JP2020041128A - Horizontally aligned liquid crystal display element, liquid crystal composition, polymerizable compound and display device, method for manufacturing horizontally aligned liquid crystal display element, and use of polymerizable compound as monomer for forming alignment control layer - Google Patents

Abstract

To efficiently form an alignment control layer in a horizontally aligned liquid crystal display element which requires neither a conventional alignment film formed of a polyimide or the like nor a process of forming the alignment film, and to provide a horizontally aligned liquid crystal display element excellent in transmittance characteristics and a contrast ratio.SOLUTION: A liquid crystal composition described below is used. The liquid crystal composition comprises a monomer for forming an alignment control layer, which has an α-alkoxyalkyl acrylate as a polymerizable group and induces at least one of photo-Fries rearrangement, photo-dimerization, photo-isomerization and photolysis by irradiation with UV rays, and the composition has positive or negative dielectric anisotropy.SELECTED DRAWING: None

Description

  The present invention relates to a horizontal alignment type liquid crystal display device and a liquid crystal composition. In particular, a liquid crystal composition having an α-alkoxyalkyl acrylate as a polymerizable group and containing an alignment control layer forming monomer that generates at least one of photo-fleece rearrangement, photo-isomerization, photo-dimerization, and photo-decomposition by light irradiation is used. Accordingly, the present invention relates to a liquid crystal display device in which horizontal alignment of liquid crystal molecules can be achieved without using an alignment film such as polyimide.

  In a liquid crystal display device, classification based on the operation mode of liquid crystal molecules includes PC (phase change), TN (twisted nematic), STN (super twisted nematic), ECB (electrically controlled birefringence), OCB (optically compensated bend), and IPS. (In-plane switching), VA (vertical alignment), FFS (fringe field switching), and FPA (field-induced photo-reactive alignment). The classification based on the element driving method is PM (passive matrix) and AM (active matrix). PM is classified into static, multiplex and the like, and AM is classified into TFT (thin film transistor), MIM (metal insulator metal) and the like. The classification of TFT is amorphous silicon and polycrystal silicon. The latter is classified into a high-temperature type and a low-temperature type according to the manufacturing process. The classification based on the light source is a reflection type using natural light, a transmission type using backlight, and a semi-transmission type using both natural light and backlight.

  The liquid crystal display device contains a liquid crystal composition having a nematic phase. This composition has suitable properties. By improving the characteristics of this composition, an AM device having good characteristics can be obtained. The relationship between the two characteristics is summarized in Table 1 below. The characteristics of the composition will be further described based on commercially available AM devices. The temperature range of the nematic phase is related to the temperature range in which the device can be used. The preferred upper limit temperature of the nematic phase is about 70 ° C. or more, and the preferred lower limit temperature of the nematic phase is about −10 ° C. or less. The viscosity of the composition is related to the response time of the device. A short response time is preferable for displaying a moving image on the element. Shorter response times are desirable even at 1 millisecond. Therefore, a small viscosity in the composition is preferred. Small viscosities at low temperatures are more preferred.

  The optical anisotropy of the composition is related to the contrast ratio of the device. Depending on the mode of the device, large or small optical anisotropy, that is, appropriate optical anisotropy is required. The product (Δn × d) of the optical anisotropy (Δn) of the composition and the cell gap (d) of the device is designed to maximize the contrast ratio. The appropriate product value depends on the type of operating mode. This value is about 0.45 μm for a device in a mode such as TN. This value ranges from about 0.30 μm to about 0.40 μm for a VA mode device, and from about 0.20 μm to about 0.30 μm for an IPS mode or FFS mode device. In these cases, a composition having a large optical anisotropy is preferable for a device having a small cell gap. The large dielectric anisotropy in the composition contributes to a low threshold voltage, small power consumption and a large contrast ratio in the device. Therefore, a large positive or negative dielectric anisotropy is preferable. A large specific resistance in the composition contributes to a large voltage holding ratio and a large contrast ratio in the device. Therefore, a composition having a large specific resistance in the initial stage is preferable. A composition having a large specific resistance after long-term use is preferred. The stability of the composition to ultraviolet light and heat is related to the lifetime of the device. When this stability is high, the lifetime of the device is long. Such characteristics are preferable for an AM device used for a liquid crystal monitor, a liquid crystal television, and the like.

  In an AM device having a TN mode, a composition having a positive dielectric anisotropy is used. In an AM device having a VA mode, a composition having a negative dielectric anisotropy is used. In an AM device having the IPS mode or the FFS mode, a composition having a positive or negative dielectric anisotropy is used. In a polymer sustained alignment (PSA) type AM device, a composition having a positive or negative dielectric anisotropy is used. In a polymer sustained alignment (PSA) type liquid crystal display device, a liquid crystal composition containing a polymer is used. First, a composition to which a small amount of a polymerizable compound is added is injected into a device. Next, the composition is irradiated with ultraviolet rays while applying a voltage between the substrates of the device. The polymerizable compound polymerizes to form a polymer network in the composition. In this composition, the orientation of the liquid crystal molecules can be controlled by the polymer, so that the response time of the device is shortened and the image sticking is improved. Such effects of the polymer can be expected for devices having modes such as TN, ECB, OCB, IPS, VA, FFS, and FPA.

In the IPS mode, FFS mode, and ECB mode, it is necessary to align liquid crystal molecules in a direction substantially horizontal to the main surface of the substrate when no voltage is applied. In order to realize such alignment control of liquid crystal molecules, an alignment film such as polyimide has been used. In recent years, as the frame of the liquid crystal panel has become narrower, the bonding strength between the alignment film and the sealant has been narrowed, whereby the bonding strength has been weakened, and peeling may have progressed from the interface between the alignment film and the sealant. In order to prevent such a problem, a method that does not use an alignment film such as a conventional polyimide has been proposed. (Patent Documents 1 to 3)
In the methods of Patent Documents 1 to 3, a low-molecular compound having a cinnamate group, polyvinyl cinnamate, a low-molecular compound having a chalcone structure, or a polymerizable compound is used instead of an alignment film such as polyimide. These low molecular compounds, polymerizable compounds and polymers are dissolved in the liquid crystal composition as additives. Next, a thin film composed of the additive is formed on the substrate by phase-separating the additive. Finally, the substrate is irradiated with linearly polarized light at a temperature higher than the upper limit temperature of the liquid crystal composition. When a low molecular compound or polymer is dimerized or isomerized by the linearly polarized light, the molecules are arranged in a certain direction. In this method, by selecting the type of the additive, a device having a horizontal alignment mode such as IPS or FFS and a device having a vertical alignment mode such as VA can be manufactured. In this method, it is important that the additive easily dissolves at a temperature higher than the upper limit temperature of the liquid crystal composition, and that when the temperature is returned to room temperature, the compound easily undergoes phase separation from the liquid crystal composition. However, depending on the liquid crystal compound to be combined, there were cases where sufficient horizontal alignment was not obtained.
Patent Documents 4 and 5 disclose a liquid crystal composition containing a polymerizable compound having α-hydroxymethoxymethyl diacrylate and having a central skeleton structure of biphenyl or terphenyl. Patent Documents 4 and 5 illustrate a polymerizable compound having α-methoxymethyldiacrylate as a preferable compound and having a central skeleton structure of biphenyl or terphenyl. Here, a liquid crystal compound is used as a substrate. It is disclosed as an additive for orienting vertically. Further, even when the liquid crystal composition containing the polymerizable compound was irradiated with polarized light, it was difficult to obtain uniform horizontal alignment.

WO 2015/146369 WO 2017/057162 International Publication No. WO2018008581 International Publication No. WO 2017/047177 International Publication No. WO2018 / 025974

  An object of the present invention is to use a liquid crystal composition containing an alignment control layer-forming monomer having an α-alkoxyalkyl acrylate as a polymerizable group, thereby requiring a conventional alignment film formed of polyimide or the like and a step of forming the same. An object of the present invention is to provide a horizontal alignment type liquid crystal display element in which an alignment control layer in a liquid crystal display element is not formed efficiently and which has excellent transmittance characteristics and contrast ratio.

  The present inventors contain an alignment control layer-forming monomer having α-alkoxyalkyl acrylate as a polymerizable group, which causes photo-Fries rearrangement, photo-dimerization, photo-isomerization and photo-decomposition by ultraviolet irradiation, and The inventors have found that the above problem can be solved by using a liquid crystal composition having a positive or negative dielectric anisotropy, and have completed the present invention. The present invention includes the following aspects.

[1] A liquid crystal layer is sandwiched between a pair of substrates arranged opposite to each other,
An alignment control layer for controlling alignment of liquid crystal molecules between the pair of substrates and the liquid crystal layer,
The liquid crystal layer is formed from a liquid crystal composition,
The liquid crystal composition comprises at least one liquid crystal compound and, as a first additive, at least one of photo-Fries rearrangement, photo-isomerization, photo-dimerization, and photo-decomposition by light irradiation, which is represented by formula (1). Containing an orientation control layer forming monomer that produces
The horizontal alignment type liquid crystal display device, wherein the alignment control layer contains a polymer obtained by polymerizing the first additive.

In equation (1),
R ¹ , R ² and R ³ are independently hydrogen or alkyl having 1 to 10 carbons, wherein at least one —CH ₂ — is replaced by —O— or —NH— Well;
n is independently 0, 1 or 2;
a is 0, 1, 2, or 3;
Ring ^{A 1} is cyclohexyl, cyclohexenyl, phenyl, 1-naphthyl, 2-naphthyl, tetrahydropyran-2-yl, tetrahydropyran-3-yl, 1,3-dioxan-2-yl, 1,3-dioxane - 3-yl, pyrimidin-2-yl, pyrimidin-5-yl, pyridin-2-yl, pyridin-3-yl, fluoren-2-yl, fluoren-7-yl, phenanthren-2-yl, phenanthrene-7- Yl, anthracen-2-yl, anthracen-6-yl, perhydrocyclopenta [a] phenanthren-3-yl, perhydrocyclopenta [a] phenanthrene-17-yl, 2,3,4,7,8, 9,10,11,12,13,14,15,16,17-tetradecahydrocyclopenta [a] phenanthrene-3- Or 2,3,4,7,8,9,10,11,12,13,14,15,16,17-tetradecahydrocyclopenta [a] phenanthrene-17-yl,
Ring A ² is 1,4-cyclohexylene, 1,3-cyclohexylene, 1,2-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, 1,3-phenylene, , 2-Phenylene, naphthalene-2,6-diyl, naphthalene-1,4-diyl, decahydronaphthalene-2,6-diyl, decahydronaphthalene-1,4-diyl, 1,2,3,4-tetrahydro Naphthalene-2,6-diyl, 1,2,3,4-tetrahydronaphthalene-1,4-diyl, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, pyrimidine-2, 5-diyl, pyridine-2,5-diyl, cyclopentane-1,3-diyl, cyclopentene-1,3-diyl, fluorene-2,7-diyl,
Carbazole-2,7-diyl, phenanthrene-2,7-diyl, anthracene-2,6-diyl, anthracene-1,4-diyl, perhydrocyclopenta [a] phenanthrene-3,17-diyl, or 2, 3,4,7,8,9,10,11,12,13,14,15,16,17-tetradecahydrocyclopenta [a] phenanthrene-3,17-diyl,
Ring ^{A 3} 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, pyridine-2,5-diyl, fluorene-2,7- Diyl, phenanthrene-2,7-diyl, anthracene-2,6-diyl, anthracene-1,4-diyl, perhydrocyclopenta [a] phenanthrene-3,17-di Or 2,3,4,7,8,9,10,11,12,13,14,15,16,17-tetradecahydrocyclopenta [a] phenanthrene-3,17-diyl;
Z ¹ and Z ² are each independently a single bond or alkylene having 1 to 10 carbon atoms, wherein at least one —CH ₂ — is —O—, —CO—, —COO—, — OCO -, - CONH -, - NHCO- or -OCOO- may be replaced by at least one - _{(CH 2) 2} - may be replaced by -CH = CH- or -C≡C- , In these groups, at least one hydrogen may be replaced by halogen, but at least one of Z ¹ and Z ² is —COO—, —OCO—, —CH ＝ CHCOO—, —OCOCH ＝ CH—, —CH ＝ CH—, —CH ＝ CHCO—, or —COCH ＝ CH—, and when a is 2 or 3, each Z ² may be different;
Sp ¹ , Sp ² , Sp ³ and Sp ⁴ are each independently a single bond or alkylene having 1 to 10 carbon atoms, wherein at least one —CH ₂ — is —O—, —COO— , —OCO— or —OCOO—, and at least one — (CH ₂ ) ₂ — may be replaced by —CH ＝ CH— or —C≡C—, in these groups: At least one hydrogen may be replaced by fluorine or chlorine;
c, d and e are independently 0, 1, 2, 3 or 4; the sum of c, d and e is 1, 2, 3 or 4;
P ¹ , P ² , P ³ and P ⁴ are each independently a polymerizable group represented by the formula (1P-1);

In the equation (1P-1),
M ⁴¹ and M ⁴² are independently hydrogen, fluorine, alkyl having 1 to 5 carbons, or alkyl having 1 to 5 carbons in which at least one hydrogen is replaced by fluorine or chlorine;
R ⁴¹ is alkyl having 1 to 10 carbons, alkoxy having 1 to 9 carbons, or alkoxyalkyl having 1 to 9 carbons. In these groups, at least one — (CH ₂ ) ₂ — is represented by — CH ＝ CH— or —C≡C—, in which at least one hydrogen may be replaced by fluorine or chlorine, but P ¹ , P ² , P ³ and P ⁴ In at least one formula (1P-1), R ⁴¹ is alkoxyalkyl having 1 to 9 carbons.

[2] In equation (1),
R ¹ , R ² and R ³ are independently hydrogen or alkyl having 1 to 10 carbons, wherein at least one —CH ₂ — is replaced by —O— or —NH— Well;
n is independently 0, 1 or 2;
a is 0, 1, 2, or 3;
Ring ^{A 1} is cyclohexyl, phenyl, 1-naphthyl, 2-naphthyl, pyrimidin-2-yl, pyrimidin-5-yl, pyridin-2-yl, pyridin-3-yl, fluoren-2-yl, fluorene -7 -Yl, phenanthren-2-yl, phenanthren-7-yl or anthracen-2-yl, anthracen-6-yl,
Ring ^{A 2} is 1,4-cyclohexylene, cyclohexylene 1,3-cyclohexylene, 1,4-phenylene, 1,3-phenylene, naphthalene-2,6-diyl, naphthalene-1,4-diyl, pyrimidine -2,5-diyl, pyridine-2,5-diyl, fluorene-2,7-diyl, carbazole-2,7-diyl, phenanthrene-2,7-diyl or anthracene-2,6-diyl, anthracene-1 , 4-diyl,
Ring ^{A 3} is 1,4-cyclohexylene, 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, pyrimidine -2,5-diyl, pyridine-2,5-diyl, fluorene-2,7-diyl, phenanthrene-2,7-diyl, anthracene-2,6-diyl or anthracene-1,4-diyl;
Z ¹ and Z ² are each independently a single bond or alkylene having 1 to 10 carbon atoms, wherein at least one —CH ₂ — is —O—, —CO—, —COO—, — OCO -, - CONH -, - NHCO- or -OCOO- may be replaced by at least one - _{(CH 2) 2} - may be replaced by -CH = CH- or -C≡C- , In these groups, at least one hydrogen may be replaced by halogen, but at least one of Z ¹ and Z ² is —COO—, —OCO—, —CH ＝ CHCOO—, —OCOCH ＝ CH—, —CH ＝ CH—, —CH ＝ CHCO—, or —COCH ＝ CH—, and when a is 2 or 3, each Z ² may be different;
Sp ¹ , Sp ² , Sp ³ and Sp ⁴ are each independently a single bond or alkylene having 1 to 10 carbon atoms, wherein at least one —CH ₂ — is —O—, —COO— , —OCO— or —OCOO—, and at least one — (CH ₂ ) ₂ — may be replaced by —CH ＝ CH— or —C≡C—, in these groups: At least one hydrogen may be replaced by fluorine;
c, d and e are independently 0, 1, 2, 3 or 4; the sum of c, d and e is 1, 2, 3 or 4;
P ¹ , P ² , P ³ and P ⁴ are each independently a polymerizable group represented by the formula (1P-1);

In the equation (1P-1),
M ⁴¹ and M ⁴² are independently hydrogen, fluorine, alkyl having 1 to 5 carbons, or alkyl having 1 to 5 carbons in which at least one hydrogen is replaced by fluorine;
R ⁴¹ is alkyl having 1 to 10 carbons, alkoxy having 1 to 9 carbons, or alkoxyalkyl having 1 to 9 carbons. In these groups, at least one — (CH ₂ ) ₂ — is represented by — CH ＝ CH— or —C≡C—, in which at least one hydrogen may be replaced by fluorine, but at least one of P ¹ , P ² , P ³ and P ⁴ In one formula (1P-1), the horizontal alignment liquid crystal display element according to [1], wherein R ⁴¹ is alkoxyalkyl having 1 to 9 carbon atoms.

