CN109997074B

CN109997074B - Method for manufacturing liquid crystal display element without alignment film, and display device

Info

Publication number: CN109997074B
Application number: CN201780073225.1A
Authority: CN
Inventors: 平井吉治; 片野裕子; 近藤史尚; 荻田和寛; 远藤浩史; 黄名鸿; 宋依霖; 谢松年
Original assignee: JNC Corp
Current assignee: JNC Corp
Priority date: 2016-11-28
Filing date: 2017-11-20
Publication date: 2022-05-17
Anticipated expiration: 2037-11-20
Also published as: TW201820009A; WO2018097093A1; JPWO2018097093A1; CN109997074A

Abstract

The invention provides a method for manufacturing a liquid crystal display element without an alignment film and a display device, comprising a method for forming an alignment control layer which has an effect of uniformly aligning liquid crystal molecules when polymerizing a polymerizable polar compound added to a liquid crystal composition. In a liquid crystal display element including a first substrate, a plurality of pixel electrodes formed on the first substrate, a second substrate, a counter electrode formed on the second substrate and facing the pixel electrodes, and a liquid crystal layer interposed between the pixel electrodes and the counter electrode, ultraviolet rays are irradiated at a specific illuminance without applying a voltage to a polymerizable polar compound contained in the liquid crystal layer in a first stage, and ultraviolet rays are irradiated at a specific illuminance while applying a predetermined voltage in a second stage.

Description

Method for manufacturing liquid crystal display element without alignment film and display device

Technical Field

The present invention relates to a method for manufacturing a liquid crystal display element having no alignment film, and a display device. More specifically, the present invention relates to a method for manufacturing a liquid crystal display element having a liquid crystal composition containing a polymerizable polar compound and having positive or negative dielectric anisotropy.

Background

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

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

TABLE 1 Properties of the compositions and AM elements

The optical anisotropy of the composition correlates with the contrast ratio of the element. Depending on the mode of the element, the optical anisotropy needs to be large or small, that is, the optical anisotropy needs to be appropriate. The product (Δ n × d) of the optical anisotropy (Δ n) of the composition and the cell gap (d) of the element is designed to maximize the contrast ratio. The value of the appropriate product depends on the type of operation mode. The value is about 0.45 μm in the cell as in the TN mode. In the VA mode element, the value is in the range of about 0.30 μm to about 0.40 μm, and in the IPS mode or FFS mode element, the value is in the range of about 0.20 μm to about 0.30 μm. In these cases, a composition having a large optical anisotropy is preferable for an element having a small cell gap. The large dielectric anisotropy of the composition contributes to a low threshold voltage, a small power consumption, and a large contrast ratio of the device. Therefore, the positive or negative dielectric anisotropy is preferably large. The large specific resistance of the composition contributes to a large voltage holding ratio and a large contrast ratio of the device. Therefore, a composition having a large specific resistance in the initial stage is preferable. A composition having a large specific resistance after a long-term use is preferable. The stability of the composition to ultraviolet light and heat correlates with the lifetime of the component. When the stability is high, the life of the element is long. Such characteristics are preferable for AM elements used for liquid crystal monitors, liquid crystal televisions, and the like.

In a general-purpose liquid crystal display device, the vertical alignment of liquid crystal molecules can be achieved by a specific polyimide alignment film. In a liquid crystal display element of a Polymer Sustained Alignment (PSA) type, a polymer is combined with an alignment film. First, a composition to which a small amount of a polymerizable compound is added is injected into an element having an alignment film. Next, the composition was irradiated with ultraviolet rays while applying a voltage between the substrates of the element. The polymerizable compound is polymerized to form a network structure of the polymer in the composition. In the composition, the orientation of the liquid crystal molecules can be controlled by the polymer, so that the response time of the element is shortened, and the afterimage of the image is improved. However, when the device is large, it is difficult to uniformly coat the solution of the polyimide precursor on the substrate and to obtain a uniform thin film by firing.

On the other hand, a liquid crystal composition containing a polymer and a polar compound having no polymerizable group is used for a liquid crystal display element having no alignment film such as polyimide. First, a composition to which a small amount of a polymerizable compound and a small amount of a polar compound are added is injected into an element. Here, the polar compound is adsorbed to the substrate surface and aligned. The liquid crystal molecules are aligned according to the alignment. Next, the composition was irradiated with ultraviolet rays while applying a voltage between the substrates of the element. Here, the polymerizable compound is polymerized to stabilize the alignment of the liquid crystal molecules. In the composition, the orientation of the liquid crystal molecules can be controlled by the polymer and the polar compound, so that the response time of the element is shortened, and the afterimage of the image is improved. Further, the element having no alignment film does not require a step of forming an alignment film. Since the alignment film is not present, the resistance of the element is not lowered by the interaction between the alignment film and the composition. Such an effect of using a combination of a polymer and a polar compound can be expected in an element having a mode such as TN, ECB, OCB, IPS, VA, FFS, and FPA.

In the production of a device having no alignment film such as polyimide, the following two methods are disclosed for reducing alignment defects of liquid crystal molecules. 1) A method for manufacturing a liquid crystal display device, wherein a liquid crystal composition containing a polymerizable compound is irradiated with ultraviolet rays while applying a voltage, and further, additional ultraviolet rays are irradiated without applying a voltage. 2) A method of irradiating a liquid crystal composition containing a polymerizable compound with ultraviolet rays while applying a voltage, and further performing additional ultraviolet irradiation while applying a voltage that does not substantially drive liquid crystal molecules (patent document 1). In the production of such an element, the uniformity of vertical alignment varies depending on the conditions of the production process (patent documents 2 and 3). In the present invention, a method for manufacturing a liquid crystal display element having no alignment film has been studied by combining a polar compound having a polymerizable group and a liquid crystal compound instead of a polymer and a polar compound and effectively using the combination.

Documents of the prior art

Patent document

Patent document 1: japanese patent laid-open No. 2008-134668

Patent document 2: japanese patent laid-open No. 2005-181582

Patent document 3: japanese patent laid-open No. 2006-58755

Disclosure of Invention

Problems to be solved by the invention

An object of the present invention is to provide a method for changing the order of ultraviolet irradiation and voltage application from the above-described conventional technique in order to obtain uniform alignment in the production of a liquid crystal display element without an alignment film such as polyimide. Another object is to provide a method for producing a liquid crystal display element having characteristics such as a wide temperature range in which the element can be used, a short response time, a high voltage holding ratio, a low threshold voltage, a large contrast ratio, and a long lifetime by adding a polymerizable polar compound having high chemical stability, high ability to align liquid crystal molecules, and high solubility in a liquid crystal composition to the liquid crystal composition and polymerizing the compound. Another object is to provide a method for manufacturing a liquid crystal display element having a liquid crystal composition that satisfies at least one of characteristics such as a high upper limit temperature of a nematic phase, a low lower limit temperature of the nematic phase, a low viscosity, an appropriate optical anisotropy, a large positive or negative dielectric anisotropy, a large specific resistance, a high stability to ultraviolet light, a high stability to heat, and a large elastic constant.

Means for solving the problems

The present inventors have studied the order of ultraviolet irradiation and voltage application, and have found that the above problems can be solved by adding a polymerizable polar compound having a mesogen portion composed of at least one ring as an alignment monomer to a liquid crystal composition and polymerizing the compound under specific conditions, thereby completing the present invention. The present invention includes the following aspects, and the like.

[1]A method for manufacturing a liquid crystal display element, wherein in the liquid crystal display element having a first substrate, a plurality of pixel electrodes formed on the first substrate, a second substrate, a counter electrode formed on the second substrate and facing the pixel electrodes, and a liquid crystal layer sandwiched between the pixel electrodes and the counter electrode, the liquid crystal layer contains a liquid crystal composition containing a polymerizable polar compound having a mesogen portion composed of at least one ring as an alignment monomer and a liquid crystal compound; wherein the liquid crystal composition is first applied with no voltage or a voltage substantially not driving the liquid crystal composition at 1J/cm²To 60J/cm²Illumination intensity of 2mW/cm²To 200mW/cm²A first ultraviolet ray in the range of (1), and then applying a voltage of not less than a threshold voltage and not more than 30V to the liquid crystal composition at a voltage of 5J/cm²To 100J/cm²Illumination intensity of 2mW/cm²To 200mW/cm²And (b) a second ultraviolet ray in the range of (a) to form an orientation control layer containing a polymer produced by polymerizing the polymerizable polar compound.

[2]According to [1]The method for manufacturing a liquid crystal display element, wherein in [1]]In the ultraviolet irradiation, first, no voltage or a voltage substantially not driving the liquid crystal composition is applied to the liquid crystal composition and the voltage is set to 3J/cm²To 50J/cm²Illumination intensity of 2mW/cm²To 100mW/cm²A first ultraviolet ray in the range of (1), and then applying a voltage of not less than a threshold voltage and not more than 30V to the liquid crystal composition at a voltage of 5J/cm²To 55J/cm²Illumination intensity of 2mW/cm²To 100mW/cm²A second ultraviolet ray of the range of (1).

[3]According to [1]Or [ 2]]The method for manufacturing a liquid crystal display element, wherein in [1]]Or [ 2]]In the ultraviolet irradiation, after the second ultraviolet irradiation, a voltage is further applied to the liquid crystal composition at 1J/cm without applying a voltage or without substantially driving the liquid crystal composition²To 60J/cm²Illumination intensity of 2mW/cm²To 200mW/cm²A third ultraviolet ray in the range of (1).

[4] The method for manufacturing a liquid crystal display element according to any one of [1] to [3], wherein the alignment monomer is a compound represented by formula (1 α);

in the formula (1. alpha.) in the formula,

R¹is an alkyl group having 1 to 15 carbon atoms, in which at least one-CH group₂-may be substituted by-O-or-S-, at least one- (CH)₂)₂-may be substituted by-CH ═ CH-or-C ≡ C-, at least one of these groups being substituted by fluorine or chlorine;

MES is a mesogen having at least one ring;

Sp¹is a single bond or an alkylene group having 1 to 10 carbon atoms, in which at least one-CH group₂-may be substituted by-O-, -CO-, -COO-, -OCO-, or-OCOO-, at least one- (CH)₂)₂-may be substituted by-CH ═ CH-or-C ≡ C-, at least one of these groups being substituted by fluorine or chlorine;

M¹and M²Independently hydrogen, fluorine, chlorine, alkyl of carbon number 1 to 5, or alkyl of carbon number 1 to 5 in which at least one hydrogen is substituted with fluorine or chlorine;

R²a group represented by formula (1 α a), formula (1 α b) or formula (1 α c);

in the formulae (1. alpha. a), (1. alpha. b) and (1. alpha. c),

Sp²and Sp³Independently a single bond or an alkylene group having 1 to 10 carbon atoms, in which at least one-CH group₂May be substituted by-O-, -NH-, -CO-, -COO-, -OCO-or-OCOO-, at least one- (CH)₂)₂-may be substituted by-CH ═ CH-or-C ≡ C-, at least one of these groups being substituted by fluorine or chlorine;

S¹is > CH-or > N-;

S²is > C < or > Si <;

X¹independently is-OH, -NH₂、-OR³、-N(R³)₂Formula (x1), -COOH, -SH, -B (OH)₂or-Si (R)³)₃The radicals represented, herein, R³Is hydrogen or alkyl with 1 to 10 carbon atoms, in which at least one-CH₂-may be substituted by-O-at least one- (CH)₂)₂-may be substituted by-CH ═ CH-, where at least one hydrogen may be substituted by fluorine or chlorine, and w in formula (x1) is 1,2,3 or 4;

[5] the method for manufacturing a liquid crystal display element according to any one of [1] to [3], wherein the alignment monomer is a compound represented by formula (1 β);

in the formula (1 beta), the compound (B),

MES is a mesogen having at least one ring;

R²、M¹、M²and M³Independently hydrogen, fluorine, chlorine or an alkyl group of 1 to 10 carbon atoms, in which at least one-CH group₂-may be substituted by-O-or-S-, at least one- (CH)₂)₂-may be substituted by-CH ═ CH-or-C ≡ C-, at least one of these groups being substituted by fluorine or chlorine.

[6] The method for manufacturing a liquid crystal display element according to any one of [1] to [3], wherein the alignment monomer is a compound represented by formula (1 γ);

in the formula (1. gamma.) wherein,

R¹、R²and R³Independently hydrogen or an alkyl group of 1 to 15 carbon atoms, in which at least one-CH group₂-may be substituted by-O-, -S-or-NH-, at least one- (CH)₂)₂-may be substituted by-CH ═ CH-, where at least one hydrogen may be substituted by fluorine or chlorine;

n is independently 0,1 or 2;

ring A⁴Is cyclohexylene, cyclohexenylene, phenylene, naphthalene, decahydronaphthalene, tetrahydronaphthalene, tetrahydropyran, 1, 3-dioxane, pyrimidine or pyridine, ring A¹And ring A⁵Independently cyclohexyl, cyclohexenyl, phenyl, 1-naphthyl, 2-naphthyl, tetrahydropyran-2-yl, 1, 3-dioxan-2-yl, pyrimidin-2-yl, or pyridin-2-yl,

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

Z¹and Z⁵Independently a single bond or an alkylene group having 1 to 10 carbon atoms, in which at least one-CH group₂At least one- (CH) which may be substituted by-O-, -COO-, -OCO-or-OCOO-₂)₂-may be substituted by-CH ═ CH-or-C ≡ C-, in which groups at least one hydrogen may be substituted by fluoro or chloro;

Sp¹、Sp²and Sp³Independently a single bond or an alkylene group having 1 to 10 carbon atoms, in which at least one-CH group₂At least one- (CH) which may be substituted by-O-, -COO-, -OCO-or-OCOO-₂)₂-may be substituted by-CH ═ CH-or-C ≡ C-, at least one of these groups being substituted by fluorine or chlorine;

a and b are independently 0,1, 2,3 or 4, and the sum of a and b is 1,2,3 or 4;

c. d and e are independently 0,1, 2,3, or 4;

c. the sum of d and e is 2,3, or 4;

P¹、P²and P³Independently a polymerizable group represented by the formula (P-1);

in the formula (P-1), the compound,

R⁴is a group selected from the group of groups represented by formula (1 γ a), formula (1 γ b) and formula (1 γ c);

in the formulae (1. gamma. a), (1. gamma. b) and (1. gamma. c),

Sp⁵and Sp⁶Independently a single bond or an alkylene group having 1 to 10 carbon atoms, in which at least one-CH group₂At least one- (CH) which may be substituted by-O-, -NH-, -CO-, -COO-, -OCO-or-OCOO-₂)₂-may be substituted by-CH ═ CH-or-C ≡ C-, at least one of these groups being substituted by fluorine or chlorine;

S¹is > CH-or > N-;

S²is > C < or > Si <;

X¹independently is-OH, -NH₂、-OR⁵、-N(R⁵)₂、-COOH、-SH、-B(OH)₂or-Si (R)⁵)₃The radicals represented, herein, R⁵Is hydrogen or alkyl with 1 to 10 carbon atoms, in which at least one-CH₂-may be substituted by-O-at least one- (CH)₂)₂-may be substituted by-CH ═ CH-, where at least one hydrogen may be substituted by fluorine or chlorine.

[7] The method for manufacturing a liquid crystal display element according to any one of [1] to [6], wherein in the alignment monomer having a mesogen site composed of at least one ring, the mesogen site includes a cyclohexane ring.

[8] The method for manufacturing a liquid crystal display element according to any one of [1] to [3], wherein the alignment monomer is a compound represented by formula (1-1);

in the formula (1-1),

R¹is alkyl with carbon number of 1 to 15, the R¹In (1), at least one-CH₂-may be substituted by-O-or-S-, at least one-CH₂CH₂-may be substituted by-CH-or-C ≡ C-, at least one hydrogen may be substituted by halogen;

ring A¹And ring A²Independently 1, 4-cyclohexylene, 1, 4-cyclohexenylene, 1, 4-phenylene, naphthalene-2, 6-diyl, decahydronaphthalene-2, 6-diyl, 1,2,3, 4-tetrahydronaphthalene-2, 6-diyl, tetrahydropyran-2, 5-diyl, 1, 3-dioxane-2, 5-diyl, pyrimidine-2, 5-diyl, pyridine-2, 5-diyl, fluorene-2, 7-diyl, phenanthrene-2, 7-diyl, anthracene-2, 6-diyl, perhydrocyclopenta [ a ] a]Phenanthrene-3, 17-diyl, or 2,3,4,7,8,9,10,11,12,13,14,15,16, 17-tetradecahydrocyclopenta [ a ]]Phenanthrene-3, 17-diyl, in which at least one hydrogen in a ring may be substituted with fluorine, chlorine, an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an alkoxy group having 1 to 11 carbon atoms, or an alkenyloxy group having 2 to 11 carbon atoms, and in which at least one hydrogen may be substituted with fluorine or chlorine;

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

Z¹is a single bond or alkylene group having 1 to 6 carbon atoms, the Z¹In (1), at least one-CH₂-may be substituted by-O-, -CO-, -COO-, -OCO-, or-OCOO-, at least one-CH₂CH₂-may be substituted by-CH ═ CH-or-C ≡ C-, in which groups at least one hydrogen may be substituted by fluoro or chloro;

Sp¹is a single bond or alkylene with 1 to 10 carbon atoms, and Sp¹In (1), at least one-CH₂-may be substituted by-O-, -CO-, -COO-, -OCO-, or-OCOO-, at least one-CH₂CH₂-may be substituted by-CH ═ CH-or-C ≡ C-, in which at least one hydrogen may be substituted by a halogen, and in which at least one hydrogen is substituted by a group selected from the groups represented by formula (1 a);

in the formula (1a), the compound (A),

Sp¹²is a single bond or alkylene with 1 to 10 carbon atoms, and Sp¹²In (1), at least one-CH₂-may be substituted by-O-, -CO-, -COO-, -OCO-, or-OCOO-, at least one-CH₂CH₂-may be substituted by-CH-or-C ≡ C-, of which groups at least one hydrogen may be substituted by halogen;

M¹¹and M¹²Independently hydrogen, halogen, alkyl of carbon number 1 to 5, or alkyl of carbon number 1 to 5 with at least one hydrogen substituted with halogen;

R¹²is alkyl with carbon number of 1 to 15, the R¹²In (1), at least one-CH₂-may be substituted by-O-or-S-, at least one-CH₂CH₂-may be substituted by-CH-or-C ≡ C-, at least one hydrogen may be substituted by halogen;

in the formula (1-1),

P¹¹is a group selected from the group consisting of the groups represented by the formulae (1e) and (1 f);

in the formulae (1e) and (1f),

Sp¹³is a single bond or alkylene with 1 to 10 carbon atoms, and Sp¹³In at least one-CH₂-may be substituted by-O-, -NH-, -CO-, -COO-, -OCO-, or-OCOO-, at least one-CH₂CH₂-may be substituted by-CH-or-C ≡ C-, of which groups at least one hydrogen may be substituted by halogen;

M¹³and M¹⁴Independently hydrogen, halogen, alkyl of carbon number 1 to 5, or alkyl of carbon number 1 to 5 with at least one hydrogen substituted with halogen;

R¹³is a group selected from the group consisting of the groups represented by the formula (1g), the formula (1h) and the formula (1 i);

in the formulae (1g), (1h) and (1i),

Sp¹⁴and Sp¹⁵Independently a single bond or an alkylene group having 1 to 10 carbon atoms, in which at least one-CH group₂-may be substituted by-O-, -NH-, -CO-, -COO-, -OCO-, or-OCOO-, at least one-CH₂CH₂-may be substituted by-CH-or-C ≡ C-, at least one hydrogen may be substituted by halogen;

in the formulae (1g) and (1i), S¹Is > CH-or > N-, S²Is > C < or > Si <;

X¹is-OH, -NH₂、-OR¹⁵、-N(R¹⁵)₂、-COOH、-SH、-B(OH)₂or-Si (R)¹⁵)₃；

-OR¹⁵、-N(R¹⁵)₂and-Si (R)¹⁵)₃In (1),

R¹⁵is hydrogen or alkyl with 1 to 10 carbon atoms, the R¹⁵In (1), at least one-CH₂-may be substituted by-O-at least one-CH₂CH₂-may be substituted by-CH ═ CH-, where at least one hydrogen may be substituted by halogen.

