CN112334441B

CN112334441B - Polymerizable polar compound, liquid crystal composition, and liquid crystal display element

Info

Publication number: CN112334441B
Application number: CN201980040468.4A
Authority: CN
Inventors: 田中裕之; 稲垣顺一; 矢野智広; 矢野匡一
Original assignee: JNC Corp; JNC Petrochemical Corp
Current assignee: JNC Corp; JNC Petrochemical Corp
Priority date: 2018-06-27
Filing date: 2019-02-21
Publication date: 2023-08-01
Anticipated expiration: 2039-02-21
Also published as: WO2020003599A1; CN112334441A; TW202000637A; TWI823904B; JPWO2020003599A1; JP7248025B2

Abstract

The invention provides a liquid crystal display device with high chemical stabilityA polymerizable polar compound, a liquid crystal composition, and a liquid crystal display element, each of which has high capability of sub-alignment, high solubility in the liquid crystal composition, and high voltage holding ratio. A polymerizable compound represented by formula (1).

Description

Polymerizable polar compound, liquid crystal composition, and liquid crystal display element

Technical Field

The invention relates to a polymerizable polar compound, a liquid crystal composition and a liquid crystal display element. More specifically, the present invention relates to a compound having both a polymerizable group such as a methacryloxy group and a polymerizable group such as a propionyloxy group substituted with a polar group such as an-OH group, a liquid crystal composition containing the compound and having positive or negative dielectric anisotropy, and a liquid crystal display element containing the composition or a part of cured product thereof.

Background

When classifying the liquid crystal display element based on the operation mode of the liquid crystal molecules, the liquid crystal display element may be classified into Phase Change (PC), twisted Nematic (TN), super twisted nematic (super twisted nematic, STN), electrically controlled birefringence (electrically controlled birefringence, ECB), optically compensated bend (optically compensated bend, OCB), in-plane switching (IPS), vertical alignment (vertical alignment, VA), fringe field switching (fringe field switching, FFS), field-induced photo-reactive alignment (FPA), and the like. In addition, the driving method of the element can be classified into Passive Matrix (PM) and Active Matrix (AM). PM is classified into static type (static), multiplex type (multiplex) and the like, and AM is classified into thin film transistor (thin film transistor, TFT), metal-insulator-metal (metal insulator metal, MIM) and the like. Further, TFTs can be classified into amorphous silicon (amorphous silicon) and polysilicon (polycrystal silicon). The latter is classified into a high temperature type and a low temperature type according to the manufacturing steps. The classification based on the light source may be classified into a reflection type using natural light, a transmission type using backlight, and a semi-transmission type using both natural light and backlight.

The liquid crystal composition having a nematic phase has appropriate characteristics. By improving the characteristics of the composition, an AM element having good characteristics can be obtained. The correlation between the characteristics of the composition and the characteristics of the AM element is summarized in table 1 below.

TABLE 1 Properties of compositions and AM elements

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

The properties of the composition are further described based on commercially available AM elements. The temperature range of the nematic phase (the temperature range in which the nematic phase is present) is associated with the temperature range in which the element can be used. The preferable upper limit temperature of the nematic phase is about 70 ℃ or higher, and the preferable lower limit temperature of the nematic phase is about-10 ℃ or lower.

The viscosity of the composition is related to the response time of the element. In order to display a moving image in an element, the response time is preferably short. Ideally less than 1 millisecond of response time. Therefore, the viscosity of the composition is preferably low, and further, even at low temperature, the viscosity of the composition is more preferably low.

The optical anisotropy of the composition is related to the contrast of the element. Depending on the mode of the element, it is necessary that the optical anisotropy is large or small, that is, the optical anisotropy is appropriate. The product (Δn×d) of the optical anisotropy (Δn) of the composition and the cell gap (d) of the element is designed to maximize the contrast. The appropriate value of the product depends on the type of operation mode. In TN and the like mode elements, the value is about 0.45. Mu.m. In VA mode elements, the values are in the range of about 0.30 μm to about 0.40 μm, and in IPS mode or FFS mode elements, the values are in the range of about 0.20 μm to about 0.30 μm. In these cases, a composition having large optical anisotropy is preferable for an element having a small cell gap.

The large dielectric anisotropy of the composition contributes to low threshold voltage, low power consumption and high contrast of the element. Therefore, positive or negative dielectric anisotropy is preferably large. The high specific resistance of the composition contributes to a high voltage holding ratio and a high contrast ratio of the element. Therefore, a composition having a high specific resistance at not only room temperature but also a temperature close to the upper limit temperature of the nematic phase in the initial stage is preferable. It is preferable that the composition has a high specific resistance after a long period of use not only at room temperature but also at a temperature close to the upper limit temperature of the nematic phase.

The stability of the composition to ultraviolet light and heat is related to the lifetime of the element. When the stability is high, the lifetime of the element is long. Such characteristics are preferable for AM elements used in liquid crystal projectors, liquid crystal televisions, and the like.

In a liquid crystal display element of polymer stable alignment (polymer sustained alignment, PSA), a liquid crystal composition containing a polymer is used. First, a composition to which a small amount of a polymerizable compound is added is injected into an element. Here, a polymerizable compound having a plurality of polymerizable groups is generally used. Then, the composition is irradiated with ultraviolet rays while applying a voltage between substrates sandwiching the element. The polymerizable compound is polymerized to form a network of polymer in the composition. When the composition is used, the orientation of liquid crystal molecules can be controlled by the polymer, and thus the response time of the element is shortened and the afterimage of the image is improved. Such effects of the polymer can be expected for elements having a mode of TN, ECB, OCB, IPS, VA, FFS, FPA or the like.

In a general-purpose liquid crystal display element, vertical alignment of liquid crystal molecules is achieved by a polyimide alignment film. On the other hand, as a liquid crystal display element having no alignment film, a mode in which a polar compound is added to a liquid crystal composition to align liquid crystal molecules has been proposed. First, a composition to which a small amount of a polar compound and a small amount of a polymerizable compound are added is injected into an element. As the polymerizable compound, a polymerizable compound having a plurality of polymerizable groups is generally used. Here, the liquid crystal molecules are aligned by the action of the polar compound. Then, the composition is irradiated with ultraviolet rays while applying a voltage between substrates sandwiching the element. Here, the polymerizable compound is polymerized, and the orientation of the liquid crystal molecules is stabilized. If the composition is used, the alignment of liquid crystal molecules can be controlled by the polar compound and the polymer, and thus the response time of the element is shortened and the afterimage of the image is improved. Further, in the element having no alignment film, a step of forming the alignment film is not required. Since the alignment film is not present, there is no case where the resistance of the element is lowered due to the interaction of the alignment film and the composition. Elements having modes such as TN, ECB, OCB, IPS, VA, FFS, FPA can be expected to take advantage of such effects of a combination of polar compounds and polymers.

In a liquid crystal display element having no alignment film, a polymerizable polar compound has been synthesized as a compound having both the function of a polar compound and the function of a polymerizable compound (for example, patent document 1, patent document 2, and patent document 3). Patent document 1 describes a polymerizable compound (S-1) and a polymerizable compound (S-2) each having both a methacryloyloxy group and a polymerizable group substituted with-OH.

Prior art literature

Patent literature

Patent document 1: international publication No. 2017/209161

Patent document 2: international publication No. 2017/047177

Patent document 3: international publication No. 2016/129490

Disclosure of Invention

Problems to be solved by the invention

The first object of the present invention is to provide a compound which satisfies at least one of high chemical stability, high ability to orient liquid crystal molecules, high polymerization reactivity due to ultraviolet irradiation, and high solubility in a liquid crystal composition, and which has a high voltage holding ratio when used in a liquid crystal display element. The second object is to provide a liquid crystal composition containing the compound and satisfying at least one of the characteristics of high upper limit temperature of nematic phase, low lower limit temperature of nematic phase, low viscosity, proper optical anisotropy, large positive or negative dielectric anisotropy, large specific resistance, high stability to ultraviolet light, high stability to heat, large elastic constant and the like. The third object is to provide a liquid crystal display element having at least one of characteristics of a usable element such as a wide temperature range, a short response time, a high transmittance, a high voltage holding ratio, a low threshold voltage, a high contrast ratio, a long lifetime, and a good vertical alignment.

Technical means for solving the problems

The present invention relates to a compound represented by formula (1), a liquid crystal composition containing the compound, and a liquid crystal display element containing a polymer obtained by polymerizing the composition and/or at least a part of the composition.

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

R ¹ is hydrogen or alkyl of 1 to 15 carbon atoms, at least one of which is-CH ₂ -may be substituted by-O-or-S-, at least one- (CH) ₂ ) ₂ -may be substituted by-ch=ch-or-c≡c-, in which groups at least one hydrogen may be substituted by fluorine or chlorine;

ring A ¹ Ring A ² Independently 1, 2-cyclopropyl, 1, 3-cyclobutylidene, 1, 3-cyclopentyl, 1, 4-cyclohexyl, 1, 4-cycloheptylidene, 1, 4-cyclohexenylidene, 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, or pyridine-2, 5-diyl, wherein at least one hydrogen in these rings may be substituted by fluorine, chlorine, alkyl having 1 to 10 carbon atoms, alkenyl having 2 to 10 carbon atoms, alkoxy having 1 to 9 carbon atoms, or alkenyloxy having 2 to 9 carbon atoms, at least one hydrogen of these groups may be substituted by fluorine or chlorine;

a is 0, 1,2,3, or 4;

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

Sp ¹ 、Sp ² 、Sp ³ and Sp ⁴ Independently a single bond or an alkylene group of 1 to 10 carbon atoms, of which at least one-CH ₂ -can be substituted by-O-, -CO-, -COO-, -OCO-, or-OCOO-, at least one- (CH) ₂ ) ₂ -may be substituted by-ch=ch-or-c≡c-, in which groups at least one hydrogen may be substituted by fluorine or chlorine;

M ¹ 、M ² 、M ³ 、M ⁴ 、M ⁵ and M ⁶ Independently hydrogen, fluorine, chlorine, an alkyl group of 1 to 5 carbon atoms, or an alkyl group of 1 to 5 carbon atoms in which at least one hydrogen is substituted with fluorine or chlorine;

R ² r is R ³ Independently hydrogen or C1-10 alkyl, at least one of which-CH ₂ -optionally substituted by-O-at least one- (CH) ₂ ) ₂ -may be substituted by-ch=ch-or-c≡c-, in which groups at least one hydrogen may be substituted by fluorine or chlorine;

R ⁴ is a group selected from the group consisting of groups represented by formula (1-a), formula (1-b), and formula (1-c);

in the formula (1-a), the formula (1-b) and the formula (1-c),

Sp ⁵ sp and Sp ⁶ Independently a single bond or an alkylene group of 1 to 10 carbon atoms, of which at least one-CH ₂ -can be substituted by-O-, -CO-, -COO-, -OCO-, or-OCOO-, at least one- (CH) ₂ ) ₂ -may be substituted by-ch=ch-or-c≡c-, in which groups at least one hydrogen may be substituted by fluorine or chlorine;

R ⁵ Is hydrogen, alkyl of 1 to 10 carbon atoms, alkoxy of 1 to 9 carbon atoms, or alkoxyalkyl of 1 to 9 carbon atoms;

X ¹ independently-OH, -NH ₂ 、-N(R ⁶ ) ₂ -COOH, -SH, or-Si (R) ⁶ ) ₃ ；

-N(R ⁶ ) ₂ and-Si (R) ⁶ ) ₃ In the process, ,

R ⁶ is hydrogen or alkyl of 1 to 10 carbon atoms, at least one of which is-CH ₂ -optionally substituted by-O-at least one- (CH) ₂ ) ₂ -may be substituted by-ch=ch-, of which at least one hydrogen may be substituted by fluorine or chlorine.

ADVANTAGEOUS EFFECTS OF INVENTION

The first advantage of the present invention is to provide a compound which satisfies at least one of high chemical stability, high polymerization reactivity caused by ultraviolet irradiation, high ability to orient liquid crystal molecules, high solubility in a liquid crystal composition, and high voltage holding ratio in the case of being used for a liquid crystal display element. A second advantage is to provide a liquid crystal composition containing the compound and satisfying at least one of the characteristics of high upper limit temperature of a nematic phase, low lower limit temperature of a nematic phase, low viscosity, proper optical anisotropy, large positive or negative dielectric anisotropy, large specific resistance, high stability to ultraviolet light, high stability to heat, large elastic constant, and the like. A third advantage is to provide a liquid crystal display element having at least one of characteristics of a usable element such as a wide temperature range, a short response time, a high transmittance, a high voltage holding ratio, a low threshold voltage, a high contrast ratio, a long lifetime, and a good vertical alignment.

Detailed Description

The usage of the terms in the specification is as follows. The terms "liquid crystalline compound", "liquid crystal composition", and "liquid crystal display element" are sometimes abbreviated as "compound", "composition", and "element", respectively.

The "liquid crystalline compound" is a general term for a compound having a liquid crystal phase such as a nematic phase or a smectic phase, and a compound added for the purpose of adjusting the physical properties of a composition such as an upper limit temperature, a lower limit temperature, viscosity, or dielectric anisotropy, although not having a liquid crystal phase. The compound usually has a six-membered ring such as 1, 4-cyclohexylene or 1, 4-phenylene, and its molecular structure is rod-like.

The "polymerizable compound" is a compound added for the purpose of forming a polymer in the composition. The liquid crystalline compound having an alkenyl group is not a polymerizable compound in its meaning.

"polar compounds" are compounds that assist in alignment of liquid crystal molecules by polar groups interacting with substrate surfaces and the like.

The term "liquid crystal display element" refers to a general term for a liquid crystal display panel, a liquid crystal display module, or the like.