[3] The sum of the weight of the unit derived from the first additive in the polymer obtained by polymerizing the first additive in the alignment control layer and the weight of the first additive in the liquid crystal layer The horizontal alignment type liquid crystal display according to [1] or [2], wherein the ratio of the amount is in the range of 0.01 part by weight to 10 parts by weight when the total amount of the liquid crystal compound is 100 parts by weight. element.

[4] The liquid crystal composition according to any one of [1] to [3], wherein the liquid crystal composition contains at least one liquid crystal compound selected from the group of compounds represented by formulas (2) to (4). The horizontal alignment type liquid crystal display element as described in the above.

In equations (2) to (4),
R ¹¹ and R ¹² are each independently an alkyl having 1 to 10 carbons or an alkenyl having 2 to 10 carbons. In the alkyl and alkenyl, at least one —CH ₂ — is —O—, —COO -Or -OCO- and at least one hydrogen may be replaced by fluorine;
Ring B ¹ , ring B ² , ring B ³ and ring B ⁴ are each independently 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, 2,5-difluoro- 1,4-phenylene or pyrimidine-2,5-diyl;
Z ¹¹ , Z ¹² and Z ¹³ are each independently a single bond, — (CH ₂ ) ₂ —, —CH ＝ CH—, —C≡C—, or —COO—.

[5] Any of [1] to [4], wherein the liquid crystal composition further contains at least one liquid crystal compound selected from the group of compounds represented by formulas (5) to (7). 3. The horizontal alignment type liquid crystal display device according to item 1.

In equations (5) to (7),
R ¹³ is alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons. In the alkyl and alkenyl, at least one —CH ₂ — may be replaced by —O—, and at least one Hydrogen may be replaced by fluorine;
X ¹¹ is fluorine, _{chlorine, -OCF 3, -OCHF 2, -CF} 3, -CHF 2, be -CH ₂ F, -OCF 2 CHF 2 or -OCF ₂ CHFCF _3;
Ring C ¹ , ring C ² and ring C ³ are independently 1,4-cyclohexylene, 1,4-phenylene wherein at least one hydrogen may be replaced by fluorine, tetrahydropyran-2,5-diyl , 1,3-dioxane-2,5-diyl, or pyrimidine-2,5-diyl;
Z ¹⁴ , Z ¹⁵ and Z ¹⁶ are each independently a single bond,-(CH ₂ ) _2- , -CH = CH-, -CH = CF-, -CF = CF-, -C≡C-,- COO—, —CF ₂ O—, —OCF ₂ —, —CH ₂ O—, —CH ＝ CF—CF ₂ O—, —CFＣＦCF—CF ₂ O— or — (CH ₂ ) ₄ —;
L ¹¹ and L ¹² are independently hydrogen or fluorine.

[6] The horizontal alignment according to any one of [1] to [5], wherein the liquid crystal composition further contains at least one liquid crystal compound selected from the group of compounds represented by Formula (8). Liquid crystal display device.

In equation (8),
R ¹⁴ is alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons. In the alkyl and alkenyl, at least one —CH ₂ — may be replaced by —O—, and at least one Hydrogen may be replaced by fluorine;
X ¹² is an -C≡N or -C≡C-C≡N;
Ring D ¹ is independently 1,4-cyclohexylene, 1,4-phenylene in which at least one hydrogen may be replaced by fluorine, tetrahydropyran-2,5-diyl, 1,3-dioxane-2 , 5-diyl, or pyrimidine-2,5-diyl;
Z ¹⁷ are each independently a single _{bond, - (CH 2) 2 -} , - C≡C -, - COO -, - CF 2 O -, - OCF 2 - or _-CH 2 O-;
L ¹³ and L ¹⁴ are independently hydrogen or fluorine;
i is 1, 2, 3 or 4.

[7] Any of [1] to [6], wherein the liquid crystal composition further contains at least one liquid crystal compound selected from the group of compounds represented by formulas (9) to (21). 3. The horizontal alignment type liquid crystal display device according to item 1.

In equations (9) to (21),
R ¹⁵ and R ¹⁶ are independently alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, wherein at least one —CH ₂ — is replaced with —O— in the alkyl and alkenyl. And at least one hydrogen may be replaced by fluorine;
R ¹⁷ is hydrogen, fluorine, alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons. In the alkyl and alkenyl, at least one —CH ₂ — may be replaced by —O—. Well, at least one hydrogen may be replaced by fluorine;
Ring E ¹ , ring E ² , ring E ³ and ring E ⁴ are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, wherein at least one hydrogen may be replaced by fluorine, 4-phenylene, tetrahydropyran-2,5-diyl or decahydronaphthalene-2,6-diyl;
Ring E ⁵ and ring E ⁶ are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, tetrahydropyran-2,5-diyl or decahydronaphthalene-2,6 -Diyl;
^{Z 18, Z 19, Z 20} , and ^{Z 21} are each independently a single _{bond, - (CH 2) 2 -} , - COO -, - CH 2 O -, - OCF 2 -, or -OCF ₂ CH ₂ CH ₂ —;
L ¹⁵ and L ¹⁶ are independently fluorine or chlorine;
S ¹¹ is hydrogen or methyl;
X is independently, -CHF- or -CF ₂ - and is;
j, k, m, n, p, q, r, and s are each independently 0 or 1, and the sum of k, m, n, and p is 0, 1, 2, or 3, and q, The sum of r and s is 0, 1, 2 or 3, and t is 1, 2 or 3.

[8] The liquid crystal composition further contains, as a second additive, a polymerizable compound different from the first additive, and the alignment control layer polymerizes the first additive and the second additive. The horizontal alignment type liquid crystal display device according to any one of [1] to [7], comprising a polymer obtained by the above method.

[9] The horizontal alignment type liquid crystal display device according to [8], wherein the second additive is represented by a formula (16α).

In the equation (16α),
Ring F and Ring I are independently cyclohexyl, cyclohexenyl, phenyl, 1-naphthyl, 2-naphthyl, tetrahydropyran-2-yl, tetrahydropyran-3-yl, 1,3-dioxan-2-yl, 1,3-dioxan-3-yl, pyrimidin-2-yl, pyridin-2-yl, pyrimidin-5-yl, fluoren-2-yl, fluoren-7-yl, phenanthren-2-yl, phenanthrene-7- Yl, anthracen-2-yl, anthracen-6-yl, perhydrocyclopenta [a] phenanthren-3-yl, perhydrocyclopenta [a] phenanthren-17-yl, 2,3,4,7,8, 9,10,11,12,13,14,15,16,17-tetradecahydrocyclopenta [a] phenanthrene-3-i Or 2,3,4,7,8,9,10,11,12,13,14,15,16,17-tetradecahydrocyclopenta [a] phenanthrene-17-yl, in these rings The at least one hydrogen may be replaced by fluorine, chlorine, alkyl having 1 to 12 carbons, or alkyl having 1 to 12 carbons in which at least one hydrogen is replaced by fluorine or chlorine;
Ring G is 1,4-cyclohexylene, 1,3-cyclohexylene, 1,2-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, 1,3-phenylene, 1, 2-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, fluorene-2,7-diyl, carbazole-2,7-diyl, phenanthrene-2,7-diyl, anthracene-2,6-diyl, anthracene-1,4 Diyl, perhydrocyclopenta [a] phenanthrene-3,17-diyl, pyrimidine-2,5-diyl or pyridine-2,5-diyl, in which at least one hydrogen is fluorine, chlorine, Alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, or alkyl having 1 to 12 carbons in which at least one hydrogen is replaced by fluorine or chlorine;
Z ²² and Z ²³ are each independently a single bond or alkylene having 1 to 10 carbons, wherein at least one —CH ₂ — is —O—, —COO—, —OCO— or — may be replaced by -OCOO-, at least one - _{(CH 2) 2} - is, -CH = CH -, - C≡C -, - C (CH 3) = CH -, - CH = C (CH 3 ) - or _{-C (CH 3) = C (} CH 3) - may be replaced by, in these groups, at least one hydrogen may be replaced by fluorine or chlorine;
P ¹¹ , P ¹² and P ¹³ are each independently a polymerizable group, but at least one of Z ²² and Z ²³ has —COO—, —OCO—, —CH ＝ CHCOO—, and —OCOCH = When CH—, —CH ＝ CH—, —CH ＝ CHCO—, or —COCH ＝ CH—, all of P ¹¹ , P ¹² and P ¹³ are not simultaneously represented by the formula (1P-1). ;

In the equation (1P-1),
M ⁴¹ and M ⁴² are independently hydrogen, fluorine, alkyl having 1 to 5 carbons, or alkyl having 1 to 5 carbons in which at least one hydrogen is replaced by fluorine or chlorine;
R ⁴¹ is alkyl having 1 to 10 carbons, alkoxy having 1 to 9 carbons, or alkoxyalkyl having 1 to 9 carbons. In these groups, at least one — (CH ₂ ) ₂ — is represented by — CH ＝ CH— or —C≡C—, in which at least one hydrogen may be replaced by fluorine or chlorine, but P ¹ , P ² , P ³ and P ⁴ In at least one formula (1P-1), R ⁴¹ is alkoxyalkyl having 1 to 9 carbons;
In the equation (16α),
Sp ¹¹ , Sp ¹² and Sp ¹³ are each independently a single bond or alkylene having 1 to 10 carbon atoms, wherein at least one —CH ₂ — is —O—, —COO—, —OCO - or it may be replaced by -OCOO-, at least one - _{(CH 2) 2} - may be replaced by -CH = CH- or -C≡C-, and in the groups, at least one Hydrogen may be replaced by fluorine or chlorine;
u is 0, 1 or 2;
f, g, and h are each independently 0, 1, 2, 3, or 4, and the sum of f, g, and h is 2 or more.

[10] The weight of the unit derived from the second additive in the polymer obtained by polymerizing the first additive and the second additive in the alignment control layer, and the second additive in the liquid crystal layer [8] or [9], wherein the ratio of the total amount with respect to the weight of the liquid crystal compound is in the range of 0.03 parts by weight to 10 parts by weight when the total amount of the liquid crystal compound is 100 parts by weight. Horizontal alignment type liquid crystal display device.

[11] A method for manufacturing a horizontal alignment type liquid crystal display element for manufacturing the horizontal alignment type liquid crystal display element according to any one of [1] to [10],
Sandwiching the liquid crystal composition between a pair of substrates,
The liquid crystal composition is maintained in a temperature range equal to or higher than a transition temperature T _NI from a nematic phase to an isotropic phase, and the liquid crystal composition is irradiated with polarized ultraviolet rays, and at least the first additive is polymerized, whereby the alignment is performed. A method for manufacturing a horizontal alignment type liquid crystal display device, comprising a step of forming a control layer.

[12] In the step of forming the alignment control layer, the liquid crystal composition has a peak in a wavelength range of 300 nm to 400 nm while maintaining the liquid crystal composition in a temperature range of T _NI or higher and T _NI + 15 ° C. or lower. from 2 mW / cm ² in the range of 300 mW / cm ^2, is performed by irradiating polarized ultraviolet rays in the range of from 0.03 J / cm ² to an exposure amount of 20 J / cm ^2, a horizontal alignment type as described in [11] A method for manufacturing a liquid crystal display element.

[13] The step of forming the alignment control layer includes irradiating the polarized ultraviolet light, and further applying additional non-polarized ultraviolet light to the liquid crystal composition while maintaining the liquid crystal composition in a temperature range of 20 ° C. or more and 45 ° C. or less. Or [11], which has a peak at a wavelength of from 1 to 400 nm, and has an illuminance in the range of 1 mW / cm ² to 50 mW / cm ² and an exposure amount of 1 J / cm ² to 10 J / cm ² . The method for producing a horizontal alignment type liquid crystal display device according to [12].

[14] A liquid crystal composition used in the method for producing a horizontal alignment type liquid crystal display device according to any one of [11] to [13],
It has a transition temperature T _NI from a nematic phase to an isotropic phase, at least one liquid crystalline compound, and as a first additive, an alignment control layer forming monomer represented by the formula (1) according to [1]. A liquid crystal composition comprising at least one of the following.

[15] A polymerizable compound used in the method for producing a horizontal alignment type liquid crystal display device according to any one of [11] to [13], which is represented by the formula (1) according to [1]. Compounds.

[16] Use of the polymerizable compound according to [15] as a monomer for forming an alignment control layer.

[17] A display device comprising: the horizontal alignment type liquid crystal display element according to any one of [1] to [10]; and a backlight.

  This example also includes the following section. (A) at least two 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; The liquid crystal composition described above. (B) A polymerizable composition prepared by adding a polymerizable compound different from compound (1) or compound (16α) to the above liquid crystal composition. (C) A polymerizable composition prepared by adding the compound (1) and the compound (16α) to the above liquid crystal composition. (D) A liquid crystal composite prepared by polymerizing the polymerizable composition.

  According to the present invention, by using a liquid crystal display element using a liquid crystal composition containing a monomer for forming an alignment control layer having α-alkoxyalkyl acrylate as a polymerizable group, a horizontal alignment type liquid crystal having excellent transmittance characteristics and contrast ratio A display element can be realized.

  The usage of terms in this specification is as follows. The terms "liquid crystal composition" and "liquid crystal display element" may be abbreviated as "composition" and "element", respectively. “Liquid crystal display element” is a general term for a liquid crystal display panel and a liquid crystal display module. "Liquid crystal compound" is a compound having a liquid crystal phase such as a nematic phase or a smectic phase, or a compound having no liquid crystal phase, but having a composition for the purpose of adjusting properties such as temperature range, viscosity, and dielectric anisotropy of the nematic phase. It is a general term for compounds that are mixed with products. This compound has a six-membered ring such as 1,4-cyclohexylene and 1,4-phenylene, and has a rod-like molecular structure. "Polymerizable compound" is a compound added for the purpose of forming a polymer in the composition.