[9] The method for manufacturing a liquid crystal display element according to [8], wherein the alignment monomer is at least one polymerizable compound selected from the group of compounds represented by formulae (1-2) to (1-3);

in the formulae (1-2) and (1-3),

R¹is an alkyl group having 1 to 12 carbon atoms, in which at least one-CH group₂-may be substituted by-O-at least one-CH₂CH₂-may be substituted by-CH ═ CH-or-C ≡ C-, in which groups at least one hydrogen may be substituted by fluorine;

ring A¹And ring A²Independently 1, 4-cyclohexylene, 1, 4-cyclohexenylene, 1, 4-phenylene, naphthalene-2, 6-diyl, tetrahydropyran-2, 5-diyl, 1, 3-dioxane-2, 5-diyl, fluorene-2, 7-diyl, phenanthrene-2, 7-diyl, perhydrocyclopenta [ a ] o]Phenanthrene-3, 17-diyl, or 2,3,4,7,8,9,10,11,12,13,14,15,16, 17-tetradecylcyclopenta [ a [ ]]Phenanthrene-3, 17-diyl, in which at least one hydrogen in a ring may be substituted with fluorine, an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, or an alkenyloxy group having 2 to 7 carbon atoms, and in which at least one hydrogen may be substituted with fluorine;

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

Z¹is a single bond or alkylene having 1 to 6 carbon atoms, the Z¹In (1), at least one-CH₂-may be substituted by-O-, -CO-, -COO-, -OCO-, or-OCOO-, at least one-CH₂CH₂-may be substituted by-CH ═ CH-or-C ≡ C-, at least one of these groups being substituted by fluorine or chlorine;

l is 0,1, 2,3,4, 5, or 6, at least one-CH of said alkylene group₂-may be substituted by-O-, -CO-, -COO-, -OCO-, or-OCOO-, at least one-CH₂CH₂-may be substituted by-CH ═ CH-or-C ≡ C-, in which groups at least one hydrogen may be substituted by fluorine;

Sp¹²is a single bond or an alkylene group having 1 to 5 carbon atoms, in which at least one-CH group₂-may be substituted by-O-, -CO-, -COO-, -OCO-, or-OCOO-, at least one-CH₂CH₂-may be substituted by-CH ═ CH-or-C ≡ C-, in which groups at least one hydrogen may be substituted by fluorine;

M¹¹and M¹²Independently hydrogen, fluoro, methyl, ethyl, or trifluoromethyl;

R¹²is hydrogen or alkyl with 1 to 5 carbon atoms, in which at least one-CH₂-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;

Sp¹³is a single bond or an alkylene group having 1 to 5 carbon atoms, in which at least one-CH group₂-may be substituted by-O-, -CO-, or-COO-, at least one-CH₂CH₂-may be substituted by-CH ═ CH-or-C ≡ C-, in which groups at least one hydrogen may be substituted by fluorine;

M¹³and M¹⁴Independently hydrogen, fluoro, methyl, ethyl, or trifluoromethyl;

Sp¹⁴is a single bond or an alkylene group having 1 to 5 carbon atoms, in which at least one-CH group₂-may be substituted by-O-, -CO-, or-COO-, at least one-CH₂CH₂-may be substituted by-CH ═ CH-or-C ≡ C-, in which groups at least one hydrogen may be substituted by fluorine;

X¹is-OH or-N (R)¹⁵)₂；

-N(R¹⁵)₂In (1),

R¹⁵is hydrogen or alkyl with 1 to 5 carbon atoms, in which at least one-CH₂-may be substituted by-O-at least one-CH₂CH₂-may be substituted by-CH ═ CH-, where at least one hydrogen may be substituted by fluorine.

[10] The method for manufacturing a liquid crystal display element according to [8], wherein the alignment monomer is at least one polymerizable compound selected from the group of compounds represented by formulae (1-4) to (1-60);

in the formulae (1-4) to (1-60),

R¹an alkyl group having 1 to 10 carbon atoms;

Z¹、Z¹²and Z¹³Independently a single bond, -CH₂CH₂-, or- (CH)₂)₄-；

Sp¹²、Sp¹³And Sp¹⁴Independently a single bond or an alkylene group having 1 to 5 carbon atoms, in which at least one-CH group₂-may be substituted by-O-;

L¹、L²、L³、L⁴、L⁵、L⁶、L⁷、L⁸、L⁹、L¹⁰、L¹¹and L¹²Independently hydrogen, fluoro, methyl or ethyl;

l is 0,1, 2,3,4, 5, or 6.

[11] The method for manufacturing a liquid crystal display element according to any one of [1] to [10], wherein the liquid crystal composition further contains at least one compound selected from the group of compounds represented by formulae (2) to (4);

in the formulae (2) to (4),

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

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

Z¹¹、Z¹²and Z¹³Independently a single bond, - (CH)₂)₂-, -CH ═ CH-, -C ≡ C-, or-COO-.

[12] The method for manufacturing a liquid crystal display element according to any one of [1] to [11], wherein the liquid crystal composition further contains at least one compound selected from the group of compounds represented by formulae (5) to (7);

in the formulae (5) to (7),

R¹³is an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms, at least one-CH group being present in the alkyl group or the alkenyl group₂-may be substituted by-O-, at least one hydrogen may be substituted by fluorine;

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

Ring C¹Ring C²And ring C³Independently 1, 4-cyclohexylene, 1, 4-phenylene in which at least one hydrogen may be substituted by fluorine, tetrahydropyran-2, 5-diyl, 1, 3-dioxane-2, 5-diyl or pyrimidine-2, 5-diyl;

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

L¹¹And L¹²Independently hydrogen, or fluorine.

[13] The method for manufacturing a liquid crystal display element according to any one of [1] to [12], wherein the liquid crystal composition further contains at least one compound selected from the group of compounds represented by formula (8);

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

R¹⁴is an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms, at least one-CH group being present in the alkyl group or the alkenyl group₂-may be substituted by-O-, at least one hydrogen may be substituted by fluorine;

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

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

Z¹⁷is a single bond, - (CH)₂)₂-、-C≡C-、-COO-、-CF₂O-、-OCF₂-, or-CH₂O-；

L¹³And L¹⁴Independently hydrogen or fluorine;

i is 1,2,3 or 4.

[14] The method for manufacturing a liquid crystal display element according to any one of [1] to [13], wherein the liquid crystal composition further contains at least one compound selected from the group of compounds represented by formulae (9) to (15);

in the formulae (9) to (15),

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

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

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

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

Z¹⁸、Z¹⁹、Z²⁰and Z²¹Independently a single bond, - (CH)₂)₂-、-COO-、-CH₂O-、-OCF₂-or-OCF₂CH₂CH₂-；

L¹⁵And L¹⁶Independently fluorine or chlorine;

S¹¹is hydrogen or methyl;

x is independently-CHF-or-CF₂-；

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

[15] The method for manufacturing a liquid crystal display element according to any one of [1] to [14], wherein the liquid crystal composition further contains a polymerizable compound represented by formula (16 α) as a reactive monomer, and thereby forms an orientation control layer comprising a copolymer produced by polymerizing these compounds;

in the formula (16 a), in the formula,

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

ring G is 1, 4-cyclohexylene, 1, 4-cyclohexenylene, 1, 4-phenylene, naphthalene-1, 2-diyl, naphthalene-1, 3-diyl, naphthalene-1, 4-diyl, naphthalene-1, 5-diyl, naphthalene-1, 6-diyl, naphthalene-1, 7-diyl, naphthalene-1, 8-diyl, naphthalene-2, 3-diyl, naphthalene-2, 6-diyl, naphthalene-2, 7-diyl, tetrahydropyran-2, 5-diyl, 1, 3-dioxane-2, 5-diyl, pyrimidine-2, 5-diyl, or pyridine-2, 5-diyl, and in these rings, at least one of them is substituted with fluorine, chlorine, an alkyl group having 1 to 12 carbon atoms, Alkoxy having 1 to 12 carbon atoms, or alkyl having 1 to 12 carbon atoms in which at least one hydrogen is substituted with fluorine or chlorine;

Z²²and Z²³Independently a single bond or an alkylene group having 1 to 10 carbon atoms, in which at least one-CH group₂-may be substituted by-O-, -CO-, -COO-, or-OCO-, at least one- (CH)₂)₂-may be via-CH ═ CH-, -C (CH)₃)＝CH-、-CH＝C(CH₃) -, or-C (CH)₃)＝C(CH₃) -substitution, of which at least one hydrogen may be substituted by fluorine or chlorine;

P¹¹、P¹²and P¹³Independently a polymerizable group;

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

u is 0,1 or 2;

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

[16]According to [15]]The method for manufacturing a liquid crystal display element, wherein in [15]]In the formula (16 α), P¹¹、P¹²And P¹³Independently 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),

M¹¹、M¹²and M¹³Independently hydrogen, fluorine, an alkyl group having 1 to 5 carbon atoms, or an alkyl group having 1 to 5 carbon atoms in which at least one hydrogen is substituted with fluorine or chlorine.

[17] The method for manufacturing a liquid crystal display element according to any one of [1] to [16], wherein the liquid crystal composition has negative dielectric anisotropy.

[18] The method for manufacturing a liquid crystal display element according to any one of [1] to [17], wherein the orientation control layer has a film thickness of 10nm to 100nm, and a particle diameter of the polymer in the orientation control layer is in a range of 1nm to 90 nm.

[19] The method for manufacturing a liquid crystal display element according to any one of [1] to [18], wherein the particle diameter of the polymer in the orientation control layer is in a range of 1nm to 70 nm.

[20] The method for manufacturing a liquid crystal display element according to any one of [1] to [19], wherein an orientation of molecules of the liquid crystalline compound is vertical, and an angle of the molecules to the substrate is 90 ° ± 10 °.

[21] The method for manufacturing a liquid crystal display element according to any one of [1] to [20], wherein the orientation of the molecules of the liquid crystalline compound is divided for each pixel.

[22] A display device provided with a liquid crystal display element manufactured by the method for manufacturing a liquid crystal display element according to any one of [1] to [21], and a backlight.

ADVANTAGEOUS EFFECTS OF INVENTION

An advantage of the present invention is to provide a method for obtaining uniform alignment in the manufacture of a liquid crystal display element that does not have an alignment film such as polyimide. Another advantage is to provide a method of manufacturing a liquid crystal display element having characteristics such as a wide temperature range in which the element can be used, a short response time, a high voltage holding ratio, a low threshold voltage, a large contrast ratio, and a long lifetime by adding a polymerizable polar compound having high chemical stability, high ability to align liquid crystal molecules, and high solubility in a liquid crystal composition to the liquid crystal composition and polymerizing it. Another advantage is to provide a method for manufacturing a liquid crystal display element having a liquid crystal composition that satisfies at least one of characteristics such as a high upper limit temperature of a nematic phase, a low lower limit temperature of the nematic phase, a low viscosity, an appropriate optical anisotropy, a large positive or negative dielectric anisotropy, a large specific resistance, a high stability to ultraviolet light, a high stability to heat, and a large elastic constant.

Drawings

Fig. 1 is a schematic view showing an element 11 in which a polymerizable polar compound 5 as an orientation monomer is arranged on a color filter substrate 1 and an array substrate 2 by interaction between a polar group and a substrate surface (an electrode layer is not shown), and an orientation control layer of a polymer is formed by polymerization.

Fig. 2 is a schematic view (electrode layer not shown) showing the element 12 in a state in which the polymerizable polar compound 5 as an orientation monomer and the polymerizable compound 6 as a reactive monomer are arranged on the color filter substrate 1 and the array substrate 2 by the interaction between the polar group and the substrate surface, and an orientation control layer of a copolymer is formed by polymerization.

Fig. 3 is a schematic view of a conventional element 21 having an alignment film 7 and containing a polymerizable compound (an electrode layer is not shown).

Description of the symbols

1: color filter substrate

2: array substrate

3: liquid crystal composition

4: liquid crystalline compound (liquid crystal molecule)

5: polymerizable polar Compound (1) (as an orientation monomer)

6: polymerizable Compound (16) (as a reactive monomer)

7: alignment film

8: polymerizable compound

Detailed Description

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

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

The compound represented by the formula (1) may be simply referred to as "compound (1)". The compound (1) refers to a compound or a mixture of two compounds represented by the formula (1)Or a mixture of three or more compounds. The rule also applies to at least one compound selected from the group of compounds represented by formula (2), and the like. B surrounded by hexagon¹、C¹The symbols F and the like correspond to the ring B¹Ring C¹Ring F, etc. The hexagon represents a six-membered ring such as a cyclohexane ring or a benzene ring or a condensed ring such as a naphthalene ring. In the formula (1. gamma.), the straight line crossing one side of the hexagon means that any hydrogen on the ring can pass through-Sp¹-P¹And the like. The subscripts 'c' etc. indicate the number of substituted groups. When the subscript is 0, there is no such substitution. When the subscript 'c' is 2 or more, at ring A¹Having a plurality of-Sps¹-P¹。-Sp¹-P¹The various groups shown may be the same or different. In the formula (1. gamma.), (R) is used¹)n、(R²) n and (R)³) n is a symbol. The 3 numbers represented by the 3 'n's may be the same or may be different. These rules are applicable to other formulas as well. In the expression "ring a and ring B are independently X, Y or Z", the subject is plural, and thus "independently" is used. When the subject is "ring a," independent "is not used since the subject is singular.

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

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

In the liquid crystalline compound, the alkyl group is linear or branched, and does not include a cyclic alkyl group. Straight chain alkyls are generally preferred over branched alkyls. The same applies to terminal groups such as alkoxy groups and alkenyl groups. In order to raise the upper temperature limit of the nematic phase, the steric configuration associated with the 1, 4-cyclohexylene group is trans rather than cis. 2-fluoro-1, 4-phenylene refers to the following two divalent radicals. In the chemical formula, fluorine can be towards left (L) or right (R). The rules also apply to asymmetric divalent radicals generated by the removal of two hydrogens from the ring, such as tetrahydropyran-2, 5-diyl.

In the method for manufacturing a liquid crystal display element of the present invention, a liquid crystal composition obtained by adding a polymerizable polar compound to a liquid crystal composition is sealed in the element. The polymerizable polar compound functions as an orientation monomer. The polar groups of the compounds have an interaction with the substrate surface and thus contribute to the orientation. The compounds have a mesogenic site consisting of at least one ring. At least one ring is preferredA cyclohexane ring is selected. The mesogen portion is a rigid portion contributing to the development of liquid crystallinity. The compound is polymerizable and provides a polymer by polymerization. The polymer helps the orientation of the liquid crystal molecules. The polar compound is an organic compound having polarity. Here, no compound having an ionic bond is contained. Atoms such as oxygen, sulfur and nitrogen are negatively charged and tend to have a partial negative charge. Carbon and hydrogen are neutral or tend to have a partial positive charge. Polarity arises because part of the charge is distributed unequally among the atoms of different species in the compound. For example, the polar compound has-OH, -COOH, -SH, -NH₂At least one of partial structures such as NH and N-.

The polymerizable polar compound is referred to as a compound (1) in the present specification. Further, the compounds are referred to as compound (1 α), compound (1 β), compound (1 γ), compound (1-1) to compound (1-60), respectively, as required for the details of the structure and the like. Hereinafter, 1. synthesis of compound (1 α), 2. synthesis of compound (1 α), 3. synthesis of compound (1 β), 4. synthesis of compound (1 β), 5. synthesis of compound (1 γ), 6. synthesis of compound (1 γ), 7. synthesis of compounds (1-1) to (1-60), 8. synthesis of compounds (1-1) to (1-60), 9. a liquid crystal composition as a composition containing compound (1), and 10. a liquid crystal display element as an element containing the composition will be described in this order.

1. Compound (1 alpha)

1-1. exemplary Compound (1. alpha.) and liquid Crystal composition Using the same

The present example includes the following items and the like.

Item 1. a compound represented by formula (1 α);

in the formula (1 alpha), the compound (A),

R¹is an alkyl group having 1 to 15 carbon atoms, in which at least one-CH group₂-may be substituted by-O-or-S-, at least one- (CH)₂)₂-may be substituted by-CH ═ CH-or-C ≡ C-In which at least one hydrogen may be substituted by fluorine or chlorine;

MES is a mesogen having at least one ring;

M¹and M²Independently hydrogen, fluorine, chlorine, an alkyl group having 1 to 5 carbon atoms, or an alkyl group having 1 to 5 carbon atoms in which at least one hydrogen is substituted with fluorine or chlorine;

in the formulae (1. alpha. a), (1. alpha. b) and (1. alpha. c),

Sp²and Sp³Independently a single bond or an alkylene group having 1 to 10 carbon atoms, in which at least one-CH group₂At least one- (CH) which may be substituted by-O-, -NH-, -CO-, -COO-, -OCO-or-OCOO-₂)₂-may be substituted by-CH ═ CH-or-C ≡ C-, in which groups at least one hydrogen may be substituted by fluoro or chloro;

S¹is > CH-or > N-;

S²is > C < or > Si <;

the compound according to item 1, which is represented by formula (1 α -1);

in the formula (1 alpha-1),

ring A¹And ring A⁴Independently 1, 4-cyclohexylene, 1, 4-cyclohexenylene, 1, 4-phenylene, naphthalene-2, 6-diyl, decahydronaphthalene-2, 6-diyl, 1,2,3, 4-tetrahydronaphthalene-2, 6-diyl, tetrahydropyran-2, 5-diyl, 1, 3-dioxane-2, 5-diyl, pyrimidine-2, 5-diyl, pyridine-2, 5-diyl, fluorene-2, 7-diyl, phenanthrene-2, 7-diyl, anthracene-2, 6-diyl, perhydrocyclopenta [ a ] group]Phenanthrene-3, 17-diyl, or 2,3,4,7,8,9,10,11,12,13,14,15,16, 17-tetradecylcyclopenta [ a [ ]]Phenanthrene-3, 17-diyl, in which at least one hydrogen in a ring may be substituted with fluorine, chlorine, an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an alkoxy group having 1 to 11 carbon atoms, or an alkenyloxy group having 2 to 11 carbon atoms, and in which at least one hydrogen may be substituted with fluorine or chlorine;

Z¹is a single bond or an alkylene group having 1 to 10 carbon atoms, in which at least one-CH group₂-may be substituted by-O-, -CO-, -COO-, -OCO-, or-OCOO-, at least one- (CH)₂)₂-may be substituted by-CH ═ CH-or-C ≡ C-, at least one of these groups being substituted by fluorine or chlorine;

Sp¹is a single bond or an alkylene group having 1 to 10 carbon atoms, in which at least one-CH group₂-may be substituted by-O-, -CO-, -COO-, -OCO-, or-OCOO-, at least one- (CH)₂)₂-may be substituted by-CH ═ CH-or-C ≡ C-, of these groups up toAt least one hydrogen may be substituted by fluorine or chlorine;

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

R²a group represented by the formula (1. alpha. a) or the formula (1. alpha. b);

in the formulae (1. alpha. a) and (1. alpha. b),

Sp²and Sp³Independently a single bond or an alkylene group having 1 to 10 carbon atoms, in which at least one-CH group₂At least one- (CH) which may be substituted by-O-, -NH-, -CO-, -COO-, -OCO-or-OCOO-₂)₂-may be substituted by-CH ═ CH-or-C ≡ C-, at least one of these groups being substituted by fluorine or chlorine;

S¹is > CH-or > N-;

item 3. the compound according to item 1 or item 2, which is represented by formula (1 α -2);

in the formula (1 alpha-2),

R¹an 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, wherein at least one hydrogen may be substituted by fluorine or chlorine;

ring A¹And ring A⁴Independently 1, 4-cyclohexylene, 1, 4-cyclohexenylene, 1, 4-phenylene, naphthalene-2, 6-diyl, decahydronaphthalene-2, 6-diyl, 1,2,3, 4-tetrahydronaphthalene-2, 6-diyl, tetrahydropyran-2, 5-diyl, 1, 3-dioxane-2, 5-diyl, pyrimidine-2, 5-diyl, pyridine-2, 5-diyl, perhydrocyclopenta [ a ] o [ a]Phenanthrene-3, 17-diyl or 2,3,4,7,8,9,10,11,12,13,14,15,16, 17-tetradecylcyclopenta [ a [ ]]Phenanthrene-3, 17-diyl, in which at least one hydrogen in a ring may be substituted with fluorine, chlorine, an alkyl group having 1 to 2 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an alkoxy group having 1 to 11 carbon atoms, or an alkenyloxy group having 2 to 11 carbon atoms, and in which at least one hydrogen may be substituted with fluorine or chlorine;