Liquid crystal compositions are generally prepared by mixing a plurality of liquid crystalline compounds. To the composition, 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, a pigment, and an antifoaming agent are added as needed for the purpose of further adjusting physical properties. The proportion (content) of the liquid crystalline compound in the liquid crystal composition is expressed by a weight percentage (wt%) based on the weight of the liquid crystal composition containing no additive even when the additive is added. The proportion (addition amount) of the additive in the liquid crystal composition is expressed by a weight percentage (wt%) based on the weight of the liquid crystal composition containing no additive. That is, the ratio of the liquid crystalline compound or the additive is calculated based on the total weight of the liquid crystalline compound. Weight parts per million (ppm) are also sometimes used. The proportion of the polymerization initiator and the polymerization inhibitor in the liquid crystal composition is expressed by the weight of the polymerizable compound.

The "transparent dot" is the transition temperature of the liquid crystal phase-isotropic phase in the liquid crystalline compound. The "lower limit temperature of liquid crystal phase" is the transition temperature of the solid-liquid crystal phase (smectic phase, nematic phase, etc.) in the liquid crystalline compound. The "upper limit temperature of the nematic phase" is a transition temperature of a nematic phase-isotropic phase in a mixture of a liquid crystalline compound and a mother liquid crystal or a liquid crystal composition, and is sometimes simply referred to as "upper limit temperature". The "lower limit temperature of the nematic phase" is sometimes simply referred to as "lower limit temperature". The expression "improving dielectric anisotropy" or "large dielectric anisotropy" means that the absolute value of the value thereof is increased or large. The term "the voltage holding ratio is large" means that the voltage holding ratio is large not only at room temperature but also at a temperature close to the upper limit temperature in the initial stage, and that the voltage holding ratio is also large not only at room temperature but also at a temperature close to the upper limit temperature after the element is used for a long time. In the composition or element, the characteristics may be studied before and after the time-lapse change test (including the accelerated degradation test). The expression "high solubility in a liquid crystal composition" means that the solubility is high with respect to any composition containing a liquid crystal compound at ordinary temperature, but as the composition, a composition for evaluating the solubility in the following examples may be used as a reference.

The compound represented by the formula (1) may be referred to simply as "compound (1)". The compound (1) is one compound represented by the formula (1), a mixture of two compounds, or a mixture of three or more compounds. The rule is also applicable to at least one compound selected from the group of compounds represented by formula (2), and the like.

A surrounded by hexagons ¹ 、B ¹ 、C ¹ Equal marks are respectively with ring A ¹ Ring B ¹ Ring C ¹ And the like. Hexagonal represents a six-membered ring such as a cyclohexane ring or a benzene ring, or a condensed ring such as a naphthalene ring. The straight line intersecting one side of the hexagon represents any hydrogen available on the ring via-Sp ¹ -P ¹ And the like.

f. Subscripts g, h, etc. represent the number of substituted groups. When the subscript is 0, no such substitution is present.

In the expression "ring a and ring C are independently X, Y, or Z", since the subject is plural, the expression "independently" is used. When the subject is "ring a is", since the subject is single, "independent" is not used.

In the chemical formula of the compound, the terminal group R ¹¹ The notation of (2) is used in a variety of compounds, but R in these compounds ¹¹ The radicals represented may be identical or different, respectively. For example, R in Compound (2) ¹¹ In the case of ethyl, R of the compound (3) ¹¹ The group may be an ethyl group or other groups such as propyl group. The rules are also applicable to other tokens. In the compound (8), when i is 2, two rings D are present ¹ . In the compound, two rings D ¹ The two groups represented may be the same or may be different. When i is greater than 2, the method is also applicable to any two rings D ¹ . The rules are also applicable to other tokens.

The expression "at least one of" A' "means that the number of" A "is arbitrary. The expression "at least one 'a' may be substituted with 'B' includes the case of 'a' itself not substituted with 'B', the case of one 'a' substituted with 'B', the case of two or more 'a' substituted with 'B', and in these cases, the position of 'a' substituted with 'B' is arbitrary. The rule that the substitution position is arbitrary also applies to the expression "at least one 'a' is substituted by 'B'. The expression "at least one A may be substituted by B, C, or D" is meant to include the cases where A is unsubstituted, at least one A is substituted by B, at least one A is substituted by C, and at least one A is substituted by D,And the case where a plurality of a are substituted with at least two of B, C, D. For example, at least one-CH ₂ - (or-CH) ₂ CH ₂ (-) alkyl which may be substituted by-O- (or-ch=ch-) includes alkyl, alkenyl, alkoxy, alkoxyalkyl, alkoxyalkenyl, alkenyloxyalkyl. Furthermore, two consecutive-CH ₂ -O-substitution to-O-is less preferred. In alkyl groups and the like, a methyl moiety (-CH) ₂ -CH of H) ₂ The case of-O-substitution to-O-H is also less preferred.

Sometimes use "R ¹¹ R is R ¹² Independently is an alkyl group of 1 to 10 carbon atoms or an alkenyl group of 2 to 10 carbon atoms, at least one of which-CH ₂ -may be substituted by-O-and of these groups at least one hydrogen may be substituted by fluorine. In the description, "in these bases" may be interpreted in accordance with the statement. In the expression, "these groups" refer to alkyl groups, alkenyl groups, alkoxy groups, alkenyloxy groups, and the like. That is, "these groups" means all groups described before the term "among these groups". The common sense interpretation is also applicable to other terms.

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

The present invention includes the following items and the like.

Item 1.

A compound represented by formula (1).

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

a is 0, 1,2,3, or 4;

in the formula (1-a), the formula (1-b) and the formula (1-c),

-N(R ⁶ ) ₂ and-Si (R) ⁶ ) ₃ In the process, ,

Item 2.

The compound according to item 1, wherein, in formula (1),

Z ¹ independently a single bond, - (CH) ₂ ) ₂ -、-(CH ₂ ) ₄ -、-CH＝CH-、-C≡C-、-COO-、-OCO-、-CF ₂ O-、-OCF ₂ -、-CH ₂ O-、-OCH ₂ -, or-cf=cf-.

Item 3.

The compound according to item 1 or item 2, wherein, in formula (1),

ring A ¹ Ring A ² Independently 1, 4-cyclohexylene, 1, 4-cyclohexenylene, 1, 4-phenylene, naphthalene-2, 6-diyl, tetrahydropyran-2, 5-diyl, 1, 3-dioxane-2, 5-diyl, pyrimidine-2, 5-diyl, or pyridine-2, 5-diyl, wherein at least one hydrogen in these rings is substituted by fluorine, chlorine, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkoxy group having 1 to 9 carbon atoms, or an alkenyloxy group having 2 to 9 carbon atoms, wherein at least one hydrogen in these groups is substituted by fluorine or chlorine.

Item 4.

The compound according to any one of items 1 to 3, which is represented by any one of formulas (1-1) to (1-4).

In the formulae (1-1) to (1-4),

R ¹ is an alkyl group having 1 to 15 carbon atoms, an alkenyl group having 2 to 15 carbon atoms, an alkoxy group having 1 to 14 carbon atoms, or an alkenyloxy group having 2 to 14 carbon atoms, at least one hydrogen of which may be substituted with fluorine;

Ring A ¹ Ring A ² Ring A ³ Ring A ⁴ Independently 1, 4-cyclohexylene, 1, 4-cyclohexenylene, 1, 4-phenylene, naphthalene-2, 6-diyl, tetrahydropyran-2, 5-diyl, or 1, 3-dioxane-2, 5-diyl, wherein at least one hydrogen in these rings is substituted by fluorine, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkoxy group having 1 to 9 carbon atoms, or an alkenyloxy group having 2 to 9 carbon atoms, wherein at least one hydrogen in these groups is substituted by fluorine;

Z ¹ 、Z ² and Z ³ Independently a single bond, - (CH) ₂ ) ₂ -、-CH＝CH-、-C≡C-、-COO-、-OCO-、-CF ₂ O-、-OCF ₂ -、-CH ₂ O-、-OCH ₂ -or-cf=cf-;

Sp ¹ 、Sp ² 、Sp ³ and Sp ⁴ Independently a single bond or an alkylene group of 1 to 7 carbon atoms, of which at least one-CH ₂ -can be prepared by-O-, -COO-; or-OCO-substitution, at least one- (CH) ₂ ) ₂ -may be substituted by-ch=ch-, of which groups at least one hydrogen may be substituted by fluorine;

M ¹ 、M ² 、M ³ 、M ⁴ 、M ⁵ and M ⁶ Independently hydrogen, fluorine, an alkyl group of 1 to 5 carbon atoms, or at least one hydrogen-fluorine substituted alkyl group of 1 to 5 carbon atoms;

R ² r is R ³ Independently hydrogen, C1-7 alkyl, C1-6 alkoxy, or C1-6 alkoxyalkyl, at least one of these groups- (CH) ₂ ) ₂ -may be substituted by-ch=ch-or-c≡c-, at least one hydrogen may be substituted by fluorine;

In the formula (1-a), the formula (1-b) and the formula (1-c),

R ⁵ is hydrogen, alkyl of 1 to 7 carbon atoms, alkoxy of 1 to 6 carbon atoms, or alkoxyalkyl of 1 to 6 carbon atoms;

X ¹ independently-OH, -NH ₂ -COOH, or-SH.

Item 5.

The compound according to any one of items 1 to 4, which is represented by any one of formulas (1-5) to (1-7).

In the formulae (1-5) to (1-7),

R ¹ is alkyl with 1-10 carbon atoms, alkenyl with 2-10 carbon atoms or alkoxy with 1-9 carbon atoms;

ring A ¹ Ring A ² Ring A ³ Ring A ⁴ Independently 1, 4-cyclohexylene, 1, 4-cyclohexenylene, 1, 4-phenylene, naphthalene-2, 6-diyl, tetrahydropyran-2, 5-diyl, or 1, 3-dioxane-2, 5-diyl, wherein at least one hydrogen in these rings may be substituted with fluorine, an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms;

Z ¹ 、Z ² and Z ³ Independently a single bond, - (CH) ₂ ) ₂ -、-CH＝CH-、-C≡C-、-CH ₂ O-, or-OCH ₂ -；

Sp ¹ 、Sp ² 、Sp ³ And Sp ⁴ Independently a single bond or an alkylene group of 1 to 5 carbon atoms, of which at least one-CH ₂ -optionally substituted by-O-at least one- (CH) ₂ ) ₂ -may be substituted with-ch=ch-;

R ² r is R ³ Independently is an alkyl group of 1 to 5 carbon atoms, an alkoxy group of 1 to 4 carbon atoms, or an alkoxyalkyl group of 1 to 4 carbon atoms, at least one hydrogen of which may be substituted with fluorine;

R ⁴ is a group selected from the group consisting of groups represented by the formula (1-a-1) and the formula (1-b-1);

in the formula (1-a-1) and the formula (1-b-1),

Sp ⁵ sp and Sp ⁶ Independently a single bond or an alkylene group of 1 to 10 carbon atoms, of which at least one-CH ₂ -may be substituted by-O-;

R ⁵ is hydrogen or alkyl of 1 to 7 carbon atoms.

Item 6.

The compound according to any one of items 1 to 5, which is represented by any one of formulas (1-8) to (1-37).

In the formulae (1-8) to (1-37),

ring A ¹ Ring A ² Ring A ³ Independently 1, 4-cyclohexylene or 1, 4-phenylene, in which rings at least one hydrogen may be substituted by fluorine, alkyl of 1 to 5 carbon atoms;

Z ¹ z is as follows ² Independently is a single bond or- (CH) ₂ ) ₂ -；

Sp ¹ 、Sp ² 、Sp ³ And Sp ⁴ Independently a single bond or an alkylene group of 1 to 5 carbon atoms, of which at least one-CH ₂ -may be substituted by-O-;

R ⁵ is hydrogen or alkyl with 1 to 5 carbon atoms.

Item 7.

The compound according to any one of items 1 to 6, which is represented by any one of formulas (1-38) to (1-49).

In the formulae (1-38) to (1-49),

R ¹ is alkyl with 1-10 carbon atoms;

Z ¹ z is as follows ² Independently is a single bond or- (CH) ₂ ) ₂ -；

Y ¹ 、Y ² 、Y ³ 、Y ⁴ 、Y ⁵ And Y ⁶ Independently hydrogen, fluorine, methyl, or ethyl;

Sp ¹ sp and Sp ⁴ Independently a single bond or an alkylene group of 1 to 5 carbon atoms, of which at least one-CH ₂ -may be substituted by-O-;

R ⁵ is hydrogen, methyl, or ethyl.

Item 8.

The compound according to any one of items 1 to 6, which is represented by any one of formulas (1-50) to (1-55).

In the formulae (1-50) to (1-55),

R ¹ is alkyl with 1-10 carbon atoms;

Z ¹ z is as follows ² Independently is a single bond or- (CH) ₂ ) ₂ -；

Y ¹ 、Y ² 、Y ³ 、Y ⁴ 、Y ⁵ And Y ⁶ Independently hydrogen, fluorine, methyl, or ethyl；

Sp ¹ Sp and Sp ⁴ Independently a single bond or an alkylene group of 1 to 5 carbon atoms, of which at least one-CH ₂ -may be substituted by-O-.

Item 9.

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

Item 10.

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

In the formulas (2) to (4),

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

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

Z ¹¹ 、Z ¹² and Z ¹³ Independently a single bond, -COO-, -CH ₂ CH ₂ -, -CH=CH-, or-C≡C-.

Item 11.