  The liquid crystal composition is prepared by mixing a plurality of liquid crystal compounds. Additives such as an optically active compound, an antioxidant, an ultraviolet absorber, a dye, an antifoaming agent, a polymerizable compound, a polymerization initiator, a polymerization inhibitor, and a polar compound are added to the liquid crystal composition as necessary. You. The ratio of the liquid crystal compound is represented by a weight percentage (% by weight) based on the weight of the liquid crystal composition containing no additive, even when the additive is added. The proportion of the additive is represented by a weight percentage (parts by weight) based on the weight of the liquid crystal composition containing no additive. That is, the ratio of the liquid crystal compound or the additive is calculated based on the total weight of the liquid crystal compound. Parts per million by weight (ppm) may be used. The proportion of the polymerization initiator is exceptionally expressed based on the weight of the polymerizable compound.

The compound represented by the formula (A) may be abbreviated as “compound (A)”. Compound (A) means one compound represented by formula (A), a mixture of two compounds, or a mixture of three or more compounds. This rule is also applied to at least one compound selected from the group of compounds represented by the formula (2). Symbols such as B ¹ , C ¹ , D ¹ , E ¹ , and F surrounded by a hexagon correspond to ring B ¹ , ring C ¹ , ring D ¹ , ring E ¹ , ring F, and the like, respectively. 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), the formula (16α), and the like, a straight line that crosses one side of the hexagon indicates that any hydrogen on the ring is replaced with a group such as-(R ¹ ) n or -Sp ¹¹ -P ^11. Indicates good things. Subscripts such as 'f' indicate the number of replaced groups. When the subscript is 0, there is no such replacement. When the subscript 'f' is 2 or more, a plurality of -Sp ¹¹ -P ¹¹ exist on the ring F. A plurality of groups represented by -Sp ¹¹ -P ¹¹ may be the same or different. These rules apply in other expressions as well. In the expression "ring F and ring G are independently X, Y, or Z", "independently" is used because the subject has a plurality. When the subject is "ring F", "independent" is not used because the subject is singular.

The symbol of the terminal groups R ¹¹ was used in a plurality of component compounds. In these compounds, the two groups represented by any two R ¹¹ may be the same or different. For example, in some cases, R ^{11 of} compound (2) is ethyl and R ¹¹ of compound (3) is ethyl. In some cases, R ^{11 of} compound (2) is ethyl and R ¹¹ of compound (3) is propyl. This rule applies to symbols such as other end groups, rings, and linking groups. In the formula (8), when i is 2, two rings ^{D 1} are present. In this compound, the two groups represented by the two rings D ¹ may be the same or different. This rule, i applies to any two rings D ¹ of the case 2 larger. This rule also applies to symbols such as other rings and linking groups.

The expression "at least one 'A'" means that the number of 'A' is arbitrary. The expression "at least one 'A' may be replaced by 'B'" means that when the number of 'A' is one, the position of 'A' is arbitrary and the number of 'A' is two. In more than one case, their positions can be selected without restriction. This rule also applies to the expression "at least one 'A' has been replaced by 'B'". The expression "at least one A may be replaced by B, C or D" means that at least one A is replaced by B, at least one A is replaced by C, and at least This means that a case where one A is replaced with D further includes a case where a plurality of A are replaced with at least two of B, C and D. For example, at least one -CH ₂ - _{(or, - (CH 2) 2 -} ) is -O- (or, -CH = CH-) in the alkyl which may be replaced by an alkyl, alkenyl, alkoxy, alkoxy Alkyl, alkoxyalkenyl and alkenyloxyalkyl are included. It is not preferable that two consecutive —CH ₂ — are replaced with —O— to become —O—O—. Alkyl such as in, -CH ₂ methyl moiety _(-CH 2 -H) - by is replaced by -O- is not preferred also be the -O-H.

  In the liquid crystal compound, alkyl is linear or branched and does not include cyclic alkyl. Linear alkyls are generally preferred over branched alkyls. The same applies to terminal groups such as alkoxy and alkenyl. Regarding the configuration of 1,4-cyclohexylene, trans is preferable to cis for increasing the maximum temperature of the nematic phase. 2-Fluoro-1,4-phenylene means the following two divalent groups. In the chemical formula, fluorine may be leftward (L) or rightward (R). This rule also applies to asymmetric divalent groups generated by removing two hydrogens from a ring, such as tetrahydropyran-2,5-diyl.

In the horizontal alignment type liquid crystal display device of the present invention, the liquid crystal composition has α-alkoxyalkyl acrylate as a polymerizable group, and at least one of photo-fleece rearrangement, photo-isomerization, photo-dimerization and photo-decomposition by light irradiation. The liquid crystal composition to which the monomer for forming an alignment control layer that causes the above is added is sealed in the device.
Since the α-alkoxyalkyl acrylate easily interacts with the substrate as the alignment control layer forming monomer as the first additive, the alignment control layer forming monomer is added to the substrate in the liquid crystal composition encapsulation step which is a step prior to the ultraviolet exposure step. It is considered to move to the interface side. Further, it is considered that the alignment control layer-forming monomer having an α-alkoxyalkyl acrylate as a polymerizable group tends to have higher compatibility with the liquid crystal compound than the α-hydroxyalkyl acrylate, so that precipitation can be suppressed.
The alignment control layer forming monomer having an α-alkoxyalkyl acrylate as a polymerizable group is a compound represented by the formula (1).

Since the structure of the alignment control layer forming monomer changes directionally by polarized light irradiation, it contributes to the alignment control of liquid crystal molecules. Further, since it has a polymerizable group, the polymer composed of the monomer for forming the alignment control layer has a role as an alignment control film.
When the orientation control layer forming monomer has an aromatic ester structure, light-fleece rearrangement is caused by irradiation with polarized light. When it has an aromatic ester structure, it absorbs ultraviolet light and radically cleaves the aromatic ester site, causing rearrangement to hydroxyketone, that is, Fries rearrangement. In the optical Fries rearrangement, the photolysis of the aromatic ester site occurs when the polarization direction of the polarized ultraviolet light and the long axis direction of the aromatic ester site are the same. After photolysis, they are recombined and a tautomerization forms a hydroxyl group in the molecule. It is considered that this hydroxyl group causes an interaction at the substrate interface, and the monomer for forming the orientation control layer is easily anisotropically adsorbed on the substrate interface side. In addition, since the polymer has a polymerizable group such as α-alkoxyalkyl acrylate, polymerization at the interface of the substrate is likely to occur, whereby the polymer is fixed to the interface of the substrate. By utilizing this property, a thin film capable of aligning liquid crystal molecules can be formed. In order to form this thin film, linearly polarized ultraviolet light is suitable for irradiation. Examples of such an orientation control layer forming monomer include compounds represented by Formulas (1-1) to (1-37) and Formula (1-42).
When the alignment control layer forming monomer has a vinylene structure, irradiation with ultraviolet light causes photodimerization, photoisomerization, and photodecomposition. It is considered that the irradiation of ultraviolet light with the monomer for forming an alignment control layer having a vinylene group causes photoisomerization from a trans form to a cis form and formation of a cyclobutane ring due to dimerization. By utilizing this property, a thin film capable of aligning liquid crystal molecules can be formed. It is preferable to have a chalcone structure or a cinnamate structure containing a vinylene group, because the same effect is obtained. In order to form this thin film, linearly polarized ultraviolet light is suitable for irradiation. Examples of such an alignment control layer forming monomer include compounds represented by formulas (1-38) to (1-41).

  The preferred amount of the monomer for forming an alignment control layer contained in the liquid crystal composition is in the range of 0.01 part by weight to 10 parts by weight when the total amount of the liquid crystal compound is 100 parts by weight. After the addition, the composition is heated to dissolve the alignment control layer forming monomer. This composition is injected into a device having no alignment film. Next, by irradiating the device with linearly polarized light while heating the device, the alignment control layer-forming monomer is polymerized by photo-fleece rearrangement, photo-dimerization, photo-isomerization or photo-decomposition. By irradiation with linearly polarized light, the alignment control layer forming monomers are arranged in a certain direction to form a polymer, and a thin film made of the polymer has a function as a liquid crystal alignment film.

The orientation control layer-forming monomer having the α-alkoxyalkyl acrylate as the first additive is referred to as compound (1) in the present specification. The polymerizable compound as a second additive different from the first additive is referred to as compound (16α) in the present specification. Furthermore, the compound (16α), the compound (16α-A), and the compound (16α-B) may be referred to as necessary, for example, when referring to details of the structure.
Below, 1. 1. Compound (1) and compound (16α); 2. Synthesis of compound (1) and compound (16α), as a composition containing compound (1) and compound (16α). 3. a liquid crystal composition, and an element containing the composition. The liquid crystal display device will be described in order.

1. Examples of Compound (1) and Compound (16α), and Liquid Crystal Compositions Using the Same 1-1. Compound (1) and compound (16α)
A compound represented by the formula (1).

In equation (1),
R ¹ , R ² and R ³ are independently hydrogen or alkyl having 1 to 10 carbons, wherein at least one —CH ₂ — is replaced by —O— or —NH— Is also good.
n is independently 0, 1 or 2.
a is 0, 1, 2, or 3.
Ring ^{A 1} is cyclohexyl, cyclohexenyl, phenyl, 1-naphthyl, 2-naphthyl, tetrahydropyran-2-yl, tetrahydropyran-3-yl, 1,3-dioxan-2-yl, 1,3-dioxane - 3-yl, pyrimidin-2-yl, pyrimidin-5-yl, pyridin-2-yl, pyridin-3-yl, fluoren-2-yl, fluoren-7-yl, phenanthren-2-yl, phenanthrene-7- Yl, anthracen-2-yl, anthracen-6-yl, perhydrocyclopenta [a] phenanthren-3-yl, perhydrocyclopenta [a] phenanthrene-17-yl, 2,3,4,7,8, 9,10,11,12,13,14,15,16,17-tetradecahydrocyclopenta [a] phenanthrene-3- Or 2,3,4,7,8,9,10,11,12,13,14,15,16,17-tetradecahydrocyclopenta [a] phenanthrene-17-yl, preferably Cyclohexyl, phenyl, 1-naphthyl, 2-naphthyl, pyrimidin-2-yl, pyrimidin-5-yl, pyridin-2-yl, pyridin-3-yl, fluoren-2-yl, fluoren-7-yl, phenanthrene- 2-yl, phenanthren-7-yl or anthracen-2-yl, anthracen-6-yl.
Ring A ² is 1,4-cyclohexylene, 1,3-cyclohexylene, 1,2-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, 1,3-phenylene, , 2-Phenylene, naphthalene-2,6-diyl, naphthalene-1,4-diyl, decahydronaphthalene-2,6-diyl, decahydronaphthalene-1,4-diyl, 1,2,3,4-tetrahydro Naphthalene-2,6-diyl, 1,2,3,4-tetrahydronaphthalene-1,4-diyl, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, pyrimidine-2, 5-diyl, pyridine-2,5-diyl, cyclopentane-1,3-diyl, cyclopentene-1,3-diyl, fluorene-2,7-diyl, carbazole-2,7-diyl, Enanthrene-2,7-diyl, anthracene-2,6-diyl, anthracene-1,4-diyl, perhydrocyclopenta [a] phenanthrene-3,17-diyl, or 2,3,4,7,8, 9,10,11,12,13,14,15,16,17-tetradecahydrocyclopenta [a] phenanthrene-3,17-diyl, preferably 1,4-cyclohexylene, 1,3 -Cyclohexylene, 1,4-phenylene, 1,3-phenylene, naphthalene-2,6-diyl, naphthalene-1,4-diyl, pyrimidine-2,5-diyl, pyridine-2,5-diyl, fluorene -2,7-diyl, carbazole-2,7-diyl, phenanthrene-2,7-diyl or anthracene-2,6-diyl, anthracene-1,4- Yl.
Ring ^{A 3} 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, pyridine-2,5-diyl, fluorene-2,7- Diyl, phenanthrene-2,7-diyl, anthracene-2,6-diyl, anthracene-1,4-diyl, perhydrocyclopenta [a] phenanthrene-3,17-di Or 2,3,4,7,8,9,10,11,12,13,14,15,16,17-tetradecahydrocyclopenta [a] phenanthrene-3,17-diyl, preferably Is 1,4-cyclohexylene, 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, pyrimidine-2, 5-diyl, pyridine-2,5-diyl, fluorene-2,7-diyl, phenanthrene-2,7-diyl, anthracene-2,6-diyl or anthracene-1,4 Diyl.
Z ¹ and Z ² are each independently a single bond or alkylene having 1 to 10 carbon atoms, wherein at least one —CH ₂ — is —O—, —CO—, —COO—, — OCO -, - CONH -, - NHCO- or -OCOO- may be replaced by at least one - _{(CH 2) 2} - may be replaced by -CH = CH- or -C≡C- , In these groups, at least one hydrogen may be replaced by halogen, but at least one of Z ¹ and Z ² is —COO—, —OCO—, —CH ＝ CHCOO—, —OCOCH CH—, —CH ＝ CH—, —CH ＝ CHCO—, or —COCH ＝ CH—, and when a is 2 or 3, each Z ² may be different.
Sp ¹ , Sp ² , Sp ³ and Sp ⁴ are each independently a single bond or alkylene having 1 to 10 carbon atoms, wherein at least one —CH ₂ — is —O—, —COO— , —OCO— or —OCOO—, and at least one — (CH ₂ ) ₂ — may be replaced by —CH ＝ CH— or —C≡C—, in these groups: At least one hydrogen may be replaced by fluorine or chlorine, but preferably, at least one hydrogen may be replaced by fluorine.
c, d and e are independently 0, 1, 2, 3 or 4, and the sum of c, d and e is 1, 2, 3 or 4.
P ¹ , P ² , P ³ and P ⁴ are each independently a polymerizable group represented by the formula (1P-1).

In the equation (1P-1),
M ⁴¹ and M ⁴² are independently hydrogen, fluorine, alkyl having 1 to 5 carbons, or alkyl having 1 to 5 carbons in which at least one hydrogen is replaced by fluorine or chlorine; , Fluorine, alkyl having 1 to 5 carbons, or alkyl having 1 to 5 carbons in which at least one hydrogen is replaced by fluorine.
R ⁴¹ is alkyl having 1 to 10 carbons, alkoxy having 1 to 9 carbons, or alkoxyalkyl having 1 to 9 carbons. In these groups, at least one — (CH ₂ ) ₂ — is represented by — CH = CH- or -C≡C-, in which at least one hydrogen may be replaced by fluorine or chlorine, but preferably at least one hydrogen is replaced by fluorine. It may be replaced.
However, in at least one formula (1P-1) of P ¹ , P ² , P ³ and P ⁴ , R ⁴¹ is alkoxyalkyl having 1 to 9 carbon atoms.