Z¹is a single bond, - (CH)₂)₂-、-CH＝CH-、-C≡C-、-COO-、-OCO-、-CF₂O-、-OCF₂-、-CH₂O-、-OCH₂-or-CF ═ CF —;

Sp¹and Sp²Independently a single bond or an alkylene group having 1 to 10 carbon atoms, in which at least one-CH group₂-may be substituted by-O-, -COO-or-OCO-, at least one- (CH)₂)₂-may be substituted by-CH ═ CH-, where at least one hydrogen may be substituted by fluorine or chlorine;

M¹and M²Independently hydrogen, fluorine, alkyl of carbon number 1 to 5, or alkyl of carbon number 1 to 5 wherein at least one hydrogen is substituted with fluorine;

X¹is-OH, -NH₂、-OR³、-N(R³)₂Formula (x1), -COOH, -SH, -B (OH)₂or-Si (R)³)₃The radicals represented, herein, R³Is hydrogen or alkyl with 1 to 10 carbon atoms, in which at least one-CH₂-may be substituted by-O-at least one- (CH)₂)₂-may be substituted by-CH ═ CH-, where at least one hydrogen may be substituted by fluorine or chlorine, in formula (x1)W of (a) is 1,2,3 or 4;

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

The compound according to any one of items 1 to 3, which is represented by any one of formula (1 α -3) to formula (1 α -6);

in the formulae (1 alpha-3) to (1 alpha-6),

R¹an 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, wherein at least one hydrogen may be substituted by fluorine;

ring A¹Ring A²Ring A³And ring A⁴Independently 1, 4-cyclohexylene, 1, 4-cyclohexenylene, 1, 4-phenylene, naphthalene-2, 6-diyl, decahydronaphthalene-2, 6-diyl, tetrahydropyran-2, 5-diyl, 1, 3-dioxane-2, 5-diyl, perhydrocyclopenta [ a ] pentalene]Phenanthrene-3, 17-diyl or 2,3,4,7,8,9,10,11,12,13,14,15,16, 17-tetradecylcyclopenta [ a [ ]]Phenanthrene-3, 17-diyl, in which at least one hydrogen may be substituted with fluorine, chlorine, an alkyl group having a carbon number of 1 to 7, an alkenyl group having a carbon number of 2 to 7, or an alkoxy group having a carbon number of 1 to 6;

Z¹、Z²and Z³Independently a single bond, - (CH)₂)₂-、-CH＝CH-、-C≡C-、-COO-、-OCO-、-CF₂O-、-OCF₂-、-CH₂O-、-OCH₂-or-CF ═ CF —;

Sp¹and Sp²Independently a single bond or an alkylene group having 1 to 7 carbon atoms, in which at least one-CH group₂-may be substituted by-O-, -COO-, or-OCO-, at least one- (CH)₂)₂-may be substituted by-CH ═ CH-, where at least one hydrogen may be substituted by fluorine;

M¹and M²Independently of one another hydrogen or fluorineMethyl, ethyl, or trifluoromethyl;

X¹is-OH, -NH₂、-OR³、-N(R³)₂Formula (x1), or-Si (R)³)₃The radicals represented, herein, R³Is hydrogen or alkyl with 1 to 5 carbon atoms, in which at least one-CH₂-may be substituted by-O-at least one- (CH)₂)₂-may be substituted by-CH ═ CH-, where at least one hydrogen may be substituted by fluorine, and w in formula (x1) is 1,2,3 or 4;

the compound according to any one of items 1 to 4, which is represented by any one of formula (1 α -7) to formula (1 α -10);

in the formulae (1 alpha-7) to (1 alpha-10),

R¹an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or an alkoxy group having 1 to 9 carbon atoms, wherein at least one hydrogen may be substituted with fluorine;

ring A¹Ring A²Ring A³And ring A⁴Independently 1, 4-cyclohexylene, 1, 4-cyclohexenylene, 1, 4-phenylene, tetrahydropyran-2, 5-diyl, 1, 3-dioxane-2, 5-diyl, perhydrocyclopenta [ a ] o]Phenanthrene-3, 17-diyl or 2,3,4,7,8,9,10,11,12,13,14,15,16, 17-tetradecylcyclopenta [ a [ ]]Phenanthrene-3, 17-diyl, in which at least one hydrogen may be substituted by fluorine, chlorine, 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;

Z¹、Z²and Z³Independently a single bond, - (CH)₂)₂-, or-CH ═ CH-;

Sp¹is a single bond or an alkylene group having 1 to 7 carbon atoms, in which at least one-CH group₂-may be substituted by-O-at least one- (CH)₂)₂-may be substituted by-CH ═ CH-;

Sp²is alkylene with 1 to 7 carbon atoms, in which at least one-CH₂-may be substituted by-O-;

X¹is-OH, -NH₂or-N (R)³)₂Here, R³Is hydrogen or alkyl with 1 to 5 carbon atoms, in which at least one-CH₂-may be substituted by-O-at least one- (CH)₂)₂-may be substituted by-CH ═ CH-, where at least one hydrogen may be substituted by fluorine.

The compound according to any one of items 1 to 5, which is represented by any one of formula (1 α -11) to formula (1 α -14);

in the formulae (1. alpha. -11) to (1. alpha. -14),

ring A¹Ring A²Ring A³And ring A⁴Independently 1, 4-cyclohexylene, 1, 4-phenylene, perhydrocyclopenta [ a ]]Phenanthrene-3, 17-diyl or 2,3,4,7,8,9,10,11,12,13,14,15,16, 17-tetradecylcyclopenta [ a [ ]]Phenanthrene-3, 17-diyl, in which at least one hydrogen may be substituted with fluorine or an alkyl group having 1 to 5 carbon atoms;

Z¹、Z²and Z³Independently is a single bond or- (CH)₂)₂-；

Sp¹Is a single bond or an alkylene group having 1 to 5 carbon atoms, in which at least one-CH group₂-may be substituted by-O-;

Sp²is alkylene with 1 to 5 carbon atoms, in which at least one-CH₂-may be substituted by-O-;

X¹is-OH, -NH₂or-N (R)³)₂Here, R³Is hydrogen or of carbon number 1 to 5Alkyl, in which at least one-CH₂-may be substituted by-O-at least one- (CH)₂)₂-may be substituted by-CH ═ CH-, where at least one hydrogen may be substituted by fluorine.

The compound according to any one of items 1 to 6, which is represented by any one of formula (1 α -15) to formula (1 α -31);

in the formulae (1. alpha. -15) to (1. alpha. -31),

Z¹、Z²and Z³Independently is a single bond or- (CH)₂)₂-；

L¹、L²、L³、L⁴、L⁵、L⁶、L⁷、L⁸、L⁹and L¹⁰Independently hydrogen, fluoro, methyl, or ethyl;

Y¹、Y²、Y³and Y⁴Independently hydrogen or methyl;

X¹is-OH, -NH₂or-N (R)³)₂Here, R³Is hydrogen or alkyl with 1 to 4 carbon atoms, in which at least one-CH₂-may be substituted by-O-, of which groups at least one hydrogen may be substituted by fluorine.

The compound according to any one of items 1 to 7, which is represented by any one of formula (1 α -32) to formula (1 α -43);

in the formulae (1. alpha. -32) to (1. alpha. -43),

R¹an alkyl group having 1 to 10 carbon atoms;

Sp¹is a single bond or an alkylene group having 1 to 5 carbon atoms, in which at least one-CH group₂-may be substituted by-O-, of which groups at least one hydrogen may be substituted by fluorine;

L¹、L²、L³、L⁴、L⁵、L⁶、L⁷、L⁸and L⁹Independently hydrogen, fluoro, methyl or ethyl;

Y¹and Y²Independently hydrogen or methyl;

X¹is-OH, -NH₂or-N (R)³)₂Here, R³Is hydrogen or alkyl with 1 to 4 carbon atoms, in which at least one-CH₂-may be substituted by-O-.

The compound according to any one of items 1 to 8, which is represented by any one of formula (1 α -44) to formula (1 α -63);

in the formulae (1. alpha. -44) to (1. alpha. -63),

R¹an alkyl group having 1 to 10 carbon atoms;

Sp¹is a single bond or an alkylene group having 1 to 3 carbon atoms, in which at least one-CH group₂-may be substituted by-O-, in which groups at least one hydrogen may be substituted by fluorine;

L¹、L²、L³、L⁴and L⁵Independently hydrogen, fluoro, methyl or ethyl;

Y¹and Y²Independently hydrogen or methyl;

R³independently hydrogen, methyl or ethyl.

An item 10. a liquid crystal composition containing at least one compound according to any one of items 1 to 9 as an orientation monomer.

Item 11. the liquid crystal composition according to item 10, which further contains at least one compound selected from the group of compounds represented by formulae (2) to (4);

in the formulae (2) to (4),

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

Item 12. the liquid crystal composition according to item 10 or item 11, which further contains at least one compound selected from the group of compounds represented by formulae (5) to (7);

in the formulae (5) to (7),

R¹³is alkyl with 1 to 10 carbon atoms or alkenyl with 2 to 10 carbon atoms, and at least one-CH in the alkyl and the alkenyl₂-may be substituted by-O-, at least one hydrogen may be substituted by fluorine;

L¹¹And L¹²Independently hydrogen, or fluorine.

Item 13. the liquid crystal composition according to item 10 or item 11, which further contains at least one compound selected from the group of compounds represented by formula (8);

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

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

L¹³And L¹⁴Independently hydrogen or fluorine;

i is 1,2,3 or 4.

Item 14. the liquid crystal composition according to item 10 or item 11, which further contains at least one compound selected from the group of compounds represented by formulae (9) to (15);

in the formulae (9) to (15),

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

L¹⁵And L¹⁶Independently fluorine or chlorine;

S¹¹is hydrogen or methyl;

x is independently-CHF-or-CF₂-；

Item 15. the liquid crystal composition according to any one of item 10 to item 14, which contains at least one compound selected from the group of polymerizable compounds represented by formula (16 α) as a reactive monomer;

in the formula (16 a), in the formula,

Z²²and Z²³Independently a single bond or an alkylene group having 1 to 10 carbon atoms in which at least one-CH group₂-may be substituted by-O-, -CO-, -COO-, or-OCO-, at least one- (CH)₂)₂-may be via-CH ═ CH-, -C (CH)₃)＝CH-、-CH＝C(CH₃) -, or-C (CH)₃)＝C(CH₃) -substitution, of which at least one hydrogen may be substituted by fluorine or chlorine;

P¹¹、P¹²and P¹³Independently a polymerizable group;

u is 0,1 or 2;

Item 16. the liquid crystal composition of item 15, wherein in the formula (16 α) of item 15, P¹¹、P¹²And P¹³Independently 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),

Item 17. the liquid crystal composition according to any one of item 10 to item 16, which contains at least one polymerizable compound selected from the group of compounds represented by formulae (16 α -1) to (16 α -27);

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

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

Sp¹¹、Sp¹²and Sp¹³Independently a single bond or an alkylene group having 1 to 10 carbon atoms, in which at least one-CH group₂-may be substituted by-O-, -COO-, -OCO-, or-OCOO-, at least one- (CH)₂)₂-may be substituted by-CH ═ CH-or-C ≡ C-, at least one of these groups being substituted by fluorine or chlorine.

The liquid crystal composition according to any one of items 10 to 17, further comprising at least one selected from a polymerizable compound different from the polymerizable compounds represented by the formulae (1 α) and (16 α), a polymerization initiator, a polymerization inhibitor, an optically active compound, an antioxidant, an ultraviolet absorber, a light stabilizer, a heat stabilizer, and an antifoaming agent.

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

1-2 forms of Compound (1. alpha.)

The compound (1 α) has a mesogen portion comprising at least one ring and an acryloyloxy group substituted with a polar group such as a hydroxyalkyl group. The compound (1 α) is useful because the polar group interacts with the substrate surface in a noncovalent manner. One of the applications is an additive for a liquid crystal composition used in a liquid crystal display element. The compound (1 α) is added for the purpose of controlling the alignment of liquid crystal molecules. Such an additive preferably has high solubility in a liquid crystal composition, is chemically stable under the condition of being sealed in an element, and has a large voltage holding ratio when used in a liquid crystal display element. The compound (1 α) satisfies this characteristic to a considerable extent.

Preferred examples of the compound (1 α) are described below. R in Compound (1 α)¹、MES、Sp¹、R²、M¹Or M²The preferred embodiment of (2) also applies to the lower formula of the compound (1. alpha.). In the compound (1 α), the properties can be arbitrarily adjusted by appropriately combining the types of these groups. Since there is no great difference in the characteristics of the compounds, the compound (1. alpha.) may also be contained in an amount larger than that of the naturally occurring ratio²H (deuterium),¹³C is an isotope.

In the formula (1 α), R¹Is an alkyl group having 1 to 15 carbon atoms, in which at least one-CH group₂-may be substituted by-O-or-S-, at least one- (CH)₂)₂-may be substituted by-CH ═ CH-or-C ≡ C-, at least one of these groups being substituted by fluorine or chlorine.

In the formula (1. alpha.), R is preferred¹Is alkyl group having 1 to 15 carbon atoms, alkenyl group having 2 to 15 carbon atoms, alkoxy group having 1 to 14 carbon atoms, or alkenyloxy group having 2 to 14 carbon atoms. Further preferred is R¹Is an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or an alkoxy group having 1 to 9 carbon atoms. Particularly preferred R¹Is an alkyl group having 1 to 10 carbon atoms.

In the formula (1 α), MES is a mesogen having at least one ring. Mesogenic groups are well known to those skilled in the art. The mesogen refers to a portion that contributes to the formation of a liquid crystal phase when the compound has a liquid crystal phase (mesophase). A preferable example of the compound (1 α) is a compound (1 α -1).

Preferred ring A in formula (1. alpha. -1)¹Or ring A⁴Is 1, 4-cyclohexylene, 1, 4-cyclohexenylene, 1, 4-phenylene, naphthalene-2, 6-diyl, decahydronaphthalene-2, 6-diyl, 1,2,3, 4-tetrahydronaphthalene-2, 6-diyl, tetrahydropyran-2, 5-diyl, 1, 3-dioxane-2, 5-diyl, pyrimidine-2, 5-diyl, pyridine-2, 5-diyl, perhydrocyclopenta [ a ] a]Phenanthrene-3, 17-diyl or 2,3,4,7,8,9,10,11,12,13,14,15,16, 17-tetradecylcyclopenta [ a [ ]]Phenanthrene-3, 17-diyl, in which at least one hydrogen may be substituted by fluorine, chlorine, an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an alkoxy group having 1 to 11 carbon atoms, or an alkenyloxy group having 2 to 11 carbon atoms, and in which at least one hydrogen may be substituted by fluorine or chlorine. Further preferred is ring A¹Or ring A⁴Is 1, 4-cyclohexylene, 1, 4-phenylene, perhydrocyclopenta [ a ]]The content of the phenanthrene-3,17-diyl or 2,3,4,7,8,9,10,11,12,13,14,15,16, 17-tetradecylcyclopenta [ a ]]Phenanthrene-3, 17-diyl, in which at least one hydrogen may be substituted by fluorine or an alkyl group having 1 to 5 carbon atoms. Particularly preferred ring A¹Or ring A⁴Is 1, 4-cyclohexylene, 1, 4-phenylene, perhydrocyclopenta [ a ]]Phenanthrene-3, 17-diyl, in which rings at least one hydrogen may be substituted by fluorine, methyl or ethyl, for example as 1-methyl-1, 4-cyclohexylene, 2-ethyl-1, 4-cyclohexylene, 2-fluoro-1, 4-phenylene.

In the formula (1 alpha-1), Z¹Is a single bond or an alkylene group having 1 to 10 carbon atoms, in which at least one-CH group₂-may be substituted by-O-, -CO-, -COO-, -OCO-, or-OCOO-, at least one- (CH)₂)₂-may be substituted by-CH ═ CH-or-C ≡ C-, at least one of these groups being substituted by fluorine or chlorine.

In the formula (1. alpha. -1), Z is preferred¹Is a single bond, - (CH)₂)₂-、-CH＝CH-、-C≡C-、-COO-、-OCO-、-CF₂O-、-OCF₂-、-CH₂O-、-OCH₂-, or-CF ═ CF-. Further preferred is Z¹Is a single bond, - (CH)₂)₂-, or-CH ═ CH-. Particularly preferred Z¹Is a single bond.

In the formula (1 alpha-1), a is 0,1, 2,3 or 4. Preferably a is 0,1, 2, or 3. Further, a is preferably 0,1 or 2.

Sp in the formula (1 alpha) and the formula (1 alpha-1)¹Is a single bond or an alkylene group having 1 to 10 carbon atoms, in which at least one-CH group₂At least one- (CH) which may be substituted by-O-, -CO-, -COO-, -OCO-or-OCOO-₂)₂-may be substituted by-CH ═ CH-or-C ≡ C-, at least one of these groups being substituted by fluorine or chlorine.

In the formula (1 α), Sp is preferred¹Is a single bond, alkylene having 1 to 5 carbon atoms, or one-CH₂-C1 to C5 alkylene substituted by-O-. Further preferred is Sp¹Is a single bond, alkylene having 1 to 3 carbon atoms, or one-CH₂-C1 to C3 alkylene substituted by-O-.

In the formula (1 alpha) and the formula (1 alpha-1), M¹And M²Independently hydrogen, fluorine, chlorine, an alkyl group having 1 to 5 carbon atoms, or an alkyl group having 1 to 5 carbon atoms in which at least one hydrogen is substituted with fluorine or chlorine. Preferred M¹Or M²Is hydrogen, fluorine, methyl, ethyl or trifluoromethyl. Further preferred is M¹Or M²Is hydrogen.

In the formula (1 alpha) and the formula (1 alpha-1), R²Is a group represented by the formula (1. alpha. a), the formula (1. alpha. b) or the formula (1. alpha. c). Preferred R²Is a group represented by the formula (1. alpha. a) or the formula (1. alpha. b). Further preferred is R²Is a group represented by the formula (1. alpha. a).

In the formulae (1. alpha. a), (1. alpha. b) and (1. alpha. c), Sp²And Sp³Independently a single bond or an alkylene group having 1 to 10 carbon atoms, in which at least one-CH group₂At least one- (CH) which may be substituted by-O-, -NH-, -CO-, -COO-, -OCO-or-OCOO-₂)₂-may be substituted by-CH ═ CH-or-C ≡ C-, at least one of these groups being substituted by fluorine or chlorine.

Among the formulae (1 α a), (1 α b) and (1 α c), Sp is preferable²Or Sp³Is alkylene having 1 to 7 carbon atoms, or one-CH₂-C1 to C5 alkylene substituted by-O-. Further preferred is Sp²Or Sp³Is alkylene having 1 to 5 carbon atoms, or one-CH₂-C1 to C5 alkylene substituted by-O-. Particularly preferred is Sp²Or Sp³is-CH₂-。

In the formulae (1. alpha. a), (1. alpha. b) and (1. alpha. c), S¹Is > CH-or > N-; s²Is > C < or > Si <. Preferred is S¹Is > CH-or > N-, preferably S²Is > C <. Formula (1b) is superior to formula (1 c).

In the formulae (1. alpha. a), (1. alpha. b) and (1. alpha. c), X¹Independently is-OH, -NH₂、-OR³、-N(R³)₂Formula (x1), -COOH, -SH, -B (OH)₂or-Si (R)³)₃The radicals represented, herein, R³Is hydrogenOr an alkyl group having 1 to 10 carbon atoms, in which at least one-CH group₂-may be substituted by-O-at least one- (CH)₂)₂-may be substituted by-CH ═ CH-, where at least one hydrogen may be substituted by fluorine or chlorine, and w in formula (x1) is 1,2,3 or 4.

Among the formulae (1 α a), (1 α b) and (1 α c), X is preferable¹is-OH, -NH₂、-OR³、-N(R³)₂Formula (x1), or-Si (R)³)₃The radicals represented, herein, R³Is hydrogen or alkyl with 1 to 5 carbon atoms, in which at least one-CH₂-may be substituted by-O-at least one- (CH)₂)₂-may be substituted by-CH ═ CH-, where at least one hydrogen may be substituted by fluorine, and w in formula (x1) is 1,2,3 or 4. Further preferred is X¹is-OH, -NH₂or-N (R)³)₂. Particularly preferred X¹is-OH.

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

In the formula (16 α), P¹¹、P¹²And P¹³Independently a polymerizable group. Preferred P¹¹、P¹²Or P¹³Is a polymerizable group selected from the group of groups represented by the formulae (P-1) to (P-5). Further preferred is P¹¹、P¹²Or P¹³Is a group (P-1), a group (P-2) or a group (P-3). A particularly preferred radical (P-1) is-OCO-CH＝CH₂or-OCO-C (CH)₃)＝CH₂. The wavy line from the group (P-1) to the group (P-5) represents the site of the bond.