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

In the formulas (5) to (7),

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

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

Ring C ¹ Ring C ² Ring C ³ Independently 1, 4-cyclohexylene, 1, 4-phenylene, tetrahydropyran-2, 5-diyl, 1, 3-dioxane-2, 5-diyl, pyrimidine-2, 5-diyl, or at least one hydrogen-fluoro-substituted 1, 4-phenylene;

Z ¹⁴ 、Z ¹⁵ and Z ¹⁶ Independently a single bond, -COO-, -OCO-, -CH ₂ O-、-OCH ₂ -、-CF ₂ O-、-OCF ₂ -、-CH ₂ CH ₂ -, -CH=CH-, -C≡C-, or- (CH) ₂ ) ₄ -；

L ¹¹ L and L ¹² Independently hydrogen or fluorine.

Item 12.

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

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

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

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

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

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

L ¹³ l and L ¹⁴ Independently hydrogen or fluorine;

i is 1, 2, 3, or 4.

Item 13.

The liquid crystal composition according to any one of items 9 to 12, which contains at least one compound selected from the group of compounds represented by formulas (11) to (19).

In the formulae (11) to (19),

R ¹⁵ 、R ¹⁶ and R is ¹⁷ Independently is an alkyl group of 1 to 10 carbon atoms or an alkenyl group of 2 to 10 carbon atoms, at least one of which-CH ₂ -may be substituted by-O-, in which groups at least one hydrogen may be substituted by fluorine, and R ¹⁷ Hydrogen or fluorine;

ring E ¹ Ring E ² Ring E ³ Ring E and ring E ⁴ Independently 1, 4-cyclohexylene, 1, 4-cyclohexenylene, 1, 4-phenylene, tetrahydropyran-2, 5-diyl, decalin-2, 6-diyl, or at least one hydrogen fluorine substituted 1, 4-phenylene;

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

Z ¹⁸ 、Z ¹⁹ 、Z ²⁰ and Z ²¹ Independently a single bond, -COO-, -OCO-, -CH ₂ O-、-OCH ₂ -、-CF ₂ O-、-OCF ₂ -、-CH ₂ CH ₂ -、-CF ₂ OCH ₂ CH ₂ -, or-OCF ₂ CH ₂ CH ₂ -；

L ¹⁵ L and L ¹⁶ Independently fluorine or chlorine;

S ¹¹ is hydrogen or methyl;

x is-CHF-or-CF ₂ -；

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

t is 1,2, or 3.

Item 14.

The liquid crystal composition according to any one of items 9 to 13, which contains at least one polymerizable compound represented by formula (20) other than the compound represented by formula (1).

In the formula (20), the amino acid sequence of the compound,

ring F and ring I are independently cyclohexyl, cyclohexenyl, phenyl, 1-naphthyl, 2-naphthyl, tetrahydropyran-2-yl, 1, 3-dioxan-2-yl, pyrimidin-2-yl, or pyridin-2-yl, at least one hydrogen of which may be substituted with halogen, alkyl of 1 to 12 carbon atoms, alkoxy of 1 to 12 carbon atoms, or alkyl of 1 to 12 carbon atoms 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, phenanthrene-2, 7-diyl, tetrahydropyran-2, 5-diyl, 1, 3-dioxane-2, 5-diyl, pyrimidine-2, 5-diyl, or pyridine-2, 5-diyl, at least one hydrogen in these rings being substituted by halogen, alkyl of 1 to 12 carbon atoms, alkoxy of 1 to 12 carbon atoms, or at least one hydrogen is substituted by halogen-substituted alkyl of 1 to 12 carbon atoms;

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

P ¹¹ 、P ¹² p and P ¹³ Independently a polymerizable group;

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

u is 0, 1, or 2;

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

Item 15.

The liquid crystal composition according to item 14, wherein in the formula (20),

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

In the formulae (P-1) to (P-5),

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

Item 16.

The liquid crystal composition according to item 14 or item 15, wherein the polymerizable compound represented by formula (20) is at least one compound selected from the group of polymerizable compounds represented by formulas (20-1) to (20-7).

In the formulae (20-1) to (20-7),

L ³¹ 、L ³² 、L ³³ 、L ³⁴ 、L ³⁵ 、L ³⁶ 、L ³⁷ and L ³⁸ Independently hydrogen, fluorine, or methyl;

P ¹¹ 、P ¹² p and P ¹³ Independently a group selected from the group of polymerizable groups represented by the formulae (P-1) to (P-3),

in the formulae (P-1) to (P-3),

Item 17.

The liquid crystal composition according to any one of items 9 to 16, which contains at least one selected from the group consisting of a polymerizable compound different from the compound represented by formula (1) or (20), a polymerization initiator, a polymerization inhibitor, an optically active compound, an antioxidant, an ultraviolet absorber, a light stabilizer, a heat stabilizer, a pigment, and a defoaming agent.

Item 18.

A liquid crystal display element containing at least one selected from the group consisting of the liquid crystal composition according to any one of items 9 to 17 and a liquid crystal composition according to any one of items 9 to 17, at least a part of which is polymerized.

The present invention also includes the following items.

(a) The liquid crystal composition further contains at least two additives such as a polymerizable compound, a polymerization initiator, a polymerization inhibitor, an optically active compound, an antioxidant, an ultraviolet absorber, a light stabilizer, a heat stabilizer, a pigment, and a defoaming agent.

(b) A polymerizable composition is prepared by adding a polymerizable compound different from the compound (1) or the compound (20) to the liquid crystal composition.

(c) A polymerizable composition is prepared by adding a compound (1) and a compound (20) to the liquid crystal composition.

(d) A liquid crystal composite prepared by polymerizing the polymerizable composition.

(e) A polymer-stabilized aligned element comprising said liquid crystal composite.

(f) A polymer-stabilized alignment element is produced by using a polymerizable composition prepared by adding a compound (1) and a compound (20) and a polymerizable compound different from the compound (1) or the compound (20) 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 this order.

1. Morphology of Compound (1)

The compound (1) of the present invention is characterized in that: the liquid crystal composition has a mesogen portion composed of at least one ring, and has two polymerizable groups such as methacryloxy groups connected to the same carbon atom via a spacer, and an acryloxy group substituted with a polar group such as-OH. The compound (1) is useful because a polar group interacts with the surface of a substrate such as glass (or metal oxide) in a non-covalent bond. One of the uses is an additive for a liquid crystal composition used in a liquid crystal display element, in which the compound (1) is added for the purpose of controlling the orientation of liquid crystal molecules. Such an additive is preferably chemically stable under the condition of being sealed in an element, has a high ability to orient liquid crystal molecules, has a high voltage holding ratio when used in a liquid crystal display element, and has a high solubility in a liquid crystal composition. Since the compound (1) has two polymerizable groups such as methacryloyloxy groups connected to the same carbon atom via a spacer, a polymer network of good quality can be formed with high symmetry in polymerization, and thus the voltage holding ratio in the case of being used for a liquid crystal display element is extremely high, and an element excellent in orientation and long-term stability can be easily obtained as compared with the case of using a conventional compound.

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

R ¹ Is hydrogen or alkyl of 1 to 15 carbon atoms, at least one of which is-CH ₂ -may be substituted by-O-or-S-, at least one- (CH) ₂ ) ₂ -may be substituted by-ch=ch-or-c≡c-, in which groups at least one hydrogen may be substituted by fluorine or chlorine.

Preferred R ¹ Is an alkyl group having 1 to 15 carbon atoms, an alkenyl group having 2 to 15 carbon atoms, an alkoxy group having 1 to 14 carbon atoms, or an alkenyloxy group having 2 to 14 carbon atoms, and at least one hydrogen of these groups may be substituted with fluorine.

Further preferred R ¹ Is alkyl group with 1 to 10 carbon atoms, alkenyl group with 2 to 10 carbon atoms or alkoxy group with 1 to 9 carbon atoms.

Particularly preferred R ¹ Is an alkyl group having 1 to 10 carbon atoms.

R ¹ The chemical stability of the compound, which is an alkyl group having 1 to 15 carbon atoms or an alkoxy group having 1 to 14 carbon atoms, is high. R is R ¹ The solubility of the compound which is an alkyl group having 1 to 15 carbon atoms, an alkenyl group having 2 to 15 carbon atoms, or an alkenyloxy group having 2 to 14 carbon atoms in the liquid crystal composition is large. R is R ¹ The compound which is an alkyl group having 1 to 15 carbon atoms has a high ability to orient liquid crystal molecules.

Ring A ¹ Ring A ² Independently 1, 2-cyclopropyl, 1, 3-cyclobutyl, 1, 3-cyclopentyl, 1, 4-cyclohexyl, 1, 4-cycloheptylene, 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, or pyridine-2, 5-diyl, at least one hydrogen in these rings being substituted by fluorine, chlorine, alkyl having 1 to 10 carbon atoms, alkenyl having 2 to 10 carbon atoms, alkoxy having 1 to 9 carbon atoms, or alkenyloxy having 2 to 9 carbon atoms, at least one hydrogen in these groups being substituted by fluorine or chlorine.

Preferred ring A ¹ Ring A ² Is 1, 4-cyclohexylene, 1, 4-cyclohexenylene, 1, 4-phenylene, naphthalene-2, 6-diyl, tetrahydropyran-2, 5-diyl, 1, 3-dioxane-2, 5-diyl, pyrimidine-2, 5-diyl, or pyridine-2, 5-diyl, and at least one hydrogen in these rings is substituted with fluorine, chlorine, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkoxy group having 1 to 9 carbon atoms, or an alkenyloxy group having 2 to 9 carbon atoms, and at least one hydrogen in these groups is substituted with fluorine or chlorine.

More preferred ring A ¹ Ring A ² Is 1, 4-cyclohexylene, 1, 4-cyclohexenylene, 1, 4-phenylene, naphthalene-2, 6-diyl, tetrahydropyran-2, 5-diyl, or 1, 3-dioxane-2, 5-diyl, in which rings at least one hydrogen is substituted by fluorine, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkoxy group having 1 to 9 carbon atoms, or an alkenyloxy group having 2 to 9 carbon atoms, in which groups at least one hydrogen is substituted by fluorine.

Further preferred ring A ¹ Ring A ² Is 1, 4-cyclohexylene, 1, 4-cyclohexenylene, 1, 4-phenylene, naphthalene-2, 6-diyl, tetrahydropyran-2, 5-diyl, or 1, 3-dioxane-2, 5-diyl, and at least one hydrogen in these rings may be substituted with fluorine, an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms.

Particularly preferred ring A ¹ Ring A ² Is 1, 4-cyclohexylene, 1, 4-phenylene, 2-substituted 1, 4-phenylene, 3-substituted 1, 4-phenylene, or 2-and 3-substituted 1, 4-phenylene, and as the substituent, hydrogen, fluorine, an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, orAlkoxy having 1 to 4 carbon atoms, more preferably hydrogen, fluorine, methyl, or ethyl.

Ring A ¹ Ring A ² The chemical stability of the compound independently being 1, 3-cyclopentylene, 1, 4-cyclohexylene, 1, 4-cycloheptylene, 1, 4-phenylene in which at least one hydrogen is substituted by fluorine, 1, 4-phenylene in which at least one hydrogen is substituted by an alkyl group having 1 to 5 carbon atoms, decahydronaphthalene-2, 6-diyl, or tetrahydropyran-2, 5-diyl is high. Ring A ¹ Ring A ² The solubility of the compound independently being 1, 4-cyclohexylene, 1, 4-cyclohexenylene, 1, 4-phenylene, at least one hydrogen-fluorine-substituted 1, 4-phenylene, at least one hydrogen-substituted 1, 4-phenylene having 1 to 5 carbon atoms with an alkyl group, or at least one hydrogen-substituted 1, 4-phenylene having 2 to 5 carbon atoms with an alkenyl group in the liquid crystal composition is large. Ring A ¹ Ring A ² Compounds which are independently 1, 4-cyclohexylene, 1, 4-phenylene, or 1, 4-phenylene in which at least one hydrogen is substituted with an alkyl group having 1 to 2 carbon atoms have a high ability to orient liquid crystal molecules. Ring A ¹ Ring A ² The compounds independently being 1, 4-phenylene, 1, 4-phenylene in which at least one hydrogen is substituted with an alkyl group having 1 to 5 carbon atoms, 1, 4-phenylene in which at least one hydrogen is substituted with an alkoxy group having 1 to 4 carbon atoms, naphthalene-2, 6-diyl, pyrimidine-2, 5-diyl, or pyridine-2, 5-diyl are high in polymerization reactivity caused by ultraviolet irradiation.

a is 0, 1, 2, 3, or 4, preferably 0, 1, 2, or 3, more preferably 1, 2, or 3, and particularly preferably 1 or 2.

The solubility of the compound of which a is 0 in the liquid crystal composition is large. The compound of a is 3 or 4 has high ability to orient liquid crystal molecules. The compound a is 1 or 2 has high solubility in a liquid crystal composition, high ability to orient liquid crystal molecules, and high polymerization reactivity due to ultraviolet irradiation.

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

Preferred Z ¹ Is a single bond, - (CH) ₂ ) ₂ -、-(CH ₂ ) ₄ -、-CH＝CH-、-C≡C-、-COO-、-OCO-、-CF ₂ O-、-OCF ₂ -、-CH ₂ O-、-OCH ₂ -, or-cf=cf-.

More preferably Z ¹ Is a single bond, - (CH) ₂ ) ₂ -、-CH＝CH-、-C≡C-、-COO-、-OCO-、-CF ₂ O-、-OCF ₂ -、-CH ₂ O-、-OCH ₂ -, or-cf=cf-.

Further preferably Z ¹ Is a single bond, - (CH) ₂ ) ₂ -、-CH＝CH-、-C≡C-、-CH ₂ O-, or-OCH ₂ -, more preferably Z ¹ Is a single bond or- (CH) ₂ ) ₂ -, particularly preferred Z ¹ Is a single bond.