  A compound represented by the formula (16α):

In the equation (16α),
Ring F and Ring I are independently cyclohexyl, cyclohexenyl, phenyl, 1-naphthyl, 2-naphthyl, tetrahydropyran-2-yl, tetrahydropyran-3-yl, 1,3-dioxan-2-yl, 1,3-dioxan-3-yl, pyrimidin-2-yl, pyridin-2-yl, pyrimidin-5-yl, fluoren-2-yl, fluoren-7-yl, phenanthren-2-yl, phenanthrene-7- Yl, anthracen-2-yl, anthracen-6-yl, perhydrocyclopenta [a] phenanthren-3-yl, perhydrocyclopenta [a] phenanthren-17-yl, 2,3,4,7,8, 9,10,11,12,13,14,15,16,17-tetradecahydrocyclopenta [a] phenanthrene-3-i Or 2,3,4,7,8,9,10,11,12,13,14,15,16,17-tetradecahydrocyclopenta [a] phenanthrene-17-yl, in these rings , At least one hydrogen may be replaced by fluorine, chlorine, alkyl having 1 to 12 carbons, or alkyl having 1 to 12 carbons in which at least one hydrogen is replaced by fluorine or chlorine.
Ring G is 1,4-cyclohexylene, 1,3-cyclohexylene, 1,2-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, 1,3-phenylene, 1, 2-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, fluorene-2,7-diyl, carbazole-2,7-diyl, phenanthrene-2,7-diyl, anthracene-2,6-diyl, anthracene-1,4 Diyl, perhydrocyclopenta [a] phenanthrene-3,17-diyl, pyrimidine-2,5-diyl or pyridine-2,5-diyl, in which at least one hydrogen is fluorine, chlorine, Alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, or alkyl having 1 to 12 carbons in which at least one hydrogen is replaced by fluorine or chlorine may be used.
Z ²² and Z ²³ are each independently a single bond or alkylene having 1 to 10 carbons, wherein at least one —CH ₂ — is —O—, —COO—, —OCO— or — may be replaced by -OCOO-, at least one - _{(CH 2) 2} - is, -CH = CH -, - C≡C -, - C (CH 3) = CH -, - CH = C (CH 3 ) - or _{-C (CH 3) = C (} CH 3) - may be replaced by, in these groups, at least one hydrogen may be replaced by fluorine or chlorine.
P ¹¹ , P ¹² and P ¹³ are each independently a polymerizable group. ^However, at least one in ^{Z 22} and ^{Z 23, -COO -, - OCO} -, - CH = CHCOO -, - OCOCH = CH -, - CH = CH -, - CH = CHCO-, or -COCH = When CH-, all of P ¹¹ , P ¹² and P ¹³ are not simultaneously represented by the formula (1P-1).
Desirable P ¹¹ , P ¹² or P ¹³ is a polymerizable group selected from the group of groups represented by formulas (P-1) to (P-6). More preferred P ¹¹ , P ¹² or P ¹³ is a group represented by the formula (P-1), the formula (P-2), the formula (P-3) or the formula (P-6). More preferred P ¹¹ , P ¹² or P ¹³ is a group represented by the formula (P-1). Particularly preferred P ¹¹ , P ¹² or P ¹³ is —OCO—CH ＝ CH ₂ or —OCO—C (CH ₃ ) ＝ CH ₂ .

In the equations (P-1) to (P-6),
M ¹¹ , M ¹² and M ¹³ are each independently hydrogen, fluorine, alkyl having 1 to 5 carbons, or alkyl having 1 to 5 carbons in which at least one hydrogen is replaced by fluorine or chlorine. Preferred M ¹¹ , M ¹² or M ¹³ is hydrogen or methyl for increasing the reactivity. More preferred M ¹¹ is methyl, and more preferred M ¹² or M ¹³ is hydrogen.
R ⁴ is alkyl having 1 to 10 carbons, alkoxy having 1 to 9 carbons, or alkoxyalkyl having 1 to 9 carbons. In these groups, at least one — (CH ₂ ) ₂ — is- CH = CH- or -C≡C-, in which at least one hydrogen may be replaced by fluorine or chlorine, but preferably at least one hydrogen is replaced by fluorine. It may be replaced.

In the equation (16α),
Sp ¹¹ , Sp ¹² and Sp ¹³ are each independently a single bond or alkylene having 1 to 10 carbon atoms, wherein at least one —CH ₂ — is —O—, —COO—, —OCO - or it may be replaced by -OCOO-, at least one - _{(CH 2) 2} - may be replaced by -CH = CH- or -C≡C-, and in the groups, at least one Hydrogen may be replaced by fluorine or chlorine.
u is 0, 1 or 2.
f, g, and h are each independently 0, 1, 2, 3, or 4, and the sum of f, g, and h is 2 or more.

Preferred compounds among the compounds represented by the formula (16α) include the compound (16α-A) and the compound (16α-B).
The compound (16α-A) satisfies the following conditions among the compounds represented by the formula (16α).
u is 0 or 1.
When u is 0,
Ring F and Ring I are cyclohexyl, in which at least one hydrogen may be replaced by fluorine or chlorine.
Z ²² is a single bond.
When u is 1,
Ring F and ring I are cyclohexyl, cyclohexenyl, phenyl, 1-naphthyl, 2-naphthyl, tetrahydropyran-2-yl, tetrahydropyran-3-yl, 1,3-dioxan-2-yl, 1,3- Dioxan-3-yl, pyrimidin-2-yl, pyrimidin-5-yl, pyridin-2-yl, or pyridin-3-yl.
Ring G is 1,4-cyclohexylene.
In these rings, at least one hydrogen may be replaced by fluorine or chlorine.
Z ²² and ^{Z 23} are independently a single bond or alkylene having 1 to 10 carbon atoms, in the alkylene, at least one hydrogen may but be replaced by fluorine or ^{chlorine, Z 22} and ^{Z 23} Is a single bond.

  As the compound represented by the formula (16α-B), a compound represented by the formula (16α-B-1), a compound represented by the formula (16α-B-2), and a compound represented by the formula (16α-B-3) )).

In the above equation,
P ¹⁰ and P ²⁰ are each independently a polymerizable group, preferably acryloyloxy, methacryloyloxy, α-fluoroacryloyloxy, trifluoromethylacryloyloxy, vinyl, vinyloxy, or epoxy.
Sp ¹⁰ and Sp ²⁰ are each independently a single bond or alkylene having 1 to 12 carbons, wherein at least one hydrogen of the alkylene may be replaced by fluorine or hydroxy, and at least one —CH ₂ - is, -O -, - COO -, - OCO-, or formula (Q-1) may be replaced by a group represented by at least one _-CH 2 -CH ₂ - is, -CH = CH -Or -C≡C-.
In the formula (Q-1), M ¹⁰ , M ²⁰ and M ^{30 each} independently represent hydrogen, fluorine, alkyl having 1 to 5 carbons, or 1 carbon having at least one hydrogen replaced with fluorine or chlorine. And Sp ¹⁰¹ is a single bond or an alkylene having 1 to 12 carbons, wherein at least one hydrogen of the alkylene may be replaced by fluorine or hydroxy, and at least one —CH ₂ - is -O -, - COO- or -OCO- may be replaced by at least one _-CH 2 -CH ₂ - may be replaced by -CH = CH- or -C≡C- .
Z ^{10, Z 20} and ^{Z 30} are each independently a single bond, -COO -, - OCO -, - OCOO -, - OCO-CH 2 CH 2 -, - CH 2 CH 2 -COO -, - CH 2 _{O -, - OCH 2 -,} - CF 2 O -, - OCF 2 -, - C≡C -, - C≡C-C≡C -, - CONH -, - NHCO -, - (CH 2) 4 - , _-CH 2 CH ₂ - or _-CF 2 CF ₂ - and it is, preferably, a single _{bond, -COO -, - OCO -,} - OCO-CH 2 CH 2 -, - CH 2 CH 2 -COO -, - CH ₂ O—, —OCH ₂ —, —CF ₂ O—, —OCF ₂ —, —C≡C—, —C≡C—C≡C—, or —CH ₂ CH ₂ —.
A ¹⁰ and A ³⁰ are independently 1,4-phenylene, 1,4-cyclohexylene, pyridine-2,5-diyl, pyrimidine-2,5-diyl, naphthalene-2,6-diyl, naphthalene- 1,5-diyl, tetrahydronaphthalene-2,6-diyl, fluorene-2,7-diyl, biphenylene-4,4′-diyl or 1,3-dioxane-2,5-diyl; In phenylene, at least one hydrogen is fluorine, chlorine, cyano, hydroxy, formyl, acetoxy, acetyl, trifluoroacetyl, difluoromethyl, trifluoromethyl, alkyl having 1 to 5 carbons, alkoxy having 1 to 5 carbons or ^{P 10 -Sp} 10 ^-Z 10 - it may be replaced by, in this 2,7-diyl And at least one hydrogen may be replaced by fluorine, alkyl having 1 to 5 carbon atoms, and in the biphenylene-4,4′-diyl, at least one hydrogen is fluorine, difluoromethyl, trifluoromethyl , Which may be substituted by alkyl having 1 to 5 carbons or alkoxy having 1 to 5 carbons, and preferred A ¹⁰ and A ³⁰ are independently 1,4-phenylene, 1,4-cyclohexylene, Naphthalene-2,6-diyl, naphthalene-1,5-diyl, fluorene-2,7-diyl, or biphenylene-4,4′-diyl, wherein at least one hydrogen in the 1,4-phenylene is Fluorine, cyano, hydroxy, acetoxy, acetyl, trifluoroacetyl, difluoromethyl, trifluoromethyl May be replaced by alkyl having 1 to 5 carbons or alkoxy having 1 to 5 carbons. In this fluorene-2,7-diyl, at least one hydrogen is fluorine, alkyl having 1 to 5 carbons In the biphenylene-4,4′-diyl, at least one hydrogen atom is fluorine, difluoromethyl, trifluoromethyl, alkyl having 1 to 5 carbons, or alkoxy having 1 to 5 carbons. May be replaced by
A ²⁰ is a group represented by the formula (A20-1), pyridine-2,5-diyl, pyrimidine-2,5-diyl, a group represented by the formula (A20-2), naphthalene-1,5- Diyl, a group represented by the formula (A20-3) or a group represented by the formula (A20-4), preferably a group represented by the formula (A20-1), A group represented by the formula (A20-3) or a group represented by the formula (A20-4), more preferably a group represented by the formula (A20-1), -3) or a group represented by the formula (A20-4).
In the formula (A20-1), Y ¹⁰ , Y ¹¹ , Y ¹² and Y ^{13 each} independently represent hydrogen, fluorine, chlorine, cyano, hydroxy, formyl, acetoxy, acetyl, trifluoroacetyl, difluoromethyl, trifluoromethyl Methyl, alkyl having 1 to 5 carbons, or alkoxy having 1 to 5 carbons, wherein at least one of Y ¹⁰ and Y ¹³ is hydrogen. Desirable Y ¹⁰ , Y ¹¹ , Y ¹² and Y ¹³ are each independently hydrogen, fluorine, chlorine, cyano, hydroxy, formyl, acetoxy, acetyl, trifluoroacetyl, difluoromethyl, trifluoromethyl, having 1 to 5 carbon atoms. Or an alkoxy having 1 to 5 carbon atoms, and at least one of Y ¹⁰ and Y ¹³ is hydrogen. More preferred Y ¹⁰ , Y ¹¹ , Y ¹² and Y ¹³ are independently hydrogen, fluorine, hydroxy, difluoromethyl, trifluoromethyl, alkyl having 1 to 5 carbons, or alkoxy having 1 to 5 carbons. However, at least one of Y ¹⁰ and Y ¹³ is hydrogen.
In the formula (A20-2), Y ¹⁴ , Y ¹⁵ , Y ¹⁶ , Y ¹⁷ , Y ¹⁸ and Y ¹⁹ are each independently hydrogen, fluorine, alkyl having 1 to 5 carbons, or alkyl having 1 to 5 carbons. Alkoxy, but at least one of Y ¹⁴ and Y ¹⁹ is hydrogen.
In the formula (A20-3), Y ²⁰ , Y ²¹ , Y ²² , Y ²³ , Y ²⁴ , Y ²⁵ , Y ²⁶ and Y ²⁷ are each independently hydrogen, fluorine, difluoromethyl, trifluoromethyl, or the number of carbon atoms. It is alkyl having 1 to 5 or alkoxy having 1 to 5 carbon atoms, and at least one of Y ²⁰ and Y ²⁷ is hydrogen.
In formula ^{(A20-4), Y 28, Y} 29, Y 30, Y 31, Y 32 and ^{Y 33} are independently hydrogen, fluorine, is an alkyl having 1 to 5 carbon ^{atoms, Y 28} and Y ^At least one of ³¹ is hydrogen.
In the formula (16α-B), n ¹⁰ and n ³⁰ are independently 0, 1, 2, or 3.
In the equations (16α-B-1) to (16α-B-3),
R ¹⁰ is independently hydrogen, fluorine or methyl, preferably hydrogen or methyl.
R ³¹ is independently hydrogen or methyl, preferably hydrogen.
L ¹⁰ are independently hydrogen, fluorine, difluoromethyl, trifluoromethyl, alkyl of 1 to 5 carbon atoms, from 1 to 5 carbon atoms in the alkoxy or ^{P 10 -Sp} 10 ^-Z 10 - is, preferably, Hydrogen, fluorine, trifluoromethyl, alkyl having 1 to 5 carbons, or alkoxy having 1 to 5 carbons.
n ¹⁰ is 0, 1, 2, or 3.
n ¹¹ is independently 0, 1, 2, 3 or 4, preferably 0, 1 or 2, more preferably 0 or 1.

1-2. Aspects of Compound (1) and Compound (16α) 1-2-1. Embodiment of Compound (1) Compound (1) is characterized by having an α-alkoxyalkyl acrylate. When a radical is generated in the system by ultraviolet irradiation, the compound (1) reacts with a polymerizable group to form a polymer. An α-alkoxyalkyl acrylate structure is useful because it tends to interact non-covalently with the substrate surface. One of the uses is an additive for a liquid crystal composition used for a liquid crystal display device. Compound (1) is added for the purpose of forming a polymer for orienting a liquid crystal compound. Such an additive preferably has high solubility in the liquid crystal composition and is chemically stable under the conditions sealed in the device. Compound (1) fulfills such properties to a large extent.

  Preferred examples of the compound (1) will be described. Preferred compounds (1) are compound (1-1) to compound (1-42) as described below. N1 and m1 in the following compounds are each independently an integer of 2 to 8, preferably 2 to 6, and more preferably 2 to 4. Compound (1) may be used alone or in combination of two or more.

1-2-2. Embodiments of Compound (16α), Compound (16α-A) and Compound (16α-B) Compound (16α), compound (16α-A) and compound (16α-B) are different polymerizable groups from compound (1). Or the structure of the central skeleton is different.
The compound (16α) is apt to generate radicals upon irradiation with ultraviolet light, and is useful for increasing reactivity (polymerizability). By increasing the reactivity, the amount of monomer components remaining after irradiation with ultraviolet rays can be reduced, so that the electrical reliability of the device is improved.
The compound (16α-A) has a bicyclohexyl structure and a polymerizable group. When a radical is generated in the system by irradiation with ultraviolet light, the compound reacts with a polymerizable group to form a polymer. Compounds having α-hydroxymethyl acrylate or α-methoxymethyl acrylate are useful because they tend to interact non-covalently with the substrate surface. This compound may be added for the purpose of increasing the electric resistance of the polymer. This compound preferably has high solubility in a liquid crystal composition, is chemically stable under the conditions sealed in the device, and has a large voltage holding ratio when used in a liquid crystal display device. This compound fulfills such properties to a large extent.
Compound (16α-B) is characterized by having an aromatic ester structure and a polymerizable group different from compound (1). Since the polymerizable group is a different combination from the compound (1) and has an aromatic ester structure, it causes photo-fleece rearrangement and also acts as an alignment controlling monomer. The combined use is expected to promote the copolymerization reaction between the alignment control monomers and to improve the function of the polymer as the alignment control film.

