-2, 5-diyl, pyrimidine-2, 5-diyl or pyridine-2, 5-diyl, in these rings, at least one hydrogen may be substituted with a halogen, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or an alkyl group having 1 to 12 carbon atoms in which at least one hydrogen is substituted with a halogen. Particularly preferred ring G is 1, 4-phenylene or 2-fluoro-1, 4-phenylene.

Z²²And Z²³Independently a single bond or an alkylene group having 1 to 10 carbon atoms, in which at least one-CH group₂-may be substituted by-O-, -CO-, -COO-or-OCO-, at least one-CH₂CH₂-may be via-CH ═ CH-, -C (CH)₃)＝CH-、-CH＝C(CH₃) -or-C (CH)₃)＝C(CH₃) -substitution, of which at least one hydrogen may be substituted by fluorine or chlorine.

Preferred Z²²And Z²³Is a single bond, -CH₂CH₂-、-CH₂O-、-OCH₂-, -COO-or-OCO-. Further preferred is Z²²And Z²³Is a single bond.

u is 0,1 or 2.

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

2. Synthesis of Compound (1)

The synthesis method of the compound (1) will be described. The compound (1) can be synthesized by appropriately combining the methods of organic synthetic chemistry. The compounds not described in the Synthesis methods were synthesized by methods described in books such as "Organic Synthesis (Organic Syntheses)" (John Wiley & Sons, Inc), "Organic reaction (Organic Reactions)" (John Wiley & Sons, Inc), "Comprehensive Organic Synthesis (Comprehensive Organic Synthesis)" (pegman Press), and "new experimental chemistry lecture" (bolus).

2-1. a bonding group Z¹A bonding group Z²A bonding group Z³A bonding group Z⁴And a bonding group Z⁵Generation of

Examples of the method for forming the bonding group in the compound (1) are described in the following schemes. In the process, MSG¹(or MSG)²) Is a monovalent organic group having at least one ring. Multiple MSGs¹(or MSG)²) The monovalent organic groups represented may be the same or may be different. The compounds (1A) to (1J) correspond to the compound (1) or an intermediate of the compound (1).

(I) Formation of single bonds

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

Formation of (II) -COO-and-OCO-)

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

(III)-CF₂O-and-OCF₂Generation of

Compound (26) is obtained by sulfurizing compound (1B) with a lawson's reagent. Synthesis of a Compound having-CF by fluorination of Compound (26) with pyridine hydrogen fluoride Complex and N-Bromosuccinimide (NBS)₂Compound (1C) of O-. Reference is made to "quick chemical report (chem. lett.) to m.nigrosine (m.kuroboshi), et al, 1992, phase 827. Compound (1C) can also be synthesized by fluorinating compound (26) with (diethylamino) sulflur trifluoride (DAST). Reference is made to "journal of organic chemistry (j.org.chem.) of w.h. banille (w.h.bunnelle) et al, 1990, 55 th page 768. Having a-OCF₂-is also synthesized using the method.

Formation of (IV) -CH ═ CH-

Compound (22) is reacted with N-butyllithium, followed by reaction with N, N-Dimethylformamide (DMF) to give aldehyde (27). Compound (1D) is synthesized by reacting phosphonium salt (28) with potassium tert-butoxide to produce phosphorus ylide, and reacting the phosphorus ylide with aldehyde (27). Since the cis-isomer is produced under reaction conditions, the cis-isomer is isomerized to the trans-isomer by a known method as required.

(V)-CH₂CH₂Generation of

Compound (1D) is hydrogenated in the presence of a palladium on carbon catalyst to synthesize compound (1E).

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

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

(VII)-CH₂O-and-OCH₂Generation of

Compound (27) is reduced with sodium borohydride to obtain compound (30). This was brominated with hydrobromic acid to obtain compound (31). Compound (1G) is synthesized by reacting compound (25) with compound (31) in the presence of potassium carbonate. Has a-OCH₂-is also synthesized using the method.

Formation of (VIII) -CF ═ CF-

Compound (23) is treated with n-butyllithium, and thereafter tetrafluoroethylene is reacted to obtain compound (32). Compound (22) is treated with n-butyllithium, and then reacted with compound (32) to synthesize compound (1H).

Formation of (VIV) -CH ═ CHCO-and-COCH ═ CH-

Compound (1I) is synthesized by subjecting compound (40) and compound (27) to an aldol condensation reaction in the presence of NaOH.

Formation of (X) -CH ═ CHCOO-and-OCOCH ═ CH-

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

2-2. Ring A¹Ring A²Ring A³And ring A⁴Generation of

With respect to 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, decahydronaphthalene-2, 6-diyl, 1,2,3, 4-tetrahydronaphthalene-2, 6-diyl, tetrahydropyran-2, 5-diyl, 1, 3-dioxane-2, 5-diyl, pyrimidine-2, 5-diyl, pyridine-2, 5-diyl, perhydrocyclopenta [ a ] phenanthrene-3, 17-diyl, 2,3,4,7,8,9,10,11,12,13,14,15,16, 17-tetradecylcyclopenta [ a ] phenanthrene-3, 17-diyl, etc., and the initiator is commercially available or is well known in the art. The group represented by (A-1) and the group represented by (A-2) can be synthesized by referring to the production of-C.ident.C-.

2-3. linking group Sp¹Or a linking group Sp²And a polymerizable group P¹Or a polymerizable groupP²Generation of

Polymerizable group P¹Or a polymerizable group P²Preferred examples of (a) are acryloxy (1b), maleimide (1c), itaconate (1d), vinyl ester (1e), oxetanyl (1g) or vinyloxy (1 h).

Synthesis of said polymerizable group through a linking group Sp¹Or a linking group Sp²Examples of the method of bonding the compound to the ring are as follows. First, a linking group Sp is shown¹Or a linking group Sp²An example of a single bond.

(1) Synthesis of Compounds which are Single bonds

Sp¹Or Sp²The synthesis of the compounds having a single bond is described in the following scheme. In the process, MSG¹Is a monovalent organic group having at least one ring. The compounds (1S) to (1Z) correspond to the compound (1). When the polymerizable group is an acrylate derivative, the polymerizable group is derived from the corresponding acrylic acid and HO-MSG¹By esterification. Ethyleneoxy is through HO-MSG¹Etherification with vinyl bromide. The oxetanyl group is synthesized by oxidation of a terminal double bond. Maleimide groups are synthesized by the reaction of an amino group with maleic anhydride. The itaconate is prepared from corresponding itaconic acid and HO-MSG¹By esterification. The vinyl ester is obtained by reacting vinyl acetate with HOOC-MSG¹By transesterification reaction.

The above describes the linking group Sp¹Or a linking group Sp²Synthesis of compounds having a single bond. The method of generating other linking groups can be referred to as the linking group Z¹A bonding group Z²A bonding group Z³A bonding group Z⁴And a bonding group Z⁵The synthesis method of (3).

2-4 Synthesis examples

Examples of the method for synthesizing the compound (1) are as follows. In these compounds, MES is a mesogen having at least one ring. P¹、M¹、M²、Sp¹And Sp²Are as defined above.