Z ¹ The chemical stability of the compound which is a single bond is high. Z is Z ¹ Is a single bond, - (CH) ₂ ) ₂ -、-CF ₂ O-, or-OCF ₂ The solubility of the compounds in the liquid-crystalline composition is great. Z is Z ¹ Is a single bond or- (CH) ₂ ) ₂ The ability of the compounds to orient the liquid crystal molecules is high. Z is Z ¹ Is a single bond, -CH=CH-, -C≡C-, -COO-, -OCO-, -CH ₂ O-、-OCH ₂ The compounds have high polymerization reactivity due to ultraviolet irradiation.

Sp ¹ 、Sp ² 、Sp ³ And Sp ⁴ Independently a single bond or an alkylene group of 1 to 10 carbon atoms, of which at least one-CH ₂ -can be substituted by-O-, -CO-, -COO-, -OCO-, or-OCOO-, at least one- (CH) ₂ ) ₂ -may be substituted by-ch=ch-or-c≡c-, in which groups at least one hydrogen may be substituted by fluorine or chlorine.

Preferred Sp ¹ 、Sp ² 、Sp ³ And Sp ⁴ Independently a single bond or an alkylene group of 1 to 7 carbon atoms, of which at least one-CH ₂ -can be prepared by-O-, -COO-; or-OCO-substitution, at least one- (CH) ₂ ) ₂ -may be substituted by-ch=ch-, of which groups at least one hydrogen may be substituted by fluorine.

Sp ¹ 、Sp ² 、Sp ³ And Sp ⁴ The chemical stability of the compound independently being a single bond or an alkylene group of 1 to 7 carbon atoms is high. Sp (Sp) ¹ 、Sp ² 、Sp ³ And Sp ⁴ At least one-CH independently being an alkylene group of 1 to 7 carbon atoms, or an alkylene group of 1 to 7 carbon atoms ₂ -the solubility of the-O-substituted radical compound in the liquid crystal composition is large.

More preferred Sp ¹ 、Sp ² 、Sp ³ And Sp ⁴ Independently a single bond or an alkylene group of 1 to 5 carbon atoms, of which at least one-CH ₂ -optionally substituted by-O-at least one- (CH) ₂ ) ₂ -may be substituted with-ch=ch-.

In terms of being a compound having more excellent solubility in the liquid crystal composition, the compound is particularly preferably:

Sp ² and Sp ³ An alkylene group having 1 to 5 carbon atoms or a single bond, at least one of the alkylene groups-CH ₂ -may be substituted by-O-, and is further preferably-CH ₂ -。

M ¹ 、M ² 、M ³ 、M ⁴ 、M ⁵ And M ⁶ Independently hydrogen, fluorine, chlorine, an alkyl group having 1 to 5 carbon atoms, or at least one alkyl group having 1 to 5 carbon atoms, preferably hydrogen, fluorine, an alkyl group having 1 to 5 carbon atoms, or at least one alkyl group having 1 to 5 carbon atoms, which is substituted with fluorine, and hydrogen is more preferable in terms of being a compound having particularly high polymerization reactivity due to ultraviolet irradiation.

R ² R is R ³ Independently hydrogen or C1-10 alkyl, at least one of which-CH ₂ -optionally substituted by-O-at least one- (CH) ₂ ) ₂ -may be substituted by-ch=ch-or-c≡c-, in which groups at least one hydrogen may be substituted by fluorine or chlorine.

Preferred R ² R is R ³ Independent and independentIs hydrogen, C1-7 alkyl, C1-6 alkoxy, or C1-6 alkoxyalkyl, at least one of these radicals- (CH) ₂ ) ₂ -may be substituted by-ch=ch-or-c≡c-, at least one hydrogen may be substituted by fluorine. R is further preferable in terms of being a compound which is more excellent in solubility in a liquid crystal composition, has high chemical stability, and has high ability to orient liquid crystal molecules ² R is R ³ Independently is an alkyl group of 1 to 5 carbon atoms, an alkoxy group of 1 to 4 carbon atoms, or an alkoxyalkyl group of 1 to 4 carbon atoms, at least one hydrogen of which may be substituted with fluorine. Particularly preferred R ² R is R ³ Is methyl.

R ⁴ Is a group selected from the group consisting of groups represented by the formula (1-a), the formula (1-b), and the formula (1-c). Preferred R ⁴ Is a group represented by the formula (1-a) or the formula (1-b).

At R ⁴ When the group represented by the formula (1-a) is used, the solubility in the liquid crystal composition is large, and the voltage holding ratio is large in the case of being used for a liquid crystal display element. At R ⁴ When the group represented by the formula (1-b) or the formula (1-c) is used, the ability to orient the liquid crystal molecules is high. At R ⁴ When the group represented by the formula (1-b) is used, the solubility in the liquid crystal composition is high, and the ability to orient liquid crystal molecules is high.

In the formula (1-a), the formula (1-b) and the formula (1-c), sp ² Sp and Sp ³ Independently a single bond or an alkylene group of 1 to 10 carbon atoms, of which at least one-CH ₂ -can be substituted by-O-, -CO-, -COO-, -OCO-, or-OCOO-, at least one- (CH) ₂ ) ₂ -may be substituted by-ch=ch-or-c≡c-, in which groups at least one hydrogen may be substituted by fluorine or chlorine.

Preferred Sp ⁵ Sp and Sp ⁶ Independently a single bond or an alkylene group of 1 to 10 carbon atoms, of which at least one-CH ₂ -optionally substituted by-O-at least one- (CH) ₂ ) ₂ Can be substituted by-ch=ch-, of which groups at least one hydrogen can beSubstituted with fluorine. More preferred Sp ⁵ Sp and Sp ⁶ An alkylene group having 1 to 10 carbon atoms, at least one of the alkylene groups being-CH ₂ -may be substituted by-O-.

Sp ⁵ Sp and Sp ⁶ The chemical stability of the compound independently being a single bond or an alkylene group of 1 to 10 carbon atoms is high. Sp (Sp) ⁵ Sp and Sp ⁶ At least one-CH independently being an alkylene group of 1 to 10 carbon atoms, or an alkylene group of 1 to 10 carbon atoms ₂ -the solubility of the-O-substituted compound in the liquid crystal composition is high, the ability to orient the liquid crystal molecules is high.

In the formula (1-b), R ⁵ Is hydrogen, alkyl of 1 to 10 carbon atoms, alkoxy of 1 to 9 carbon atoms, or alkoxyalkyl of 1 to 9 carbon atoms. Preferred R ⁵ Is hydrogen, alkyl of 1 to 7 carbon atoms, alkoxy of 1 to 6 carbon atoms, or alkoxyalkyl of 1 to 6 carbon atoms. Further preferred R ⁵ Is hydrogen or alkyl of 1 to 7 carbon atoms. Particularly preferred R ⁵ Is hydrogen or alkyl with 1 to 5 carbon atoms.

In the formula (1-a), the formula (1-b) and the formula (1-c), X ¹ independently-OH, -NH ₂ 、-N(R ⁶ ) ₂ -COOH, -SH, or-Si (R) ⁶ ) ₃ ，-N(R ⁶ ) ₂ and-Si (R) ⁶ ) ₃ Wherein R is ⁶ Is hydrogen or alkyl of 1 to 10 carbon atoms, at least one of which is-CH ₂ -optionally substituted by-O-at least one- (CH) ₂ ) ₂ -may be substituted by-ch=ch-, of which at least one hydrogen may be substituted by fluorine or chlorine.

Preferred X ¹ independently-OH, -NH ₂ -COOH, or-SH. Particularly preferred X ¹ is-OH. At X ¹ independently-OH, -NH ₂ In the case of-COOH or-SH, the ability to orient the liquid crystal molecules is high. At X ¹ In the case of-OH, the solubility in the liquid crystal composition is high, the ability to orient liquid crystal molecules is high, and the voltage holding ratio is high in the case of using the liquid crystal composition in a liquid crystal display element.

Examples of preferred compounds (1) are the compounds (1-1) to (1-4) described in item 4. More preferable examples of the compound (1) are the compounds (1-5) to (1-7) described in item 5. Further preferable examples of the compound (1) are the compounds (1-8) to (1-37) described in item 6. Examples of the most preferable compounds (1) are the compounds (1-38) described in item 7 to the compounds (1-49).

2. Synthesis of Compound (1)

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

2-1 Generation of bond groups

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

(I) Single bond formation

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

(II) -COO-and-OCO-formation

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

(III)-CF ₂ O-and-OCF ₂ -generation of

Compound (1B) was sulfided using Lawesson's reagent to give compound (26). Fluorination of Compound (26) with Hydrogen fluoride pyridine Complex and N-bromosuccinimide (NBS) to give a compound having-CF ₂ O-compound (1C). Reference is made to "chemical flash report (chem. Lett.)" of m. black star (m.kuroboshi) et al, 1992, 827. Compound (1C) can also be synthesized by fluorinating compound (26) with (diethylamino) sulfur trifluoride (DAST, sulphur trifluoride). Refer to "journal of organic chemistry (j. Org. Chem.)" in 1990, page 55 768, of w.h. banel (w.h. bunnelle) et al. with-OCF ₂ The compounds can also be synthesized by the process.

Formation of (IV) -ch=ch

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

(V)-CH ₂ CH ₂ -generation of

The compound (1D) is hydrogenated in the presence of a palladium carbon catalyst to synthesize the 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 comprising palladium dichloride and copper iodide, and then deprotected under basic conditions to give compound (29). Compound (29) and compound (22) are reacted in the presence of a catalyst comprising bis (triphenylphosphine) palladium dichloride and a copper halide to synthesize compound (1F).

(VII)-CH ₂ O-and-OCH ₂ -generation of

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

Formation of (VIII) -cf=cf

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

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

As the ring such as 1, 2-cyclopropylene, 1, 3-cyclobutylene, 1, 3-cyclopentylene, 1, 4-cyclohexylene, 1, 4-cycloheptylene, 1, 4-cyclohexenylene, 1, 4-phenylene, naphthalene-2, 6-diyl, decalin-2, 6-diyl, 1,2,3, 4-tetrahydronaphthalene-2, 6-diyl, tetrahydropyran-2, 5-diyl, 1, 3-dioxane-2, 5-diyl, pyrimidine-2, 5-diyl and pyridine-2, 5-diyl, the starting materials are commercially available or the synthesis method is known.

2-3 Synthesis examples

Examples of the method for synthesizing the compound (1) are as follows. In these compounds, R ¹ 、A ¹ 、A ² 、Z ¹ 、Sp ¹ 、Sp ⁴ And a are as defined in item 1.

In formula (1), sp ² Sp and Sp ³ is-CH ₂ -，M ¹ 、M ² 、M ³ And M ⁴ Is hydrogen, R ⁴ Sp is a group represented by the formula (1-a) ⁵ is-CH ₂ -，X ¹ The compound (1-51) which is-OH can be synthesized by the following method.

Sodium hydride and the compound (52) are allowed to act on the compound (51) to obtain a compound (53). Compound (54) is obtained by allowing palladium hydroxide to act on compound (53) under a hydrogen atmosphere. 3, 4-dihydro-2H-pyran and pyridine p-Toluenesulfonate (PPTS) was allowed to act on compound (54), to obtain compound (55). Compound (56) is obtained by reducing compound (55) with lithium aluminum hydride. After methacryloyl chloride and triethylamine were allowed to act on compound (56) to obtain compound (57), deprotection was performed using PPTS to obtain compound (58). Compound (1-51) can be obtained by reacting compound (58) with compound (59) in the presence of DCC and DMAP to obtain compound (60), and then deprotecting with PPTS.

In formula (1), sp ² Sp and Sp ³ is-CH ₂ -，M ¹ 、M ² 、M ³ And M ⁴ Is hydrogen, R ⁴ Sp is a group represented by the formula (1-a) ⁵ Is- (CH) ₂ ) ₂ -，X ¹ Compounds (1-52) which are-OH can be synthesized by the following method. The compounds (1-52) can be derived by brominating phosphorus tribromide on the compounds (1-51) and then allowing formaldehyde to act in the presence of an indium catalyst.

In formula (1), sp ² Sp and Sp ³ is-CH ₂ -，M ¹ 、M ² 、M ³ And M ⁴ Is hydrogen, R ⁴ Sp is a group represented by the formula (1-a) ⁵ is-CH ₂ O(CH ₂ ) _a -，X ¹ Compounds (1-53) which are-OH can be synthesized by the following method. By reacting trifluoromethanesulfonic anhydride (T)f ₂ After O) and triethylamine act on the compound (1-51), a diol (HO- (CH) corresponding to the carbon number a ₂ ) _a -OH) to give the compound (1-53).

In formula (1), sp ² Sp and Sp ³ is-CH ₂ -，M ¹ 、M ² 、M ³ And M ⁴ Is hydrogen, R ⁴ Sp is a group represented by the formula (1-b) ⁵ Sp and Sp ⁶ is-CH ₂ -，R ⁵ Is hydrogen, X ¹ Compounds (1-54) which are-OH can be synthesized by the following method.

The compound (61) was iodinated with iodine, triphenylphosphine, and imidazole to obtain a compound (62), and then reacted with the compound (63), sodium hydride, formaldehyde, and potassium carbonate in this order to obtain a compound (64). The compound (64) was hydrolyzed using lithium hydroxide to obtain a compound (65). Compounds (1-54) can be derived by reacting compound (58) with compound (65) in the presence of DCC and DMAP to obtain compound (66), and then deprotecting with PPTS.