  Preferred examples of the compound (16α) will be described. Preferred compounds (16α) are compounds (16α-1) to (16α-29) as described below. Compound (16α) may be used alone, or two or more kinds may be used in combination.

In Expressions (16α-1) to (16α-29),
P ¹¹ , P ¹² and P ¹³ are independently a group selected from the group of polymerizable groups represented by formulas (P-1) to (P-3) and (P-6). Wherein M ¹¹ , M ¹² and M ¹³ are independently hydrogen, fluorine, alkyl having 1 to 5 carbons, or alkyl having 1 to 5 carbons in which at least one hydrogen is replaced by fluorine or chlorine. is there. R ⁴ is alkyl having 1 to 10 carbons, alkoxy having 1 to 9 carbons, or alkoxyalkyl having 1 to 9 carbons. In these groups, at least one — (CH ₂ ) ₂ — is , -CH = CH- or -C≡C-, in which at least one hydrogen may be replaced by fluorine or chlorine, but preferably at least one hydrogen is It may be replaced by fluorine.

Sp ¹¹ , Sp ¹² and Sp ¹³ are each independently a single bond or alkylene having 1 to 10 carbon atoms, wherein at least one —CH ₂ — is —O—, —COO—, —OCO - or it may be replaced by -OCOO-, at least one - _{(CH 2) 2} - may be replaced by -CH = CH- or -C≡C-, and in the groups, at least one Hydrogen may be replaced by fluorine or chlorine.

Preferred examples of the compound (16α-A) will be described. Preferred compounds (16α-A) are the compounds (16α-A-1) to (16α-A-13) as described below. M ¹¹ in the following compounds is independently hydrogen, methyl or fluorine. The compound (16α-A) may be used alone, or two or more kinds may be used in combination.

Preferred examples of the compound (16α-B) will be described. Preferred compounds are the following compounds. In the following compounds, n and m are independently 2 to 6, and R ¹⁰ is independently hydrogen, methyl, fluorine or trifluoromethyl. The compound (16α-B) may be used alone, or two or more kinds may be used in combination.

  Formulas (2) to (21) show liquid crystal compounds that are components of the liquid crystal composition. Compounds (2) to (4) have small dielectric anisotropy. Compounds (5) to (7) have a very large dielectric anisotropy. Since the compound (8) has a cyano group, it has a positively larger dielectric anisotropy. Compounds (9) to (21) have a large negative dielectric anisotropy. Specific examples of these compounds will be described later.

2. Synthesis of compound (1) and compound (16α) 2-1. Synthesis of Compound (1) A method for synthesizing Compound (1) will be described. Compound (1) is synthesized according to the method described in WO 2017/047177 and the like.

2-2. Synthesis of Compound (16α) A method for synthesizing compound (16α-A-13) from compound (16α-A-1) will be described. These compounds are synthesized according to the method described in WO 2008/061606 and the like.
A method for synthesizing compound (16α-B-2) from compound (16α-B-1) will be described. These compounds are described in WO 1995/022586, JP-A-2005-206579, WO 2006/049111, Macromolecules, 26, 1244-1247 (1993), JP-A-2003-238491, No. 2010/133278, JP-A-2000-178233, JP-A-2012-1623, and JP-A-2011-227187.
The compound having an α-fluoroacrylate group is synthesized according to the method described in JP-A-2005-112850. The alignment control layer forming monomer having an α-trifluoromethyl acrylate group is synthesized according to the method described in JP-A-2004-175728. The compound having an aromatic ester moiety and a tolan moiety in the molecule is synthesized according to WO 2001/053248.
Compounds whose synthesis methods are not described can be synthesized by appropriately combining known organic synthetic chemistry methods. Organic Synthesis, John Wiley & Sons, Inc., Organic Reactions, John Wiley & Sons, Inc., Comprehensive Organic Synthesis, Pergamon Press. , "New Experimental Chemistry Course" (Maruzen) and the like.

3. Liquid crystal composition 3-1. First additive and second additive (component A)
The liquid crystal composition preferably includes a first additive and a second additive as component A, and further includes a liquid crystal compound selected from components B, C, D, and E shown below.
The liquid crystal composition contains the compound (1) as a polymerizable compound having an α-alkoxyalkyl acrylate as a first additive. Compound (1) has a polymerizable group in which a reaction is initiated by a radical generated in the system. Examples of the compound (1) are as described above. The compound (1) contributes as a polymer having alignment control ability by polymerizing as an alignment control monomer.

  The preferable ratio of the compound (1) is about 0.01 part by weight or more when the total amount of the liquid crystal compound is 100 parts by weight in order to obtain high reactivity to ultraviolet rays, and the compound (1) is dissolved in the liquid crystal composition. Less than about 10 parts by weight. A more desirable ratio is in the range of about 0.03 parts by weight to about 7 parts by weight. When compound (16α), compound (16α-A) or compound (16α-B) is further added, the preferable ratio of compound (1) is in the same range as described above.

  The liquid crystal composition may contain the compound (16α) as a second additive. As described above, the second additive includes the compound (16α), the compound (16α-A) and the compound (16α-B).

  The preferable ratio of the compound (16α) is about 0.03 parts by weight or more when the total amount of the liquid crystal compound is 100 parts by weight in order to obtain high reactivity to ultraviolet rays, and the compound (16α) is dissolved in the liquid crystal composition. Less than about 10 parts by weight. A more desirable ratio is in the range of about 0.05 parts to about 7.0 parts by weight. The most preferred proportions range from about 0.05 parts to about 5.0 parts by weight.

  The preferable ratio of the compound (16α-A) is about 0.03 part by weight or more when the total amount of the liquid crystal compound is 100 parts by weight in order to obtain high reactivity to ultraviolet light. About 10 parts by weight or less for dissolving in water. A more desirable ratio is in the range of about 0.05 parts by weight to about 5.0 parts by weight. The most preferred ratio is in the range of about 0.2 parts by weight to about 3.0 parts by weight.

  The preferable ratio of the compound (16α-B) is about 0.01 part by weight or more when the total amount of the liquid crystal compound is 100 parts by weight in order to obtain high reactivity to ultraviolet light. About 10 parts by weight or less for dissolving in water. A more desirable ratio is in the range of about 0.03 parts to about 5.0 parts by weight. The most preferred ratio is in the range of about 0.1 parts to about 3.0 parts by weight.

  The weight ratio of compound (16α) or compound (16α-A) to compound (1) (compound (1) / compound (16α) or compound (16α-A)) is about It is 1/9 or more and about 9/1 or less in order to obtain high reactivity to ultraviolet rays. A more preferred weight ratio ranges from about 4/1 to about 1/2. Most preferred weight ratios range from about 2/1 to about 1/2.

  The weight ratio of the compound (16α-B) to the compound (1) (compound (1) / compound (16α-B)) is about 5/95 or more and about 95/5 or less in order to promote the copolymerization. It is. A more preferred weight ratio ranges from about 1/9 to about 9/1. The most preferred weight ratio ranges from about 1/4 to about 4/1.

3-2. Liquid crystalline compounds (components B to E)
Component B is compounds (2) to (4). Component C is compounds (5) to (7). Component D is compound (8). Component E is compounds (9) to (21). This composition may contain other liquid crystal compounds different from the compounds (2) to (21). When preparing this composition, it is preferable to select components B, C, D and E in consideration of the magnitude of the positive or negative dielectric anisotropy and the like. A composition with properly selected components has a high upper temperature limit, a lower lower temperature limit, a low viscosity, a suitable optical anisotropy (ie, large or small optical anisotropy), and a positive or negative large dielectric constant. It has anisotropy, high resistivity, stability to heat or ultraviolet light, and an appropriate elastic constant (ie, a large elastic constant or a small elastic constant).

Component B is a compound wherein the two terminal groups are alkyl or the like. Preferred examples of Component B include compounds (2-1) to (2-11), compounds (3-1) to (3-19), and compounds (4-1) to (4-7). it can. In the compound of Component B, R ¹¹ and R ¹² are independently alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, and in this alkyl or alkenyl, at least one —CH ₂ — is It may be replaced by -O-, -COO- or -OCO-, and at least one hydrogen may be replaced by fluorine.

  Component B is a nearly neutral compound because the absolute value of the dielectric anisotropy is small. The compound (2) is effective mainly for decreasing the viscosity or adjusting the optical anisotropy. Compounds (3) and (4) have an effect of increasing the maximum temperature and thereby broadening the temperature range of the nematic phase, or an effect of adjusting the optical anisotropy.

  As the content of the component B increases, the dielectric anisotropy of the composition decreases, but the viscosity decreases. Therefore, as long as the required value of the threshold voltage of the element is satisfied, the content is preferably higher. When a composition for a mode such as IPS or VA is prepared, the content of the component B is preferably 30% by weight or more, more preferably 40% by weight or more, based on the weight of the liquid crystal composition.

Component C is a compound having fluorine, chlorine, or a fluorine-containing group at the right end. Preferred examples of the component C include compounds (5-1) to (5-16), compounds (6-1) to (6-113), and compounds (7-1) to (7-61). it can. In the compound of Component C, R ¹³ is alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons. In the alkyl and alkenyl, at least one —CH ₂ — is replaced with —O—. well, at least one hydrogen may be replaced by ^{fluorine, X 11} is fluorine, _{chlorine, -OCF 3, -OCHF 2, -CF} 3, -CHF 2, -CH 2 F, -OCF 2 CHF 2 or —OCF ₂ CHFCF ₃ .

  Component C has a positive dielectric anisotropy and has extremely excellent stability to heat, light, and the like, and is therefore used when preparing a composition for a mode such as IPS, FFS, or OCB. The content of the component C is suitably in the range of 1% by weight to 99% by weight based on the weight of the liquid crystal composition, preferably in the range of 10% by weight to 97% by weight, and more preferably in the range of 40% by weight. It is in the range of 95% by weight. When Component C is added to a composition having a negative dielectric anisotropy, the content of 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 device can be adjusted.

Component D is compound (8) wherein the right terminal group is -C−N or -C≡CC-N. Preferred examples of the component D include the compounds (8-1) to (8-64). In the compound of Component D, R ¹⁴ is alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons. In the alkyl and alkenyl, at least one —CH ₂ — is replaced with —O—. Alternatively, at least one hydrogen may be replaced by fluorine and X ¹² is -C≡N or -C≡C-C≡N.

  Component D is mainly used when preparing a composition for a mode such as TN since the dielectric anisotropy is positive and its value is large. By adding this component D, the dielectric anisotropy of the composition can be increased. 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 is also useful for adjusting the voltage-transmittance curve of the device.

  When preparing a composition for a mode such as TN, the content of the component D is suitably in the range of 1% by weight to 99% by weight, preferably 10% by weight based on the weight of the liquid crystal composition. It is in the range of 97% by weight, more preferably in the range of 40% to 95% by weight. When component D is added to a composition having a negative dielectric anisotropy, the content of 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 device can be adjusted.

Component E is compounds (9) to (21). These compounds have phenylene in which the lateral position is substituted with two fluorines or chlorines, such as 2,3-difluoro-1,4-phenylene. Preferred examples of component E include compounds (9-1) to (9-8), compounds (10-1) to (10-17), compound (11-1), and compounds (12-1) to (12-). 3), compounds (13-1) to (13-11), compounds (14-1) to (14-3), compounds (15-1) to (15-3) and compounds (16) to (21) Can be mentioned. In the compound of Component E, R ¹⁵ and R ¹⁶ are independently alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons. In the alkyl and alkenyl, at least one —CH ₂ — is May be replaced by —O—, at least one hydrogen may be replaced by fluorine, and R ¹⁷ is hydrogen, fluorine, alkyl having 1 to 10 carbons, or alkenyl having 2 to 10 carbons. , and in the alkyl and alkenyl, at least one -CH 2 _- may be replaced by -O-, at least one hydrogen may be replaced by fluorine.

  Component E has a large negative dielectric anisotropy. Component E is used when preparing a composition for a mode such as IPS, VA, and PSA. As the content of the component E is increased, the dielectric anisotropy of the composition is negatively increased, but the viscosity is increased. Therefore, as long as the required value of the threshold voltage of the element is satisfied, it is preferable that the content is small. Considering that the dielectric anisotropy is about −5, the content is preferably 40% by weight or more in order to perform sufficient voltage driving.

  Among the components E, the compound (9) is a bicyclic compound, and thus is effective mainly in decreasing the viscosity, adjusting the optical anisotropy, or increasing the dielectric anisotropy. Since compounds (10) and (11) are tricyclic compounds, they have the effect of increasing the maximum temperature, increasing the optical anisotropy, or increasing the dielectric anisotropy. Compounds (12) to (21) have the effect of increasing the dielectric anisotropy.

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

  By appropriately combining the components B, C, D, and E described above, a high maximum temperature, a low minimum temperature, a small viscosity, an appropriate optical anisotropy, a positive or negative large dielectric anisotropy, a large A liquid crystal composition that satisfies at least one of properties such as specific resistance, high stability to ultraviolet light, high stability to heat, and a large elastic constant can be prepared. If necessary, a liquid crystal compound different from the components B, C, D and E may be added.

The polymerizable compound such as the first additive and the second additive used in the liquid crystal composition of the present invention is added for the purpose of forming a polymer in the liquid crystal composition. Compound (1) may be used alone or in combination of two or more. Compound (16α), compound (16α-A) and compound (16α-B) may be used alone or in combination of two or more. A copolymer may be formed from compound (1) and any of compound (16α), compound (16α-A) and compound (16α-B). When forming a copolymer, the compound (1) is immobilized by a covalent bond with any of the compound (16α), the compound (16α-A) and the compound (16α-B). Compound (1) is immobilized in a state where the alkoxy acrylate interacts non-covalently with the substrate surface.
This further enhances the ability of the liquid crystal molecules to align, and at the same time, prevents the compound (1), the compound (16α), the compound (16α-A), and the compound (16α-B) from diffusing into the liquid crystal composition. It is considered that the compound (1), the compound (16α), the compound (16α-A) and the compound (16α-B) give a polymer by polymerization, and the resistance is increased by the compound (16α-A). Since this polymer is arranged, an appropriate pretilt angle can be given to liquid crystal molecules on the substrate surface. This polymer stabilizes the alignment of liquid crystal molecules, thereby shortening the response time of the device and improving image burn-in. Preferred examples of the compound (16α) are an acrylate compound, a methacrylate compound, a fluoroacrylate compound, a vinyl compound, a vinyloxy compound, a propenyl ether compound, an epoxy compound (oxirane, oxetane), and a vinyl ketone compound. Further preferred examples are compounds having at least one acryloyloxy and compounds having at least one methacryloyloxy. Further preferred examples include compounds having both acryloyloxy and methacryloyloxy.

3-3. Other Additives The liquid crystal composition is prepared by a known method. For example, the component compounds are mixed and dissolved together by heating. Depending on the application, other additives other than the first additive and the second additive may be added to the composition. Examples of the additives include 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. Such additives are well known to those skilled in the art and have been described in the literature.

  By adding a polymerization initiator, the polymerizable compound can be rapidly polymerized. By optimizing the reaction temperature, the amount of the remaining polymerizable compound can be reduced. Examples of photoradical polymerization initiators are TPO, 1173, 4265, 184, 369, 500, 651, 784, 819, 907, 1300, 1700, 1800, 1850, and 2959 from the Omnirad series of IGM Resins.