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

In the synthesis of MES and Sp¹In the case of the compound linked by an ether bond, the compound (53A) can be obtained by etherifying the compound (51A) as an initiator with the compound (52) and a base such as potassium hydroxide. In addition, in the synthesis of MES and Sp¹In the case of a compound linked by a single bond, the compound (53B) can be obtained by using the compound (51B) as an initiator, and performing a cross-coupling reaction using the compound (52), a metal catalyst such as palladium, and a base. The compound (53A) or the compound (53B) may be derived as the compound (54A) or the compound (54B) which functions as a protecting group such as Trimethylsilyl (TMS) or Tetrahydropyranyl (THP) as required.

Then, compound (57A) or compound (57B) can be obtained by etherifying compound (53A), compound (53B), compound (54A) or compound (54B) again in the presence of compound (55) and a base such as potassium hydroxide. In this case, when the protecting group is allowed to act in the previous stage, the protecting group is removed by a deprotection reaction.

P²The compound (1A) which is a group represented by the formula (1b-3) can be synthesized from the compound (57) by the following method. By chemical combinationCompound (57) can be derived from compound (1A) by esterification in the presence of compound (58), DCC and DMAP.

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 the control of the alignment of the 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. The component B is a compound (2) to a compound (4). The component C is a compound (5) to a compound (7). The component D is the compound (8). The component E is a compound (9) to a compound (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 the component B, the component C, the component D, and the component E in consideration of the magnitude of positive or negative dielectric anisotropy, and the like. A composition with properly selected ingredients has a high upper limit temperature, a low lower limit temperature, a small viscosity, a proper 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 light, and a proper elastic constant (i.e., a large elastic constant or a small elastic constant).

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 in order to maintain high stability against ultraviolet rays, and the preferable proportion of the compound (1) is usually about 10% by weight or less in order to be dissolved in the liquid crystal composition. Even more preferred is a ratio in the range of about 0.1 wt% to about 5 wt%, based on the weight of the liquid crystal composition. The most preferred ratio is in the range of about 0.5% to about 3% by weight based on the weight of the liquid crystal composition.

The component B is a compound having an alkyl group or the like at both terminal groups. Preferable examples of the component B include compoundsThe compounds (2-1) to (2-11), the compounds (3-1) to (3-19) and the compounds (4-1) to (4-7). In the compound of component B, R¹¹And R¹²Independently an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms, at least one-CH group being present in the alkyl group or the alkenyl group₂-may be substituted by-O-and at least one hydrogen may be substituted by fluorine.

The component B is a nearly neutral compound 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 have an effect of adjusting the optical anisotropy.

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

The component C is a compound (5) to a compound (7) each having a halogen or a fluorine-containing group at the right terminal. Preferable examples of the component C include compounds (5-1) to (5-16), compounds (6-1) to (6-120), and compounds (7-1) to (7-63). In the compound of component C, R¹³Is C1-10 alkyl or C2-10 alkenyl, at least one-CH in the alkyl and alkenyl₂-may be substituted by-O-, at least one hydrogen may be substituted by fluorine; x¹¹Is fluorine, chlorine, -OCF₃、-OCHF₂、-CF₃、-CHF₂、-CH₂F、-OCF₂CHF₂or-OCF₂CHFCF₃。

Since the component C has positive dielectric anisotropy and very excellent stability against heat, light, and the like, it can be used for the production of a composition for IPS, FFS, OCB, and other modes. The content of the component C is suitably in the range of 1 to 99% by weight, preferably in the range of 10 to 97% by weight, and more preferably in the range of 40 to 95% by weight, based on the weight of the liquid crystal composition. In the case where the component C is added to a 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 the 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 the right terminal group-C.ident.N or-C.ident.C-C.ident.N. Preferable examples of the component D include compounds (8-1) to (8-64). In the compound of component D, R¹⁴Is C1-10 alkyl or C2-10 alkenylAt least one-CH in the alkyl and alkenyl groups₂-may be substituted by-O-, at least one hydrogen may be substituted by fluorine; x¹²is-C.ident.N or-C.ident.C-C.ident.N.

Since the component D has positive dielectric anisotropy and a large value, it is mainly used in the case of producing a composition for TN or the like. By adding the component D, the dielectric anisotropy of the composition can be increased. The component D brings about an effect of expanding the temperature range of the liquid crystal phase, adjusting the viscosity, or adjusting the optical anisotropy. The 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 the component D is suitably in the range of 1 to 99% by weight, preferably in the range of 10 to 97% by weight, and more preferably in the range of 40 to 95% by weight, based on the weight of the liquid crystal composition. In the case where the component D is added to a 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 the component D, the elastic constant of the composition can be adjusted, and the voltage-transmittance curve of the element can be adjusted.

The component E is a compound (9) to a compound (16). These compounds have phenylene radicals which are substituted laterally (with two halogens) like 2, 3-difluoro-1, 4-phenylene.

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 compounds of component E, R¹⁵And R¹⁶Independently of the carbon number1 to 10 alkyl groups or 2 to 10 carbon atoms alkenyl groups, at least one-CH group being present in the alkyl and alkenyl groups₂-may be substituted by-O-, at least one hydrogen may be substituted by fluorine; r¹⁷Is hydrogen, fluorine, C1-10 alkyl or C2-10 alkenyl, at least one-CH in the alkyl and alkenyl₂-may be substituted by-O-and at least one hydrogen may be substituted by fluorine.

The dielectric anisotropy of the component E is negative and large. Component E can be used in the case of preparing compositions for IPS, VA, PSA, etc. modes. As the content of the component E is increased, the dielectric anisotropy of the composition is negative and increased, 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 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 the component E, the compound (9) is a bicyclic compound, and is therefore effective mainly in reducing the viscosity, adjusting the optical anisotropy, or increasing the dielectric anisotropy. Since the compound (10) and the compound (11) are tricyclic compounds, they have the 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 the dielectric anisotropy.

In the case of producing a composition for IPS, VA, PSA, or other modes, the content of the component E is preferably 40% by weight or more, and more preferably in the range of 50% by weight to 95% by weight, based on the weight of the liquid crystal composition. In the case where the component E is added to a 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 the 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, appropriate 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 component compounds are mixed and then dissolved in each other by heating. Additives may also be added to the composition depending on the use. Examples of the additives include polymerizable compounds other than those represented by the formulae (1) and (16), polymerization initiators, polymerization inhibitors, optically active compounds, antioxidants, ultraviolet absorbers, light stabilizers, heat stabilizers, and antifoaming agents. 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. The polymerizable compound and the compound (1) are copolymerized by irradiating ultraviolet rays while applying a voltage between the electrodes, thereby forming a polymer in the liquid crystal composition. At this time, the compound (1) is immobilized in a state where 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 the liquid crystal molecules is further improved, and the compound (1) does not leak into the liquid crystal composition. In addition, since a proper pretilt angle is obtained also on the surface of the glass (or metal oxide) substrate, a liquid crystal display element having a short response time and a large voltage holding ratio can be obtained.

Preferable examples of the polymerizable compound are acrylate, methacrylate, vinyl compound, vinyloxy compound, propenyl ether, epoxy compound (oxetane ) and vinyl ketone. Further preferable examples are a compound having at least one acryloyloxy group and a compound having at least one methacryloyloxy group. Further preferred examples include compounds having both an acryloyloxy group and a methacryloyloxy group.