3. Liquid crystal composition

3-1 component Compounds

The liquid crystal composition of the present invention contains the compound (1) as the component a. The compound (1) can control the orientation of liquid crystal molecules by interacting with the substrate of the element in a non-covalent bonding manner. The composition preferably contains the compound (1) as the component a, and further contains at least one liquid crystalline compound selected from the following components B, C, D, and E. Component B is compounds (2) to (4). Component C is compounds (5) to (7). Component D is compound (8). Component E is compounds (11) to (19). The composition may also contain other liquid crystalline compounds different from the compounds (2) to (8) and the compounds (11) to (19). In preparing the composition, it is preferable to select component B, component C, component D, and component E in consideration of the magnitude of positive or negative dielectric anisotropy, and the like. The composition of the components is appropriately selected to have a high upper limit temperature, a low lower limit temperature, a low viscosity, an appropriate optical anisotropy (i.e., large optical anisotropy or small optical anisotropy), a large positive or negative dielectric anisotropy, a large specific resistance, stability to heat or ultraviolet rays, and an appropriate elastic constant (i.e., large elastic constant or small elastic constant).

The compound (1) is added to the composition for the purpose of controlling the orientation of liquid crystal molecules. The proportion of the compound (1) is preferably 0.05 wt% or more in terms of easy alignment of liquid crystal molecules, etc., and preferably 10 wt% or less in terms of further preventing defective display of the element, etc., with respect to 100 wt% of the liquid crystal composition. Further, the preferable ratio is in the range of 0.1 to 7 wt%, and the particularly preferable ratio is in the range of 0.4 to 5 wt%. These proportions are also applicable to compositions comprising compound (20).

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

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

As the content of component B increases, the dielectric anisotropy of the composition becomes smaller, but the viscosity becomes smaller. Therefore, the content of the component B is more preferable as long as the required value of the threshold voltage of the element is satisfied. The content of the component B is preferably 30 wt% or more, more preferably 40 wt% or more, based on 100 wt% of the liquid crystal composition, and the upper limit thereof is not particularly limited, for example, 99.95 wt%.

Component C is a compound having fluorine, chlorine or a fluorine-containing group at least one terminal. Component C has a large positive dielectric anisotropy. Preferable examples of the component C include compounds (5-1) to (5-16), compounds (6-1) to (6-116), and compounds (7-1) to (7-59). In the compound of component C, R ¹³ Is an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms, at least one of the alkyl and alkenyl groups being-CH ₂ -may be substituted by-O-, at least one hydrogen may be substituted by fluorine; x is X ¹¹ Is fluorine, chlorine, -OCF ₃ 、-OCHF ₂ 、-CF ₃ 、-CHF ₂ 、-CH ₂ F、-OCF ₂ CHF ₂ or-OCF ₂ CHFCF ₃ 。

The component C has positive dielectric anisotropy and very good stability to heat, light and the like, and thus can be preferably used in the case of preparing a composition for a pattern such as IPS, FFS, OCB. The content of the component C is suitably in the range of 1 to 99% by weight, preferably in the range of 10 to 97% by weight, and more preferably in the range of 40 to 95% by weight, relative to 100% by weight of the liquid crystal composition. When component C is added to a composition having negative dielectric anisotropy, the content of component C is preferably 30% by weight or less relative to 100% by weight of the liquid crystal composition. By adding component C, the elastic constant of the composition can be adjusted and the voltage-transmittance curve of the element can be adjusted.

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

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

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, relative to 100% by weight of the liquid crystal composition. When component D is added to a composition having negative dielectric anisotropy, the content of component D is preferably 30% by weight or less relative to 100% by weight of the liquid crystal composition. By adding component D, the elastic constant of the composition can be adjusted and the voltage-transmittance curve of the element can be adjusted.

Component E is compounds (11) to (19). Component E has a large negative dielectric anisotropy. These compounds have a phenylene group substituted in the side position with two halogens (fluorine or chlorine) such as 2, 3-difluoro-1, 4-phenylene group. Preferable examples of the component E include compounds (11-1) to (11-9), compounds (12-1) to (12-19), compounds (13-1) and (13-2), compounds (14-1) to (14-3), compounds (15-1) to (15-3), compounds (16-1) to (16-11), compounds (17-1) to (17-3), compounds (18-1) to (18-3), and compounds (19-1). In these compounds, R ¹⁵ 、R ¹⁶ And R is ¹⁷ Independently is an alkyl group of 1 to 10 carbon atoms or an alkenyl group of 2 to 10 carbon atoms, at least one of which-CH ₂ -may be substituted by-O-, in which groups at least one hydrogen may be substituted by fluorine, and R ¹⁷ But also hydrogen or fluorine.

The dielectric anisotropy of component E is negative and large. Component E can be preferably used in the case of preparing a composition for a mode such as IPS, VA, PSA. As the content of the component E increases, the dielectric anisotropy of the composition becomes negative and large, but the viscosity becomes large. Therefore, the content is preferably small as long as the required value of the threshold voltage of the element is satisfied. When considering that the dielectric anisotropy is about-5, the content of the component E is preferably 40% by weight or more relative to 100% by weight of the liquid crystal composition in order to perform sufficient voltage driving.

In component E, the compound (11) is a bicyclic compound, and therefore has an effect of reducing viscosity, adjusting optical anisotropy, or improving dielectric anisotropy. Since the compound (12) and the compound (13) are tricyclic compounds and the compound (14) is tetracyclic compound, the effect of increasing the upper limit temperature, increasing the optical anisotropy, or increasing the dielectric anisotropy is exhibited. The compounds (15) to (19) have an effect of improving dielectric anisotropy.

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, relative to 100% by weight of the liquid crystal composition. When component E is added to a composition having positive dielectric anisotropy, the content of component E is preferably 30% by weight or less relative to 100% by weight of the liquid crystal composition. By adding component E, the elastic constant of the composition can be adjusted and the voltage-transmittance curve of the element can be adjusted.

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

3-2. Additives

The liquid crystal composition is prepared by an existing method. For example, a method of mixing the above-mentioned components and then dissolving them in each other by heating is mentioned. Additives may also be added to the composition according to the use. Examples of the additives are polymerizable compounds other than the compound (1), polymerization initiators, polymerization inhibitors, optically active compounds, antioxidants, ultraviolet absorbers, light stabilizers, heat stabilizers, pigments, antifoaming agents, and the like. Such additives are well known to those of ordinary skill in the art and are described in the literature.

The polymerizable compound is added for the purpose of forming a polymer in the liquid crystal composition. The compound (1) is polymerized by irradiating ultraviolet rays in a state where a voltage is applied between the electrodes, whereby a polymer can be produced. At this time, the compound (1) is immobilized in a state in which its polar group interacts with the substrate surface of the glass (or metal oxide) in a non-covalent bonding manner. Thus, the ability to control the alignment of liquid crystal molecules is further improved, and an appropriate pretilt angle can be obtained, and thus the response time can be shortened.

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

Particularly preferred examples of the polymerizable compound include compound (20). The compound (20) is a different compound from the compound (1). The compound (1) has a polar group. On the other hand, the compound (20) preferably has no polar group.

In formula (20), ring F and ring I are independently cyclohexyl, cyclohexenyl, phenyl, 1-naphthyl, 2-naphthyl, tetrahydropyran-2-yl, 1, 3-dioxan-2-yl, pyrimidin-2-yl, or pyridin-2-yl, at least one hydrogen of which may be substituted with halogen, alkyl of 1 to 12 carbon atoms, alkoxy of 1 to 12 carbon atoms, or alkyl of 1 to 12 carbon atoms substituted with halogen.

Preferred ring F or ring I is cyclohexyl, cyclohexenyl, phenyl, fluorophenyl, difluorophenyl, 1-naphthyl, or 2-naphthyl. Further preferred ring F or ring I is cyclohexyl, cyclohexenyl, or phenyl. Particularly preferred ring F or ring I is phenyl.

In the formula (20), the ring G is a 1, 4-cyclohexylene group, a 1, 4-cyclohexenylene group, a 1, 4-phenylene group, a naphthalene-1, 2-diyl group, a naphthalene-1, 3-diyl group, a naphthalene-1, 4-diyl group, a naphthalene-1, 5-diyl group, a naphthalene-1, 6-diyl group, a naphthalene-1, 7-diyl group, a naphthalene-1, 8-diyl group, a naphthalene-2, 3-diyl group, a naphthalene-2, 6-diyl group, a naphthalene-2, 7-diyl group, a phenanthrene-2, 7-diyl group, a tetrahydropyran-2, 5-diyl group, a 1, 3-dioxane-2, 5-diyl group, a pyrimidine-2, 5-diyl group, or a pyridine-2, 5-diyl group, and in these rings, at least one hydrogen may be substituted with halogen, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or at least one hydrogen is substituted with halogen.

Preferred rings G are 1, 4-cyclohexylene, 1, 4-cyclohexenylene, 1, 4-phenylene, 2-fluoro-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 and naphthalene-2, 7-diyl. Further, the ring G is preferably 1, 4-cyclohexylene, 1, 4-cyclohexenylene, 1, 4-phenylene, or 2-fluoro-1, 4-phenylene. Particularly preferred ring G is 1, 4-phenylene or 2-fluoro-1, 4-phenylene. Most preferred ring G is 1, 4-phenylene.

In the formula (20), Z ²² Z is as follows ²³ Independently a single bond or an alkylene group of 1 to 10 carbon atoms, of which at least one-CH ₂ -can be substituted by-O-, -CO-, -COO-, or-OCO-, at least one-CH ₂ CH ₂ Can be modified by-ch=ch-, -C (CH ₃ )＝CH-、-CH＝C(CH ₃ ) -, or-C (CH) ₃ )＝C(CH ₃ ) -substitution, in which at least one hydrogen may be substituted by fluorine or chlorine. Preferred Z ²² Or Z is ²³ Is a single bond, -CH ₂ CH ₂ -、-CH ₂ O-、-OCH ₂ -, -COO-, or-OCO-. Further preferably Z ²² Or Z is ²³ Is a single bond.

In the compound (20), P ¹¹ 、P ¹² P and P ¹³ Independently is a polymerizable group. Preferred P ¹¹ To P ¹³ Is a group selected from the group of polymerizable groups represented by the formulas (P-1) to (P-5). Further preferably P ¹¹ To P ¹³ Is a group represented by the formula (P-1), the formula (P-2), or the formula (P-3). Particularly preferred P ¹¹ To P ¹³ Is a group represented by the formula (P-1). A preferable group represented by the formula (P-1) is an acryloyloxy group (-OCO-CH=CH) ₂ ) Or methacryloxy (-OCO-C (CH) ₃ )＝CH ₂ ). The wavy lines of the formulae (P-1) to (P-5) represent the sites where bonding is performed.

In the formulae (P-1) to (P-5), M ¹¹ 、M ¹² And M ¹³ Independently hydrogen, fluorine, an alkyl group of 1 to 5 carbon atoms, or an alkyl group of 1 to 5 carbon atoms in which at least one hydrogen is substituted with halogen. In order to increase the reactivity, M is preferably ¹¹ 、M ¹² Or M ¹³ Is hydrogen or methyl. Further preferably M ¹¹ Is hydrogen or methyl, and further preferably M ¹² Or M ¹³ Is hydrogen.

In formula (20), sp ¹¹ 、Sp ¹² And Sp ¹³ Independently a single bond or an alkylene group of 1 to 10 carbon atoms, of which at least one-CH ₂ -can be substituted by-O-, -COO-, -OCO-, or-OCOO-, at least one-CH ₂ CH ₂ -may be substituted by-ch=ch-or-c≡c-, in which groups at least one hydrogen may be substituted by fluorine or chlorine. Preferred Sp ¹¹ 、Sp ¹² Or Sp ¹³ Is a single bond.

In formula (20), u is 0, 1, or 2. Preferably u is 0 or 1.

In formula (20), f, g, and h are independently 0, 1, 2, 3, or 4, and the sum of f, g, and h is 1 or more. Preferably f, g, or h is 1 or 2. The preferred sum is 2, 3 or 4. Further, the sum is preferably 2 or 3.

Preferred examples of the compound (20) are the compounds (20-1) to (20-7) and the compounds (20-8) to (20-11) described in item 15. Further preferable examples are the compound (20) 1-1) to compound (20-1-5), compound (20-2-1) to compound (20-2-5), compound (20-4-1), compound (20-5-1), compound (20-6-1), and compound (20-7-1). In these compounds, R ²⁵ To R ³¹ Independently hydrogen or methyl; r is R ³² 、R ³³ And R is ³⁴ Independently hydrogen or alkyl of 1 to 5 carbon atoms, and R ³² 、R ³³ And R is ³⁴ At least one of (2) is an alkyl group having 1 to 5 carbon atoms; v, and x are independently 0 or 1; t and u are independently integers from 1 to 10; t+v and x+u are each up to 10; l (L) ³¹ To L ³⁶ Independently hydrogen or fluorine, L ³⁷ L and L ³⁸ Independently hydrogen, fluorine, or methyl.

The polymerizable compound in the composition can be rapidly polymerized by using a polymerization initiator such as a photo radical polymerization initiator. In addition, by optimizing the reaction conditions at the time of polymerization, the amount of the remaining polymerizable compound can be reduced. Examples of the photo radical polymerization initiator include TPO, 1173, and 4265 in Darocure (Darocure) series of BASF corporation, and 184, 369, 500, 651, 784, 819, 907, 1300, 1700, 1800, 1850, and 2959 in Irgacure (Irgacure) series.

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

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

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

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

Antioxidants are effective for maintaining large voltage holding ratios. Preferred examples of the antioxidant include: the following compound (AO-1) and compound (AO-2); brilliant-jia-no (Irganox) 415, brilliant-jia-no (Irganox) 565, brilliant-jia-no (Irganox) 1010, brilliant-jia-no (Irganox) 1035, brilliant-jia-no (Irganox) 3114, and brilliant-jia-no (Irganox) 1098 (trade name; BASF).