  Additional examples of photoradical polymerization initiators include 4-methoxyphenyl-2,4-bis (trichloromethyl) triazine, 2- (4-butoxystyryl) -5-trichloromethyl-1,3,4-oxadiazole, 9-phenylacridine, 9,10-benzphenazine, benzophenone / Michler's ketone mixture, hexaarylbiimidazole / mercaptobenzimidazole mixture, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, benzyl Dimethyl ketal, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2,4-diethylxanthone / methyl p-dimethylaminobenzoate, and benzophenone / methyltriethanolamine It is a mixture.

  Polymerization can be performed by irradiating the liquid crystal composition with an ultraviolet ray after adding the photoradical polymerization initiator to the liquid crystal composition. However, the unreacted polymerization initiator or the decomposition product of the polymerization initiator may cause display defects such as image sticking on the device. In order to prevent this, photopolymerization may be performed without adding a polymerization initiator. The preferred wavelength of the irradiating light is in the range of 150 nm to 500 nm. More preferred wavelengths are in the range from 250 nm to 450 nm, and most preferred wavelengths are in the range from 300 nm to 400 nm.

  When storing the polymerizable compound, a polymerization inhibitor may be added to prevent polymerization. The polymerizable compound is usually added to the composition without removing the polymerization inhibitor. Examples of polymerization inhibitors are hydroquinone, hydroquinone derivatives such as methylhydroquinone, 4-tert-butylcatechol, 4-methoxyphenol, phenothiazine and the like.

The optically active compound has an effect of inducing a helical structure in liquid crystal molecules to give a necessary twist angle, thereby preventing reverse twist. The helical 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 helical pitch. Preferred examples of the optically active compound include the following compounds (Op-1) to (Op-18). In the compound (Op-18), ring J is 1,4-cyclohexylene or 1,4-phenylene, and R ²⁸ is alkyl having 1 to 10 carbons.

  Antioxidants are effective for maintaining a large voltage holding ratio. Preferred examples of the antioxidant include the following compounds (AO-1) and (AO-2); IRGANOX 415, IRGANOX 565, IRGANOX 1010, IRGANOX 1035, IRGANOX 3114, and IRGANOX 1098 (trade name: BASF). be able to. The ultraviolet absorber is effective for preventing the lowering of the maximum temperature. Preferred examples of the ultraviolet absorber include a benzophenone derivative, a benzoate derivative, and a triazole derivative. Specific examples of the following compounds (AO-3) and (AO-4); TINUVIN 329, TINUVIN P, TINUVIN 326, TINUVIN 234, TINUVIN 213, TINUVIN 400, TINUVIN 328, and TINUVIN 99-2 (trade name: BASF) ); And 1,4-diazabicyclo [2.2.2] octane (DABCO).

  Light stabilizers such as sterically hindered amines are preferred to maintain high voltage holding. Preferred examples of the light stabilizer include the following compounds (AO-5) and (AO-6); TINUVIN 144, TINUVIN 765, and TINUVIN 770DF (trade name: BASF). A heat stabilizer is also effective for maintaining a large voltage holding ratio, and a preferred example is IRGAFOS 168 (trade name: BASF). Defoamers are effective in preventing foaming. Preferred examples of the antifoaming agent include dimethyl silicone oil and methylphenyl silicone oil.

In the compound (AO-1), R ⁴⁰ is alkyl having 1 to 20 carbons, alkoxy having 1 to 20 carbons, —COOR ⁴¹ , or —CH ₂ CH ₂ COOR ⁴¹ , wherein R ⁴¹ is carbon It is an alkyl of the formulas 1 to 20. In the compounds (AO-2) and (AO-5), R ⁴² is alkyl having 1 to 20 carbons. In the compound ^{(AO-5), R 43} is hydrogen, methyl or O ^·, (oxygen radical), ring K is 1,4-cyclohexylene or 1,4-phenylene, z is 1 , 2 or 3.

4. Liquid crystal display device The above liquid crystal composition has an operation mode such as PC, TN, STN, OCB, or PSA, and can be used for a liquid crystal display device driven by an active matrix system. This composition has an operation mode such as PC, TN, STN, OCB, VA, or IPS, and can be used for a liquid crystal display element driven by a passive matrix system. These elements can be applied to any of a reflection type, a transmission type, and a transflective type.

  This composition comprises an NCAP (nematic curvilinear aligned phase) device produced by microencapsulating a nematic liquid crystal, a polymer dispersed liquid crystal display device (PDLCD) produced by forming a three-dimensional network polymer in the liquid crystal, and a polymer It can also be used for a network liquid crystal display (PNLCD). In addition, a PSA mode liquid crystal display element is manufactured using this composition. The element in the PSA mode can be driven by a driving method such as an active matrix and a passive matrix. Such an element can be applied to any of a reflection type, a transmission type, and a transflective type. By increasing the amount of the polymerizable compound added, a device in a polymer dispersed mode can be manufactured.

The alignment film is a film for aligning liquid crystal molecules in a certain direction. Generally, a polyimide thin film is used. In such a liquid crystal display element having no alignment film, a composition containing the compound (1) or the like as an alignment control layer forming monomer is used. Compound (1) gives a polymer by polymerization. Since this polymer has the function of an alignment film, it can be used instead of the alignment film. An example of a method for manufacturing such an element is as follows. An element having two substrates called an array substrate and a color filter substrate is prepared. This substrate has no alignment film. At least one of the substrates has an electrode layer. A liquid crystal composition is prepared by mixing a liquid crystal compound. Compound (1) is added to the liquid crystal composition. Additives may be further added to the liquid crystal composition as needed. This liquid crystal composition is injected into the device. The device is heated to a temperature equal to or higher than the transition temperature (T _NI ) of the liquid crystal composition from a nematic phase to an isotropic phase, and the liquid crystal composition is changed to an isotropic phase. This polarized ultraviolet irradiation may be referred to as “first ultraviolet irradiation”.
Next, the liquid crystal layer may be kept in a temperature range of 20 ° C. or more and less than _{TNI, and} may be irradiated with non-polarized ultraviolet light. This non-polarized ultraviolet irradiation may be referred to as “second ultraviolet irradiation”. By performing the second ultraviolet irradiation, the polymerizable compound remaining in the system or the unreacted polymerizable group may be completely consumed in some cases. Here, since the alignment control layer is almost formed by the polarized ultraviolet light irradiation as the first ultraviolet light irradiation, as described later, the second ultraviolet light irradiation maintains the uniformity of the liquid crystal alignment even in the non-polarized state. . By such ultraviolet irradiation, an alignment control layer that induces uniform horizontal alignment in liquid crystal molecules is generated, and a target element is manufactured.

In this procedure, when the liquid crystal layer is kept in a temperature range equal to or higher than the transition temperature (T _NI ) of the liquid crystal composition to the isotropic phase and irradiated with polarized ultraviolet light having a peak in the wavelength range of 300 nm to 400 nm, for example, the alignment control layer When the compound (1), which is a forming monomer, has an aromatic ester site, the aromatic ester site is photolyzed, radicals are formed, and photo-Fries rearrangement occurs. In the optical Fries rearrangement, the photolysis of the aromatic ester site occurs when the polarization direction of polarized ultraviolet light and the long axis direction of the aromatic ester site are the same. After photolysis, they are recombined and a tautomerization forms a hydroxyl group in the molecule. It is considered that this hydroxyl group causes an interaction at the substrate interface, and the monomer for forming the orientation control layer easily interacts with anisotropy on the substrate interface side. When the compound (1), which is a monomer for forming an alignment control layer, has a vinylene structure, irradiation with ultraviolet light causes photodimerization, photoisomerization, and photodecomposition. The monomer for forming an alignment control layer having a vinylene group is irradiated with ultraviolet light to cause photoisomerization from a trans-isomer to a cis-isomer and to form a cyclobutane ring by dimerization, thereby forming anisotropy and controlling the alignment. It is considered that the layer-forming monomer interacts with the substrate interface side.
In either case, since the compound (1) has a polymerizable group, the polymer is immobilized on the interface side of the substrate by polymerization. This polymer becomes an alignment control layer for uniformly aligning liquid crystal molecules. When compound (16α), compound (16α-A) or compound (16α-B) is added, when compound (1) is polymerized, compound (16α) compound (16α-A) or compound (16α-B) is also added. Since it is copolymerized, it is incorporated in the orientation control layer.
Next, as the second ultraviolet irradiation, the liquid crystal layer is kept in a temperature range of 20 ° C. or more and less than T _NI , for example, when a non-polarized ultraviolet light having a peak at a wavelength of 330 nm to 400 nm is irradiated, a compound as an alignment control layer forming monomer is obtained. When (1) has an aromatic ester site, the aromatic ester site remaining in the alignment control layer undergoes photo-fleece rearrangement, or the unreacted alignment control layer-forming monomer and compound (16α), compound (16α) -A) or the compound (16α-B) is considered to polymerize along the orientation control layer. Since the photo-Fries dislocation is generated inside the polymer oriented by the first ultraviolet irradiation, it is considered that the dislocation reaction tends to proceed in a direction in which the anisotropy of the orientation control layer increases. When the compound (1), which is an alignment control layer forming monomer, has a vinylene structure, unreacted vinylene remaining in the alignment control layer undergoes photodimerization or photoisomerization, or an unreacted alignment control layer forming monomer It is considered that compound (16α), compound (16α-A) or compound (16α-B) polymerizes along the orientation control layer. Since the photodimerization or photoisomerization occurs inside the polymer oriented by the first ultraviolet irradiation, it is considered that the dislocation reaction tends to proceed in a direction in which the anisotropy of the orientation control layer increases. Can be
It is considered that the additional polymerization of the unreacted monomer for forming the orientation control layer and the compound (16α), the compound (16α-A) or the compound (16α-B) also contributes to imparting anisotropy to the orientation control layer. Such an increase in the anisotropy of the alignment control layer means that the alignment control force acting on the liquid crystal molecules increases. The effect of such a polymer additionally stabilizes the alignment of liquid crystal molecules, thereby improving the device contrast. Response time is reduced. Since image sticking is a malfunction of liquid crystal molecules, sticking is also improved by the effect of the polymer. When such additional polymerization is performed, the amount of unreacted substances is extremely small. Therefore, it is expected that an element having a large voltage holding ratio can be obtained.

The UV irradiation on the substrate will be described. In the present invention, there are a case where ultraviolet irradiation is performed in one stage and a case where ultraviolet irradiation is performed in at least two stages. When performing ultraviolet irradiation in one stage, only the first ultraviolet irradiation is performed. When the ultraviolet irradiation is performed in two stages, the first ultraviolet irradiation and the second ultraviolet irradiation are performed. Examples of light sources are low-pressure mercury lamps (germicidal lamps, fluorescent chemical lamps, black lights), high-pressure discharge lamps (high-pressure mercury lamps, metal halide lamps), and short arc discharge lamps (ultra-high-pressure mercury lamps, xenon lamps, mercury xenon lamps) It is. Preferred examples of the light source are a metal halide lamp, a xenon lamp, an ultra-high pressure mercury lamp and a high pressure mercury lamp. The wavelength region of the irradiation light source may be selected by installing a filter or the like between the light source and the liquid crystal element and passing only a specific wavelength region.
The holding temperature of the liquid crystal layer in the first ultraviolet irradiation is in a temperature range _{equal to} or higher than _TNI . A preferable holding temperature of the liquid crystal layer is in a temperature range of T _NI or more and T _NI + 15 ° C. or less.
The polarized ultraviolet light applied in the first ultraviolet irradiation is an ultraviolet light having a peak in a wavelength range from about 280 nm to about 400 nm. Preferred polarized ultraviolet has a peak at about 400nm wavelength of about 300 nm, in the range illuminance of about 2 mW / cm ² to about 300 mW / cm ^2, the exposure amount of from about 0.03 J / cm ² to about 20 J / cm ² It is an ultraviolet ray in a range of (illuminance (unit: mW / cm ² ) and irradiation time (unit: second)). More preferably polarized UV light has a peak at about 400nm wavelength of about 300 nm, illuminance in the range of about 2 mW / cm ² to about 300 mW / cm ^2, exposure of about 0.03 J / cm ² to about 10J / cm ² Ultraviolet light, which is a range of quantity. Especially preferred polarized UV, near 313 nm, has a peak near and around 365 nm 335 nm, illuminance in the range of about 2 mW / cm ² to about 300 mW / cm ^2, from about 0.03 J / cm ² to about 10J / cm ² UV light within the range of the exposure amount. Most of the polymerizable compounds are polymerized by the first ultraviolet irradiation.

The holding temperature of the liquid crystal layer in the second ultraviolet irradiation is in a temperature range of 20 ° C. or more and less than T _NI . A preferable holding temperature of the liquid crystal layer is in a temperature range of 20 ° C. or more and 45 ° C. or less.
The unpolarized ultraviolet light to be irradiated by the second ultraviolet irradiation is an ultraviolet light having a peak at a wavelength of about 330 nm to about 400 nm. Preferred unpolarized ultraviolet light has a peak at a wavelength of about 330 nm to about 400 nm, an illuminance of about 1 mW / cm ² to about 50 mW / cm ² , and an exposure of about 1 J / cm ² to about 10 J / cm ^2. UV light in a certain range. More preferred unpolarized UV light is UV light having an illuminance in the range of about 1 mW / cm ² to about 50 mW / cm ² and an exposure of about 1 J / cm ² to about 10 J / cm ² . Particularly preferred unpolarized ultraviolet light has peaks near 335 nm and 365 nm, an illuminance in the range of about 1 mW / cm ² to about 50 mW / cm ² , and an exposure of about 1 J / cm ² to about 10 J / cm ^2. UV light in a certain range. This second UV irradiation can cause additional Fries rearrangement, photodimerization, photoisomerization or photolysis. The unreacted monomer for forming the orientation control layer and the compound (16α), the compound (16α-A) or the compound (16α-B) can be converted into a polymer.

  In a horizontal alignment type element, liquid crystal molecules are aligned substantially horizontally with respect to the substrate surface when no voltage is applied. Usually, in order to horizontally align liquid crystal molecules, a horizontal alignment film such as polyimide is disposed between a color filter substrate and a liquid crystal layer or between an array substrate and a liquid crystal layer. On the other hand, the horizontal alignment element of the present invention does not require such an alignment film on at least one substrate side. In this device, the liquid crystal molecules are horizontally aligned with respect to the substrate by the action of the alignment control layer. The angle between the liquid crystal molecules and the substrate (that is, the pretilt angle) is 0 ° or more and 5 ° or less. Preferably it is 0 ° or more and 3 ° or less. A wide viewing angle can be achieved by combining such horizontal alignment with a comb-shaped electrode.

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

  Reactions were performed under a nitrogen atmosphere unless otherwise noted. The compound (1) and the compound (16α), the compound (16α-A) or the compound (16α-B) were synthesized according to the procedures shown in Synthesis Examples and the like. The synthesized compound was identified by a method such as NMR analysis. The characteristics were measured by the following methods.