In the groups (P-1) to (P-5), M¹¹、M¹²And M¹³Independently hydrogen, fluorine, alkyl of carbon number 1 to 5 or alkyl of carbon number 1 to 5 wherein at least one hydrogen is substituted by fluorine or chlorine. For the purpose of enhancing reactivity, M is preferred¹¹、M¹²Or M¹³Is hydrogen or methyl. Further preferred is M¹¹Is methyl, more preferably M¹²Or M¹³Is hydrogen.

In the formula (16 α), Sp¹¹、Sp¹²And Sp¹³Independently a single bond or an alkylene group having 1 to 10 carbon atoms, in which at least one-CH group₂At least one- (CH) which may be substituted by-O-, -COO-, -OCO-or-OCOO-₂)₂-may be substituted by-CH ═ CH-or-C ≡ C-, at least one of these groups being substituted by fluorine or chlorine. Preferred is Sp¹¹、Sp¹²Or Sp¹³Is a single bond.

In formula (16 α), 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, and in these rings, at least one hydrogen may be substituted with fluorine or chlorine, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or an alkyl group having 1 to 12 carbon atoms in which at least one hydrogen is substituted with fluorine or chlorine. Preferred ring F or ring I is phenyl. Ring G is 1, 4-cyclohexylene, 1, 4-cyclohexenylene, 1, 4-phenylene, naphthalene-1, 2-diyl, naphthalene-1, 3-diyl, naphthalene-1, 4-diyl, naphthalene-1, 5-diyl, naphthalene-1, 6-diyl, naphthalene-1, 7-diyl, naphthalene-1, 8-diyl, naphthalene-2, 3-diyl, naphthalene-2, 6-diyl, naphthalene-2, 7-diyl, tetrahydropyran-2, 5-diyl, 1, 3-dioxane-2, 5-diyl, pyrimidine-2, 5-diyl, or pyridine-2, 5-diyl, and in these rings, at least one of them is substituted with fluorine, chlorine, an alkyl group having 1 to 12 carbon atoms, An alkoxy group having 1 to 12 carbon atoms, or an alkyl group having 1 to 12 carbon atoms in which at least one hydrogen is substituted with fluorine or chlorine. Particularly preferred ring G is 1, 4-phenylene or 2-fluoro-1, 4-phenylene.

In the formula (16 α), Z²²And Z²³Independently a single bond or an alkylene group having 1 to 10 carbon atoms, in which at least one-CH group₂-may be substituted by-O-, -CO-, -COO-, or-OCO-, at least one- (CH)₂)₂-may be via-CH ═ CH-, -C (CH)₃)＝CH-、-CH＝C(CH₃) -, or-C (CH)₃)＝C(CH₃) -substitution, of which at least one hydrogen may be substituted by fluorine or chlorine. Preferred Z⁷Or Z⁸Is a single bond, - (CH)₂)₂-、-CH₂O-、-OCH₂-, -COO-, or-OCO-. Further preferred is Z²²Or Z²³Is a single bond.

In the formula (16 α), u is 0,1 or 2. Preferably u is 0 or 1. f. g and h are independently 0,1, 2,3 or 4, and the sum of f, g and h is 1 or more. Preferred f, g or h is 1 or 2.

2. Synthesis of Compound (1. alpha.)

The synthesis method of compound (1 α) will be described. Compound (1. alpha.) can be synthesized by the method described in International publication No. 2016/129490. In addition, the compound can also be synthesized by appropriately combining known methods of organic synthetic chemistry. Reference may also be made to "Organic Synthesis" (Organic Synthesis, John Wiley & Sons, Inc.), "Organic Reactions" (Organic Reactions, John Wiley & Sons, Inc.), "Integrated Organic Synthesis" (Pergamon Press), and "New Experimental chemistry lecture" (Bolus).

3. Compound (1 beta)

3-1. exemplary Compound (1. beta.) and liquid Crystal composition Using the same

The present example includes the following items and the like.

A compound represented by formula (1 β);

in the formula (1 beta), the compound (B),

MES is a mesogen having at least one ring;

Sp¹is a single bond or an alkylene group having 1 to 10 carbon atoms, in which at least one-CH group₂-may be substituted by-O-, -CO-, -COO-, -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 fluoro or chloro;

The compound of item 22, which is represented by formula (1 β -1);

in the formula (1 beta-1),

ring A¹And ring A⁴Independently 1, 4-cyclohexylene, 1, 4-cyclohexenylene, 1, 4-phenylene, naphthalene-2, 6-diyl, decahydronaphthalene-2, 6-diyl, 1,2,3, 4-tetrahydronaphthalene-2, 6-diyl, tetrahydropyran-2, 5-diyl, 1, 3-dioxane-2, 5-diyl, pyrimidine-2, 5-diyl, pyridine-2, 5-diyl, fluorene-2, 7-diyl, phenanthrene-2, 7-diyl, anthracene-2, 6-diyl, perhydrocyclopenta [ a]Phenanthrene-3, 17-diyl, or 2,3,4,7,8,9,10,11,12,13,14,15,16, 17-tetradecylcyclopenta [ a [ ]]Phenanthrene-3, 17-diyl, in which at least one hydrogen in a ring may be substituted with fluorine, chlorine, an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an alkoxy group having 1 to 11 carbon atoms, or an alkenyloxy group having 2 to 11 carbon atoms, and in which at least one hydrogen may be substituted with fluorine or chlorine;

Z¹is a single bond or an alkylene group having 1 to 4 carbon atoms, in which at least one-CH group₂-may be substituted by-O-, -CO-, -COO-, -OCO-, or-OCOO-, at least one- (CH)₂)₂-may be substituted by-CH ═ CH-or-C ≡ C-, at least one of these groups being substituted by fluorine or chlorine;

R²、M¹、M²and M³Independently hydrogen, fluorine, chlorine or an alkyl group of carbon number 1 to 8, in which at least one-CH₂-may be substituted by-O-or-S-, at least one- (CH)₂)₂-may be substituted by-CH ═ CH-or-C ≡ C-, at least one of these groups being substituted by fluorine or chlorine;

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

in which a is 0 and ring A⁴In the case of 1, 4-cyclohexylene or 1, 4-phenylene, R¹Is an alkyl group having 5 to 15 carbon atoms, in which at least one-CH group₂-may be substituted by-O-or-S-, at least one- (CH)₂)₂-may be substituted by-CH ═ CH-or-C ≡ C-, at least one of these groups being substituted by fluorine or chlorine;

in which a is 0 and ring A⁴Is perhydrocyclopenta [ a ]]Phenanthrene-3, 17-diyl or 2,3,4,7,8,9,10,11,12,13,14,15,16, 17-tetradecylcyclopenta [ a [ ]]Phenanthrene-3, 17-diyl, M¹Is fluorine, chlorine or alkyl with 1 to 8 carbon atoms, and at least one-CH in the alkyl₂Optionally via-O-or-S-extractionGeneration, at least one- (CH)₂)₂-may be substituted by-CH ═ CH-or-C ≡ C-, at least one of these groups being substituted by fluorine or chlorine.

The compound of item 21 or item 22, represented by any one of formula (1 β -3) to formula (1 β -6);

in the formulae (1. beta. -3) to (1. beta. -6),

Sp¹is a single bond or an alkylene group having 1 to 7 carbon atoms, in which at least one-CH group₂-may be substituted by-O-, -COO-or-OCO-, at least one- (CH)₂)₂-may be substituted by-CH ═ CH-, where at least one hydrogen may be substituted by fluorine;

R²、M¹、M²and M³Independently hydrogen or an alkyl group of 1 to 8 carbon atoms, in which at least one-CH group₂-may be substituted by-O-at least one- (CH)₂)₂-may be substituted by-CH ═ CH-In which at least one hydrogen may be substituted by fluorine or chlorine;

in the formula (1. beta. -3), in the ring A⁴In the case of 1, 4-cyclohexylene or 1, 4-phenylene, R¹An alkyl group having 5 to 15 carbon atoms, an alkenyl group having 5 to 15 carbon atoms, an alkoxy group having 4 to 14 carbon atoms or an alkenyloxy group having 4 to 14 carbon atoms, wherein at least one hydrogen may be substituted by fluorine;

in the formula (1. beta. -3), at ring A⁴Is perhydrocyclopenta [ a ]]Phenanthrene-3, 17-diyl or 2,3,4,7,8,9,10,11,12,13,14,15,16, 17-tetradecylcyclopenta [ a [ ]]Phenanthrene-3, 17-diyl, M¹Is an alkyl group having 1 to 8 carbon atoms, in which at least one-CH group₂-may be substituted by-O-at least one- (CH)₂)₂-may be substituted by-CH ═ CH-, where at least one hydrogen may be substituted by fluorine or chlorine.

The compound of any one of items 21 to 23, represented by any one of formulae (1 β -3) to (1 β -6);

in the formulae (1. beta. -3) to (1. beta. -6),

M²and M³Is hydrogen;

R¹is alkyl with 1 to 10 carbon atoms, alkenyl with 2 to 10 carbon atoms or alkoxy with 1 to 9 carbon atoms;

Z¹、Z²and Z³Independently is a single bond or- (CH)₂)₂-；

M¹and R²Independently of each otherIs hydrogen or alkyl with 1 to 5 carbon atoms, in which at least one-CH₂-may be substituted by-O-;

in the formula (1. beta. -3), in the ring A⁴In the case of 1, 4-cyclohexylene or 1, 4-phenylene, R¹Is alkyl with carbon number of 5 to 10, alkenyl with carbon number of 5 to 10 or alkoxy with carbon number of 4 to 9;

in the formula (1. beta. -3), in the ring A⁴Is perhydrocyclopenta [ a ]]Phenanthrene-3, 17-diyl or 2,3,4,7,8,9,10,11,12,13,14,15,16, 17-tetradecylcyclopenta [ a [ ]]Phenanthrene-3, 17-diyl, M¹Is an alkyl group having 1 to 5 carbon atoms, in which at least one-CH group₂-may be substituted by-O-.

The compound of any one of items 21 to 24, represented by any one of formulae (1 β -7) to (1 β -20);

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

Z¹、Z²and Z³Independently is a single bond or- (CH)₂)₂-；

L¹、L²、L³、L⁴、L⁵、L⁶、L⁷、L⁸、L⁹、L¹⁰、L¹¹、L¹²、L¹³and L¹⁴Independently hydrogen, fluoro, methyl or ethyl;

Y¹、Y²、Y³and Y⁴Independently of the other substituents, is hydrogen or methyl,

M¹hydrogen or alkyl having 1 to 5 carbon atoms;

M⁴an alkyl group having 1 to 5 carbon atoms;

R²is hydrogen, methyl or ethyl.

The compound of any one of items 21 to 24, represented by any one of formula (1 β -21) to formula (1 β -29);

in the formulae (1. beta. -21) to (1. beta. -29),

R¹an alkyl group having 1 to 10 carbon atoms;

L¹、L²、L³、L⁴、L⁵、L⁶、L⁷、L⁸、L⁹、L¹⁰、L¹¹and L¹²Independently hydrogen, fluoro, methyl, or ethyl;

Y¹and Y²Independently hydrogen or methyl;

M¹is hydrogen, methyl or ethyl;

M⁴is methyl or ethyl;

R²is hydrogen or methyl.

The compound of any one of items 21 to 24, represented by any one of formulae (1 β -30) to (1 β -36);

in the formulae (1. beta. -30) to (1. beta. -36),

R¹an alkyl group having 1 to 10 carbon atoms;

Sp¹is a single bond or an alkylene group having 1 to 3 carbon atoms, in which at least one-CH group₂optionally-through-O-substitution;

L¹、L²、L³、L⁴and L⁵Independently hydrogen, fluoro, methyl or ethyl;

Y¹and Y²Independently hydrogen or methyl;

R²is hydrogen or methyl.

A liquid crystal composition comprising at least one compound according to any one of items 21 to 27 as an orientation monomer.

Item 29. the liquid crystal composition according to item 28, which further contains at least one compound selected from the group of compounds represented by formulae (2) to (4). The structural formulae and symbols of these compounds are as defined in item 11.

Item 30. the liquid crystal composition of item 28 or item 29, further comprising at least one compound selected from the group of compounds represented by formulae (5) to (7). The structural formulae and symbols of these compounds are as defined in item 12.

Item 31 the liquid crystal composition of item 28 or item 29, further comprising at least one compound selected from the group of compounds represented by formula (8). The structural formulae and symbols of these compounds are as defined in item 13.

Item 32. the liquid crystal composition of item 28 or item 29, further comprising at least one compound selected from the group of compounds represented by formulae (9) to (15). The structural formulae and symbols of these compounds are as defined in item 14.

Item 33. the liquid crystal composition of any one of items 28 to 32, which further contains at least one compound selected from the group of polymerizable compounds represented by formula (16 α) as a reactive monomer. The structural formulae and symbols of these compounds are as defined in item 15. The preferred form of the compound (16 α) is as described above.

Item 34 the liquid crystal composition of item 33, wherein in the formula (16 α) of item 33, P¹¹、P¹²And P¹³Independently a group selected from the group of polymerizable groups represented by the formulae (P-1) to (P-5). The structural formulae and symbols of these compounds are as defined in item 16.

Item 35. the liquid crystal composition according to any one of item 28 to item 34, which contains at least one compound selected from the group of polymerizable compounds represented by formulae (16 α -1) to (16 α -27). The structural formulae and symbols of these compounds are as defined in item 17.

The liquid crystal composition according to any one of items 28 to 35, further comprising at least one selected from the group consisting of a polymerizable compound different from the polymerizable compounds represented by the formulae (1 α) and (16 α), a polymerization initiator, a polymerization inhibitor, an optically active compound, an antioxidant, an ultraviolet absorber, a light stabilizer, a heat stabilizer, and an antifoaming agent.

The present example also includes the items (a) to (f) described in the next paragraph of the item 18.

3-2 form of Compound (1. beta.)

The compound (1 β) has a mesogen portion composed of at least one ring and an acrylamide group. The compound (1 β) is useful because the polar group interacts with the substrate surface in a noncovalent manner. One of the applications is an additive for a liquid crystal composition used in a liquid crystal display element. The compound (1 β) is added for the purpose of controlling the alignment of liquid crystal molecules. Such an additive preferably has high solubility in a liquid crystal composition and is chemically stable under the condition of being sealed in an element, and has a large voltage holding ratio when used in a liquid crystal display element. The compound (1 β) satisfies this property to a considerable extent.

Preferred examples of the compound (1 β) will be described. R in Compound (1. beta.)¹、MES、Sp¹、M¹、R²、M²Or M³The preferred embodiment of (4) also applies to the lower formula of the compound (1. beta.). In the compound (1 β), the properties can be arbitrarily adjusted by appropriately combining the types of these groups. Since there is no great difference in the characteristics of the compounds, the compound (1. beta.) may be usedContaining more than the amount of naturally occurring²H (deuterium),¹³C is an isotope.

In the formula (1. beta.), R¹Is an alkyl group having 1 to 15 carbon atoms, in which at least one-CH group₂-may be substituted by-O-or-S-, at least one- (CH)₂)₂-may be substituted by-CH ═ CH-or-C ≡ C-, in which groups at least one hydrogen may be substituted by fluorine or chlorine.

In the formula (1. beta.), R is preferred¹Is alkyl group having 1 to 15 carbon atoms, alkenyl group having 2 to 15 carbon atoms, alkoxy group having 1 to 14 carbon atoms, or alkenyloxy group having 2 to 14 carbon atoms. Further preferred is R¹Is an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or an alkoxy group having 1 to 9 carbon atoms. Particularly preferred R¹Is an alkyl group having 1 to 10 carbon atoms.

In the formula (1. beta.), MES is a mesogen having at least one ring. Mesogenic groups are well known to those skilled in the art. The mesogen refers to a portion that contributes to the formation of a liquid crystal phase when the compound has a liquid crystal phase (mesophase). A preferable example of the compound (1. beta.) is a compound (1. beta. -1).

Preferred ring A in formula (1. beta. -1)¹Or ring A⁴Is 1, 4-cyclohexylene, 1, 4-cyclohexenylene, 1, 4-phenylene, naphthalene-2, 6-diyl, decahydronaphthalene-2, 6-diyl, 1,2,3, 4-tetrahydronaphthalene-2, 6-diyl, tetrahydropyran-2, 5-diyl, 1, 3-dioxane-2, 5-diyl, pyrimidine-2, 5-diyl, pyridine-2, 5-diyl, perhydrocyclopenta [ a ] a]Phenanthrene-3, 17-diyl or 2,3,4,7,8,9,10,11,12,13,14,15,16, 17-tetradecylcyclopenta [ a [ ]]Phenanthrene-3, 17-diyl, in which at least one hydrogen may be substituted by fluorine, chlorine, an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an alkoxy group having 1 to 11 carbon atoms, or an alkenyloxy group having 2 to 11 carbon atoms, and in which at least one hydrogen may be substituted by fluorine or chlorine. Further preferred isRing A of¹Or ring A⁴Is 1, 4-cyclohexylene, 1, 4-phenylene, perhydrocyclopenta [ a ]]Phenanthrene-3, 17-diyl or 2,3,4,7,8,9,10,11,12,13,14,15,16, 17-tetradecylcyclopenta [ a [ ]]Phenanthrene-3, 17-diyl, in which at least one hydrogen may be substituted by fluorine or an alkyl group having 1 to 5 carbon atoms. Particularly preferred ring A¹Or ring A⁴Is 1, 4-cyclohexylene, 1, 4-phenylene, perhydrocyclopenta [ a ]]Phenanthrene-3, 17-diyl, in which rings at least one hydrogen may be substituted by fluorine, methyl or ethyl.

In the formula (1 beta-1), Z¹Is a single bond or an alkylene group having 1 to 10 carbon atoms, in which at least one-CH group₂-may be substituted by-O-, -CO-, -COO-, -OCO-, or-OCOO-, at least one- (CH)₂)₂-may be substituted by-CH ═ CH-or-C ≡ C-, at least one of these groups being substituted by fluorine or chlorine.

In the formula (1. beta. -1), Z is preferred¹Is a single bond, - (CH)₂)₂-、-CH＝CH-、-C≡C-、-COO-、-OCO-、-CF₂O-、-OCF₂-、-CH₂O-、-OCH₂-, or-CF ═ CF-. Further preferred is Z¹Is a single bond, - (CH)₂)₂-, or-CH ═ CH-. Particularly preferred Z¹Is a single bond.

In the formula (1 beta-1), a is 0,1, 2,3 or 4. Preferably a is 0,1, 2, or 3. Further, a is preferably 0,1 or 2.

In the formulae (1. beta.) to (1. beta. -1), Sp¹Is a single bond or an alkylene group having 1 to 10 carbon atoms, in which at least one-CH group₂At least one- (CH) which may be substituted by-O-, -CO-, -COO-, -OCO-or-OCOO-₂)₂-may be substituted by-CH ═ CH-or-C ≡ C-, at least one of these groups being substituted by fluorine or chlorine.

Among the formula (1. beta.), Sp is preferred¹Is a single bond, alkylene having 1 to 5 carbon atoms, or one-CH₂-C1 to C5 alkylene substituted by-O-. Further preferred is Sp¹Is a single bond, alkylene having 1 to 3 carbon atoms, or one-CH₂-C1 to C3 alkylene substituted by-O-.

In the formula (1. beta.) and the formula (1. beta. -1), M²And M³Independently hydrogen, fluorine, chlorine, an alkyl group having 1 to 5 carbon atoms, or an alkyl group having 1 to 5 carbon atoms in which at least one hydrogen is substituted with fluorine or chlorine. Preferred M²Or M³Is hydrogen, fluorine, methyl, ethyl or trifluoromethyl. Further preferred is M²Or M³Is hydrogen.

In the formula (1. beta.) and the formula (1. beta. -1), R²Hydrogen, fluorine, chlorine, an alkyl group having 1 to 5 carbon atoms, or an alkyl group having 1 to 5 carbon atoms in which at least one hydrogen is substituted with fluorine or chlorine. Preferred R²Hydrogen, methyl, ethyl. Further preferred is R²Is hydrogen.