The ultraviolet absorber is effective for preventing the upper limit temperature from decreasing. Preferable examples of the ultraviolet absorber include benzophenone derivatives, benzoate derivatives, triazole derivatives, and the like, and specific examples thereof include: the following compound (AO-3) and compound (AO-4); di Nun 329, di Nun P326, di Nun 234, di Nun 213, di Nun 400, di Nun 328, and Di Nun 99-2 (trade name; basf) company; and 1,4-Diazabicyclo [2.2.2] octane (1, 4-Diazabicyclo [2.2.2] octane; triethylenedimine, DABCO).

Light stabilizers such as hindered amines are preferred because they maintain a large voltage holding ratio. Preferred examples of the light stabilizer include: the following compound (AO-5), compound (AO-6) and compound (AO-7); di Nuvin 144, di Nuvin 765, di Nuvin 770DF (trade name; basf company); LA-77Y and LA-77G (trade name; ai Dike (ADEKA)) were used.

The heat stabilizer is also effective for maintaining a large voltage holding ratio, and preferred examples thereof include gorgeous (Irgafos) 168 (trade name; basf (BASF)).

In order to be suitable for a Guest Host (GH) mode element, a dichroic dye (dichromatic dye) such as an azo dye or an anthraquinone dye is added to the composition as needed.

To prevent foaming, an antifoaming agent is effective. Preferred examples of the antifoaming agent are simethicone, methyl phenyl silicone oil and the like.

In the compound (AO-1), R ⁴⁰ Alkyl of 1 to 20 carbon atoms, alkoxy of 1 to 20 carbon atoms, -COOR ⁴¹ or-CH ₂ CH ₂ COOR ⁴¹ Here, R is ⁴¹ Is an alkyl group having 1 to 20 carbon atoms. In the compound (AO-2) and the compound (AO-5), R ⁴² Is an alkyl group having 1 to 20 carbon atoms. In the compound (AO-5), R ⁴³ Is hydrogen, methyl or O ^· (oxygen radical); ring G ¹ 1,4-cyclohexylene or 1, 4-phenylene; in the compound (AO-7), ring G ² At least one hydrogen-substituted fluorine group that is 1, 4-cyclohexylene, 1, 4-phenylene, or 1, 4-phenylene; in the compound (AO-5) and the compound (AO-7), z is 1, 2, or 3.

4. Liquid crystal display element

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

The composition is also suitable for nematic curvilinear aligned phase (nematic curvilinear aligned phase, NCAP) elements, where the composition is microencapsulated. The composition may also be used in a polymer dispersed liquid crystal display element (polymer dispersed liquid crystal display, PDLCD) or a polymer network liquid crystal display element (polymer network liquid crystal display, PNLCD). To these compositions, a polymerizable compound is added in a large amount. On the other hand, regarding the composition for a liquid crystal display element of PSA mode, the proportion of the polymerizable compound is preferably 10% by weight or less, more preferably in the range of 0.1% by weight to 2% by weight, and still more preferably in the range of 0.2% by weight to 1.0% by weight, relative to 100% by weight of the liquid crystal composition. The PSA mode elements may be driven in an active matrix mode, a passive matrix mode, or the like. Such a device can be applied to any of a reflective type, a transmissive type, and a semi-transmissive type.

In the polymer-stabilized alignment element, the polymer contained in the composition aligns liquid crystal molecules. The polar compounds assist in alignment of the liquid crystal molecules. That is, a polar compound may be used instead of the alignment film. An example of a method of manufacturing such a device is as follows. An element having two substrates called an array substrate and a color filter substrate is prepared. The substrate has no alignment film. At least one of the substrates has an electrode layer. A liquid crystal composition is prepared by mixing liquid crystalline compounds. To the composition, the compound (1) and, if necessary, other polymerizable compounds and polar compounds are added. Additives may be further added as needed. The composition is injected into the component. The light irradiation is performed in a state where a voltage is applied to the element. Preferably ultraviolet light. The polymerizable compound is polymerized by light irradiation. A composition comprising a polymer is produced by the polymerization, thereby making an element having a PSA mode.

In the procedure, the polar compound is arranged on the substrate because the polar group interacts with the substrate surface. The polar compound orients the liquid crystal molecules. In the case where a plurality of polar groups are present, the interaction with the substrate surface becomes stronger, and orientation can be performed at a low concentration. When a voltage is applied, the alignment of the liquid crystal molecules is further promoted by the action of an electric field. Depending on the orientation, the polymerizable compound is also oriented. In this state, the polymerizable compound is polymerized by ultraviolet rays, and thus a polymer maintaining the orientation is produced. By the effect of the polymer, the orientation of the liquid crystal molecules is additionally stabilized, and thus the response time of the element is shortened. Since the afterimage of an image is a defective operation of liquid crystal molecules, the afterimage is also improved by the effect of the polymer. Since the compound (1) is polymerizable, it is consumed by polymerization. The compound (1) is also consumed by copolymerization with another polymerizable compound. Therefore, the compound (1) has a polar group but is consumed, and thus a liquid crystal display element having a large voltage holding ratio can be obtained. Further, when a polar compound having polymerizability is used, the effect of both the polar compound and the polymerizable compound can be achieved by one compound, and therefore, a polymerizable compound having no polar group may not be required.

Examples

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

1. Examples of Compound (1)

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

NMR analysis: DRX-500 manufactured by Bruker Biospin was used for the measurement. At the position of ¹ In the measurement of H-NMR, a sample was dissolved in CDCl ₃ The measurement was performed in an isotonic medium at room temperature under conditions of 500MHz and 16 times of cumulative number of times. Tetramethylsilane was used as an internal standard. At the position of ¹⁹ In the determination by F-NMR, CFCl was used ₃ As an internal standard, measurement was performed 24 times in total. In the description of nuclear magnetic resonance spectroscopy, s refers to a single peak (single), d refers to a double peak (doublet), t refers to a triple peak (triplet), q refers to a quadruple peak (quateset), quint refers to a quintet peak (quintet), sett refers to a hexa peak (setet), m refers to a multiple peak (multiplet), and br refers to a broad peak (broad).

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

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

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

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

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

(1) Phase structure

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

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

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

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

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

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

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

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

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

For measurement, an E-type rotational viscometer manufactured by Tokyo counter (Strand) was used.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

Negative dielectric anisotropy: for measurement, an LCD5100 type luminance meter manufactured by tsukamu electronics (stock) was used. The light source is a halogen lamp. A sample was placed in a VA element having a gap (cell gap) between two glass substrates of 4 μm and a normally black mode (normally black mode) having an antiparallel rubbing direction, and the element was sealed with an adhesive cured by ultraviolet rays. The voltage (60 Hz, rectangular wave) applied to the element was increased stepwise from 0V to 20V in units of 0.02V. At this time, the element was irradiated with light from the vertical direction, and the amount of light transmitted through the element was measured. A voltage-transmittance curve was produced in which the transmittance was 100% when the light amount was maximum and 0% when the light amount was minimum. The threshold voltage is expressed as a voltage at which the transmittance becomes 10%.

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

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

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

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

(13) Voltage holding ratio

Ultraviolet rays were irradiated with invisible light (black light) F40T10/BL (peak wavelength 369 nm) manufactured by Eye Graphics (strand), thereby polymerizing the polymerizable compound. The element was charged by applying a pulsed voltage (1V and 60 microseconds) at 60 ℃. The decaying voltage was measured with a high-speed voltmeter for a period of 1.67 seconds to determine the area a between the voltage curve and the horizontal axis of the unit cycle. Area B is the area when unattenuated. The voltage holding ratio is expressed as a percentage of the area a to the area B.

Raw materials

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

Synthesis example 1

Synthesis of Compound (1-2-1)

First step

Sodium hydride (6.52 g) and Tetrahydrofuran (THF) (380 ml) were placed in a reactor and cooled to 0 ℃. A solution of compound (T-1) (39.3 g) in THF (210 ml) was slowly added dropwise thereto, and the mixture was stirred for 20 minutes while returning to room temperature. Benzyl chloromethyl ether (27.5 ml) was added dropwise thereto, and heated under reflux at 55℃for 6 hours. The reaction mixture was poured into water, and the aqueous layer was extracted with ethyl acetate. The obtained organic layer was washed with water, and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (volume ratio, heptane: ethyl acetate=10:1) to give compound (T-2) (38.6 g; 75%).

A second step of

Compound (T-2) (38.6 g), palladium hydroxide (1.93 g), toluene (115 ml), and IPA (115 ml) were placed in a reactor, and stirred under a hydrogen atmosphere at room temperature for 12 hours. The catalyst was separated by filtration, concentrated under reduced pressure, and the residue was purified by silica gel chromatography (volume ratio, heptane: ethyl acetate=2:1) to obtain compound (T-3) (25.0 g; 79%).

Third step

Compound (T-3) (25.0 g), 3, 4-dihydro-2H-pyran (5.45 g), and methylene chloride (250 ml) were placed in a reactor, and cooled to 0 ℃. Pyridine p-toluene sulfonate (PPTS) (1.48 g) was slowly added thereto, and stirred for 8 hours while returning to room temperature. The reaction mixture was poured into water, and the aqueous layer was extracted with dichloromethane. The obtained organic layer was washed with water, and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (volume ratio, heptane: ethyl acetate=10:1) to give compound (T-4) (29.7 g; 99%). Further, THP represents a tetrahydropyranyl group.

Fourth step

Lithium aluminum hydride (3.68 g) and THF (300 ml) were placed in a reactor and cooled to 0 ℃. A solution of Compound (T-4) (29.7 g) in THF (200 ml) was slowly added dropwise thereto, and the mixture was stirred for 2 hours while returning to room temperature. The reaction mixture was poured into a saturated aqueous ammonium chloride solution, and after insoluble matter was separated by filtration, the aqueous layer was extracted with ethyl acetate. The obtained organic layer was washed with brine, and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure to obtain compound (T-5) (19.7 g; 77%).

Fifth step

Compound (T-5) (8.00 g), triethylamine (7.88 ml), and THF (160 ml) were placed in a reactor, and cooled to 0 ℃. Methacryloyl chloride (4.56 ml) was slowly added dropwise thereto, and the mixture was stirred for 8 hours while returning to room temperature. The reaction mixture was poured into water, and the aqueous layer was extracted with ethyl acetate. The obtained organic layer was washed with water, and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (volume ratio, heptane: ethyl acetate=10:1) to obtain compound (T-6) (6.84 g; 65%).

Sixth step

Compound (T-6) (6.84 g), PPTS (1.53 g), THF (34.0 ml), and methanol (34.0 ml) were placed in a reactor, and stirred at 50℃for 4 hours. The reaction mixture was poured into water, and the aqueous layer was extracted with ethyl acetate. The obtained organic layer was washed with water, and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure and the residue was purified by silica gel chromatography (volume ratio, heptane: ethyl acetate=4:1). Further, the mixture was recrystallized from a mixed solvent of heptane and ethyl acetate (volume ratio: 20:1) to obtain compound (T-7) (3.77 g; 65%).

Seventh step

Compound (T-8) (1.77 g), compound (T-7) (3.77 g), DMAP (0.483 g) and methylene chloride (45.0 ml) synthesized according to the method described in WO2017209161A1 were placed in a reactor and cooled to 0 ℃. To this was slowly added dropwise a solution of DCC (2.45 g) in methylene chloride (10.0 ml) and stirred for 12 hours while returning to room temperature. After insoluble matter was separated by filtration, the reaction mixture was poured into water, and the aqueous layer was extracted with methylene chloride. The obtained organic layer was washed with water, and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (volume ratio, heptane: ethyl acetate=6:1) to give compound (T-9) (5.05 g; 99%).

Eighth step

Compound (T-9) (5.05 g), PPTS (0.984 g), THF (25.0 ml), and methanol (25.0 ml) were placed in a reactor, and stirred at 50℃for 4 hours. The reaction mixture was poured into water, and the aqueous layer was extracted with ethyl acetate. The obtained organic layer was washed with water, and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure and the residue was purified by silica gel chromatography (volume ratio, heptane: ethyl acetate=3:1). Further, the mixture was recrystallized from a mixed solvent of heptane and ethyl acetate (volume ratio, 5:1) to obtain compound (1-2-1) (3.30 g; 75%).

The NMR analysis values of the obtained compound (1-2-1) were as follows.

¹ H-NMR: chemical shift delta (ppm; CDCl) ₃ )：6.22(s,1H)，6.08(s,2H)，5.86(s,1H)，5.58(t,J＝1.2Hz,2H),4.45-4.38(m,2H)，4.38-4.29(m,6H)，2.22(t,J＝6.4Hz,1H)，1.93(s,6H)，1.86-1.78(m,4H)，1.78-1.65(m,4H)，1.55-1.48(m,2H)，1.34-1.07(m,10H)，1.07-0.78(m,11H).

Synthesis example 2

Synthesis of Compound (1-2-15)

First step

Trifluoromethanesulfonic anhydride (43.6 g) and methylene chloride (230 ml) were placed in a reactor and cooled to 0 ℃. To this was slowly added dropwise a solution of compound (T-10) (30.9 g) and triethylamine (37.1 ml) in methylene chloride (460 ml). The obtained solution was poured into ethylene glycol (500 ml) and stirred at room temperature for 12 hours. The reaction mixture was poured into water, and the aqueous layer was extracted with dichloromethane. The obtained organic layer was washed with water, and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (volume ratio, heptane: ethyl acetate=1:1) to obtain compound (T-11) (21.9 g; 51%).

A second step of

Using the compound (T-11) (19.6 g) as a starting material, compound (T-12) (29.0 g; 97%) was obtained by the same method as the third step of synthesis example 1.

Third step

Compound (T-12) (29.0 g), THF (145 ml), and water (145 ml) were placed in a reactor, and cooled to 0 ℃. Lithium hydroxide monohydrate (9.96 g) was added thereto, and stirred for 8 hours while returning to room temperature. The reaction mixture was poured into water, and 10% aqueous citric acid (150 ml) was gradually added thereto to make it acidic, followed by extraction of the aqueous layer with ethyl acetate. The obtained organic layer was washed with water, and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure to give compound (T-13) (26.0 g; 95%).