NMR analysis: For measurement, DRX-500 manufactured by Bruker Biospin was used. ^{In the 1} H-NMR measurement, the sample was dissolved in a deuterated solvent such as CDCl _3, and the measurement was performed at room temperature under the conditions of 500 MHz and 16 accumulations. Tetramethylsilane was used as an internal standard. ^In the measurement of ¹⁹ F-NMR, CFCl ₃ was used as an internal standard, and the measurement was performed 24 times. In the description of the nuclear magnetic resonance spectrum, s means singlet, d means doublet, t means triplet, q means quartet, quin means quintet, sex means sextet, m means multiplet, and br means broad.

  Gas chromatographic analysis: For measurement, a GC-2010 gas chromatograph manufactured by Shimadzu Corporation was used. As a column, a capillary column DB-1 (length 60 m, inner diameter 0.25 mm, film thickness 0.25 μm) manufactured by Agilent Technologies Inc. was used. Helium (1 mL / min) was used as a carrier gas. The temperature of the sample vaporization chamber was set to 300 ° C., and the temperature of the detector (FID) was set to 300 ° C. The sample was dissolved in acetone to prepare a 1% by weight solution, and 1 μL of the obtained solution was injected into the sample vaporization chamber. As a recorder, a GC Solution system manufactured by Shimadzu Corporation was used.

  HPLC analysis: For measurement, Prominence (LC-20AD; SPD-20A) manufactured by Shimadzu Corporation was used. The column used was YMC-Pack ODS-A manufactured by YMC (length: 150 mm, inner diameter: 4.6 mm, particle diameter: 5 μm). The eluent used was an appropriate mixture of acetonitrile and water. As the detector, a UV detector, an RI detector, a CORONA detector and the like were used as appropriate. When a UV detector was used, the detection wavelength was 254 nm. The sample was dissolved in acetonitrile to prepare a 0.1% by weight solution, and 1 μL of this solution was introduced into the sample chamber. The recorder used was C-R7Aplus manufactured by Shimadzu Corporation.

  Measurement sample: When measuring the phase structure and the transition temperature (clearing point, melting point, polymerization initiation temperature, etc.), the compound itself was used as a sample.

  Measurement method: The characteristics were measured by the following methods. Most of these methods are based on the method described in the JEITA standard (JEITA ED-2521B) established by the Japan Electronics and Information Technology Industries Association (JEITA) or a method modified from this method. there were. No thin film transistor (TFT) was attached to the TN device used for the measurement.

(1) Phase Structure The sample was placed on a hot plate (Mettler FP-52 hot stage) of a melting point measuring apparatus equipped with a polarizing microscope. While heating the sample at a rate of 3 ° C./min, the phase state and its change were observed with a polarizing microscope to identify the type of phase.

(2) Transition temperature (° C)
For the measurement, a scanning calorimeter manufactured by PerkinElmer, a Diamond DSC system or a high-sensitivity differential scanning calorimeter manufactured by SSI Nanotechnology, Inc., X-DSC7000 was used. The sample was heated and cooled at a rate of 3 ° C./min, and the transition point was determined by extrapolating the starting point of the endothermic peak or exothermic peak accompanying the phase change of the sample. The melting point of the compound and the polymerization initiation temperature were also measured using this apparatus. The temperature at which a compound transitions from a solid to a liquid crystal phase such as a smectic phase or a nematic phase may be abbreviated as “the lower limit temperature of the liquid crystal phase”. The temperature at which a compound transitions from a liquid crystal phase to a liquid may be abbreviated as “clearing point”.

The crystals were designated C. When the types of crystals can be distinguished, they are represented as C ₁ and C ₂ , respectively. The smectic phase was represented by S, and the nematic phase was represented by N. Among the smectic phase, a smectic A phase, a smectic B phase, if can be distinguished in the smectic C phase, or a smectic F phase, respectively _{S A,} S B, expressed as _{S C} or _{S F,.} The liquid (isotropic) was designated I. The transition temperature is represented, for example, as “C 50.0 N 100.0 I”. This indicates that the transition temperature from the crystal to the nematic phase is 50.0 ° C., and the transition temperature from the nematic phase to the liquid is 100.0 ° C.

(3) Maximum temperature of nematic phase (T _NI or NI; ° C.)
The sample was placed on a hot plate of a melting point apparatus equipped with a polarizing microscope and heated at a rate of 1 ° C./min. The temperature when a part of the sample changed from a nematic phase to an isotropic liquid was measured. The maximum temperature of the nematic phase may be abbreviated as “maximum temperature”. When the sample is a mixture of a liquid crystal compound and mother liquid crystals, shown by symbol T _NI. When the sample was a mixture of a liquid crystal compound and a compound such as components B, C and D, the mixture was indicated by the symbol of NI.

(4) Minimum Temperature of a Nematic Phase _{(T C;} ° C.)
After storing the sample having a nematic phase in a freezer at 0 ° C., −10 ° C., −20 ° C., −30 ° C., and −40 ° C. for 10 days, a liquid crystal phase was observed. For example, when the sample remained in a nematic phase at −20 ° C. and changed to a crystalline or smectic phase at −30 ° C., _TC was described as ≦ −20 ° C. The lower limit temperature of the nematic phase may be abbreviated as “minimum temperature”.

(5) Viscosity (bulk viscosity; η; measured at 20 ° C .; mPa · s)
For the measurement, an E-type viscometer manufactured by Tokyo Keiki Co., Ltd. was used.

(6) Optical anisotropy (refractive index anisotropy; measured at 25 ° C .; Δn)
The measurement was performed by using an Abbe refractometer having a polarizing plate attached to the eyepiece using light having a wavelength of 589 nm. After rubbing the surface of the main prism in one direction, a sample was dropped on the main prism. The refractive index (n‖) was measured when the direction of polarized light was parallel to the direction of rubbing. The refractive index (n⊥) was measured when the direction of polarized light was perpendicular to the direction of rubbing. The value of optical anisotropy (Δn) was calculated from the equation: Δn = n∥−n⊥.

(7) Specific resistance (ρ; measured at 25 ° C .; Ωcm)
1.0 mL of the sample was injected into a container equipped with electrodes. A DC voltage (10 V) was applied to the container, and a DC current after 10 seconds was measured. The specific resistance was calculated from the following equation. (Specific resistance) = {(voltage) × (electrical capacity of container)} / {(direct current) × (dielectric constant of vacuum)}.

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

(8a) Viscosity (rotational viscosity; γ1; measured at 25 ° C .; mPa · s)
Positive dielectric anisotropy: The measurement was performed according to the method described in M. Imai et al., Molecular Crystals and Liquid Crystals, Vol. 259, 37 (1995). A sample was placed in a TN device having a twist angle of 0 degree and a distance (cell gap) between two glass substrates of 5 μm. A voltage of 16 V to 19.5 V was applied to the device in steps of 0.5 V. After 0.2 seconds of no application, application was repeated under the condition of only one rectangular wave (rectangular pulse; 0.2 seconds) and no application (2 seconds). The peak current and the peak time of the transient current generated by this application were measured. These measurements and M.P. The rotational viscosity value was obtained from the calculation formula (10) on page 40 of the paper by Imai et al. The value of the dielectric anisotropy required for this calculation was determined by the method described below using the element whose rotational viscosity was measured.

(8b) Viscosity (rotational viscosity; γ1; measured at 25 ° C .; mPa · s)
Negative dielectric anisotropy: The measurement was performed according to the method described in M. Imai et al., Molecular Crystals and Liquid Crystals, Vol. 259, 37 (1995). A sample was placed in a VA device in which a distance (cell gap) between two glass substrates was 20 μm. A voltage of 39 V to 50 V was applied stepwise to the device every 1 V. After 0.2 seconds of no application, application was repeated under the condition of only one rectangular wave (rectangular pulse; 0.2 seconds) and no application (2 seconds). The peak current and the peak time of the transient current generated by this application were measured. These measurements and M.P. The rotational viscosity value was obtained from the calculation formula (10) on page 40 of the paper by Imai et al. As the dielectric anisotropy necessary for this calculation, a value measured in the following section on dielectric anisotropy was used.

(9a) Dielectric anisotropy (Δε; measured at 25 ° C.)
Positive dielectric anisotropy: A sample was placed in a TN device in which a distance (cell gap) between two glass substrates was 9 μm and a twist angle was 80 degrees. Sine waves (10 V, 1 kHz) were applied to the device, and after 2 seconds, the dielectric constant (ε‖) in the major axis direction of the liquid crystal molecules was measured. Sine waves (0.5 V, 1 kHz) were applied to the device, and after 2 seconds, the dielectric constant (ε （) of the liquid crystal molecules in the minor axis direction was measured. The value of the dielectric anisotropy was calculated from the equation: Δε = ε∥−ε⊥.

(9b) Dielectric anisotropy (Δε; measured at 25 ° C.)
Negative dielectric anisotropy: The value of dielectric anisotropy was calculated from the equation: Δε = ε∥−ε⊥. The dielectric constants (ε‖ and ε⊥) were measured as follows.
1) Measurement of dielectric constant (ε‖): A solution of octadecyltriethoxysilane (0.16 mL) in ethanol (20 mL) was applied to a well-cleaned glass substrate. After rotating the glass substrate with a spinner, it was heated at 150 ° C. for 1 hour. A sample was placed in a VA device in which the distance (cell gap) between two glass substrates was 4 μm, and the device was sealed with an adhesive that cured with ultraviolet light. Sine waves (0.5 V, 1 kHz) were applied to the device, and after 2 seconds, the dielectric constant (ε‖) in the major axis direction of the liquid crystal molecules was measured.
2) Measurement of dielectric constant (ε⊥): A polyimide solution was applied to a well-cleaned glass substrate. After firing this glass substrate, a rubbing treatment was performed on the obtained alignment film. A sample was placed in a TN device in which the distance between two glass substrates (cell gap) was 9 μm and the twist angle was 80 degrees. Sine waves (0.5 V, 1 kHz) were applied to the device, and after 2 seconds, the dielectric constant (ε （) of the liquid crystal molecules in the minor axis direction was measured.

(10a) Elastic constant (K; measured at 25 ° C .; pN)
Positive dielectric anisotropy: HP4284A LCR meter manufactured by Yokogawa-Hewlett-Packard Co., Ltd. was used for measurement. A sample was placed in a horizontal alignment element in which a distance (cell gap) between two glass substrates was 20 μm. A charge of 0 V to 20 V was applied to the device, and the capacitance and applied voltage were measured. The measured values of the capacitance (C) and the applied voltage (V) were fitted using the equations (2.98) and (2.101) on page 75 of “Liquid Crystal Device Handbook” (Nikkan Kogyo Shimbun). to obtain the values of _{K 11} and _{K 33} from equation (2.99). Then the equation (3.18) on page 171, to calculate the _{K 22} using the values of _{K 11} and _{K 33} was determined previously. The elastic constant K was represented by the average value of K ₁₁ , K ₂₂ and K ₃₃ thus obtained.

(10b) Elastic constants (K ₁₁ and K ₃₃ ; measured at 25 ° C .; pN)
Negative dielectric anisotropy: An EC-1 type elastic constant measuring device manufactured by Toyo Corporation was used for the measurement. A sample was placed in a vertical alignment element in which a distance (cell gap) between two glass substrates was 20 μm. A charge of 20 V to 0 V was applied to the device, and the capacitance and applied voltage were measured. The values of the capacitance (C) and the applied voltage (V) were fitted using the equations (2.98) and (2.101) on page 75 of “Liquid Crystal Device Handbook” (Nikkan Kogyo Shimbun). The value of the elastic constant was obtained from Equation (2.100).

(11a) Threshold voltage (Vth; measured at 25 ° C .; V)
Positive dielectric anisotropy: An LCD5100 luminance meter manufactured by Otsuka Electronics Co., Ltd. was used for the measurement. The light source was a halogen lamp. A sample was put in a normally white mode TN device in which the distance between two glass substrates (cell gap) was 0.45 / Δn (μm) and the twist angle was 80 degrees. The voltage (32 Hz, rectangular wave) applied to this device was increased stepwise from 0 V to 10 V in steps of 0.02 V. At this time, the device was irradiated with light from a vertical direction, and the amount of light transmitted through the device was measured. A voltage-transmittance curve was prepared in which the maximum light amount was 100% transmittance, and the minimum light amount was 0% transmittance. The threshold voltage was represented by a voltage when the transmittance became 90%.

(11b) Threshold voltage (Vth; measured at 25 ° C .; V)
Negative dielectric anisotropy: An LCD5100 luminance meter manufactured by Otsuka Electronics Co., Ltd. was used for the measurement. The light source was a halogen lamp. A sample is placed in a normally black mode VA device in which the distance between two glass substrates (cell gap) is 4 μm and the rubbing direction is antiparallel, and an adhesive that cures this device with ultraviolet light is used. And sealed.
The voltage (60 Hz, rectangular wave) applied to this device was increased stepwise from 0 V to 20 V in steps of 0.02 V. At this time, the device was irradiated with light from a vertical direction, and the amount of light transmitted through the device was measured. A voltage-transmittance curve was prepared in which the maximum light amount was 100% transmittance, and the minimum light amount was 0% transmittance. The threshold voltage was represented by a voltage at which the transmittance became 10%.

(12a) Response time (τ; measured at 25 ° C .; ms)
Positive dielectric anisotropy: An LCD5100 luminance meter manufactured by Otsuka Electronics Co., Ltd. was used for the measurement. The light source was a halogen lamp. The low-pass filter was set at 5 kHz. A sample was put in a normally white mode TN device in which a distance (cell gap) between two glass substrates was 5.0 μm and a twist angle was 80 degrees. A rectangular wave (60 Hz, 5 V, 0.5 seconds) was applied to the device. At this time, the device was irradiated with light from a vertical direction, and the amount of light transmitted through the device was measured. The maximum light amount was considered to be 100% transmittance, and the minimum light amount was considered to be 0% transmittance. The rise time (τr: rise time; millisecond) is the time required for the transmittance to change from 90% to 10%. Fall time (τf: fall time; millisecond) is the time required for the transmittance to change from 10% to 90%. The response time was represented by the sum of the rise time and the fall time thus obtained.

(12b) Response time (τ; measured at 25 ° C .; ms)
Negative dielectric anisotropy: An LCD5100 luminance meter manufactured by Otsuka Electronics Co., Ltd. was used for the measurement. The light source was a halogen lamp. The low-pass filter was set at 5 kHz. A sample was placed in a normally black mode PVA device in which the distance between two glass substrates (cell gap) was 3.2 μm and the rubbing direction was antiparallel. The device was sealed with an adhesive that cured with ultraviolet light. A voltage slightly exceeding the threshold voltage was applied to the device for 1 minute, and then 23.5 mW / cm ² ultraviolet light was applied for 8 minutes while applying a voltage of 5.6 V. A rectangular wave (60 Hz, 10 V, 0.5 seconds) was applied to the device. At this time, the device was irradiated with light from a vertical direction, and the amount of light transmitted through the device was measured. The maximum light amount was considered to be 100% transmittance, and the minimum light amount was considered to be 0% transmittance. The response time was represented by the time required for the transmittance to change from 90% to 10% (fall time; millisecond).

(13) Voltage holding ratio The element obtained by polymerizing the polymerizable compound was charged at 60 ° C. by applying a pulse voltage (1 V for 60 microseconds). The decaying voltage was measured with a high-speed voltmeter for 500 milliseconds, and the area A between the voltage curve and the horizontal axis in a unit cycle was determined. The area B is the area when there is no attenuation. The voltage holding ratio was expressed as a percentage of the area A to the area B.