Further preferable examples of the polymerizable compound are the compounds (M-1) to (M-17). In the compounds (M-1) to (M-17), R²⁵To R³¹Independently hydrogen or methyl; s, v and x are independently 0 or 1; t and u are independently integers from 1 to 10; l is²¹To L²⁶Independently of one another is hydrogen or fluorine, L²⁷And L²⁸Independently 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 residual polymerizable compound can be reduced. Examples of photo radical polymerization initiators are TPO, 1173 and 4265 of the Darocure (Darocure) series of the BASF company, 184, 369, 500, 651, 784, 819, 907, 1300, 1700, 1800, 1850 and 2959 of the Irgacure (Irgacure) series.

Additional examples of the photo radical polymerization initiator are 4-methoxyphenyl-2, 4-bis (trichloromethyl) triazine, 2- (4-butoxystyryl) -5-trichloromethyl-1, 3, 4-oxadiazole, 9-phenylacridine, 9, 10-benzophenazine, benzophenone/MILL's ketone mixture, hexaarylbiimidazole/mercaptobenzimidazole mixture, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, benzyldimethylketal, 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholinopropan-1-one, 2, 4-diethylxanthone/methyl p-dimethylaminobenzoate mixture, p-dimethylaminobenzoate, p-methyl-and p-dimethylaminobenzo, Benzophenone/methyl triethanolamine mixtures.

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

When the compound (1) having an ester bond, a cinnamate bond, a chalcone skeleton or a stilbene skeleton is mixed in the composition, 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, photodimerization, or cis-trans isomerization of a double bond is caused by polarization. Therefore, a film made of a polar compound aligns liquid crystal molecules in the same manner as an alignment film such as polyimide.

In the case of the compound (1) having an aromatic ester and a polymerizable group, irradiation with ultraviolet light causes photolysis of the aromatic ester moiety, thereby forming a radical and causing photofries rearrangement.

In the optical fries rearrangement, photodecomposition of the aromatic ester moiety occurs when the polarization direction of the polarized ultraviolet light is the same direction as the long axis direction of the aromatic ester moiety. After photolysis, recombination takes place and hydroxyl groups are produced in the molecule by tautomerization. It is considered that the polar compound is anisotropic and is easily adsorbed on the substrate interface side due to the interaction of the substrate interface caused by the hydroxyl group. Further, since the compound (1) has a polymerizable group, the compound (1) which reacts in the direction of polarization by polymerization is fixed without losing its directionality. The properties can be used to prepare films capable of orienting liquid crystal molecules. For the production of the film, the ultraviolet rays irradiated are suitably linearly polarized light. First, the compound (1) as a polar compound is added to the liquid crystal composition in a range of 0.1 to 10% by weight, and the composition is heated to dissolve the polar compound. The composition was injected into the element having no alignment film. Then, the element is heated and irradiated with linearly polarized light, thereby subjecting the polar compound to photo fries rearrangement and polymerization.

The photo-Fries-rearranged polar compound is aligned in a certain direction, and the resulting thin film after polymerization functions as a liquid crystal alignment film.

When the polymerizable compound is stored, a polymerization inhibitor may be added to prevent polymerization. The polymerizable compound is usually added to the composition in a state where the polymerization inhibitor is not removed. Examples of the polymerization inhibitor are hydroquinone, hydroquinone derivatives such as methyl hydroquinone, 4-t-butyl catechol, 4-methoxyphenol, phenothiazine and the like.

The optically active compound has an effect of inducing a helical structure in liquid crystal molecules to impart a desired twist angle and preventing reverse twist. By adding an optically active compound, the helix pitch can be adjusted. Two or more optically active compounds may also be added for the purpose of adjusting the temperature dependence of the helical pitch. 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, R²⁸Is an alkyl group having 1 to 10 carbon atoms.

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); brilliant Zeno (IRGANOX)415, Brilliant Zeno (IRGANOX)565, Brilliant Zeno (IRGANOX)1010, Brilliant Zeno (IRGANOX)1035, Brilliant Zeno (IRGANOX)3114, and Brilliant Zeno (IRGANOX)1098 (trade name: BASF corporation). In order to prevent the decrease of the upper limit temperature, the ultraviolet absorber is effective. Preferable examples of the ultraviolet absorber include benzophenone derivatives, benzoate derivatives, triazole derivatives and the like. Specific examples include: the following compound (AO-3) and compound (AO-4); bin (TINUVIN)329, Bin (TINUVIN) P, Bin (TINUVIN)326, Bin (TINUVIN)234, Bin (TINUVIN)213, Bin (TINUVIN)400, Bin (TINUVIN)328 and Bin (TINUVIN)99-2 (trade name: BASF corporation); and 1,4-Diazabicyclo [2.2.2] octane (1,4-Diazabicyclo [2.2.2] octane; triethylenediamine, 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); dennubin (TINUVIN)144, Dennubin (TINUVIN)765 and Dennubin (TINUVIN)770DF (trade name: BASF corporation). A heat stabilizer is also effective for maintaining a large voltage holding ratio, and a preferable example thereof is Brilliant enrichment (IRGAFOS)168 (trade name: BASF corporation). To prevent foaming, the antifoaming agent is effective. Preferable examples of the defoaming agent include dimethylsilicone oil, methylphenylsilicone oil and the like.

In the compound (AO-1), R⁴⁰Is alkyl with 1 to 20 carbon atoms, alkoxy with 1 to 20 carbon atoms, -COOR⁴¹or-CH₂CH₂COOR⁴¹Here, R⁴¹Is an alkyl group having 1 to 20 carbon atoms. In the compound (AO-2) and the compound (AO-5), R⁴²Is an alkyl group having 1 to 20 carbon atoms. In the compound (AO-5), R⁴³Is 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 liquid crystal display elements which have operation modes such as PC, TN, STN, OCB, PSA and the like and are driven in an active matrix manner. The composition can also be used for liquid crystal display elements which have PC, TN, STN, OCB, VA, IPS and other operation modes and are driven in a passive matrix mode. These elements can be applied to any of reflection type, transmission type, and semi-transmission type.

The composition can also be used for a Nematic Curvilinear Aligned Phase (NCAP) element prepared by microencapsulating a nematic liquid crystal, a Polymer Dispersed Liquid Crystal Display (PDLCD) element prepared by forming a three-dimensional network polymer in a liquid crystal, and a Polymer Network Liquid Crystal Display (PNLCD). When the addition amount of the polymerizable compound 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 ranges from about 0.1% to about 2% by weight based on the weight of the liquid crystal composition. Even more preferred proportions range from about 0.2 wt% to about 1.0 wt%, based on the weight of the liquid crystal composition. The PSA mode elements may be driven in an active matrix, passive matrix, or other driving manner. This element can be applied to any of reflection type, transmission type and semi-transmission type. By increasing the amount of the polymerizable compound to be added, an element of a polymer dispersed (polymer dispersed) mode can be produced.

In the polymer stabilized alignment type element, the polymer contained in the composition aligns the liquid crystal molecules. The compound (1) as a polar compound assists the liquid crystal molecules to align. That is, the compound (1) may be used instead of the alignment film. An example of a method for 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 composition is prepared by mixing liquid crystalline compounds. To the composition, a polymerizable compound and a compound (1) as a polar compound are added. Further additives may be added as required. Injecting the composition into an element. The element is irradiated with light. Ultraviolet rays are preferred. The polymerizable compound is polymerized by light irradiation. The element having a PSA pattern is produced by forming a composition containing a polymer by the polymerization.