In the formula (1. beta.) and the formula (1. beta. -1), M¹Hydrogen, fluorine, chlorine, an alkyl group having 1 to 5 carbon atoms, or an alkyl group having 1 to 5 carbon atoms in which at least one hydrogen is substituted with fluorine or chlorine. Preferred M¹Is hydrogen, fluorine, methyl, ethyl or trifluoromethyl. Further preferred is M¹Is methyl.

In the formulae (2) to (15), component compounds of the liquid crystal composition are shown. The compounds (2) to (4) have small dielectric anisotropy. The compounds (5) to (7) have positive large dielectric anisotropy. The compound (8) has a cyano group and thus has a positive and larger dielectric anisotropy. The compounds (9) to (15) have negative large dielectric anisotropy. Specific examples of these compounds will be described later. In the formula (16 α), the preferred embodiment is as described above.

4. Synthesis of Compound (1. beta.)

The synthesis method of compound (1 β) will be described. Compound (1 β) can be synthesized by the method described in international publication No. 2017/014013. In addition, the compound can also be synthesized by appropriately combining known methods of organic synthetic chemistry. Reference may also be made to "Organic Synthesis" (Organic Synthesis, John Wiley & Sons, Inc.), "Organic Reactions" (Organic Reactions, John Wiley & Sons, Inc.), "Integrated Organic Synthesis" (Pergamon Press), and "New Experimental chemistry lecture" (Bolus).

5. Compound (1 gamma)

5-1. exemplary Compound (1. gamma.) and liquid Crystal composition Using the same

The present example includes the following items and the like.

Item 41. a compound represented by formula (1 γ);

in the formula (1. gamma.) wherein,

n is independently 0,1 or 2;

Z¹and Z⁵Independently a single bond or an alkylene group having 1 to 10 carbon atoms, in which at least one-CH group₂At least one- (CH) which may be substituted by-O-, -COO-, -OCO-or-OCOO-₂)₂-may be substituted by-CH ═ CH-or-C ≡ C-, at least one of these groups being substituted by fluorine or chlorine;

Sp¹、Sp²and Sp³Independently a single bond or an alkylene group having 1 to 10 carbon atoms, in which at least one-CH group₂At least one- (CH) which may be substituted by-O-, -COO-, -OCO-or-OCOO-₂)₂-may be taken via-CH ═ CH-or-C ≡ C-And, in these radicals, at least one hydrogen may be substituted by fluorine or chlorine;

a and b are independently 0,1, 2,3 or 4, and the sum of a and b is 1,2,3 or 4;

c. d and e are independently 0,1, 2,3, or 4;

c. the sum of d and e is 2,3, or 4;

in the formula (P-1),

in the formulae (1. gamma. a), (1. gamma. b) and (1. gamma. c),

S¹is > CH-or > N-;

S²is > C < or > Si <;

X¹independently is-OH, -NH₂、-OR⁵、-N(R⁵)₂、-COOH、-SH、-B(OH)₂or-Si (R)⁵)₃The radicals represented, herein, R⁵Is hydrogen or an alkyl group having 1 to 10 carbon atoms, of which alkyl group, up toOne less-CH₂-may be substituted by-O-at least one- (CH)₂)₂-may be substituted by-CH ═ CH-, where at least one hydrogen may be substituted by fluorine or chlorine.

Item 42. the compound of item 41, wherein in formula (P-1), R⁴Is a group represented by formula (1 γ a) or formula (1 γ b).

Item 43 the compound of item 41 or item 42, wherein in formula (1 γ), R⁴Represented by formula (1 γ a), and c, d and e are 0,1, 2 or 3, and the sum of c, d and e is 2,3 or 4.

The compound of any one of items 41 to 43, represented by any one of formulae (1 γ -1) to (1 γ -6);

in the formulae (1. gamma. -1) to (1. gamma. -6),

R¹、R²and R³Independently hydrogen, an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an alkoxy group having 1 to 11 carbon atoms, or an alkenyloxy group having 2 to 11 carbon atoms, at least one of which may be substituted with fluorine;

ring A¹Ring A²Ring A³Ring A⁴Ring A⁵And ring A⁶Independently cyclohexylene, cyclohexenylene, phenylene, naphthalene, tetrahydropyran, or 1, 3-dioxane, in which at least one hydrogen may be substituted by fluorine, chlorine, an alkyl group having a carbon number of 1 to 10, an alkenyl group having a carbon number of 2 to 10, an alkoxy group having a carbon number of 1 to 9, or an alkenyloxy group having a carbon number of 2 to 9, and in which at least one hydrogen may be substituted by fluorine or chlorine;

Z¹、Z²、Z³、Z⁵and Z⁶Independently a single bond or an alkylene group having 1 to 8 carbon atoms, in which at least one-CH group₂-may be substituted by-O-, -COO-, or-OCO-, at least one- (CH)₂)₂-may be substituted by-CH ═ CH-or-C ≡ C-, at least one of these groups being substituted by fluorine or chlorine;

Sp¹、Sp²、Sp³and Sp⁴Independently a single bond or an alkylene group having 1 to 8 carbon atoms, in which at least one-CH group₂-may be substituted by-O-, -COO-, or-OCO-, at least one- (CH)₂)₂-may be substituted by-CH ═ CH-or-C ≡ C-, at least one of these groups being substituted by fluorine or chlorine;

c. d, e and f are independently 0,1, 2, or 3, and the sum of c, d, e and f is 2,3, or 4; wherein, in the formulas (1 gamma-1) to (1 gamma-3), d is 2 or 3;

P¹、P²、P³and P⁴Independently a polymerizable group represented by the formula (P-1);

in the formula (P-1),

M¹and M²Independently hydrogen, fluorine, chlorine, alkyl of carbon number 1 to 4, or alkyl of carbon number 1 to 4 wherein at least one hydrogen is substituted with fluorine or chlorine;

Sp⁵is a single bond or an alkylene group having 1 to 8 carbon atoms, in which at least one-CH group₂-may be substituted by-O-, -CO-, -COO-or-OCO-, at least one- (CH)₂)₂-may be substituted by-CH ═ CH-or-C ≡ C-, at least one of these groups being substituted by fluorine or chlorine;

X¹is-OH, -NH₂、-OR⁵、-N(R⁵)₂or-Si (R)⁵)₃The radicals represented, herein, R⁵Is hydrogen or alkyl with 1 to 8 carbon atoms, in which at least one-CH₂-may be substituted by-O-at least one- (CH)₂)₂-may be substituted by-CH ═ CH-, where at least one hydrogen may be substituted by fluorine or chlorine.

Item 45 is the compound of item 44, and in formulae (1 γ -1) to (1 γ -6), R¹、R²And R³Independently hydrogen, alkyl of carbon number 1 to 10, alkenyl of carbon number 2 to 10, alkoxy of carbon number 1 to 9 or alkenyloxy of carbon number 2 to 9At least one hydrogen may be substituted with fluorine;

ring A¹Ring A²Ring A³Ring A⁴Ring A⁵And ring A⁶Independently cyclohexylene, cyclohexenylene, phenylene, naphthalene, or tetrahydropyran, in which ring at least one hydrogen may be substituted by fluorine, chlorine, an alkyl group having a carbon number of 1 to 6, an alkenyl group having a carbon number of 2 to 6, or an alkoxy group having a carbon number of 2 to 5, and in which group at least one hydrogen may be substituted by fluorine or chlorine;

Z¹、Z²、Z³、Z⁵and Z⁶Independently a single bond or an alkylene group having 1 to 6 carbon atoms, in which at least one-CH group₂-may be substituted by-O-, -COO-, or-OCO-, at least one- (CH)₂)₂-may be substituted by-CH ═ CH-or-C ≡ C-, in which groups at least one hydrogen may be substituted by fluorine;

Sp¹、Sp²、Sp³and Sp⁴Independently a single bond or an alkylene group of 1 to 6 carbon atoms, in which at least one-CH₂-may be substituted by-O-at least one- (CH)₂)₂-may be substituted by-CH ═ CH-, where at least one hydrogen may be substituted by fluorine;

c. d, e and f are independently 0,1, 2,3, the sum of c, d, e and f is 2,3 or 4; wherein, in the formulas (1-1) to (1-3), d is 2 and 3;

in the formula (P-1),

M¹and M²Independently hydrogen, alkyl of

carbon number

1 or 3 or alkyl of

carbon number

1 or 3 with at least one hydrogen substituted by fluorine or chlorine;

Sp⁵is a single bond or an alkylene group having 1 to 6 carbon atoms, in which at least one-CH group₂-may be substituted by-O-at least one- (CH)₂)₂-may be substituted by-CH-or-C ≡ C-, of which groups at least one hydrogen may be substituted by fluorine,

X¹is-OH, -NH₂The indicated radicals.

The compound of any one of items 41 to 45, represented by any one of formulae (1 γ -7) to (1 γ -21);

in the formulae (1. gamma. -7) to (1. gamma. -21),

R¹、R²and R³Independently hydrogen, alkyl of carbon number 1 to 8, alkenyl of carbon number 2 to 8, alkoxy of carbon number 1 to 7 or alkenyloxy of carbon number 2 to 7;

ring A¹Ring A²Ring A³Ring A⁴And ring A⁵Independently a cyclohexylene group, a cyclohexenylene group, or a phenylene group, in which at least one hydrogen may be substituted by fluorine, chlorine, 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, and in which at least one hydrogen may be substituted by fluorine;

L¹、L²、L³、L⁴、L⁵、L⁷、L⁸、L¹⁰、L¹²、L¹³、L¹⁵、L¹⁶、L¹⁷、L¹⁸、L¹⁹and L²⁰Independently fluorine, methyl or ethyl;

Sp¹、Sp²、Sp³and Sp⁴Independently a single bond or an alkylene group having 1 to 5 carbon atoms, in which at least one-CH group₂-may be substituted by-O-;

c. d, e and f are independently 0,1, or 2, and the sum of c, d, e and f is 2,3 or 4; wherein, in the formulas (1 gamma-7) to (1 gamma-9), d is 2;

in the formula (P-1), the compound,

M¹and M²Independently hydrogen, fluoro, methyl, ethyl, or trifluoromethyl;

Sp⁵is a single bond or an alkylene group having 1 to 5 carbon atoms, in which at least one-CH group₂-may be substituted by-O-;

X¹is-OH, -NH₂The indicated radicals.

Item 47 is the compound of item 46, and in formulae (1 γ -7) to (1 γ -21), R¹、R²And R³Independently hydrogen, alkyl of carbon number 1 to 8, alkenyl of carbon number 2 to 8, alkoxy of carbon number 1 to 7 or alkenyloxy of carbon number 2 to 7;

ring A¹Ring A²Ring A³Ring A⁴And ring A⁵Independently cyclohexylene, cyclohexenylene, or phenylene, in which at least one hydrogen may be substituted with fluorine, an alkyl group having 1 to 3 carbon atoms, an alkenyl group having 2 to 3 carbon atoms, or an alkoxy group having 1 to 2 carbon atoms, and in which at least one hydrogen may be substituted with fluorine;

in the formula (P-1),

M¹and M²Independently hydrogen, fluoro, methyl or ethyl;

X¹is-OH, -NH₂The indicated radicals.

The compound of any one of items 41 to 47, represented by any one of formulae (1 γ -22) to (1 γ -34);

in the formulae (1. gamma. -22) to (1. gamma. -34),

R¹and R²Independently an alkyl group having 1 to 7 carbon atoms, an alkenyl group having 2 to 7 carbon atoms, an alkoxy group having 1 to 6 carbon atoms or an alkenyloxy group having 2 to 6 carbon atoms;

L⁶、L⁷、L⁸、L⁹、L¹⁰、L¹¹、L¹³、L¹⁵、L¹⁶、L¹⁷、L¹⁸、L¹⁹、L²⁰、L²¹、L²²and L²³Independently hydrogen, fluoro, methyl or ethyl;

Sp¹、Sp²and Sp³Independently a single bond or an alkylene group having 1 to 3 carbon atoms, in which at least one-CH group₂-may be substituted by-O-;

in the formula (P-1),

M¹and M²Independently hydrogen, fluorine, or methyl;

Sp⁵is a single bond or an alkylene group having 1 to 3 carbon atoms, in which at least one-CH group₂-may be substituted by-O-.

Item 49. a liquid crystal composition comprising at least one compound according to any one of items 41 to 48 as an orienting monomer.

Item 50. the liquid crystal composition of item 49, further comprising at least one compound selected from the group of compounds represented by formulae (2) to (4). The structural formulae and symbols of these compounds are as defined in item 11.

Item 51 the liquid crystal composition of item 49 or item 50, further comprising at least one compound selected from the group of compounds represented by formulae (5) to (7). The structural formulae and symbols of these compounds are as defined in item 12.

Item 52. the liquid crystal composition of item 49 or item 50, further comprising at least one compound selected from the group of compounds represented by formula (8). The structural formulae and symbols of these compounds are as defined in item 13.

Item 53. the liquid crystal composition of item 49 or item 50, further comprising at least one compound selected from the group of compounds represented by formulae (9) to (15). The structural formulae and symbols of these compounds are as defined in item 14.

Item 54. the liquid crystal composition according to any one of item 49 to item 53, which contains at least one compound selected from the group of polymerizable compounds represented by formula (16 α) as a reactive monomer. The structural formulae and symbols of these compounds are as defined in item 15.

Item 55 the liquid crystal composition of item 54, wherein in formula (16 α), P¹、P²And P³Independently a group selected from the group of polymerizable groups represented by the formulae (P-2) to (P-6). The structural formulae and symbols of these compounds are as defined in item 16.

Item 56. the liquid crystal composition according to any one of items 49 to 55, which contains at least one compound selected from the group of polymerizable compounds represented by formulae (16 α -1) to (16 α -27). The structural formulae and symbols of these compounds are as defined in item 17.

Item 57 the liquid crystal composition according to any one of items 49 to 56, which further contains at least one selected from the group consisting of a polymerizable compound different from the polymerizable compounds represented by the formulae (1 α) and (16 α), a polymerization initiator, a polymerization inhibitor, an optically active compound, an antioxidant, an ultraviolet absorber, a light stabilizer, a heat stabilizer and an antifoaming agent.

5-2 form of Compound (1. gamma.)

The compound (1 γ) has a mesogen portion composed of at least one ring and a plurality of polar groups. The compound (1 γ) is useful because the polar group interacts with the substrate surface in a noncovalent manner. One of the applications is an additive for a liquid crystal composition used in a liquid crystal display element. The compound (1 γ) is added for the purpose of controlling the orientation of liquid crystal molecules. Such an additive preferably has high solubility in a liquid crystal composition and is chemically stable under the condition of being sealed in an element, and has a large voltage holding ratio when used in a liquid crystal display element. The compound (1. gamma.) satisfies this characteristic to a considerable extent.

Preferred examples of the compound (1 γ) will be described. R in Compound (1. gamma.)¹、R²、R³、Z¹、Z²、Z³、A¹、A⁴、A⁵、Sp¹、Sp²、Sp³、P¹、P²、P³The preferred embodiment of (d) also applies to the lower formula of the compound (1. gamma.). In the compound (1 γ), the properties can be arbitrarily adjusted by appropriately combining the types of these groups. Since there is no great difference in the characteristics of the compounds, the compound (1. gamma.) may be contained in an amount larger than that of the naturally occurring compound²H (deuterium),¹³C is an isotope.

In the formula (1. gamma.), R¹、R²And R³Independently an alkyl group of carbon number 1 to 15, in which at least one-CH is present₂-may be substituted by-O-, or-S-, at least one- (CH)₂)₂-may be substituted by-CH ═ CH-or-C ≡ C-, at least one of these groups being substituted by fluorine or chlorine.

In the formula (1. gamma.), R is preferred¹、R²Or R³Is 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. Further preferred is R¹An alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or an alkoxy group having 1 to 9 carbon atoms. Particularly preferred R¹Is an alkyl group having 1 to 10 carbon atoms.

In the formula (1. gamma.), the ring A¹Ring A⁴And ring A⁵Independently cyclohexylene, cyclohexenylene, phenylene, naphthalene, decahydronaphthalene, tetrahydronaphthalene, tetrahydropyran, 1, 3-dioxane, pyrimidine, or pyridine, in which at least one hydrogen may be substituted with fluorine, chlorine, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or an alkyl group having 1 to 12 carbon atoms in which at least one hydrogen is substituted with fluorine or chlorine.

Preferred ring A in formula (1. gamma.) is¹Ring A⁴Or ring A⁵Is cyclohexylene, cyclohexenylene, phenylene, naphthalene, tetrahydropyran, or 1, 3-dioxane, in which at least one hydrogen may be substituted by fluorine, chlorine, an alkyl group having 1 to 5 carbon atoms, orAlkoxy of carbon number 1 to 4. Further preferred is ring A¹Ring A⁴Or ring A⁵Is cyclohexylene, phenylene in which at least one hydrogen is substituted by fluorine, or phenylene in which at least one hydrogen is substituted by an alkyl group having 1 to 3 carbon atoms. Particularly preferred ring A¹Ring A⁴Or ring A⁵Is cyclohexylene, phenylene in which at least one hydrogen is substituted by a methyl group, or phenylene in which at least one hydrogen is substituted by an ethyl group.

In the formula (1. gamma.), Z¹And Z⁵Independently a single bond or an alkylene group having 1 to 10 carbon atoms, in which at least one-CH group₂-may be substituted by-O-, -COO-, -OCO-, or-OCOO-, at least one- (CH)₂)₂-may be substituted by-CH ═ CH-or-C ≡ C-, at least one of these groups being substituted by fluorine or chlorine.

In the formula (1. gamma.), Z is preferred¹Or Z⁵Is a single bond, - (CH)₂)₂-、-CH＝CH-、-C≡C-、-COO-、-OCO-、-CF₂O-、-OCF₂-、-CH₂O-、-OCH₂-or-CF ═ CF-. Further preferred is Z¹Or Z⁵Is a single bond.

In the formula (1. gamma.), Sp¹、Sp²Or Sp³Independently a single bond or an alkylene group having 1 to 10 carbon atoms, in which at least one-CH group₂At least one- (CH) which may be substituted by-O-, -COO-, -OCO-or-OCOO-₂)₂-may be substituted by-CH ═ CH-or-C ≡ C-, at least one of these groups being substituted by fluorine or chlorine.

Among the formula (1. gamma.), Sp is preferred¹、Sp²Or Sp³Is a single bond, alkylene having 1 to 5 carbon atoms, or one-CH₂-C1 to C5 alkylene substituted by-O-. Sp is further preferred¹、Sp²Or Sp³Is a single bond, alkylene of 1 to 3 carbon atoms or a-CH₂-C1 to C3 alkylene substituted by-O-. Particularly preferred is Sp¹、Sp²Or Sp³is-CH₂-、-(CH₂)₂-、-(CH₂)₃-or-O (CH)₂)₂-。

In the formula (1. gamma.), P¹、P²And P³Independently a polymerizable group represented by the formula (P-1).

In the formula (P-1), M¹And M²Independently hydrogen, fluorine, chlorine, an alkyl group having 1 to 5 carbon atoms, or an alkyl group having 1 to 5 carbon atoms in which at least one hydrogen is substituted with fluorine or chlorine. For the purpose of enhancing reactivity, M is preferred¹Or M²Is hydrogen or methyl. Further preferred is M¹Or M²Is hydrogen.

In the formula (P-1), R⁴Is a group represented by the formula (1 γ a), the formula (1 γ b) or the formula (1 γ c).

Preferred R⁴Is a group represented by the formula (1. gamma.a) or (1. gamma.b). More preferred R⁴Is a group represented by the formula (1. gamma. a).

Sp in the formulae (1. gamma.a), (1. gamma.b) and (1. gamma.c)⁵And Sp⁶Independently a single bond or an alkylene group having 1 to 10 carbon atoms, in which at least one-CH group₂At least one- (CH) which may be substituted by-O-, -NH-, -CO-, -COO-, -OCO-or-OCOO-₂)₂-may be substituted by-CH ═ CH-or-C ≡ C-, at least one of these groups being substituted by fluorine or chlorine.