Fourth step

Using the compound (T-14) (40.0 g) as a starting material, compound (T-15) (50.1 g; 97%) was obtained by the same method as the first step of synthesis example 1.

Fifth step

Using the compound (T-15) (50.1 g) as a starting material, compound (T-16) (40.4 g; 97%) was obtained by the same method as the second step of synthesis example 1.

Sixth step

Using the compound (T-16) (40.4 g) as a starting material, compound (T-17) (43.2 g; 90%) was obtained by the same method as the third step of synthesis example 1.

Seventh step

Using the compound (T-17) (43.2 g) as a starting material, compound (T-18) (30.1 g; 83%) was obtained by the same method as the fourth step of synthesis example 1.

Eighth step

Using compound (T-18) (30.1 g) as a starting material, compound (T-19) (25.2 g; 63%) was obtained by the same method as in the fifth step of synthesis example 1.

Ninth step

Using the compound (T-19) (25.2 g) as a starting material, compound (T-20) (18.1 g; 84%) was obtained by the same method as in the sixth step of synthesis example 1.

Tenth step

Using compound (T-20) (5.00 g) and compound (T-13) (3.19 g) as starting materials, compound (T-21) (6.66 g; 94%) was obtained by the same method as in the seventh step of synthesis example 1.

Eleventh step

Using compound (T-21) (6.66 g) as a starting material, compound (1-2-15) (2.10 g; 36%) was obtained by the same method as in the eighth step of synthesis example 1.

The NMR analysis values of the obtained compound (1-2-15) were as follows.

¹ H-NMR: chemical shift delta (ppm; CDCl) ₃ )：6.32(d,J＝0.7Hz,1H)，6.11(s,2H)，5.91(d,J＝1.2Hz,1H)，5.61(t,J＝1.2Hz,2H),4.25(s,2H)，4.19(s,2H)，4.17(s,4H)，3.81-3.75(m,2H)，3.66-3.61(m,2H)，2.31(t,J＝6.3Hz,1H)，1.96(s,6H)，1.80-1.66(m,8H)，1.56-1.50(m,2H)，1.36-0.80(m,25H).

Synthesis example 3

Synthesis of Compound (1-2-27)

First step

Compound (T-22) (150 g), triphenylphosphine (350 g), imidazole (175 g), and toluene (2.25 l) were placed in a reactor, and cooled to 0 ℃. Iodine (326 g) was slowly added thereto, and the mixture was stirred for 2 hours while returning to room temperature. After insoluble matter was separated by filtration, the reaction mixture was poured into water, and the aqueous layer was extracted with ethyl acetate. The obtained organic layer was washed with a saturated aqueous sodium thiosulfate solution, and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (volume ratio, toluene: ethyl acetate=10:1) to give compound (T-23) (197g; 75%).

A second step of

Sodium hydride (21.8 g) and THF (800 ml) were placed in a reactor, and a solution of compound (T-24) (107 g) in THF (240 ml) was slowly dropped and stirred for 1 hour, followed by cooling to 0 ℃. A solution of compound (T-23) (61.0 g) in THF (360 ml) was slowly added dropwise thereto, and heated under reflux at 55℃for 6 hours. The reaction mixture was poured into water, and the aqueous layer was extracted with ethyl acetate. The obtained organic layer was washed with brine, and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure. The obtained intermediate was put into another reactor together with formaldehyde (28.6 g), potassium carbonate (65.8 g), and water (610 ml), and stirred at 80℃for 6 hours. The aqueous layer was extracted with ethyl acetate, and the obtained organic layer was washed with water and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (volume ratio, toluene: ethyl acetate=15:1) to give compound (T-25) (19.6 g; 36%).

Third step

Using compound (T-25) (19.6 g) as a starting material, compound (T-26) (15.4 g; 95%) was obtained by the same method as the third step of synthesis example 2.

Fourth step

Using compound (T-20) (5.00 g) and compound (T-26) (2.78 g) as starting materials, compound (T-27) (6.53 g; 96%) was obtained by the same method as in the seventh step of synthesis example 1.

Fifth step

Compound (T-27) (6.53 g), PPTS (0.478 g), THF (100 ml), and methanol (100 ml) were placed in a reactor, and stirred at room temperature for 3 hours. The reaction mixture was poured into water, and the aqueous layer was extracted with ethyl acetate. The obtained organic layer was washed with water, and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure and the residue was purified by silica gel chromatography (volume ratio, toluene: ethyl acetate=1:2). Further, the mixture was recrystallized from a mixed solvent of heptane and toluene (volume ratio, 5:1) to obtain compound (1-2-27) (5.05 g; 82%).

The NMR analysis values of the obtained compound (1-2-27) were as follows.

¹ H-NMR: chemical shift delta (ppm; CDCl) ₃ )：6.24(s,1H)，6.10(s,2H)，5.66(s,1H)，5.60(t,J＝1.2Hz,2H)，4.15(s,6H)，3.80-3.72(m,2H)，3.67-3.60(m,2H)，2.55(t,J＝5.7Hz,2H)，2.35(d,J＝7.4Hz,2H)，1.94(s,6H)，1.87-1.79(m,1H)，1.78-1.64(m,8H)，1.55-1.48(m,2H)，1.34-1.03(m,12H)，1.03-0.78(m,13H).

Synthesis example 4

Synthesis of Compound (1-2-3)

First step

Using the compound (T-20) (12.0 g) as a starting material, a compound (T-28) (13.1 g; 82%) was obtained by the same method as in the sixth step of synthesis example 1.

A second step of

Using the compound (T-28) (13.1 g) as a starting material, compound (1-2-3) (10.1 g; 88%) was obtained by the same method as in the seventh step of synthesis example 1.

The NMR analysis values of the obtained compound (1-2-3) were as follows.

¹ H-NMR: chemical shift delta (ppm; CDCl) ₃ )：6.24(s,1H)，6.09(s,2H)，5.87(d,J＝1.0Hz,1H)，5.59(t,J＝1.3Hz.2H),4.35-4.31(m,2H)，4.19-4.12(m,6H)，2.28(t,J＝6.5Hz,1H)，1.94(s,6H)，1.78-1.64(m,8H)，1.54-1.47(m,2H)，1.33-0.78(m,25H).

Synthesis example 5

Synthesis of Compound (1-3-4)

First step

Using the compound (T-29) (32.0 g) as a starting material, compound (T-30) (34.7 g; 87%) was obtained by the same method as the first step of synthesis example 1.

A second step of

Using the compound (T-30) (34.7 g) as a starting material, compound (T-31) (22.8 g; 77%) was obtained by the same method as the second step of synthesis example 1.

Third step

Using the compound (T-31) (22.8 g) as a starting material, compound (T-32) (24.5 g; 93%) was obtained by the same method as the third step of synthesis example 1.

Fourth step

Using the compound (T-32) (24.5 g) as a starting material, compound (T-33) (21.1 g; 100%) was obtained by the same method as in the fourth step of synthesis example 1.

Fifth step

Using compound (T-33) (21.1 g) as a starting material, compound (T-34) (15.0 g; 56%) was obtained by the same method as in the fifth step of synthesis example 1.

Sixth step

Using the compound (T-34) (15.0 g) as a starting material, a compound (T-35) (13.0 g; 99%) was obtained by the same method as in the sixth step of synthesis example 1.

Seventh step

Using the compound (T-35) (13.0 g) as a starting material, compound (T-36) (16.0 g; 95%) was obtained by the same method as in the seventh step of synthesis example 1.

Eighth step

Using compound (T-36) (16.0 g) as a starting material, compound (1-3-4) (5.86 g; 41%) was obtained by the same method as in the eighth step of synthesis example 1.

The NMR analysis values of the obtained compound (1-3-4) were as follows.

¹ H-NMR: chemical shift delta (ppm; CDCl) ₃ )：7.12(d,J＝8.1Hz,2H)，7.05(d,J＝8.1Hz,2H)，6.26(s,1H)，6.12(s,2H)，5.89(d,J＝1.1Hz,1H)，5.61(t,J＝1.2Hz,2H),4.36-4.32(m,2H)，4.26-4.22(m,6H)，2.67-2.60(m,2H)，2.41(tt,J＝12.2Hz,J＝3.3Hz,1H)，2.23(t,J＝6.4Hz,1H)，1.95(s,6H)，1.92-1.70(m,10H)，1.45-1.34(m,2H)，1.34-0.94(m,15H)，0.91-0.81(m,5H).

Synthesis example 6

Synthesis of Compound (1-3-40)

First step

Using the compound (T-37) (2.12 g) synthesized by the same method as in the first step to the sixth step of Synthesis example 5 as a starting material, compound (T-38) (2.57 g; 95%) was obtained by the same method as in the sixth step of Synthesis example 1.

A second step of

Using compound (T-38) (2.57 g) as a starting material, compound (1-3-40) (1.70 g; 74%) was obtained by the same method as in the seventh step of synthesis example 1.

The NMR analysis values of the obtained compound (1-3-40) were as follows.

¹ H-NMR: chemical shift delta (ppm; CDCl) ₃ )：7.17(d,J＝8.1Hz,2H)，7.07(d,J＝8.1Hz,2H)，6.28(s,1H)，6.14(s,2H)，5.91(s,1H)，5.63(s,2H)，4.36-4.32(m,2H)，4.27-4.23(m,6H)，2.68-2.62(m,2H)，2.45(tt,J＝12.1Hz,J＝3.3Hz,1H)，2.29(t,J＝6.4Hz,1H)，1.97(s,6H)，1.90-1.60(m,8H)，1.50-0.80(m,28H).

Synthesis example 7

Synthesis of Compound (1-2-37)

First step

Sodium hydride (4.96 g) and THF (200 ml) were placed in a reactor and cooled to 0 ℃. A solution of Compound (T-14) (32.0 g) in THF (120 ml) was slowly added dropwise thereto, and the mixture was stirred for 20 minutes while returning to room temperature. Benzyl 2-chloroethyl ether (23.3 ml) was added dropwise thereto, and heated under reflux at 55℃for 6 hours. The reaction mixture was poured into water, and the aqueous layer was extracted with ethyl acetate. The obtained organic layer was washed with water, and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (volume ratio, heptane: ethyl acetate=10:1) to give compound (T-39) (32.5 g; 77%).

A second step of

Using compound (T-39) (32.5 g) as a starting material, compound (T-40) (19.9 g; 73%) was obtained by the same method as the second step of synthesis example 1.

Third step

Using compound (T-40) (19.9 g) as a starting material, compound (T-41) (22.1 g; 94%) was obtained by the same method as in the third step of synthesis example 1.

Fourth step

Using compound (T-41) (22.1 g) as a starting material, compound (T-42) (17.8 g; 95%) was obtained by the same method as in the fourth step of synthesis example 1.

Fifth step

Using the compound (T-42) (17.8 g) as a starting material, compound (T-43) (15.2 g; 66%) was obtained by the same method as the fifth step of synthesis example 1.

Sixth step

Using the compound (T-43) (15.2 g) as a starting material, compound (T-44) (12.9 g; 99%) was obtained by the same method as in the sixth step of synthesis example 1.

Seventh step

Using compound (T-44) (2.00 g) as a starting material, compound (T-45) (1.74 g; 95%) was obtained by the same method as in the seventh step of synthesis example 1.

Eighth step

Using compound (T-45) (1.74 g) as a starting material, compound (1-2-37) (1.12 g; 73%) was obtained by the same method as in the eighth step of synthesis example 1.

The NMR analysis values of the obtained compound (1-2-37) were as follows.

¹ H-NMR: chemical shift delta (ppm; CDCl) ₃ )：6.23(s,1H)，6.09(s,2H)，5.84(s,1H)，5.58(t,J＝1.0Hz,2H),4.35-4.27(m,4H)，4.13-4.05(m,4H)，2.26(t,J＝6.4Hz,1H)，1.94(s,6H)，1.83(t,J＝6.7Hz,2H)，1.78-1.63(m,8H)，1.50-1.42(m,2H)，1.33-0.78(m,25H).

Comparative example 1

As comparative compounds, the compound (S-1) and the compound (S-2) were synthesized, and the characteristics were measured. Such compounds are described in International publication No. 2017/209261 and are similar to the compounds of the present invention, and are selected.

NMR analysis values of the comparative compound (S-1) are as follows.

¹ H-NMR: chemical shift delta (ppm; CDCl) ₃ )：6.24(s,1H)，6.09(s,1H)，5.84(s,1H)，5.57(s,1H),4.33-4.27(m,4H)，4.20-4.16(m,2H)，2.34-2.31(m,1H)，1.97-1.90(m,4H)，1.82-1.67(m,8H)，1.43-1.39(m,1H)，1.31-1.18(m,6H)，1.15-0.75(m,16H).

NMR analysis values of the comparative compound (S-2) are as follows.

¹ H-NMR: chemical shift delta (ppm; C)DCl ₃ )：6.24(s,1H)，6.09(s,2H)，5.87(s,1H)，5.57-5.60(m,2H),4.36-4.26(m,6H)，4.21-4.17(m,2H)，2.34-2.31(m,1H)，1.97-1.85(m,8H)，1.78-1.64(m,6H)，1.54-1.47(m,2H)，1.33-0.78(m,27H).

The Voltage Holding Ratios (VHR) of the compound (1-2-1) and the compound (1-2-3) were compared with those of the comparative compound (S-1) and the comparative compound (S-2). The composition (i) was used for the evaluation.

The proportion of the component of the composition (i) is expressed in% by weight.