A method of manufacturing a device is explained. The first step is to add the compound (1) as a polar compound to the liquid crystal composition and 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 irradiating polarized ultraviolet rays at a temperature at which the liquid crystal composition is heated to a temperature higher than the upper limit temperature. The compound (1) as a polar compound undergoes polymerization while undergoing any one of photofries rearrangement, photodimerization, and cis-trans isomerization of a double bond by linear polarization. The polymer of the compound (1) is formed as a thin film on a substrate and fixed. The polymer is aligned in a certain direction at a molecular level, and thus the film has a function as a liquid crystal alignment film. A liquid crystal display element having no alignment film such as polyimide can be manufactured by the method.

In the above-mentioned procedure, the compound (1) as a polar compound is present on the substrate in a biased manner because the polar group interacts with the surface of the substrate. The compound (1) is a compound that aligns liquid crystal molecules by irradiation of polarized ultraviolet rays, and at the same time, a polymerizable compound is polymerized by ultraviolet rays, thereby producing a polymer that maintains the alignment. By the effect of the polymer, the alignment of the liquid crystal molecules is more stabilized, and thus the response time of the element is shortened. The afterimage of the image is a poor operation of the 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 compound is copolymerized with another polymerizable compound while aligning liquid crystal molecules. 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 described in further detail with reference to examples (including synthetic examples and use examples of elements). The present invention is not limited to these examples. The invention comprises a mixture of the composition of use example 1 and the composition of use example 2. The present invention also encompasses mixtures prepared by mixing at least two of the compositions of the use examples.

1. Examples of Compound (1)

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

NMR analysis: for the measurement, DRX-500 manufactured by Bruker BioSpin was used. In that¹In the measurement of H-NMR, a sample was dissolved in CDCl₃The measurement was performed at room temperature under the conditions of 500MHz and 16 cumulative times in the deuterated solvent. Tetramethylsilane was used as an internal standard. In that¹⁹In the measurement of F-NMR, CFCl was used₃As an internal standard, measurement was performed 24 times in cumulative number. In the description of the nuclear magnetic resonance spectrum, s means a singlet, d means a doublet, t means a triplet, q means a quartet, quin means a quintet, sex means a sextuple, m means a multiplet, br means a broad peak.

Gas chromatographic analysis: for the measurement, a gas chromatograph model GC-2010 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 Inc. As carrier gas, helium (1 ml/min) was used. The sample vaporizer was set to 300 ℃ and the detector (flame ionization detector, FID) part was set to 300 ℃. The sample was prepared by dissolving in acetone to become a 1 wt% solution, and 1 μ l of the obtained solution was injected into the sample vaporization chamber. The recording meter is a GC dissolution (GC Solution) system manufactured by Shimadzu corporation, or the like.

High Performance Liquid Chromatography (HPLC) analysis: for the measurement, Proamice (LC-20 AD; SPD-20A) manufactured by Shimadzu corporation was used. The column was constructed using YMC-packed (YMC-Pack) ODS-A (length 150mm, inner diameter 4.6mm, particle diameter 5 μm) manufactured by Wimex (YMC). The dissolution liquid is used by appropriately mixing acetonitrile with water. As the detector, an Ultraviolet (UV) detector, a Refractive 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 254 nm. The sample was prepared by dissolving in acetonitrile to obtain a 0.1 wt% solution, and 1 μ L of the solution was introduced into the sample chamber. As a recording medium, a C-R7A strengthened plate (C-R7A plus) manufactured by Shimadzu corporation was used.

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

Measurement of the sample: when the phase structure and transition temperature (clearing point, melting point, polymerization initiation temperature, etc.) are measured, the compound itself is used as a sample.

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

(1) Phase structure

The sample was placed on a hot plate (FP-52 type hot stage (hot stage) of Mettler corporation) equipped with a melting point measuring apparatus of a polarizing microscope. The phase state and its change were observed by a polarization microscope while heating the sample at a rate of 3 ℃/min, and the type of phase was determined.

(2) Transition temperature (. degree.C.)

For the 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) was used. The temperature of the sample was raised and lowered at a rate of 3 ℃/min, and the initiation point of the endothermic peak 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 and the polymerization initiation temperature were also measured using the apparatus. The temperature at which the compound changes from a solid to a liquid crystal phase such as a smectic phase or a nematic phase is sometimes referred to as "lower limit temperature of liquid crystal phase". The temperature at which the compound changes from a liquid crystal phase to a liquid is sometimes simply referred to as "clearing point".

The crystals are denoted C. In the case of distinguishing the kind of crystal, each is asC₁、C₂That is shown. The smectic phase is denoted S and the nematic phase is denoted N. In the smectic phase, when the smectic A phase, the smectic B phase, the smectic C phase, or the smectic F phase are separated from each other, they are represented by S_A、S_B、S_COr S_F. The liquid (isotropic) is denoted as I. The transition temperature is expressed, for example, as "C50.0N 100.0I". It means that the temperature for self-crystallization to transition to a nematic phase was 50.0 ℃ and the temperature for transition from a nematic phase to a liquid was 100.0 ℃.

(3) Upper limit temperature (T) of nematic phase_NIOr NI; c.)

The sample was placed on a hot plate of a melting point measuring apparatus equipped with a polarizing microscope, and heated at a rate of 1 ℃ per minute. The temperature at which a part of the sample changes from nematic phase to isotropic liquid was measured. The upper limit temperature of the nematic phase may be simply referred to as "upper limit temperature". When the sample is a mixture of the compound (1) and a mother liquid crystal, T is used_NIIs denoted by the symbol (2). When the sample is a mixture of the compound (1) and compounds such as the component B, the component C, and the component D, the symbol NI is used.

(4) Lower limit temperature (T) of nematic phase_C；℃)

The nematic phase was observed after the sample was kept in a freezer at 0 ℃, -10 ℃, -20 ℃, -30 ℃ and-40 ℃ for 10 days. For example, when the sample is kept in a nematic phase at-20 ℃ and changes to a crystalline or smectic phase at-30 ℃_CSaid temperature is ≦ 20 ℃. The lower limit temperature of the nematic phase may be simply referred to as "lower limit temperature".

(5) Viscosity (bulk viscocity eta; measured at 20 ℃ C.; mPas)

For measurement, an E-type rotational viscometer manufactured by tokyo counter gmbh was used.

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

The measurement was performed by an Abbe refractometer having a polarizer attached to an eyepiece lens, using light having a wavelength of 589 nm. After rubbing the surface of the main prism in one direction, the sample was 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 ″) is measured when the direction of the polarized light is perpendicular to the direction of the rubbing. The value of the optical anisotropy (Δ n) is calculated from the formula Δ n ═ n/n ″.

(7) Specific resistance (. rho.; measured at 25 ℃ C.;. omega. cm)

1.0mL of the sample was injected into a container equipped with an electrode. A DC voltage (10V) was applied to the vessel, and a DC current after 10 seconds was measured. The specific resistance is calculated 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 method for measuring the positive dielectric anisotropy is described in the items (8a) to (12 a). When the dielectric anisotropy is negative, the measurement method is described in the items (8b) to (12 b).