Sp is preferred among the formulae (1 γ a), (1 γ b) and (1 γ c)⁵And Sp⁶Is a single bond, alkylene having 1 to 5 carbon atoms, or one-CH₂-C1 to C5 alkylene substituted by-O-. Further preferred is Sp⁵Or Sp⁶Is a single bond, alkylene of 1 to 5 carbon atoms or a-CH₂-C1 to C5 alkylene substituted by-O-. Particularly preferred is Sp⁵And Sp⁶Is a single bond, -CH₂-、-(CH₂)₂-、-(CH₂)₃-, or-O (CH)₂)₂-。

In the formulae (1. gamma. a), (1. gamma. b) and (1. gamma. c), S¹Is > CH-or > N-, S²Is > C < or > Si <. Preferred is S¹Is > CH-or > N-, preferably S²Is > C <. S¹Is superior to S²。

In the formulae (1. gamma. a), (1. gamma. b) and (1. gamma. c), X¹Independently is-OH, -NH₂、-OR³、-N(R³)₂、-COOH、-SH、-B(OH)₂or-Si (R)³)₃The radicals represented, herein, R³Is hydrogen or alkyl with 1 to 10 carbon atoms, in which at least one-CH₂-may be substituted by-O-at least one- (CH)₂)₂-may be substituted by-CH ═ CH-, where at least one hydrogen may be substituted by fluorine or chlorine.

Among the formulae (1 γ a), (1 γ b) and (1 γ c), X is preferable¹is-OH, -NH₂or-Si (R)³)₃The radical represented, herein, R³Is alkyl group having 1 to 5 carbon atoms or alkoxy group having 1 to 4 carbon atoms. Further preferred is X¹is-OH, -NH₂、-Si(OCH₃)₃or-Si (OC)₂H₅)3. Particularly preferred X¹is-OH.

In formula (1 γ), a and b are independently 0,1, 2,3 or 4, and the sum of a and b is 1,2,3 or 4. Preferred combinations of a and b are (a-1, b-0), (a-0, b-1), (a-2, b-0), (a-1, b-1), (a-0, b-2), (a-3, b-0), (a-2, b-1), (a-1, b-2) or (a-0, b-3). Further preferred combinations of a and b are (a-1, b-0), (a-2, b-0), (a-1, b-1), (a-3, b-0), (a-2, b-1), or (a-1, b-2). Particularly preferred combinations of a and b are (a-1, b-0) or (a-2, b-0).

In the formula (1. gamma.), d is 0,1, 2,3 or 4. Preferably d is 2 or 3, and more preferably d is 2.

In formula (1 γ), c and e are independently 0,1, 2,3 or 4. Preferably c or e is 0.

6. Synthesis of Compound (1. gamma.)

The synthesis method of compound (1 γ) will be described. Compound (1 γ) can be synthesized by the method described in the manual of international publication No. 2017/047177. In addition, the compound can also be synthesized by appropriately combining known methods of organic synthetic chemistry. Reference may also be made to "Organic Synthesis" (Organic Synthesis, John Wiley & Sons, Inc.), "Organic Reactions" (Organic Reactions, John Wiley & Sons, Inc.), "Integrated Organic Synthesis" (Pergamon Press), and "New Experimental chemistry lecture" (Bolus).

7. Compounds (1-1) to (1-60)

7-1. examples of Compounds (1-1) to (1-60) and liquid Crystal compositions Using the same

The compounds (1-1) to (1-60) are as shown in the above-mentioned [8] to [10 ]. The liquid crystal composition using the compounds (1-1) to (1-60) is preferably the same as in the items 11 to 18 described in the compound (1 α). In addition, this example also includes the following items. (a) And further contains at least two kinds of additives such as a polymerizable compound, a polymerization initiator, a polymerization inhibitor, an optically active compound, an antioxidant, an ultraviolet absorber, a light stabilizer, a heat stabilizer, and a defoaming agent. (b) A polymerizable composition prepared by adding a polymerizable compound different from the compound (1-1) to the compound (1-60) or the compound (16 α) to the liquid crystal composition. (c) A polymerizable composition prepared by adding a compound (1-1) to a compound (1-60) and a compound (16 α) to the liquid crystal composition. (d) A liquid crystal composite prepared by polymerizing a polymerizable composition. (e) A polymer-stabilized alignment type element comprising the liquid crystal composite. (f) A polymer stable alignment type element produced by using a polymerizable composition prepared by adding a compound (1-1) to a compound (1-60) and a compound (16 α), and a polymerizable compound other than the compound (1-1) to the compound (1-60) or the compound (16 α), to the liquid crystal composition.

7-2 forms of Compounds (1-1) to (1-60)

Since the compounds (1-1) to (1-60) have an acryloyloxy group substituted with a polar group such as a hydroxyalkyl group, the compound is adsorbed on the substrate surface to control the orientation of liquid crystal molecules. In order to obtain the desired effect, the compounds (1-1) to (1-60) must have high compatibility with the liquid crystalline compound. The compounds (1-1) to (1-60) are considered to be most suitable for the above purpose because they have a rod-like molecular structure having a six-membered ring such as 1, 4-cyclohexylene or 1, 4-phenylene and also have a branched structure at one end of the molecular structure to improve compatibility. The compounds (1-1) to (1-60) provide a polymer by polymerization. The polymer stabilizes the alignment of liquid crystal molecules, thereby shortening the response time of the element and improving the afterimage of an image. The polymer is preferably chemically stable under the condition of sealing in an element, and has a large voltage holding ratio when used in a liquid crystal display element. The compounds (1-1) to (1-60) satisfy such characteristics to a considerable extent.

Preferred compounds (1-1) to (1-60) will be described with reference to compound (1-1) as an example.

In the formula (1-1), X in the formula (1f), the formula (1g), the formula (1h) and the formula (1i)¹Is a polar group. The compound (1-1) is preferably stable because it is added to the composition. When the compound (1-1) is added to the composition, it is preferable that the compound does not lower the voltage holding ratio of the device. The compound (1-1) is preferablyHas low volatility. The preferred molar mass is 130g/mol or more. Further, the preferred molar mass is in the range of 150g/mol to 800 g/mol. Preferred compounds (1-1) have acryloyloxy (-OCO-CH ═ CH)₂) Methacryloxy (-OCO- (CH))₃)C＝CH₂) And a polymerizable group such as an α -hydroxyalkyl acrylate.

In the formulae (1f), (1g), (1h) and (1i), X¹is-OH, -NH₂、-OR¹⁵、-N(R¹⁵)₂、-COOH、-SH、-B(OH)₂or-Si (R)¹⁵)₃The radicals represented, herein, R¹⁵Is hydrogen or alkyl with 1 to 5 carbon atoms, in which at least one-CH₂-may be substituted by-O-at least one-CH₂CH₂-may be substituted by-CH ═ CH-, where at least one hydrogen may be substituted by fluorine. From the viewpoint of high solubility in the liquid crystal composition, X¹Particularly preferred is-OH or-NH₂. OH is superior to O-, -CO-, or COO-because it has a high anchoring force. Particularly preferred is a group having a plurality of hetero atoms (nitrogen, oxygen). Compounds having such polar groups are effective even at low concentrations.

In the formula (1-1), R¹Is alkyl with carbon number of 1 to 15, the R¹In (1), at least one-CH₂-may be substituted by-O-or-S-, at least one-CH₂CH₂-may be substituted by-CH-or-C ≡ C-, at least one hydrogen may be substituted by halogen.

Ring A¹And ring A²Independently 1, 4-cyclohexylene, 1, 4-cyclohexenylene, 1, 4-phenylene, naphthalene-2, 6-diyl, decahydronaphthalene-2, 6-diyl, 1,2,3, 4-tetrahydronaphthalene-2, 6-diyl, tetrahydropyran-2, 5-diyl, 1, 3-dioxane-2, 5-diyl, pyrimidine-2, 5-diyl, pyridine-2, 5-diyl, fluorene-2, 7-diyl, phenanthrene-2, 7-diyl, anthracene-2, 6-diyl, perhydrocyclopenta [ a ] group]Phenanthrene-3, 17-diyl, or 2,3,4,7,8,9,10,11,12,13,14,15,16, 17-tetradecylcyclopenta [ a [ ]]Phenanthrene-3, 17-diyl in which at least one hydrogen in the ring may be substituted by fluorine, chlorine, an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an alkoxy group having 1 to 11 carbon atoms, or an alkenyloxy group having 2 to 11 carbon atoms, and in which at least one hydrogen may be substituted by fluorine or fluorineAnd (4) chlorine substitution. Preferred ring A¹Or ring A²Is 1, 4-cyclohexylene, 1, 4-phenylene, 2-fluoro-1, 4-phenylene, naphthalene-2, 6-diyl or 3-ethyl-1, 4-phenylene.

In the formula (1-1), Z¹Is a single bond or alkylene having 1 to 6 carbon atoms, the Z¹In (1), at least one-CH₂-may be substituted by-O-, -CO-, -COO-, -OCO-, or-OCOO-, at least one-CH₂CH₂-may be substituted by-CH ═ CH-or-C ≡ C-, at least one hydrogen may be substituted by fluoro or chloro. Preferred Z¹Is a single bond, -CH₂CH₂-、-CH₂O-、-OCH₂-, -COO-, or-OCO-. Further preferred is Z¹Is a single bond.

In the formula (1-1), a is 0,1, 2,3 or 4. Preferably a is 0,1, 2, or 3. Further, a is preferably 0,1 or 2. Particularly preferred a is 1 or 2.

In the formula (1-1), Sp¹Is a single bond or alkylene with 1 to 10 carbon atoms, and Sp¹In (1), at least one-CH₂-may be substituted by-O-, -CO-, -COO-, -OCO-, or-OCOO-, at least one-CH₂CH₂-may be substituted with-CH-or-C ≡ C-, at least one hydrogen may be substituted with a halogen, and among these, at least one hydrogen is substituted with a group selected from the groups represented by formula (1 a);

in the formula (1a), the compound (A),

Sp¹²is a single bond or alkylene with 1 to 10 carbon atoms, and Sp¹²In (1), at least one-CH₂-may be substituted by-O-, -CO-, -COO-, -OCO-, or-OCOO-, at least one-CH₂CH₂-may be substituted by-CH-or-C ≡ C-, at least one hydrogen may be substituted by halogen. Preferred is Sp¹²Is a single bond, alkylene having 1 to 5 carbon atoms, or one-CH₂-C1 to C5 alkylene substituted by-O-. Sp is further preferred¹²Is a single bond, alkylene having 1 to 3 carbon atoms, or one-CH₂-C1 to C3 alkylene substituted by-O-.

M¹¹And M¹²Independently hydrogen, halogen, alkyl of carbon number 1 to 5, or alkyl of carbon number 1 to 5 with at least one hydrogen substituted with halogen. For the purpose of enhancing reactivity, M is preferred¹¹Or M¹²Is hydrogen or methyl. Further preferred is M¹¹Or M¹²Is hydrogen.

R¹²Is alkyl of carbon number 1 to 15, the R¹²In (1), at least one-CH₂-may be substituted by-O-or-S-, at least one-CH₂CH₂-may be substituted by-CH-or-C ≡ C-, at least one hydrogen may be substituted by halogen. Preferred R¹²Is hydrogen, or alkylene of 1 to 5 carbon atoms, or one-CH₂-C1 to C5 alkylene substituted by-O-. Further preferred is R¹²Is hydrogen, or alkylene of 1 to 3 carbon atoms, or one-CH₂-C1 to C3 alkylene substituted by-O-. Particularly preferred R¹²Is hydrogen or methyl. At R¹²is-CH₂In the case of-OH, vertical alignment at a low concentration can be expected due to the effect of the presence of two hydroxyl groups in the molecule.

In the formula (1-1), Sp is preferred¹Is alkylene having 1 to 5 carbon atoms, or one-CH₂-C1 to C5 alkylene substituted by-O-. Further preferred is Sp¹Is alkylene having 1 to 3 carbon atoms, or one-CH₂An alkylene group having 1 to 3 carbon atoms which is substituted with-O-, and at least one hydrogen of these groups may be substituted with a polymerizable group represented by the formula (1 a).

P¹¹Is a group selected from the group consisting of the groups represented by the formulae (1e) and (1f),

in the formula (1e), R¹³Is a group selected from the group consisting of the groups represented by the formulae (1g), (1h) and (1 i).

In the formulae (1e) and (1f),

Sp¹³is a single bond or alkylene with 1 to 10 carbon atoms, and Sp¹³In (1), at least one-CH₂-may be substituted by-O-, -NH-, -CO-, -COO-, -OCO-, or-OCOO-, at least one-CH₂CH₂-may be substituted by-CH-or-C ≡ C-, of which groups at least one hydrogen may be substituted by halogen. Preferred is Sp¹³Is alkylene having 1 to 7 carbon atoms, or one-CH₂-C1 to C5 alkylene substituted by-O-. Further preferred is Sp¹³Is alkylene having 1 to 5 carbon atoms, or one-CH₂-C1 to C5 alkylene substituted by-O-. Particularly preferred is Sp¹³is-CH₂-。

In the formula (1e), M¹³And M¹⁴Independently hydrogen, halogen, alkyl of 1 to 5 carbon atoms, or alkyl of 1 to 5 carbon atoms in which at least one hydrogen is substituted with a halogen, preferably M for improved reactivity¹³Or M¹⁴Is hydrogen or methyl. Further preferred is M¹³Or M¹⁴Is hydrogen.

In the formula (1e), R¹³Is a group selected from the group of polar groups represented by the formula (1g), the formula (1h) and the formula (1i), and R is preferably¹³Is a polar group represented by the formula (1g) or the formula (1 h). Further preferred is R¹³Is a polar group represented by the formula (1 g).

Sp in the formula (1g), formula (1h) and formula (1i)¹⁴And Sp¹⁵Independently is a single bond or alkylene with 1 to 10 carbon atoms, and Sp¹⁴And Sp¹⁵In (1), at least one-CH₂-may be substituted by-O-, -NH-, -CO-, -COO-, -OCO-, or-OCOO-, at least one-CH₂CH₂-may be substituted by-CH-or-C ≡ C-, of which groups at least one hydrogen may be substituted by halogen. Preferred is Sp¹⁴Or Sp¹⁵Is alkylene having 1 to 7 carbon atoms, or one-CH₂-C1 to C5 alkylene substituted by-O-. Further preferred is Sp¹⁴Or Sp¹⁵Is alkylene having 1 to 5 carbon atoms, or one-CH₂-C1 to C5 alkylene substituted by-O-. Particularly preferred is Sp¹⁴Or Sp¹⁵is-CH₂-。

In the formulae (1h) and (1i), S¹Is > CH-or > N-, and S²Is > C < or > Si <. Preferred is S¹Is > CH-, preferably S²Is > C <.

In the formulae (1f), (1g) and (1i), X¹is-OH, -NH₂、-OR⁵、-N(R¹⁵)₂、-COOH、-SH、-B(OH)₂or-Si (R)¹⁵)₃Here, R¹⁵Is hydrogen or alkyl with 1 to 10 carbon atoms, in which at least one-CH₂-may be substituted by-O-at least one-CH₂-CH₂-may be substituted by-CH ═ CH-, where at least one hydrogen may be substituted by fluorine or chlorine. Preferred X¹is-OH, -NH₂or-N (R)¹⁵)₂Here, R¹⁵Is hydrogen or alkyl with 1 to 10 carbon atoms, the R¹⁵In (1), at least one-CH₂-may be substituted by-O-at least one-CH₂CH₂-may be substituted with-CH ═ CH-, at least one hydrogen may be substituted with halogen. Preferred X¹Is an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 4 carbon atoms. Further preferred is X¹is-OH, -NH₂or-N (R)¹⁵)₂. Particularly preferred X¹is-OH.

Preferred Ring A in Compound (1-2) to Compound (1-3)¹Ring A²、a、M¹¹、M¹²、X¹、R¹²With ring A in Compound (1-1)¹Ring A²、a、M¹¹、M¹²、X¹、R¹²Likewise, preferred l is 0,1, 2,3,4, 5 or 6. More preferably l is 0,1, 2,3, 4.

In the formulae (1-2) to (1-60),

R¹an alkyl group having 1 to 10 carbon atoms;

L¹、L²、L³、L⁴、L⁵、L⁶、L⁷、L⁸、L⁹、L¹⁰、L¹¹and L¹²Independently hydrogen, fluorine, methyl, or ethyl.

8. Synthesis of Compounds (1-1) to (1-60)

The synthesis methods of the compounds (1-1) to (1-60) will be described. The compounds (1-1) to (1-60) can be synthesized by referring to the method described later. In addition, the compound can also be synthesized by appropriately combining known methods of organic synthetic chemistry. Reference may also be made to "Organic Synthesis" (Organic Synthesis, John Wiley & Sons, Inc.), "Organic Reactions" (Organic Reactions, John Wiley & Sons, Inc.), "Integrated Organic Synthesis" (Pergamon Press), and "New Experimental chemistry lecture" (Bolus).

9. Liquid crystal composition

9-1. component B to component E

The liquid crystal composition contains a polymerizable polar compound (1) as an alignment monomer. The compound (1) has a mesogen portion composed of at least one ring. Examples of the compound (1) are a compound (1 α), a compound (1 β), a compound (1 γ), or compounds (1-1) to (1-60). The compound (1) controls the alignment of liquid crystal molecules by non-covalent bond interaction with the substrate of the device. The composition preferably contains the compound (1) as the component a, and further contains a liquid crystalline compound selected from the group consisting of the component B, the component C, the component D, and the component E shown below. The component B is a compound (2) to a compound (4). The component C is a compound (5) to a compound (7). The component D is the compound (8). The component E is a compound (9) to a compound (15). The composition may also contain other liquid crystalline compounds different from the compounds (2) to (15). In preparing the composition, it is preferable to select the component B, the component C, the component D, and the component E in consideration of the magnitude of positive or negative dielectric anisotropy, and the like. The composition of which the components are appropriately selected has a high upper limit temperature, a low lower limit temperature, a small viscosity, an appropriate optical anisotropy (i.e., a large optical anisotropy or a small optical anisotropy), a large positive or negative dielectric anisotropy, a large specific resistance, stability to heat or ultraviolet light, and an appropriate elastic constant (i.e., a large elastic constant or a small elastic constant). For the purpose of improving reactivity (polymerizability), a polymerizable compound (16) having an action as a reactive monomer may be added to the composition.

The preferable proportion of the compound (1) is about 0.01 wt% or more for maintaining high stability against ultraviolet rays, and about 5 wt% or less for dissolving in the liquid crystal composition. Even more preferred ratios range from about 0.05 wt% to about 3 wt%. Most preferably, the ratio is in the range of about 0.05 wt% to about 1 wt%. When the compound (16) is further added, the preferable ratio is in the range of about 0.01 to about 1.0% by weight.

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

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

Increasing the amount of component B decreases the dielectric anisotropy of the composition, but the viscosity decreases. Therefore, the larger the content, the better, as long as the required value of the threshold voltage of the element is satisfied. In the case of producing a composition for IPS, VA, or other modes, the content of the component B is preferably 30% by weight or more, and more preferably 40% by weight or more, based on the weight of the liquid crystal composition.

The component C is a compound having fluorine, chlorine or a fluorine-containing group at the right terminal. Preferable examples of the component C include compounds (5-1) to (5-16), compounds (6-1) to (6-113), and compounds (7-1) to (7-57). In the compound of component C, R¹³Is an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms, at least one-CH group being present in the alkyl group and the alkenyl group₂-may be substituted by-O-, at least one hydrogen may be substituted by fluorine; x¹¹Is fluorine, chlorine, -OCF₃、-OCHF₂、-CF₃、-CHF₂、-CH₂F、-OCF₂CHF₂or-OCF₂CHFCF₃。

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

Component D is a compound (8) having the right terminal group-C.ident.N or-C.ident.C-C.ident.N. Preferable examples of the component D include compounds (8-1) to (8-64). In the compound of component D, R¹⁴Is an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms, at least one-CH group being present in the alkyl group and the alkenyl group₂-may be substituted by-O-, at least one hydrogen may be substituted by fluorine; -X¹²is-C.ident.N or-C.ident.C-C.ident.N.

Since the component D has positive dielectric anisotropy and a large value, it is mainly used in the case of producing a composition for a TN or the like mode. The dielectric anisotropy of the composition can be increased by adding the component D. The component D has the effect of expanding the temperature range of the liquid crystal phase, adjusting the viscosity, or adjusting the optical anisotropy. Component D can also be used to adjust the voltage-transmittance curve of the device.

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

The component E is the compound (9) to the compound (15). These compounds have a phenylene radical which is substituted laterally by 2 fluorines or chlorines, as is 2, 3-difluoro-1, 4-phenylene. Preferable examples of the component E include compounds (9-1) to (9-8), compounds (10-1) to (10-17), compounds (11-1), compounds (12-1) to (12-3), compounds (13-1) to (13-11), compounds (14-1) to (14-3) and compounds (15-1) to (15-3). In the compounds of component E, R¹⁵And R¹⁶Independently an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms, at least one-CH group being present in the alkyl group and the alkenyl group₂-may be substituted by-O-, at least one hydrogen may be substituted by fluorine; r¹⁷Is hydrogen, fluorine, C1-10 alkyl or C2-10 alkenyl, at least one-CH in the alkyl and alkenyl₂-may be substituted by-O-and at least one hydrogen may be substituted by fluorine.