In the composition (i), each compound was added at a ratio of 3.0 wt% to prepare a sample. The sample was injected into an element without an alignment film having a gap (cell gap) of 3.5 μm between two glass substrates. The element was irradiated with ultraviolet rays (20J) using invisible light F40T10/BL (peak wavelength 355 nm) manufactured by Eye Graphics Co., ltd, whereby the added compound was polymerized. The element was charged by applying a pulsed voltage (1V and 60 microseconds) at 60 ℃. The attenuated voltage was measured during 1.67 milliseconds by a high-speed voltmeter, and the area a between the voltage curve and the horizontal axis in the unit cycle was obtained. Area B is the area when unattenuated. The voltage holding ratio is expressed by the percentage of the area a to the area B.

TABLE 2 Voltage maintenance ratio (VHR) of Compound (1-2-1) and Compound (1-2-3) and comparative Compound (S-1) and comparative Compound (S-2)

The voltage holding ratios of the compound (1-2-1) and the compound (1-2-3) to the comparative compound (S-1) and the comparative compound (S-2) are summarized in Table 2. In the case of using the compound (1-2-1) or the compound (1-2-3), a voltage holding ratio larger than that in the case of using the comparative compound (S-1) or the comparative compound (S-2) can be obtained. The reason for this is that: the compound has a plurality of polymerizable groups such as methacryloyl groups, and the polymerizable groups are linked to the same carbon atom via a spacer, so that a polymer network of good quality can be formed with high symmetry, and thus, a decrease in voltage holding ratio is suppressed. Therefore, the compound (1-2-1) and the compound (1-2-3) can be said to be excellent compounds having a large voltage holding ratio in the case of being used for a liquid crystal display element.

The following compounds may be synthesized by referring to the methods described in the synthesis examples, or "2. Synthesis of Compound (1)".

2. Examples of compositions

The compounds in the examples are represented by symbols based on the definition of table 3 below. In Table 3, the steric configuration associated with 1, 4-cyclohexylene was the trans configuration. The numbering in brackets following the notation corresponds to the numbering of the compounds. The symbol of (-) refers to other liquid crystalline compounds. The proportion (percentage) of the liquid crystalline compound is a weight percentage (wt%) based on the weight of the liquid crystal composition. Finally, the characteristic values of the liquid crystal composition are summarized. The characteristics were measured according to the method described above, and the measurement values were directly described (without extrapolation).

TABLE 3 expression methods of compounds using markers

R-(A ₁ )-Z ₁ -·····Z _n -(A _n )-R′

Use example 1

The following compound (1-2-1) was added to the composition in a proportion of 1% by weight.

NI＝95.9℃；η＝17.7mPa·s；Δn＝0.108；Δε＝5.0.

Use example 2

The following compounds (1-2-27) were added to the composition in a proportion of 3% by weight.

NI＝71.3℃；η＝19.8mPa·s；Δn＝0.113；Δε＝5.7.

Use example 3

The following compounds (1-2-15) were added to the composition in a proportion of 7% by weight.

NI＝82.6℃；η＝24.2mPa·s；Δn＝0.109；Δε＝5.4.

Use example 4

The following compounds (1-3-15) were added to the composition in a proportion of 3.5% by weight.

NI＝119.8℃；η＝20.4mPa·s；Δn＝0.094；Δε＝3.7.

Use example 5

The following compounds (1-2-12) were added to the composition in a proportion of 5% by weight.

NI＝104.9℃；η＝32.1mPa·s；Δn＝0.122；Δε＝8.3.

Use example 6

The following compounds (1-2-30) were added to the composition in a proportion of 0.1% by weight.

NI＝85.1℃；η＝14.7mPa·s；Δn＝0.092；Δε＝4.4.

Use example 7

The following compound (1-2-1) was added to the composition in a proportion of 2% by weight.

NI＝75.7℃；η＝22.7mPa·s；Δn＝0.108；Δε＝8.8.

Use example 8

The following compounds (1-2-27) were added to the composition in a proportion of 1% by weight.

NI＝73.3℃；η＝24.7mPa·s；Δn＝0.098；Δε＝8.1.

Use example 9

The following compounds (1-2-15) were added to the composition in a proportion of 0.5% by weight.

NI＝73.1℃；η＝15.0mPa·s；Δn＝0.073；Δε＝3.0.

Use example 10

The following compounds (1-3-15) were added to the composition in a proportion of 4% by weight.

NI＝87.9℃；η＝21.5mPa·s；Δn＝0.071；Δε＝5.8.

Use example 11

The following compounds (1-2-12) were added to the composition in a proportion of 3% by weight.

NI＝81.3℃；η＝11.7mPa·s；Δn＝0.129；Δε＝7.8.

Use example 12

The following compound (1-2-3) was added to the composition in a proportion of 1% by weight.

NI＝95.9℃；η＝17.7mPa·s；Δn＝0.108；Δε＝5.0.

Use example 13

The following compounds (1-3-4) were added to the composition in a proportion of 5% by weight.

NI＝104.9℃；η＝32.1mPa·s；Δn＝0.122；Δε＝8.3.

Use example 14

The following compounds (1-3-40) were added to the composition in a proportion of 1% by weight.

NI＝73.3℃；η＝24.7mPa·s；Δn＝0.098；Δε＝8.1.

Use example 15

The following compounds (1-2-37) were added to the composition in a proportion of 3% by weight.

NI＝81.3℃；η＝11.7mPa·s；Δn＝0.129；Δε＝7.8.

Industrial applicability

The liquid crystal composition containing the compound (1) can be used for display elements of liquid crystal projectors, liquid crystal televisions and the like.

Claims

1. A polymerizable polar compound represented by the formula (1),

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

ring A ¹ Ring A ² Independently 1, 2-cyclopropylene, 1, 3-cyclobutylene, 1, 3-cyclopentylene, 1, 4-cyclohexylene, 1, 4-cycloheptylene, 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, or pyridine-2, 5-diyl, wherein at least one hydrogen may be interrupted by fluorine, chlorine, alkyl having 1 to 10 carbon atoms, alkenyl having 2 to 10 carbon atoms, alkoxy having 1 to 9 carbon atoms A group, or an alkenyloxy group of 2 to 9 carbon atoms, in which at least one hydrogen may be substituted with fluorine or chlorine;

a is 0, 1, 2, 3, or 4;

Sp ² 、Sp ³ and Sp ⁴ Independently a single bond or an alkylene group of 1 to 10 carbon atoms, of which at least one-CH ₂ -can be substituted by-O-, -CO-, -COO-, -OCO-, or-OCOO-, at least one- (CH) ₂ ) ₂ -may be substituted by-ch=ch-or-c≡c-, in which groups at least one hydrogen may be substituted by fluorine or chlorine;

Sp ¹ an alkylene group having 1 to 10 carbon atoms, at least one of the alkylene groups being-CH ₂ -can be substituted by-O-, -CO-, -COO-, -OCO-, or-OCOO-, at least one- (CH) ₂ ) ₂ -may be substituted by-ch=ch-or-c≡c-, in which groups at least one hydrogen may be substituted by fluorine or chlorine;

in the formula (1-a), the formula (1-b) and the formula (1-c),

-N(R ⁶ ) ₂ and-Si (R) ⁶ ) ₃ In the process, ,

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

3. The polymerizable polar compound according to claim 1 or 2, wherein in the formula (1),

Ring A ¹ Ring A ² Independently 1, 4-cyclohexylene, 1, 4-cyclohexenylene, 1, 4-phenylene, naphthalene-2, 6-diyl, tetrahydropyran-2, 5-diyl, 1, 3-dioxane-2, 5-diyl, pyrimidine-2, 5-diyl, or pyridine-2, 5-diyl, wherein at least one hydrogen in these rings is optionally substituted by fluorine, chlorine, alkyl having 1 to 10 carbon atoms, alkenyl having 2 to 10 carbon atoms, alkoxy having 1 to 9 carbon atoms, orAlkenyloxy having 2 to 9 carbon atoms, at least one of which groups may be substituted by fluorine or chlorine.

4. The polymerizable polar compound according to claim 1 or 2, which is represented by any one of the formulae (1-1) to (1-4),

in the formulae (1-1) to (1-4),

Sp ² 、Sp ³ and Sp ⁴ Independently a single bond or an alkylene group of 1 to 7 carbon atoms, of which at least one-CH ₂ -can be prepared by-O-, -COO-; or-OCO-substitution, at least one- (CH) ₂ ) ₂ -may be substituted by-ch=ch-, of which groups at least one hydrogen may be substituted by fluorine;

Sp ¹ an alkylene group having 1 to 7 carbon atoms, at least one of the alkylene groups being-CH ₂ -can be prepared by-O-, -COO-; or-OCO-substitution, at least one- (CH) ₂ ) ₂ -may be substituted by-ch=ch-, of which groups at least one hydrogen may be substituted by fluorine;

in the formula (1-a), the formula (1-b) and the formula (1-c),

X ¹ independently-OH, -NH ₂ -COOH, or-SH.

5. The polymerizable polar compound according to claim 1 or 2, which is represented by any one of the formulae (1-5) to (1-7),

in the formulae (1-5) to (1-7),

Sp ² 、Sp ³ And Sp ⁴ Independently a single bond or an alkylene group of 1 to 5 carbon atoms, of which at least one-CH ₂ -optionally substituted by-O-at least one- (CH) ₂ ) ₂ -may be substituted with-ch=ch-;

Sp ¹ an alkylene group having 1 to 5 carbon atoms, at least one of the alkylene groups being-CH ₂ -optionally substituted by-O-at least one- (CH) ₂ ) ₂ -may be substituted with-ch=ch-;

in the formula (1-a-1) and the formula (1-b-1),

R ⁵ is hydrogen or alkyl of 1 to 7 carbon atoms.

6. The polymerizable polar compound according to claim 1 or 2, which is represented by any one of the formulae (1-8) to (1-37),

in the formulae (1-8) to (1-37),

Z ¹ z is as follows ² Independently a single bondOr- (CH) ₂ ) ₂ -；

Sp ² 、Sp ³ And Sp ⁴ Independently a single bond or an alkylene group of 1 to 5 carbon atoms, of which at least one-CH ₂ -may be substituted by-O-;

Sp ¹ an alkylene group having 1 to 5 carbon atoms, at least one of the alkylene groups being-CH ₂ -may be substituted by-O-;

R ⁵ is hydrogen or alkyl with 1 to 5 carbon atoms.

7. The polymerizable polar compound according to claim 1 or 2, which is represented by any one of formulas (1-38) to (1-49),

in the formulae (1-38) to (1-49),

R ¹ is alkyl with 1-10 carbon atoms;

Z ¹ z is as follows ² Independently is a single bond or- (CH) ₂ ) ₂ -；

Sp ⁴ an alkylene group having 1 to 5 carbon atoms or a single bond, at least one of the alkylene groups-CH ₂ -may be substituted by-O-;

R ⁵ is hydrogenMethyl, or ethyl.

8. The polymerizable polar compound according to claim 1 or 2, which is represented by any one of the formulae (1-50) to (1-55),

in the formulae (1-50) to (1-55),

R ¹ is alkyl with 1-10 carbon atoms;

Z ¹ z is as follows ² Independently is a single bond or- (CH) ₂ ) ₂ -；

Sp ⁴ an alkylene group having 1 to 5 carbon atoms or a single bond, at least one of the alkylene groups-CH ₂ The group may be substituted by-O-groups,

Sp ¹ an alkylene group having 1 to 5 carbon atoms, at least one of the alkylene groups being-CH ₂ -may be substituted by-O-.

9. A liquid crystal composition containing at least one of the polymerizable polar compounds according to any one of claims 1 to 8.

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

In the formulas (2) to (4),

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

in the formulas (5) to (7),

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

L ¹¹ L and L ¹² Independently hydrogen or fluorine.

12. The liquid crystal composition according to claim 9 or 10, which contains at least one compound selected from the group of compounds represented by formula (8),

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

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

L ¹³ l and L ¹⁴ Independently hydrogen or fluorine;

i is 1, 2, 3, or 4.

13. The liquid crystal composition according to claim 9 or 10, which contains at least one compound selected from the group of compounds represented by the formulas (11) to (19),

in the formulae (11) to (19),

L ¹⁵ L and L ¹⁶ Independently fluorine or chlorine;

S ¹¹ is hydrogen or methyl;

x is-CHF-or-CF ₂ -；

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

t is 1, 2, or 3.

14. The liquid crystal composition according to claim 9 or 10, which comprises at least one polymerizable compound represented by formula (20) other than the compound represented by formula (1),

in the formula (20), the amino acid sequence of the compound,

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

P ¹¹ 、P ¹² p and P ¹³ Independently a polymerizable group;

u is 0, 1, or 2;

15. The liquid crystal composition according to claim 14, wherein in the formula (20),

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

in the formulae (P-1) to (P-5),

16. The liquid crystal composition according to claim 14, wherein the polymerizable compound represented by formula (20) is at least one compound selected from the group of polymerizable compounds represented by formulas (20-1) to (20-7),

in the formulae (20-1) to (20-7),

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

in the formulae (P-1) to (P-3),

17. The liquid crystal composition according to claim 9 or 10, which contains at least one selected from the group consisting of a polymerizable compound different from the compound represented by the formula (1) or the formula (20), a polymerization initiator, a polymerization inhibitor, an optically active compound, an antioxidant, an ultraviolet absorber, a light stabilizer, a heat stabilizer, a pigment, and a defoaming agent,

in the formula (20), the amino acid sequence of the compound,

P ¹¹ 、P ¹² p and P ¹³ Independently a polymerizable group;

u is 0, 1, or 2;

18. A liquid crystal display element comprising at least one selected from the group consisting of the liquid crystal composition according to any one of claims 9 to 17 and a polymerized liquid crystal composition according to any one of claims 9 to 17.