(8a) Viscosity (rotational viscosity,. gamma.1; measured at 25 ℃ C.; mPas)

Positive dielectric anisotropy: the measurement was carried out according to the method described in "Molecular Crystals and Liquid Crystals" (vol.259, 37(1995)) of M.J.et al. A sample was placed in a TN cell having a twist angle of 0 degree and a gap (cell gap) of 5 μm between two glass substrates. The element was applied with a voltage in 0.5V unit in a stepwise manner in a range of 16V to 19.5V. After 0.2 seconds of no voltage application, voltage application was repeated with only one square wave (square pulse; 0.2 seconds) and without voltage application (2 seconds). The peak current (peak current) and peak time (peak time) of the transient current (transient current) resulting from the application are measured. Values of rotational viscosity were obtained from these measured values and the calculation formula (8) on page 40 of the paper by m. The value of the dielectric anisotropy necessary for the calculation was determined by the following method using an element obtained by measuring the rotational viscosity.

(8b) Viscosity (rotational viscosity,. gamma.1; measured at 25 ℃ C.; mPas)

Negative dielectric anisotropy: the measurement was carried out according to the method described in "Molecular Crystals and Liquid Crystals" (vol.259, 37(1995)) of M.J.et al. A VA device having a gap (cell gap) of 20 μm between two glass substrates was loaded with a sample. The element is applied with a voltage in 1 volt unit in a range of 39 volts to 50 volts in stages. After 0.2 seconds of no voltage application, voltage application was repeated with only one square wave (square pulse; 0.2 seconds) and without voltage application (2 seconds). The peak current (peak current) and peak time (peak time) of the transient current (transient current) resulting from the application are measured. Values of rotational viscosity were obtained from these measured values and the calculation formula (8) on page 40 of the paper by m. The dielectric anisotropy necessary for the calculation is a value measured using the term of dielectric anisotropy described below.

(9a) Dielectric anisotropy (. DELTA.. di-elect cons.; measured at 25 ℃ C.)

Positive dielectric anisotropy: a sample was placed in a TN cell having a cell gap of 9 μm between two glass substrates and a twist angle of 80 degrees. A sine wave (10V, 1kHz) was applied to the cell, and the dielectric constant (. epsilon. /) in the long axis direction of the liquid crystal molecules was measured after 2 seconds. Sine wave (0.5V, 1kHz) was applied to the element, and the dielectric constant (∈ ∈ in the short axis direction of the liquid crystal molecules was measured after 2 seconds. The value of the dielectric anisotropy is calculated from the formula Δ ∈ ═ ε/ε ″.

(9b) Dielectric anisotropy (. DELTA.. di-elect cons.; measured at 25 ℃ C.)

Negative dielectric anisotropy: the value of the dielectric anisotropy is calculated from the formula Δ ∈ ═ ε/ε ″. The dielectric constants (. epsilon./. epsilon. mu.j.) were measured as follows.

1) Measurement of dielectric constant (. epsilon. /): a solution of octadecyltriethoxysilane (0.16mL) in ethanol (20mL) was coated on the well-cleaned glass substrate. The glass substrate was rotated by a rotator and then heated at 150 ℃ for 1 hour. A VA device having a gap (cell gap) of 4 μm between two glass substrates was put in a sample, and the device was sealed with an adhesive cured by ultraviolet rays. A sine wave (0.5V, 1kHz) was applied to the cell, and the dielectric constant (. epsilon. /) in the long axis direction of the liquid crystal molecules was measured after 2 seconds.

2) Measurement of dielectric constant (. epsilon. DELTA. -): the polyimide solution was coated on the well-cleaned glass substrate. After the glass substrate is fired, the resulting alignment film is subjected to rubbing treatment. A sample was placed in a TN cell having a cell gap of 9 μm and a twist angle of 80 degrees between two glass substrates. Sine wave (0.5V, 1kHz) was applied to the element, and the dielectric constant (∈ ∈ in the short axis direction of the liquid crystal molecules was measured after 2 seconds.

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

Positive dielectric anisotropy: for the measurement, an LCR model HP4284A manufactured by Yokogawa Hewlett Packard, Inc. was used. A sample was placed in a horizontally oriented cell having a gap (cell gap) of 20 μm between two glass substrates. An electric charge of 0 to 20 volts was applied to the element, and the electrostatic capacitance and the applied voltage were measured. The values of the measured electrostatic capacitance (C) and the applied voltage (V) were fitted using the formulas (2.98) and (2.101) on page 75 of the "handbook for liquid crystal device" (journal of the japanese industrial press), and K was obtained from the formula (2.99)₁₁And K₃₃The value of (c). Then, in equation (3.18) on page 171, the K obtained before is used₁₁And K₃₃To calculate K₂₂. The elastic constant K is K obtained in this way₁₁、K₂₂And K₃₃Is expressed as an average value of (a).

(10b) Spring constant (K)₁₁And K₃₃(ii) a Measured at 25 ℃; pN)

Negative dielectric anisotropy: for the measurement, an EC-1 elastic constant measuring instrument manufactured by TOYO technical Co., Ltd was used. A sample was placed in a vertical alignment cell having a gap (cell gap) of 20 μm between two glass substrates. A charge of 20 to 0V was applied to the element, and the electrostatic capacitance and the applied voltage were measured. The values of the electrostatic capacitance (C) and the applied voltage (V) were fitted using the equations (2.98) and (2.101) in "liquid crystal device manual" (journal of japan industrial press) page 75, and the value of the elastic constant was obtained from the equation (2.100).

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

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

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

Negative dielectric anisotropy: a luminance meter of LCD5100 model manufactured by tsukau electronics gmbh was used for the measurement. The light source is a halogen lamp. A sample was placed in a VA element of a normally black mode (normal black mode) in which the gap between two glass substrates (cell gap) was 4 μm and the rubbing directions were antiparallel, and the element was sealed with an adhesive cured by ultraviolet light. The voltage applied to the element (60Hz, 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 prepared in which the transmittance was 100% when the light amount reached the maximum and the transmittance was 0% when the light amount was the minimum. The threshold voltage is represented by a voltage at which the transmittance becomes 10%.

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

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

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

Negative dielectric anisotropy: a luminance meter of LCD5100 model manufactured by tsukau electronics gmbh was used for the measurement. The light source is a halogen lamp. The Low-pass filter (Low-pass filter) is set to 5 kHz. A sample was placed in a PVA element of a normally black mode (normal black mode) in which the gap between two glass substrates (cell gap) was 3.2 μm and the rubbing directions were antiparallel. The element is sealed using an adhesive cured with ultraviolet rays. The element was applied with a voltage slightly exceeding the threshold voltage for 1 minute, and then irradiated with 23.5mW/cm while applying a voltage of 5.6V²Ultraviolet ray of (2) for 8 minutes. A square wave (60Hz, 10V, 0.5 sec) was applied to the element. At this time, the element was irradiated with light from the vertical direction, and the amount of light transmitted through the element was measured. The transmittance was 100% when the light amount reached the maximum, and the transmittance was 0% when the light amount was the minimum. The response time is expressed as the time (fall time; millisecond) required for the transmittance to change from 90% to 10%.