The dielectric anisotropy of the component E is negative and large. Component E can be used in the case of preparing compositions for IPS, VA, PSA, etc. modes. When the content of the component E is increased, the dielectric anisotropy of the composition becomes negative and increases, but the viscosity becomes high. Therefore, as long as the required value of the threshold voltage of the element is satisfied, the content is preferably small. When the dielectric anisotropy is about-5, the content is preferably 40 wt% or more for sufficient voltage driving.

In the component E, the compound (9) is a bicyclic compound, and therefore is effective mainly in reducing viscosity, adjusting optical anisotropy, or increasing dielectric anisotropy. Since the compound (10) and the compound (11) are tricyclic compounds, they have the effect of increasing the upper limit temperature, increasing the optical anisotropy, or increasing the dielectric anisotropy. The compounds (12) to (15) have an effect of increasing the dielectric anisotropy.

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

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

9-2. additives

The liquid crystal composition is prepared by a known method. For example, the component compounds are mixed and then dissolved in one another by heating. Additives may also be added to the composition depending on the use. Examples of the additives are polymerizable compounds, polymerization initiators, polymerization inhibitors, optically active compounds, antioxidants, ultraviolet absorbers, light stabilizers, heat stabilizers, antifoaming agents, and the like. Such additives are well known to those skilled 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) may be used alone. A copolymer can also be formed from the compound (1) and the compound (16). The compound (1) is immobilized in a state where the polar group interacts with the substrate surface in a noncovalent manner. This further improves the ability to align the liquid crystal molecules, and prevents the compound (1) from diffusing in the liquid crystal composition. The compound (1) provides a polymer by polymerization. The polymers are aligned, and thus impart an appropriate pretilt angle to the liquid crystal molecules in the substrate surface. The polymer stabilizes the orientation of liquid crystal molecules, thereby shortening the response time of the element and improving the afterimage of an image. Preferable examples of the polymerizable compound are acrylate, methacrylate, vinyl compound, vinyloxy compound, propenyl ether, epoxy compound (oxetane ) and vinyl ketone. Further preferable examples are a compound having at least one acryloyloxy group and a compound having at least one methacryloyloxy group. Further preferable examples include compounds having both an acryloyloxy group and a methacryloyloxy group.

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

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

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

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

The optically active compound has an effect of preventing reverse twist by inducing a helical structure in liquid crystal molecules to impart a desired twist angle. The pitch can be adjusted by adding an optically active compound. Two or more optically active compounds may be added for the purpose of adjusting the temperature dependence of the pitch. Preferable examples of the optically active compound include the following compounds (Op-1) to (Op-18). In the compound (Op-18), the ring J is 1, 4-cyclohexylene or 1, 4-phenylene, R²⁸Is an alkyl group having 1 to 10 carbon atoms.

The antioxidant is effective for maintaining a large voltage holding ratio. Preferred examples of the antioxidant include: the following compound (AO-1) and compound (AO-2); iollonus (IRGANOX)415, Iollonus (IRGANOX)565, Iollonus (IRGANOX)1010, Iollonus (IRGANOX)1035, Iollonus (IRGANOX)3114, and Iollonus (IRGANOX)1098 (trade name; BASF corporation). The ultraviolet absorber is effective for preventing a decrease in the upper limit temperature. Preferred examples of the ultraviolet absorber are: benzophenone derivatives, benzoate derivatives, triazole derivatives, and the like. Specific examples include the following compounds (AO-3) and (AO-4); ground spike (TINUVIN)329, ground spike (TINUVIN) P, ground spike (TINUVIN)326, ground spike (TINUVIN)234, ground spike (TINUVIN)213, ground spike (TINUVIN)400, ground spike (TINUVIN)328, and ground spike (TINUVIN)99-2 (trade names; BASF corporation); and 1,4-diazabicyclo [2.2.2] octane (1,4-diazabicyclo [2.2.2] octane, DABCO).

Light stabilizers such as hindered amines are preferred to maintain a large voltage holding ratio. Preferred examples of the light stabilizer include: the following compound (AO-5) and compound (AO-6); denoxin (TINUVIN)144, denoxin (TINUVIN)765, and denoxin (TINUVIN)770DF (trade name; BASF corporation). The heat stabilizer is also effective for maintaining a large voltage holding ratio, and a preferable example thereof is Yilingoes (IRGAFOS)168 (trade name; BASF corporation). The antifoaming agent is effective for preventing foaming. Preferable examples of the defoaming agent are dimethyl silicone oil, methylphenyl silicone oil and the like.

In the compound (AO-1), R⁴⁰Is alkyl with 1 to 20 carbon atoms, alkoxy with 1 to 20 carbon atoms, -COOR⁴¹or-CH₂CH₂COOR⁴¹Here, R⁴¹Is an alkyl group having 1 to 20 carbon atoms. In the compound (AO-2) and the compound (AO-5), R⁴²Is an alkyl group having 1 to 20 carbon atoms. In the compound (AO-5), R⁴³Is hydrogen, methyl or O (oxygen radical), ring G is 1, 4-cyclohexylene or 1, 4-phenylene, and z is 1,2 or 3.

9. Liquid crystal display element

The liquid crystal composition can be used for liquid crystal display elements which have operation modes of PC, TN, STN, OCB, PSA and the like and are driven in an active matrix mode. The composition can also be used for liquid crystal display elements which have PC, TN, STN, OCB, VA, IPS and other operation modes and are driven in a passive matrix mode. These elements can be applied to any of reflection type, transmission type, and semi-transmission type.

The composition can also be used for a Nematic Curvilinear Aligned Phase (NCAP) element prepared by microencapsulating a nematic Liquid Crystal, a Polymer Dispersed Liquid Crystal Display element (PDLCD) prepared by forming a three-dimensional Network Polymer in a Liquid Crystal, and a Polymer Network Liquid Crystal Display element (PNLCD). When the amount of the polymerizable compound added is about 10% by weight or less based on the weight of the liquid crystal composition, a PSA mode liquid crystal display element can be produced. Preferred ratios range from about 0.1 wt% to about 2 wt%. Even more preferred ratios range from about 0.2 wt% to about 1.0 wt%. The PSA mode element can be driven in a driving manner such as an active matrix or a passive matrix. Such an element can be applied to any of reflection type, transmission type, and semi-transmission type. By increasing the amount of the polymerizable compound to be added, an element of a polymer dispersed (polymer dispersed) mode can be produced.

The alignment film is a film for aligning liquid crystal molecules in a certain direction. A thin film of polyimide is generally used. In a liquid crystal display element not having such an alignment film, a composition containing a polymerizable polar compound (1) is used. The compound (1) provides a polymer by polymerization. The polymer has a function of an alignment film, and thus can be used in place of the alignment film. An example of a method for manufacturing such a device is as follows. An element having two substrates called an array substrate and a color filter substrate is prepared. The substrate has no alignment film. At least one of the substrates has an electrode layer. The liquid crystal composition is prepared by mixing liquid crystalline compounds. Compound (1) is added to the composition. Further additives may be added as required. Injecting the composition into an element. The first stage of light irradiation is performed in a state where no voltage is applied to the element or a voltage that does not substantially drive the liquid crystal composition is applied, and then the second stage of light irradiation is performed in a state where a voltage of not less than a threshold voltage and not more than 30V is applied. Ultraviolet rays are preferred. The polymerizable compound is polymerized by light irradiation. By such two-stage polymerization, an alignment control layer inducing uniform vertical alignment in liquid crystal molecules is generated, and a target device is manufactured.

In the above-mentioned order, since the compound (1) interacts with the surface of the substrate due to the polar group, it is easily aligned uniformly on the substrate by applying no voltage or a voltage which does not substantially drive the liquid crystal composition. In this state, the first stage of ultraviolet irradiation is performed to fix the orientation. The polymer uniformly aligns the liquid crystal molecules. Next, when a voltage of not less than the threshold voltage and not more than 30V is applied, the alignment of the liquid crystal molecules is further promoted by the action of the electric field. Depending on the orientation, unreacted compounds also undergo orientation. In this state, the compound is substantially completely polymerized by the ultraviolet irradiation in the second stage, and thus a polymer maintaining the orientation is produced. The polymer has an effect of stabilizing the alignment of the liquid crystal molecules additionally, and thus the response time of the device is shortened. Since the afterimage of the image is a poor operation of the liquid crystal molecules, the afterimage can be improved by the effect of the polymer. Since the polymerization is carried out in two stages, the amount of unreacted product is very small. Therefore, a device having a large voltage holding ratio can be obtained.

Ultraviolet irradiation of the substrate will be described. In the present invention, the ultraviolet rays are irradiated in at least two stages. In the first stage, irradiation is performed with no voltage applied between the substrates or with a voltage that does not substantially drive the liquid crystal composition applied. The preferred illumination is about 2mW/cm²To about 200mW/cm²The preferred exposure amount (product of illuminance and irradiation time) is 1J/cm²To 60J/cm²The range of (1). The ultraviolet rays are sometimes referred to as "first ultraviolet rays". Most of the polymerizable compounds are polymerized by the ultraviolet rays. In the first ultraviolet ray, a more preferable illuminance is about 2mW/cm²To about 100mW/cm²More preferably, the exposure amount is 3J/cm²To 50J/cm²The range of (1).

In the second stage, ultraviolet rays are irradiated while applying a voltage of not less than the threshold voltage and not more than 30V between the substrates. The preferred illumination is about 2mW/cm²To about 200mW/cm²The preferred exposure amount is 5J/cm²To 100J/cm²The range of (1). The ultraviolet rays are sometimes referred to as "second ultraviolet rays". By said ultraviolet lightThe linear, unreacted compound (1) is converted into a polymer. In the second ultraviolet ray, a more preferable illuminance is about 2mW/cm²To about 100mW/cm²More preferably, the exposure amount is 5J/cm²To 55J/cm²The range of (1). In the case where the unreacted product remains even though the second stage of ultraviolet irradiation is performed, the present invention may be additionally provided with the third stage of ultraviolet irradiation. In the third stage, irradiation is performed with no voltage applied between the substrates or with a voltage that does not substantially drive the liquid crystal composition. The preferred illumination is about 2mW/cm²To about 200mW/cm²The preferred exposure amount (product of illuminance and irradiation time) is 1J/cm²To 60J/cm²The range of (1). The ultraviolet rays are sometimes referred to as "third ultraviolet rays". Almost all of the polymerizable compound is polymerized by the ultraviolet rays. In the third ultraviolet ray, a more preferable illuminance is about 2mW/cm²To about 100mW/cm²More preferably, the exposure amount is 3J/cm²To 50J/cm²The range of (1).

Fig. 1 shows an element 11 in which a polymerizable polar compound (1) is arranged on a color filter substrate 1 and an array substrate 2 by interaction between polar groups and the substrate surface. The compound (1) forms an orientation control layer by polymerization. Fig. 2 shows the element 12 in which the polymerizable polar compound (1) and the polymerizable compound (16) are arranged on the color filter substrate 1 and the array substrate 2 by the interaction between the polar group and the substrate surface. The compound (1) forms an orientation control layer by copolymerization with the compound (16). Fig. 3 is a schematic view of a conventional device 21 having an alignment film and containing a polymerizable compound. The liquid crystal display element of the present invention is not limited to the element having the structure of the two substrates, i.e., the array substrate and the color filter substrate, as shown in fig. 1 or 2. Another example is an element having a Color Filter On Array (COA) structure in which a Color Filter (CF) is formed On a TFT substrate.

The orientation control layer is a thin film having small irregularities observed by a scanning electron microscope, and can be regarded as a collection of particles. The cross section of the film is wavy. The distance between a wave apex and an adjacent wave apex is defined as the particle diameter of the polymer in the orientation control layer (hereinafter, may be simply referred to as "particle diameter"). The particle size averages from about 1nm to about 90nm, preferably from about 1nm to about 70 nm. When the particle diameter is in such a range, it is considered that the liquid crystal molecules are uniformly vertically aligned to prevent light leakage. The film thickness of the orientation control layer is about 10nm to about 100nm, preferably about 10nm to about 80nm, and more preferably about 20nm to about 80 nm. When the film thickness is about 10nm or more, the electrical characteristics can be maintained, and therefore, the film thickness is preferable. When the film thickness is 100nm or less, the driving voltage can be suitably reduced, which is preferable.

In a Vertical Alignment (VA) type element, liquid crystal molecules are aligned substantially vertically with respect to a substrate surface when no voltage is applied. In general, in order to vertically align liquid crystal molecules, as shown in fig. 3, a vertical alignment film such as polyimide, polyamide, or polysiloxane is disposed between the color filter substrate 1 and the liquid crystal layer 3 or between the array substrate 2 and the liquid crystal layer 3. On the other hand, in an element having no alignment film, such an alignment film is not required. In the element, liquid crystal molecules are vertically aligned with respect to the substrate by the action of the alignment control layer. The angle of the liquid crystal molecules to the substrate (i.e., pretilt angle) is 90 ° ± 10 °, preferably 90 ° ± 5 °, more preferably 90 ° ± 3 °. By combining this vertical orientation with pixel electrodes having slits and being pixel-divided, a wide viewing angle can be achieved.

Examples

The present invention will be described in more detail by way of examples (including synthetic examples and use examples). The present invention is not limited by these examples. The invention includes mixtures of the composition of use example 1 and the composition of use example 2. The present invention also includes mixtures prepared by mixing at least two of the compositions of the use examples.

Unless otherwise specified, the reaction was carried out under a nitrogen atmosphere. The compound (1) was synthesized by the procedure shown in synthesis examples and the like. The synthesized compound is identified by Nuclear Magnetic Resonance (NMR) analysis or the like. The properties can be measured by the following methods.

NMR analysis: use of Brukbaiserin in the assayDRX-500 manufactured by Bruker BioSpin.¹In the measurement of H-NMR, a sample was dissolved in CDCl₃The measurement was carried out in a deuterated solvent at room temperature at 500MHz for 16 cumulative times. Tetramethylsilane was used as an internal standard.¹⁹In the measurement of F-NMR, CFCl was used₃As an internal standard, the number of times is accumulated to 24 times. In the description of nmr spectra, s is a singlet (singlet), d is a doublet (doublt), t is a triplet (triplet), q is a quartet (quatet), quin is a quintet (quintet), sex is a sextant (sextet), m is a multiplet (multiplex), and br is a broad (broad).

Gas chromatographic analysis: for measurement, a gas chromatograph model GC-2010 manufactured by Shimadzu corporation was used. As the column, a capillary column DB-1 (length: 60m, inner diameter: 0.25mm, film thickness: 0.25 μm) manufactured by Agilent Technologies Inc. was used. Helium (1 ml/min) was used as the carrier gas. The temperature of the sample vaporization chamber was set to 300 ℃, and the temperature of the detector (flame ionization detector, FID) part was set to 300 ℃. The sample was prepared as a 1 wt% solution by dissolving in acetone, and 1. mu.l of the resulting solution was injected into the sample vaporization chamber. The recording meter used was a GC dissolution (GC Solution) system manufactured by shimadzu corporation.

High Performance Liquid Chromatography (HPLC) analysis: for the measurement, Promins (reference) (LC-20 AD; SPD-20A) manufactured by Shimadzu corporation was used. As the column, YMC-Pack ODS-A (length: 150mm, inner diameter: 4.6mm, particle diameter: 5 μm) manufactured by YMC was used. The dissolution liquid is used by appropriately mixing acetonitrile with water. As the detector, an Ultraviolet (UV) detector, a Refractive Index (RI) detector, a CORONA detector (CORONA detector), or the like is suitably used. In the case of using the UV detector, the detection wavelength was set to 254 nm. The sample was prepared by dissolving in acetonitrile to obtain a 0.1 wt% solution, and 1 μ L of the solution was introduced into the sample chamber. The recorder used C-R7Aplus manufactured by Shimadzu corporation.

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

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

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

(1) Phase structure

A sample was placed on a hot plate (FP-52 type heating stage, Mettler) Co., Ltd.) equipped with a melting point measuring apparatus of a polarizing microscope. The phase state and the change thereof were observed by a polarization microscope while heating the sample at a rate of 3 ℃/minute to determine the type of phase.

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

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

The crystals are denoted as C. When the crystal species are distinguished from each other, they are represented by C₁、C₂. The smectic phase is denoted S and the nematic phase is denoted N. In the smectic phase, when the smectic A phase, the smectic B phase, the smectic C phase, or the smectic F phase are added to distinguish each other, they are represented as S_A、S_B、S_COr S_F. The liquid (isotropic) is denoted as I. The transition temperature is expressed, for example, as "C50.0N 100.0I". This means that the transition temperature from the crystalline to the nematic phase is 50.0 ℃ and the transition temperature from the nematic phase to the liquid is 100.0 ℃.

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

The sample was placed on a hot plate of a melting point measuring apparatus equipped with a polarizing microscope, and heated at a rate of 1 ℃ per minute. The temperature at which a portion of the sample changes from nematic to isotropic liquid is measured. The upper limit temperature of the nematic phase may be simply referred to as "upper limit temperature". When the sample is a mixture of a liquid crystalline compound and a mother liquid crystal, the symbol T is used_NIAnd (4) showing. When the sample is a mixture of a liquid crystalline compound and compounds such as component B, component C, and component D, the symbol NI represents the mixture.

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

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

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

The measurement was performed using an E-type rotational viscometer manufactured by tokyo counter gmbh.

(6) Optical anisotropy (refractive index anisotropy; measured at 25 ℃ C.;. DELTA.n)

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

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

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

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

Positive dielectric anisotropy: the measurement was carried out according to the method described in Molecular Crystals and Liquid Crystals (vol.259, 37(1995)) of M.J.. A sample was placed in a TN cell having a twist angle of 0 degree and a gap (cell gap) of 5 μm between two glass substrates. The element was applied with a voltage in 0.5V unit in a stepwise manner in a range of 16V to 19.5V. After 0.2 seconds of no voltage application, voltage application was repeated under the condition of applying only one square wave (square pulse; 0.2 seconds) and no voltage application (2 seconds). The peak current (peak current) and peak time (peak time) of the transient current (transient current) resulting from the application are measured. The values of rotational viscosity were obtained from these measured 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 was determined by the following method using an element obtained by measuring the rotational viscosity.

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

Negative dielectric anisotropy: the measurement was carried out according to the method described in Molecular Crystals and Liquid Crystals (vol.259, 37(1995)) of M.J.. A VA device having a gap (cell gap) of 20 μm between two glass substrates was used as a sample. The element is applied with a voltage in 1 volt step in a range of 39 volts to 50 volts. After 0.2 seconds of no voltage application, voltage application was repeated under the condition of applying only one square wave (square pulse; 0.2 seconds) and no voltage application (2 seconds). The peak current (peak current) and peak time (peak time) of the transient current (transient current) resulting from the application are measured. The values of rotational viscosity were obtained from these measured 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 a value measured using the following term of the dielectric anisotropy.

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

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

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

Negative dielectric anisotropy: the value of the dielectric anisotropy is calculated according to the formula Δ ∈/∈ j. The dielectric constants (. epsilon./. epsilon. mu.j) were measured in the following manner.

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

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

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

Positive dielectric anisotropy: for the measurement, an LCR model HP4284A manufactured by Yokogawa Hewlett-Packard GmbH was used. A sample was placed in a horizontally oriented cell having a spacing (cell gap) of 20 μm between two glass substrates. An electric charge of 0 to 20 volts was applied to the element, and the electrostatic capacitance and the applied voltage were measured. K was obtained from the value of the electrostatic capacitance (C) measured and the applied voltage (V) by fitting the values of the equations (2.98) and (2.101) on page 75 of the handbook of liquid crystal devices (journal Industrial News Co., Ltd.), based on the equation (2.99)₁₁And K₃₃The value of (c). Then, in equation (3.18) on page 171, the K obtained previously is used₁₁And K₃₃Value of (D) to calculate K₂₂. The elastic constant K is K obtained in this way₁₁、K₂₂And K₃₃Is expressed as an average value of (a).