Raw materials

Solmix (registered trademark) A-11 is a mixture of ethanol (85.5%), methanol (13.4%) and isopropanol (1.1%) and was obtained from Nippon alcohol, Inc.

[ Synthesis example 1]

Synthesis of Compound (No.81)

First step of

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

Second step of

Compound (T-3) (1.55g), compound (T-4) (1.69g), DMAP (0.12g) and methylene chloride (100ml) were put into a reactor and cooled to 0 ℃. DCC (1.14g) was added thereto, and the mixture was 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 dichloromethane. The organic layer was washed with water and dried with anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (volume ratio, ethyl acetate: toluene: 1: 4), and reprecipitated with heptane, whereby compound (No.81) (2.34 g; 80%) was obtained. Further, the compound (T-4) is a known substance, and a synthesis method can be easily obtained by a person having ordinary skill in the art.

The NMR analysis value of the obtained compound (No.81) was as follows.

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

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

Transition temperature (. degree. C.): C82.5I polymerization temperature (. degree. C.): 136.49

[ Synthesis example 2]

Synthesis of Compound (No.165)

First step of

4-iodophenol (30.0g), trimethylsilylacetylene (16.1g), copper iodide (1.3g), Pd (PPh)₃)₂Cl₂(1.91g), Tetrahydrofuran (THF) (200ml) and triethylamine (200ml) were taken in a vessel and stirred overnight under a nitrogen atmosphere. To this was added THF (200ml), MeOH (200ml) and KF (15.8g), and the mixture was stirred overnight under an air atmosphere. The reaction mixture was poured into water, extracted with toluene, washed with water, then dried over anhydrous magnesium sulfate, and concentrated under reduced pressure to obtain a pale brown solid. The solid was dissolved and purified by silica gel column chromatography (vol., ethyl acetate: toluene-1: 4) to obtain compound (T-5) (12.7 g; 80%).

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

The NMR analysis value of the obtained compound (No.165) was as follows.

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

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

Transition temperature (. degree. C.): C80.0I polymerization temperature (. degree. C.): 230.8

[ Synthesis example 3]

Synthesis of Compound (No.148)

First step of

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

Second step of

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

The NMR analysis value of the obtained compound (No.148) was as follows.

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

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

Transition temperature (. degree. C.): C113.8I polymerization temperature (. degree. C.): 259.1

[ Synthesis example 4]

Synthesis of Compound (No.221)

First step of

4-iodo-2-methylphenol (6g), 1, 4-diethynylbenzene (1.53g), copper iodide (0.12g), Pd (PPh)₃)₂Cl₂(0.90g), THF (50ml) and triethylamine (50ml) were taken in a vessel and stirred overnight under nitrogen. The reaction mixture was poured into water, extracted with toluene, washed with water, then dried over anhydrous magnesium sulfate, and concentrated under reduced pressure to obtain a pale brown solid. The solid was dissolved in a mixed solution of MeOH (100ml) and THF (100ml), and purified by silica gel column chromatography (volume ratio, ethyl acetate: toluene ═ 1: 3). KF (7.7g) was added thereto, and stirred at room temperature overnight. The obtained product was concentrated and purified by silica gel column chromatography (vol., ethyl acetate: toluene-1: 4) to obtain compound (T-8) (2.95 g; 68%).

The latter two steps can be synthesized by the same procedure as in the first and second steps of Synthesis example 1, except that compound (T-8) is used in place of compound (T-1).

The NMR analysis value of the obtained compound (No.221) was as follows.

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

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

Transition temperature (. degree. C.): C77.22N 95.28I polymerization temperature (° C): 198.8

[ Synthesis example 5]

Synthesis of Compound (No.16)

In Synthesis example 1, compound (No.16) was synthesized by the same procedure as above except that compound (T-10) was used in place of compound (T-1) and compound (T-9) was used in place of compound (T-4). Further, the compound (T-9) and the compound (T-10) are known substances, and a synthesis method can be easily obtained by those skilled in the art.

The NMR analysis value of the obtained compound (No.16) was as follows.

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

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

Transition temperature (. degree. C.): C96.8N 154.3I polymerization temperature (° C): 176.8

[ Synthesis example 6]

Synthesis of Compound (No.158)

First step of

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

Second step of

Compound (T-12) (35.0g), trimethylsilylacetylene (15.6g), copper iodide (2.5g), Pd (PPh)₃)₂Cl₂(4.67g) and triethylamine (200ml) were collected in a vessel and stirred overnight. The reaction mixture was poured into water, extracted with toluene and usedThe extract was washed with water, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure to obtain a pale brown solid. The solid was dissolved in a mixed solution of methanol (100ml) and THF (100ml), and the resulting solution was purified by silica gel column chromatography (volume ratio, ethyl acetate: toluene ═ 1: 4). KF (7.7g) was added thereto, and stirred at room temperature overnight. The obtained product was concentrated and purified by silica gel column chromatography (vol., ethyl acetate: toluene-1: 4) to obtain compound (T-13) (17.9 g; 83%).

The third step

Compound (T-13) (32.5g), acrylic acid (20.0g), DMAP (2.7g) and methylene chloride (500ml) were placed in a reactor and cooled to 0 ℃. DCC (48.1g) was added thereto, and the mixture was 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 dichloromethane. The organic layer was washed with water and dried with anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (toluene) to obtain compound (T-14) (45 g; 93%).

The fourth step

Compound (T-14) (24.0g), trimethylsilylacetylene (54.5g), copper iodide (2.11g), Pd (PPh)₃)₂Cl₂(3.89g), THF (200ml) and triethylamine (200ml) were taken in a vessel and stirred overnight under oxygen. The reaction mixture was poured into water, extracted with toluene, washed with water, then dried over anhydrous magnesium sulfate, and concentrated under reduced pressure to obtain a pale brown solid. The solid was dissolved in a mixed solution of methanol (100ml) and THF (100ml), and the resulting solution was purified by silica gel column chromatography (volume ratio, ethyl acetate: toluene ═ 1: 4). KF (7.7g) was added thereto, and stirred at room temperature overnight. The obtained product was concentrated and purified by silica gel column chromatography (vol., ethyl acetate: toluene: 1: 4) to obtain compound (T-15) (12.6 g; 66%).

The fifth step

4-iodo-2-methylphenol (50.0g), compound (T-16) (65.5g), DMAP (5.2g) and dichloromethane (1000ml) were placed in a reactor and cooled to 0 ℃. DCC (46.2g) was added thereto, and the mixture was 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 dichloromethane. The organic layer was washed with water and dried with anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (vol., ethyl acetate: toluene ═ 1: 9) to obtain compound (T-17) (86 g; 79%).

The sixth step

Compound (T-17) (4.9g), compound (T-15) (2.2g), copper iodide (0.05g), Pd (PPh)₃)₂Cl₂(0.18g), THF (200ml) and triethylamine (200ml) were taken in a vessel and stirred overnight. The reaction mixture was poured into water, extracted with toluene, washed with water, then dried over anhydrous magnesium sulfate, and concentrated under reduced pressure to obtain a pale brown solid. The solid was dissolved and purified by silica gel column chromatography (volume ratio, ethyl acetate: toluene: 1: 9) to obtain compound (No.158) (21 g; 64.5%).

The NMR analysis value of the obtained compound (No.158) was as follows.

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

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

Transition temperature (. degree. C.): C77.9N 82.5I polymerization temperature (° C): 231.86

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

2. Examples of use of the elements

The compounds in the use examples are represented by symbols based on the definitions in table 2 below. In Table 2, the configuration of the 1, 4-cyclohexylene group-related solid is trans configuration. The numbers in brackets after the symbol correspond to the numbers of the compounds. The symbol (-) indicates other liquid crystalline compounds. The proportion (percentage) of the liquid crystalline compound is a weight percentage (wt%) based on the weight of the liquid crystal composition. Finally, the characteristic values of the liquid crystal composition are summarized.

TABLE 2 expression of compounds using symbols

R-(A₁)-Z₁-·····-Z_n-(A_n)-R’

1. Raw materials

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

[ composition (M1) ]

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

[ composition (M2) ]

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

[ composition (M3) ]

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

[ composition (M4) ]

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

[ composition (M5) ]

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

[ composition (M6) ]

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

[ composition (M7) ]

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

[ composition (M8) ]

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

[ composition (M9) ]

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

[ composition (M10) ]

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

[ composition (M11) ]

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

[ composition (M12) ]

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

[ composition (M13) ]

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

[ composition (M14) ]

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

[ composition (M15) ]

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

[ composition (M16) ]

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

[ composition (M17) ]

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

[ composition (M18) ]

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

[ composition (M19) ]

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

[ composition (M20) ]

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

[ composition (M21) ]

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

[ composition (M22) ]

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

[ composition (M23) ]

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

[ composition (M24) ]

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

[ composition (M25) ]

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

[ composition (M26) ]

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

[ composition (M27) ]

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

[ composition (M28) ]

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

[ composition (M29) ]

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

[ composition (M30) ]

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

[ composition (M31) ]

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

[ composition (M32) ]

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

[ composition (M33) ]

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

[ composition (M34) ]

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

[ composition (M35) ]

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

[ composition (M36) ]

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

[ composition (M37) ]

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

[ composition (M38) ]

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

[ composition (M39) ]

[ composition (M40) ]

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

[ composition (M41) ]

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

2. Alignment of liquid crystal molecules

Use examples 1 to 7

(preparation of sample)

The compound (No.148) as the first additive was added to the composition (M1) in an amount of 0.1 wt%, 0.3 wt%, 0.5 wt%, 1.0 wt%, 3.0 wt%, 5.0 wt%, 10.0 wt%, and R as an antioxidant was added in an amount of 150ppm⁴⁰A compound which is n-heptyl (AO-1). After stirring at 100 ℃ with heating, the temperature was returned to room temperature and left for one week, and as a result, the solution was completely dissolved without precipitation of crystals or the like.

(preparation of the element)

The mixture was injected at 90 ℃ (above the upper temperature limit of the nematic phase) into an IPS cell without alignment film. While heating the IPS device at 90 ℃, the device is irradiated with polarized ultraviolet rays having peaks at a wavelength of 313nm, a wavelength of 335nm, and a wavelength of 365nm from the normal direction for a certain period of time, thereby performing alignment treatment, and the irradiation is continued until the alignment becomes good.

(irradiation conditions of polarized ultraviolet rays)

Illumination at a wavelength of 313nm of 3mW/cm². UIT-150 and UVD-S313 manufactured by the Ushio electric machine company were used for the measurement.

As an ultraviolet radiation lamp, USH-250BY manufactured BY Ushio Motor corporation was used.

The exposure machine unit used ML-251A/B manufactured by Niacin (Ushio) Motor corporation.

Polarized ultraviolet rays were formed using a wire grid polarizer (ProFlux UVT260A manufactured by Polatechno (inc.).

(method of confirming orientation)

The element is parallel to the polarizing axis of linearly polarized light, and is disposed on a polarizing microscope in which a polarizing element and an analyzer are arranged orthogonally, and the element is irradiated with light from below to observe the presence or absence of light leakage. When light is not transmitted through the element, the orientation is determined to be "good". When light transmitted through the element is observed, it is determined that the alignment is "poor" and the irradiation is insufficient.

(evaluation of easiness of alignment)

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

Use examples 8 to 42

Using the composition (M1), R as an antioxidant was added in a proportion of 150ppm⁴⁰A compound (AO-1) which is an n-heptyl group, and the first additives were mixed in the ratio shown in Table 3 below. The operation was performed in the same manner as in use example 1. The irradiation time was measured by the same method as in example 1. The results are summarized in Table 3 below.

TABLE 3

In use examples 1 to 42, the compositions used were changed to M2 to M41, and the same operations were performed, resulting in: in any of the above cases, the irradiation time was not changed greatly.

The same operations were carried out with appropriate selection of the compositions from composition (M1) to composition (M41), the first addition of compound (No.1) to compound (No.224), and the results were: in any case, the irradiation time is 15 minutes or less.

Comparative examples 1 to 21

The compound (a-1-1-1), the compound (S-1) described in patent document 3, and the compound (S-2) described in patent document 2 were mixed as a first additive into the composition (M1) at the ratio shown in table 4 below, and the irradiation time was evaluated by the same procedure as in the working examples. As a result, in any of the compounds, when the longest irradiation time in the use example was 10 minutes, good alignment could not be obtained, and the irradiation time for confirming good alignment was 30 minutes or more, as compared with the compound according to the embodiment of the present invention. The same evaluations using the compositions (M2) to (M41) showed the same tendency as that of the case of using the composition (M1).

TABLE 4

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

Industrial applicability

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

Claims

1. A compound represented by formula (1).

In the formula (1), the reaction mixture is,

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

ring A¹Ring A²Ring A³And ring A⁴Independently 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 ] group]Phenanthrene-3, 17-diyl, 2,3,4,7,8,9,10,11,12,13,14,15,16, 17-decaTetrahydrocyclopenta [ a ]]Phenanthrene-3, 17-diyl group, (A-1) or (A-2), wherein at least one hydrogen in the ring may be 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, -Sp¹-P¹or-Sp²-P²In which at least one hydrogen may be substituted by fluorine or chlorine, and when a is 2, two rings A¹Can be different, when b is 2, two rings A⁴Can be different, (A-2) c is 2,3 or 4; wherein, ring A¹Ring A²Ring A³Or ring A⁴At least one of which is naphthalene-2, 6-diyl, phenanthrene-2, 7-diyl, a group represented by (A-1) or a group represented by (A-2);

Z¹、Z²、Z³、Z⁴and Z⁵Independently a single bond or an alkylene group having 1 to 10 carbon atoms, in which at least one-CH group₂At least one- (CH) which may be substituted by-O-, -CO-, -COO-, -OCO-or-OCOO-₂)₂-may be substituted by-CH-or-C ≡ C-, of which groups at least one hydrogen may be substituted by halogen; wherein Z is²、Z³Or Z⁴At least one of which is-COO-, -OCO-, -CH ═ CHCOO-, -OCOCH ═ CH-, -CH ═ CHCO-or-COCH ═ CH-, and when a is 2, two Z's are present¹Can be different, when b is 2, two Z' s⁵May be different;

P¹and P²Independently any one of the formulas (1b) to (1h)Based on the presence of a plurality of P's within the structure¹Or P²In the case of (2), each may be different;