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

Negative dielectric anisotropy: for the measurement, an elastic constant measuring instrument model EC-1 manufactured by TOYO Corporation, Toyang technology Corporation was used. A sample was placed in a vertical alignment cell having a spacing (cell gap) of 20 μm between two glass substrates. A charge of 20 to 0 volts was applied to the element, and the electrostatic capacitance and the applied voltage were measured. Values of the electrostatic capacitance (C) and the applied voltage (V) were fitted using the equations (2.98) and (2.101) on page 75 of the handbook of liquid crystal devices (journal industries, press), and values of the elastic constant were obtained from the equation (2.100).

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

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

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

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

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

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

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

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

(13) Voltage holding ratio

The polymerizable compound was polymerized by irradiating ultraviolet light with black light (black light) and F40T10 (peak wavelength of 335nm) manufactured by michael corporation. The element was charged by applying a pulse voltage (1V, 60 microseconds) at 60 ℃. The decayed voltage was measured by a high-speed voltmeter over a period of 1.67 seconds, and the area a between the voltage curve in the unit period and the horizontal axis was determined. The area B is the area when not attenuated. The voltage holding ratio is expressed by a percentage of the area a to the area B.

(14) Illuminance of light

For the measurement of the ultraviolet illuminance, an ultraviolet illuminance meter UIT-250 (sensor: UVD-S365) manufactured by Nipple (USHIO) electric machinery Co., Ltd was used.

(15) Vertical orientation

The obtained element was set on a polarizing microscope, and the element was irradiated with light from below to observe the presence or absence of light leakage. When the liquid crystal molecules were sufficiently aligned and light did not transmit through the element, the vertical alignment property was judged to be "good". When light transmitted through the element was observed, it was indicated as "having an alignment defect".

(16) Pretilt angle (degree)

For measurement of the pretilt angle, Opti-Pro manufactured by Shintech (Shintech) Ltd is used.

(17) Film thickness and particle diameter

The thickness and the particle diameter of the orientation control layer were measured by using SEM (scanning electron microscope) (SU-70 manufactured by Hitachi high tech Co., Ltd.).

The following compounds were synthesized. Synthesis methods of the compound (1. alpha. -3-A), the compound (1. alpha. -4-A) to the compound (1. alpha. -4-J), the compound (1. alpha. -5-A) to the compound (1. alpha. -5-B), the compound (1. alpha. -6-A) to the compound (1. alpha. -6-J) and specific examples of compounds which can be used are disclosed in the manual of International publication No. 2016-129490. Methods for synthesizing the compound (1. beta. -4-A) and the compound (1. gamma. -2-A) are disclosed in the handbook of International publication No. 2017-014013 and the handbook of International publication No. 2017-047177, respectively.

[ Synthesis example of Compound (1-4-3) ]

Step 1 of

Compound (T-7), 3, 4-dihydro-2H-pyran (23.3g), pyridine p-Toluenesulfonate (PPTS) (5.80g) was placed in a reactor and stirred at 50 ℃ for 10 hours. After insoluble matter was separated by filtration, the reaction mixture was poured into water, and the aqueous layer was extracted with dichloromethane. The combined organic layers were 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 ═ 2: 1) to obtain compound (T-21) (39.5 g; 80%).

Step 2

Compound (T-21) (39.5g), THF (400ml), and water (400ml) were placed in a reactor and cooled to 0 ℃. Lithium hydroxide monohydrate (15.4g) was added thereto, returned to room temperature and stirred for 12 hours. The reaction mixture was poured into water, and 6N hydrochloric acid (60ml) was slowly added to make it acidic, and then the aqueous layer was extracted with ethyl acetate. The combined organic layers were washed with water and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure to obtain compound (T-22) (32.6 g; 95%).

Step 3 of

Compound (1-23-2) (2.0g), compound (T-22) (1.18g), DMAP (0.32g), and methylene chloride (100ml) were placed in a reactor and cooled to 0 ℃. DCC (1.30g) solution in dichloromethane (60ml) was slowly added dropwise thereto, returned to room temperature and stirred for 12 hours. After insoluble matter was separated by filtration, the reaction mixture was poured into water, and the aqueous layer was extracted with dichloromethane. The combined organic layers were 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 ═ 19: 1) to obtain compound (T-23) (2.37 g; 82%).

Step 4

Compound (T-23) (2.37g), pyridine p-toluenesulfonate (PPTS) (0.54g), THF (50ml) and methanol (50ml) were placed in a reactor and stirred at 50 ℃ for 5 hours. After insoluble matter was separated by filtration, the reaction mixture was poured into water, and the aqueous layer was extracted with ethyl acetate. The combined organic layers were 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 ═ 9: 1) to obtain compound (1-4-3) (1.50 g; 75%).

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

¹H-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).

The physical properties of the compound (1-4-3) are as follows.

Transition temperature: C66.5I.

[ Synthesis examples of Compound (1-23-3) ]

Step 1 of

2- (1, 3-dioxan-2-yl) ethyltriphenylphosphonium bromide (103.7g) and THF (500ml) were charged into a reactor, cooled to-30 ℃, potassium tert-butoxide (25.4g) was added, and stirred for 1 hour. A THF (300ml) solution of compound (T-35) (50.0g) was slowly added dropwise thereto, returned to room temperature and stirred for 6 hours. After insoluble matter was separated by filtration, the reaction mixture was poured into water, and the aqueous layer was extracted with toluene. The combined organic layers were 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: heptane ═ 1: 1) to obtain compound (T-36) (63.0 g; 92%).

Step 2

Compound (T-36) (63.0g), toluene (500ml), IPA (500ml) and Pd/C (0.55g) were placed in a reactor and stirred under a hydrogen atmosphere for 16 hours. After insoluble matter was separated by filtration, the reaction mixture was poured into water, and the aqueous layer was extracted with toluene. The combined organic layers were 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: heptane ═ 1: 1) to obtain compound (T-37) (60.1 g; 95%).

Step 3 of

Compound (T-37) (60.1g), formic acid (75.8g), and toluene (1000ml) were placed in a reactor, and stirred at 100 ℃ for 6 hours. Insoluble matter was separated by filtration, neutralized with an aqueous sodium bicarbonate solution, and the aqueous layer was extracted with toluene. The combined organic layers were 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 and toluene to obtain compound (T-38) (45.0 g; 89%).

Step 4

Compound (T-38) (45.0g), potassium peroxymonosulfate (OXONE) (108.3g), and DMF (1000ml) were placed in a reactor and stirred at room temperature for 8 hours.

After insoluble matter was separated by filtration, the reaction mixture was poured into water, and the aqueous layer was extracted with ethyl acetate. The combined organic layers were washed with water and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure to obtain compound (T-39) (28.5 g; 60%).

Step 5

Compound (T-39) (28.5g), sulfuric acid (0.5ml) and methanol (500ml) were placed in a reactor and stirred at 60 ℃ for 5 hours. Insoluble matter was separated by filtration, concentrated and the residue was purified by silica gel chromatography and toluene to obtain compound (T-40) (22.3 g; 75%).

Step 6

Compound (T-41) (18.3 g; 70%) was obtained in the same manner as in 1 st step of synthetic example 4, using compound (T-40) (22.3g) as the starting material.

Step 7

Compound (T-42) (5.9 g; 38%) was obtained in the same manner as in 2 nd step of Synthesis example 4, using compound (T-41) (18.3g) as the starting material.

Step 8

Compound (1-23-3) (2.4 g; 34%) was obtained by the same method as in step 3 of Synthesis example 4, using Compound (T-42) (5.9g) as the starting material.

The NMR analysis values of the obtained compound (1-23-3) were as follows.

¹H-NMR: chemical shift delta (ppm; CDCl)₃)：6.11(s,1H)、5.81(s,1H)、4.31-4.28(m,1H)、4.17-4.14(m,1H)、3.63-3.58(m,1H)、3.54-3.49(m,1H)、1.98-1.95(m,4H)、1.84-1.69(m,9H)、1.41-1.18(m,10H)、1.15-1.06(m,4H)、1.02-0.80(m,13H).

The physical properties of the compound (1-23-3) are as follows.

Transition temperature: C33.6S_A 101I.

[ Synthesis examples of Compound (1-4-4) ]

Step 1 of

Compound (T-43) (2.1 g; 74%) was obtained in the same manner as in step 3 of Synthesis example 5, using compound (1-23-3) (2.0g) as the starting material.

Step 2

Compound (1-4-4) (1.3 g; 72%) was obtained in the same manner as in step 4 of Synthesis example 5, using compound (T-43) (2.1g) as the starting material.

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

¹H-NMR: chemical shift delta (ppm; CDCl)₃)：6.25(s,1H)、6.10(s,1H)、5.85(d,J＝1.1Hz,1H)、5.57(s,1H)、4.33(d,J＝6.5Hz,2H)、4.24-4.11(m,4H)、2.28(t,J＝6.6Hz,1H)、2.09-2.03(m,1H)、1.94(s,3H)、1.75-1.67(m,8H)、1.44-1.39(m,2H)、1.32-1.18(m,8H)、1.15-1.06(m,4H)、1.02-0.79(m,13H).

The physical properties of the compound (1-4-4) are as follows.

Transition temperature: C71.4I.

The compounds in the composition are represented by symbols based on the definitions of 1) to 5) in table 2 below. In Table 2, the configuration of the 1, 4-cyclohexylene group-related solid is trans configuration. The numbers in parentheses after the signs correspond to the numbers of the compounds. The symbol (-) indicates other liquid crystalline compounds. The proportion (percentage) of the liquid crystalline compound is a weight percentage (wt%) based on the weight of the liquid crystal composition. Finally, the characteristic values of the liquid crystal composition are summarized. The characteristics were measured according to the methods described previously, and the measured values were directly described (without extrapolation).

TABLE 2 method of expressing compounds using symbols

R-(A₁)-Z₁-……Zn-(A_n)-R’

[ composition (i) ]

NI＝76.1℃；η＝16.1mPa·s；Δn＝0.100；Δε＝-2.5；Vth＝2.4V.

[ composition (ii) ]

NI＝74.2℃；Tc＜-20℃；Δn＝0.103；Δε＝-2.5；Vth＝2.36V；η＝18.4mPa·s.

[ composition (iii) ]

NI＝74.9℃；Tc＜-20℃；Δn＝0.102；Δε＝-2.8；Vth＝2.30V；η＝19.2mPa·s.

[ composition (iv) ]

NI＝76.5℃；Tc＜-20℃；Δn＝0.098；Δε＝-3.0；Vth＝2.15V；η＝16.2mPa·s.

[ composition (v) ]

NI＝75.3℃；Tc<-20℃；Δn＝0.102；Δε＝-2.6；Vth＝2.41V；η＝17.5mPa·s.

[ example 1]

The following compound (1 α -4-a) was added to the composition (i) in a proportion of 3 parts by weight as a polymerizable polar compound.

Further, the following compound (16-6-1-A) was added as a polymerizable compound in a proportion of 0.3 part by weight. The composition was injected into an element having no alignment film and a gap (cell gap) of 3.5 μm between two glass substrates to prepare an element (1A), and the prepared element (1A) was irradiated with 29.7J/cm without applying a voltage²Ultraviolet ray (90 mW/cm) with dominant wavelength of 365nm²). For the irradiation of ultraviolet rays, an ultraviolet irradiation device manufactured by Qi of rock (Eyegraphics) GmbH, US4-X0401-FKTN type (metal halide lamp M04-L41) was used. Then, a voltage of 5.4V was applied to the element while the voltage was increased to 3V at a rate of 0.05V per second and to 5.4V at a rate of 0.15V per second, and in this state, 29.7J/cm was irradiated with the light from the same device²Ultraviolet ray (90 mW/cm) with dominant wavelength of 365nm²). The pretilt angle of the liquid crystal was measured, and found to be 88.9 °. As a result of observation with a polarizing microscope, light leakage was avoided and the vertical alignment was good. The alignment control layer present on the color filter substrate was observed with a scanning electron microscope, and as a result, the film thickness was 50nm and the particle size was 70 nm.

[ example 2]

Using the element (1A) produced by the same method as in example 1, 5.0J/cm was irradiated without applying a voltage²Ultraviolet ray (3 mW/cm) having a dominant wavelength of 335nm²). For the ultraviolet irradiation, black light (black light) manufactured by the company of Qi (Eyegraphics) and F40T10 (peak wavelength 335nm) were used. Next, a voltage of 5.4V was applied to the element by the same method as that described in example 1, and irradiation was performed at 9.9J/cm in the above state²Ultraviolet ray (3 mW/cm) having a dominant wavelength of 335nm²). To the pretilt angle of liquid crystal moleculesThe measurement result was 88.8 °. The device has no light leakage and good vertical orientation. The alignment control layer present on the color filter substrate had a film thickness of 50nm and a particle diameter of 50 nm.

[ example 3]

Using the element (1A) produced by the same method as in example 1, 5.0J/cm was irradiated without applying a voltage²Ultraviolet ray (3 mW/cm) having a dominant wavelength of 335nm²). For the ultraviolet irradiation, black light (black light) and F40T10 (peak wavelength of 335nm) manufactured by yergraph corporation were used. Next, a voltage of 5.4V was applied to the element by the same method as that described in example 1, and irradiation was performed at 49.5J/cm in the above state²Dominant wavelength of 365nm ultraviolet (90 mW/cm)²). The pretilt angle of the liquid crystal was measured, and it was 89.4 °. The device has no light leakage and good vertical orientation. The alignment control layer present on the color filter substrate had a film thickness of 50nm and a particle diameter of 65 nm.

[ example 4]

An element (1B) produced in the same manner as in example 1 was irradiated with 19.8J/cm without applying a voltage, except that the amount of the compound (16-6-1-A) added was changed to 0.05 parts by weight²Ultraviolet ray (90 mW/cm) with dominant wavelength of 365nm²). Next, a voltage of 5.4V was applied to the element by the same method as that described in example 1, and irradiation was performed at 13.2J/cm in the above state²Ultraviolet ray (3 mW/cm) having a dominant wavelength of 335nm²). The pretilt angle of the liquid crystal was measured, and found to be 89.0 °. The device has no light leakage and good vertical orientation. The alignment control layer present on the color filter substrate had a film thickness of 55nm and a particle diameter of 65 nm.

[ example 5]

Using the element (1A) produced by the same method as in example 1, 10.0J/cm was irradiated without applying a voltage²Ultraviolet ray (90 mW/cm) with dominant wavelength of 365nm²). Next, a voltage of 5.4V was applied to the element by the same method as that described in example 1, and in this state, irradiation was performed at 5.1J/cm²Main wave of365nm long ultraviolet (90 mW/cm)²). Further, the element was irradiated with 10.8J/cm without applying a voltage thereto²Ultraviolet ray (3 mW/cm) having a dominant wavelength of 335nm²). The pretilt angle of the liquid crystal was measured, and found to be 87.8 °. The device has no light leakage and good vertical orientation. The alignment control layer present on the color filter substrate had a film thickness of 50nm and a particle diameter of 55 nm.

Comparative example 1

Using the element (1A) produced by the same method as in example 1, a voltage of 5.4V was applied by the same method as the voltage application described in example 1, and in this state, 49.5J/cm was irradiated with the voltage while applying the voltage²Ultraviolet ray (90 mW/cm) with dominant wavelength of 365nm²). Next, the element was irradiated with 9.9J/cm without applying a voltage to the element²Ultraviolet ray (3 mW/cm) having a dominant wavelength of 335nm²). The pretilt angle of the liquid crystal was measured, and found to be 89.0 °. The element has light leakage as a result of "alignment defects". The alignment control layer present on the color filter substrate had a film thickness of 50nm and a particle diameter of 110 nm.

The elements of examples 1 to 5 were not light-leaking. On the other hand, light leakage was observed in comparative example 1. It is considered that light leakage occurs due to alignment defects. It was found that the particle diameters of the examples were small as compared with those of the comparative examples. It is believed that the small particle size contributes to uniform vertical orientation. The same effects can be obtained even when the constituent components of the liquid crystal composition or the kinds of the alignment monomers are different. Therefore, it can be concluded that the liquid crystal display element manufactured by the method of the present invention has a uniform vertical alignment. In the above element, light leakage can be prevented, and thus characteristics such as contrast are excellent.

Industrial applicability

The liquid crystal display element manufactured by the method of the present invention can be used for a liquid crystal monitor, a liquid crystal television, and the like.

Claims

1. A method of manufacturing a liquid crystal display element, the liquid crystal display element having:

a first substrate;

a plurality of pixel electrodes formed on the first substrate;

a second substrate;

a counter electrode formed on the second substrate to face the pixel electrode; and

a liquid crystal layer sandwiched between the pixel electrode and the counter electrode,

the liquid crystal layer includes a liquid crystal composition,

the liquid crystal composition contains a polymerizable polar compound having a mesogen portion composed of at least one ring and a liquid crystal compound as alignment monomers,

the method for manufacturing a liquid crystal display element is characterized in that:

first, a voltage is applied to the liquid crystal composition at 1J/cm without applying a voltage or substantially without driving the liquid crystal composition²To 60J/cm²Illumination intensity of 2mW/cm²To 200mW/cm²A first ultraviolet ray in the range of (1);

then, the liquid crystal composition is applied with a voltage of not less than a threshold voltage and not more than 30V, and the voltage is controlled at a rate of 5J/cm²To 100J/cm²Illumination intensity of 2mW/cm²To 200mW/cm²A second ultraviolet ray in the range of (1);

thereby forming an orientation control layer containing a polymer produced by polymerizing the polymerizable polar compound.

2. The method for manufacturing a liquid crystal display element according to claim 1, wherein a voltage which does not apply a voltage to the liquid crystal composition or does not substantially drive the liquid crystal composition is applied to the liquid crystal composition and is set to 3J/cm²To 50J/cm²Illumination intensity of 2mW/cm²To 100mW/cm²A first ultraviolet ray in the range of (1); then, the liquid crystal composition is applied with a voltage of not less than a threshold voltage and not more than 30V, and the voltage is controlled at a rate of 5J/cm²To 55J/cm²Illumination intensity of 2mW/cm²To 100mW/cm²A second ultraviolet ray of the range of (1).

3. The method for manufacturing a liquid crystal display element according to claim 1 or 2, wherein after the second ultraviolet irradiation, a voltage is further applied to the liquid crystal composition at 1J/cm without applying a voltage to the liquid crystal composition or without substantially driving the liquid crystal composition²To 60J/cm²Illumination intensity of 2mW/cm²To 200mW/cm²A third ultraviolet ray in the range of (1).

4. The method for manufacturing a liquid crystal display element according to claim 1 or 2, wherein in the alignment monomer having a mesogen site composed of at least one ring, the mesogen site includes a cyclohexane ring.

5. The method for manufacturing a liquid crystal display element according to claim 1 or 2, wherein the liquid crystal composition further contains a polymerizable compound represented by formula (16 a) as a reactive monomer, and thereby forms an orientation control layer comprising a copolymer produced by polymerizing these compounds,

in the formula (16 a), in the formula,

Z²²and Z²³Independently a single bond or an alkylene group having 1 to 10 carbon atoms, in which at least one-CH group₂-may be substituted by-O-, -CO-, -COO-, or-OCO-, at least one- (CH)₂)₂-may be via-CH ═ CH-, -C (CH)₃)＝CH-、-CH＝C(CH₃) -, or-C (CH)₃)＝C(CH₃) -substituted, in which at least one hydrogen may be substituted by fluorine or chlorine;

P¹¹、P¹²and P¹³Independently a polymerizable group;

u is 0,1 or 2;

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

wherein in formula (16 α), P¹¹、P¹²And P¹³Independently 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),

6. The method for manufacturing a liquid crystal display element according to claim 1 or 2, wherein the liquid crystal composition has negative dielectric anisotropy.

7. The method for manufacturing a liquid crystal display element according to claim 1 or 2, wherein the alignment control layer has a film thickness of 10nm to 100nm, and a particle diameter of the polymer in the alignment control layer is in a range of 1nm to 90 nm.

8. The method for manufacturing a liquid crystal display element according to claim 1 or 2, wherein a particle diameter of the polymer in the alignment control layer is in a range of 1nm to 70 nm.

9. The method for manufacturing a liquid crystal display element according to claim 1 or 2, wherein the molecules of the liquid crystalline compound are aligned vertically, and the angle of the molecules to the substrate is 90 ° ± 10 °.

10. The method for manufacturing a liquid crystal display element according to claim 1 or 2, wherein the alignment of molecules of the liquid crystalline compound is divided for each pixel.

11. A display device comprising a liquid crystal display element manufactured by the method for manufacturing a liquid crystal display element according to any one of claims 1 to 10, and a backlight.