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

2. The compound according to claim 1, wherein in formula (1),

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

ring A¹Ring A²Ring A³And ring A⁴Independently 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 ] group]Phenanthrene-3, 17-diyl, 2,3,4,7,8,9,10,11,12,13,14,15,16, 17-tetradecahydrocyclopenta [ a ]]Phenanthrene-3, 17-diyl group, (A-1) or (A-2), wherein at least one hydrogen in the ring may be 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, -Sp¹-P¹or-Sp²-P²In which at least one hydrogen may be substituted by fluorine or chlorine, and when a is 2, two rings A¹Can be different, when b is 2, two rings A⁴Can be different, (A-2) c is 2,3 or 4; wherein, ring A¹Ring A²Ring A³Or ring A⁴At least one of which is naphthalene-2, 6-diyl, phenanthrene-2, 7-diyl, a group represented by (A-1) or a group represented by (A-2);

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

3. The compound according to claim 1 or 2, which is represented by any one of formula (1-1) to formula (1-3).

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

ring A¹Ring A²Ring A³And ring A⁴Independently 1, 4-cyclohexylene group, 1, 4-phenylene group, naphthalene-2, 6-diyl group, pyrimidine-2, 5-diyl group, pyridine-2, 5-diyl group, fluorene-2, 7-diyl group, phenanthrene-2, 7-diyl group, anthracene-2, 6-diyl group, group represented by (A-1) or group represented by (A-2), in which at least one hydrogen may be substituted by fluorine, chlorine, an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an alkoxy group having 1 to 11 carbon atoms, an alkenyloxy group having 2 to 11 carbon atoms, -Sp¹-P¹or-Sp²-P²In which at least one hydrogen may be substituted by fluorine or chlorine, and when a is 2, two rings A¹Can be different, when b is 2, two rings A⁴Can be different, (A-2) c is 2,3 or 4; wherein, ring A¹Ring A²Ring A³Or ring A⁴At least one of which isNaphthalene-2, 6-diyl, phenanthrene-2, 7-diyl, a group represented by (A-1) or a group represented by (A-2);

P¹and P²Independently a group represented by any one of the formulae (1b) to (1h) in the structure, in which a plurality of P's are present¹Or P²May be different from each other;

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

R²is hydrogen, halogen, alkyl of carbon number 1 to 5, at least one hydrogen of the alkyl being substituted by halogen, at least one-CH₂Can be taken via-O-extractionGeneration;

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

ring A¹Ring A²Ring A³And ring A⁴Independently 1, 4-cyclohexylene group, 1, 4-phenylene group, naphthalene-2, 6-diyl group, fluorene-2, 7-diyl group, phenanthrene-2, 7-diyl group, group represented by (A-1) or group represented by (A-2), and in these rings, at least one hydrogen may be 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, -Sp¹-P¹or-Sp²-P²In the (A-2), c is 2,3 or 4; wherein, ring A¹Ring A²Ring A³Or ring A⁴At least one of which is naphthalene-2, 6-diyl, phenanthrene-2, 7-diyl, a group represented by (A-1) or a group represented by (A-2);

P¹and P²Independently a group represented by any one of formula (1b), formula (1c), formula (1d) or formula (1e) in the structure, in the presence of a plurality of P¹Or P²May be different from each other;

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

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

ring A¹Ring A²Ring A³And ring A⁴Independently 1, 4-cyclohexylene group, 1, 4-phenylene group, naphthalene-2, 6-diyl group, fluorene-2, 7-diyl group, phenanthrene-2, 7-diyl group, a group represented by (A-1) or a group represented by (A-2), in which at least one hydrogen in the ring may be substituted by fluorine, chlorine, methyl or ethyl, (A-2) c is 2,3 or 4; wherein, ring A¹Ring A²Ring A³Or ring A⁴At least one of which is naphthalene-2, 6-diyl, phenanthrene-2, 7-diyl, a group represented by (A-1) or a group represented by (A-2);

6. The compound according to claim 3, wherein in the compound represented by formula (1-1), formula (1-2) or formula (1-3), Z²、Z³Or Z⁴Any one of them is-COO-or-OCO-.

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

P¹-Sp¹-Y-Sp²-P² (1-A)

8. The compound according to claim 7, wherein in the compound represented by formula (1-A), Sp is¹And Sp²Independently an alkylene group having 1 to 10 carbon atoms, in which at least one-CH 2-may be substituted by-O-, -COO-, -OCOO-or-OCO-, and at least one- (CH)²)²-may be substituted by-CH ═ CH-.

9. A liquid crystal composition containing at least one of the compounds as claimed in any one of claims 1 to 8.

10. The liquid crystal composition according to claim 9, further comprising at least one compound selected from the group of compounds represented by formulae (2) to (4).

In the formulae (2) to (4),

R¹¹and R¹²Independently isAn alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms, at least one-CH group being present in the alkyl group or the alkenyl group₂-may be substituted by-O-, at least one hydrogen may be substituted by fluorine;

11. The liquid crystal composition according to claim 9 or 10, further comprising at least one compound selected from the group of compounds represented by formulae (5) to (7).

In the formulae (5) to (7),

L¹¹And L¹²Independently hydrogen or fluorine.

12. The liquid crystal composition according to any one of claims 9 to 11, further comprising at least one compound of the compounds represented by formula (8);

in the formula (8), the reaction mixture is,

X¹²is-C.ident.N or-C.ident.C-C.ident.N;

L¹³And L¹⁴Independently hydrogen or fluorine;

i is 1,2,3 or 4.

13. The liquid crystal composition according to any one of claims 9 to 12, further comprising at least one compound selected from the group of compounds represented by formulae (9) to (15).

In the formulae (9) to (15),

ring E⁵And ring E⁶Independently 1, 4-cyclohexylene, 1, 4-cyclohexenylene, 1, 4-phenylene, tetrahydropyran-2, 5-diyl, or decahydronaphthalene-2, 6-diyl;

L¹⁵And L¹⁶Independently fluorine or chlorine;

S¹¹is hydrogen or methyl;

x is-CHF-or-CF₂-；

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

In the formula (16), the compound represented by the formula,

Z²²and Z²³Independently a single bond or an alkylene group having 1 to 10 carbon atoms, in which at least one-CH group₂-may be substituted by-O-, -CO-, -COO-or-OCO-, at least one-CH₂CH₂-may be via-CH ═ CH-, -C (CH)₃)＝CH-、-CH＝C(CH₃) -or-C (CH)₃)＝C(CH₃) -substitution, of which at least one hydrogen may be substituted by fluorine or chlorine;

u is 0,1 or 2;

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

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

P¹¹、P¹²and P¹³Independently a polymerizable group selected from the group of groups represented by the formulae (P-1) to (P-3), wherein M is¹¹、M¹²And M¹³Independently hydrogen, fluorine, alkyl of carbon number 1 to 5 or alkyl of carbon number 1 to 5 wherein at least one hydrogen is substituted with a halogen:

16. The liquid crystal composition according to any one of claims 9 to 15, further comprising at least one of a polymerizable compound other than the compounds represented by the formulae (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 an antifoaming agent.

17. A liquid crystal display element comprising the liquid crystal composition according to any one of claims 9 to 16.