(14) Illuminance The ultraviolet illuminance was measured using an ultraviolet illuminometer manufactured by Ushio Inc., Model UIT-250 (sensors: UVD-S313 and UVD-S365).

(15) Uniformity of horizontal alignment The element on which the alignment control layer was formed was set on a polarizing microscope, and the alignment state of the liquid crystal was observed. The polarizer and analyzer of the polarizing microscope were arranged such that their transmission axes were orthogonal. First, so that the orientation direction of the liquid crystal molecules and the transmission axis of the polarizer of the polarization microscope are parallel, that is, the angle between the orientation direction of the liquid crystal molecules and the transmission axis of the polarizer of the polarization microscope is 0 degrees. The device was set on a horizontal rotating stage of a polarizing microscope. Light was irradiated from the lower side of the device, that is, from the polarizer side, and the presence or absence of light transmitted through the analyzer was observed. When no light transmitted through the analyzer was observed (black state), the orientation was determined to be “good”. The light transmission intensity in the black state was measured using a multimedia display tester 3298 manufactured by Yokogawa Electric Corporation. When light transmitted through the analyzer was observed in the same observation, the orientation was determined to be “poor”. Next, the element was rotated on a horizontal rotating stage of a polarizing microscope, and the angle between the transmission axis of the polarizer of the polarizing microscope and the orientation direction of the liquid crystal molecules was changed from 0 degree. The intensity of the light transmitted through the analyzer increases as the angle between the transmission axis of the polarizer of the polarizing microscope and the orientation direction of the liquid crystal molecules increases, and it becomes almost maximum when the angle is 45 degrees. confirmed. The measurement of the light intensity in this light transmission state was performed in the same manner as the measurement of the light transmission intensity in the black state. From the obtained light transmission intensity, the transmittance ratio was calculated by the following equation.
(Transmittance ratio) = (Light transmission intensity in light transmission state) / (Light transmission intensity in black state)

(16) Pretilt angle (degree)
Opti-Pro manufactured by Shintech Co., Ltd. was used for measuring the pretilt angle.

(17) Film Thickness The thickness of the orientation control layer was measured using an SEM (scanning electron microscope, SU-70 manufactured by Hitachi High-Technologies Corporation).

  Compound (1) is selected from the compounds shown below.

  Compound (16α-A) is selected from the compounds shown below.

  Compound (16α-B) is selected from the compounds shown below.

  The compounds in the composition were represented by symbols based on the definitions of 1) to 5) in Table 2 below. In Table 2, the configuration for 1,4-cyclohexylene is trans. The number in parentheses after the symbol corresponds to the compound number. The symbol (-) means other liquid crystal compounds. The ratio (percentage) of the liquid crystal compound is a percentage by weight (% by weight) based on the weight of the liquid crystal composition. Finally, the characteristic values of the liquid crystal composition were summarized. The properties were measured according to the method described above, and the measured values were described as such (without extrapolation).

[Composition (M1)]
2-HH-3 (2-1) 21% 3-HH-4 (2-1) 5% 3-HB-O2 (2-5) 2.5% 1-BB-3 (2-8) 4% 3-HHB-1 (3-1) 1.5% 3-HBB-2 (3-4) 9.5% 2-H1OB (2F, 3F) -O2 (9-5) 7% 3-H1OB (2F) , 3F) -O2 (9-5) 11% 3-HDhB (2F, 3F) -O2 (10-3) 3.5% 3-HH1OB (2F, 3F) -O2 (10-5) 8% 2- HBB (2F, 3F) -O2 (10-7) 3% 3-HBB (2F, 3F) -O2 (10-7) 9% 5-HBB (2F, 3F) -O2 (10-7) 7% V -HBB (2F, 3F) -O2 (10-7) 8%
NI = 80.8 ° C .; Tc <−20 ° C .; Δn = 0.08; Δε = −3.8; Vth = 2.02 V; η = 19.8 mPa · s; γ 1 = 1115.0 mPa · s.

[Composition (M2)]
2-HH-3 (2-1) 21% 3-HH-4 (2-1) 5% 3-HBB-2 (3-4) 9% 3-HHB-3 (3-1) 8% 5- HBB (F, F) -F (6-24) 20% 3-HBB (F, F) -F (6-24) 30% 2-HHBB (F, F) -F (7-6) 3% 3 -HHBB (F, F) -F (7-6) 4% NI = 85.1 ° C .; Tc <−20 ° C .; Δn = 0.109; Δε = 5.3; Vth = 1.83V; η = 20 .1 mPa · s; γ1 = 82.4 mPa · s.

[Composition (M3)]
3-HH-V (2-1) 18% 3-HH-4 (2-1) 11% 5-HB-O2 (2-5) 2% 3-HHB-1 (3-1) 5% 3- HHB-3 (3-1) 5% 3-HHB-O1 (3-1) 6% 3-HHB (F, F) -F (6-3) 10% 3-BB (F) B (F, F ) -F (6-69) 7% 3-BB (F, F) XB (F, F) -F (6-97) 14% 3-HHXB (F, F) -F (6-100) 2% 3-GHB (F, F) -F (6-109) 4% 4-BB (F) B (F, F) XB (F, F) -F (7-47) 10% 5-BB (F) B (F, F) XB (F, F) -F (7-47) 6% NI = 78.4 ° C .; Tc <−20 ° C .; Δn = 0.108; Δε = 10.4; Vth = 1. 35 V; η = 17.8 mPa · s; γ1 = 79.9 mPa · .

[Composition (M4)]
3-HH-V (2-1) 34% V-HHB-1 (3-1) 12% V-HBB-2 (3-4) 5% 3-HBB-2 (3-4) 5% 3- BB (F, F) XB (F, F) -F (6-97) 15% 3-GB (F, F) XB (F, F) -F (6-113) 4% 3-HHB (F, F) XB (F, F) -F (7-29) 8% 3-HBBXB (F, F) -F (7-32) 5% 3-BB (F, F) XB (F) B (F, F) -F (7-56) 4% 4-GB (F) B (F, F) XB (F, F) -F (7-57) 4% 5-GB (F) B (F, F) XB (F, F) -F (7-57) 4% NI = 77.4 ° C .; Tc <−20 ° C .; Δn = 0.108; Δε = 10.2; Vth = 1.35V; 2 mPa · s; γ1 = 69.0 mPa · s.

[Composition (M5)]
3-HH-V (2-1) 29% 3-HH-V1 (2-1) 2% V-HHB-1 (3-1) 5% 2-BB (2F, 3F) -O2 (9-3 ) 3% 3-BB (2F, 3F) -O2 (9-3) 10.5% 3-H2B (2F, 3F) -O2 (9-4) 5% V2-HHB (2F, 3F) -O2 ( 10-1) 12% V-HHB (2F, 3F) -O2 (10-1) 11.5% 3-HH2B (2F, 3F) -O2 (10-4) 9% V-HBB (2F, 3F) -O2 (10-7) 11% V-HBB (2F, 3F) -O4 (10-7) 2% NI = 89.1 ° C; Tc <-20 ° C; Δn = 0.107; Δε = -3. 7; Vth = 2.32 V; γ1 = 129.7 mPa · s.

[Composition (M6)]
2-HH-3 (2-1) 20% 3-HH-VFF (2-1) 6% V-HBB-2 (3-4) 10% 3-HB (2F, 3F) -O2 (9-1) ) 12% 5-HB (2F, 3F) -O2 (9-1) 11% 3-HHB (2F, 3F) -O2 (10-1) 10% V-HHB (2F, 3F) -O1 (10-) 1) 3% V-HHB (2F, 3F) -O2 (10-1) 8% 2-HBB (2F, 3F) -O2 (10-7) 3% 3-HBB (2F, 3F) -O2 (10-1) -7) 9% 4-HBB (2F, 3F) -O2 (10-7) 5% V-HBB (2F, 3F) -O2 (10-7) 3% NI = 85.8 ° C; Tc <-20 ° C; Δn = 0.104; Δε = -3.5; Vth = 2.11 V; γ1 = 106 mPa · s.

[Composition (M7)]
3-HH-V (2-1) 15% 3-HH-V1 (2-1) 6% 2-HH-3 (2-1) 9% 3-HH-4 (2-1) 3% 3- HH-2V1 (2-1) 3% V-HB (2F, 3F) -O2 (9-1) 7% V2-BB (2F, 3F) -O2 (9-3) 10% V-HHB (2F, 3F) -O2 (10-1) 7% V-HHB (2F, 3F) -O1 (10-1) 9% V2-HHB (2F, 3F) -O2 (10-1) 8% 3-HH2B (2F , 3F) -O2 (10-4) 9% V-HBB (2F, 3F) -O2 (10-7) 7% V-HBB (2F, 3F) -O4 (10-7) 7% NI = 87. 5 ° C .; Tc <−20 ° C .; Δn = 0.100; Δε = −3.4; Vth = 2.28 V; η = 16.6 mPa · s; γ 1 = 102 mPa · s.

[Composition (M8)]
3-HH-V (2-1) 27% 3-HH-V1 (2-1) 2% 3-HH-2V1 (2-1) 5% V2-BB (2F, 3F) -O2 (9-3 9% 3-H2B (2F, 3F) -O2 (9-4) 9% V-HHB (2F, 3F) -O2 (10-1) 10% V-HHB (2F, 3F) -O1 (10-) 1) 9% V2-HHB (2F, 3F) -O2 (10-1) 8% 3-HH2B (2F, 3F) -O2 (10-4) 9% V-HBB (2F, 3F) -O2 (10 -7) 7% V-HBB (2F, 3F) -O4 (10-7) 5% NI = 89.5 ° C .; Tc <−20 ° C .; Δn = 0.100; Δε = −3.6; Vth = 2.34 V; η = 17.1 mPa · s; γ1 = 109 mPa · s.

[Example 1]
To 100 parts by weight of the composition (M1), 3.0 parts by weight of the compound (1-12) was added as a first additive. Then, as an antioxidant, a compound (AO-1) in which R ⁴⁰ is a heptyl group (C ₇ H ₁₅ −) was added at a ratio of 150 ppm by weight based on 100 parts by weight of the composition (M1). The transition temperature from the nematic phase to the isotropic phase of this composition was about 84 ° C. Next, a liquid crystal element (hereinafter referred to as an IPS element or This composition was injected at 90 ° C. (above the upper limit temperature of the nematic phase). As the 3.2 μm spacer, Hayabeads 3DS-XD manufactured by Hayakawa Rubber Co., Ltd. was used. While maintaining the composition at 90 ° C., the device was irradiated with polarized ultraviolet rays having peaks at 313 nm, 335 nm and 365 nm from the normal direction at 22 J / cm ² as first ultraviolet irradiation (at a wavelength of 313 nm). The illuminance was 3 mW / cm ² , measured using UIT-150 and UVD-S313 manufactured by Ushio Inc.). USH-250BY manufactured by Ushio Inc. was used as an ultraviolet irradiation lamp. The exposure machine unit used was ML-251A / B manufactured by Ushio Inc. The polarized ultraviolet light was formed using a wire grid polarizer (ProFlux UVT260A manufactured by Poratechno Co., Ltd.).
Next, the element on which the alignment control layer was formed was set in a polarizing microscope, and the uniformity of the horizontal alignment of the liquid crystal was observed. As a result, no light leakage was observed and the alignment was good.
The element was rotated on a horizontal rotating stage of a polarizing microscope, and the angle between the transmission axis of the polarizer of the polarizing microscope and the orientation direction of the liquid crystal molecules was changed from 0 degree. The intensity of the light transmitted through the analyzer increases as the angle between the transmission axis of the polarizer of the polarizing microscope and the orientation direction of the liquid crystal molecules increases, and it becomes almost maximum when the angle is 45 degrees. confirmed. In the device obtained as described above, the liquid crystal molecules were oriented in a direction substantially horizontal to the main surface of the substrate of the device, and it was determined to be "horizontal orientation".
In order to evaluate the uniformity of the horizontal alignment, the light transmission intensity when the angle between the alignment direction of the liquid crystal molecules and the transmission axis of the polarizer of the polarizing microscope is 0 degree, and the light transmission intensity when the angle is 45 degrees The ratio was calculated according to the above formula to be about 1050.

[Example 2]
A composition was prepared in the same manner as in Example 1 except that the compound (1-12) in Example 1 was changed to the compound (1-39) and the amount of the first additive was changed to 1.0 part by weight. Prepared. The transition temperature of the composition from a nematic phase to an isotropic phase was about 85 ° C. Next, this composition was added at 90 ° C. (nematic phase) to an IPS device having no alignment film in which a distance (cell gap) between two glass substrates was set to 3.2 μm via a 3.2 μm spacer and a sealant. ). As the 3.2 μm spacer, Hayabeads 3DS-XD manufactured by Hayakawa Rubber Co., Ltd. was used. While maintaining the composition at 90 ° C., the first ultraviolet irradiation was performed under the same conditions as in Example 1 except that the irradiation amount of the ultraviolet light was 0.9 J / cm ² , and the device was subjected to horizontal alignment treatment. .
When the uniformity of horizontal alignment was observed in the same manner as in Example 1, no light leakage was observed and the alignment was good.
The element was rotated on a horizontal rotating stage of a polarizing microscope, and the angle between the transmission axis of the polarizer of the polarizing microscope and the orientation direction of the liquid crystal molecules was changed from 0 degree. The intensity of the light transmitted through the analyzer increases as the angle between the transmission axis of the polarizer of the polarizing microscope and the orientation direction of the liquid crystal molecules increases, and it becomes almost maximum when the angle is 45 degrees. confirmed. In the device obtained as described above, the liquid crystal molecules were oriented in a direction substantially horizontal to the main surface of the substrate of the device, and it was determined to be "horizontal orientation".
In order to evaluate the uniformity of the horizontal alignment, the light transmission intensity when the angle between the alignment direction of the liquid crystal molecules and the transmission axis of the polarizer of the polarizing microscope is 0 degree, and the light transmission intensity when the angle is 45 degrees When the ratio was calculated according to the above equation, it was about 510.

[Example 3]
A composition was prepared in the same manner as in Example 1, except that the compound (1-12) in Example 1 was changed to the compound (1-41). The transition temperature from the nematic phase to the isotropic phase of this composition was about 84 ° C. Next, this composition was added at 90 ° C. (nematic phase) to an IPS device having no alignment film in which a distance (cell gap) between two glass substrates was set to 3.2 μm via a 3.2 μm spacer and a sealant. ). As the 3.2 μm spacer, Hayabeads 3DS-XD manufactured by Hayakawa Rubber Co., Ltd. was used. While maintaining the composition at 90 ° C., the first ultraviolet irradiation was performed under the same conditions as in Example 1 except that the irradiation amount of the ultraviolet light was set to 11 J / cm ² , thereby performing a horizontal alignment treatment of the device.
When the uniformity of horizontal alignment was observed in the same manner as in Example 1, no light leakage was observed and the alignment was good.
The element was rotated on a horizontal rotating stage of a polarizing microscope, and the angle between the transmission axis of the polarizer of the polarizing microscope and the orientation direction of the liquid crystal molecules was changed from 0 degree. The intensity of the light transmitted through the analyzer increases as the angle between the transmission axis of the polarizer of the polarizing microscope and the orientation direction of the liquid crystal molecules increases, and it becomes almost maximum when the angle is 45 degrees. confirmed. In the device obtained as described above, the liquid crystal molecules were oriented in a direction substantially horizontal to the main surface of the substrate of the device, and it was determined to be "horizontal orientation".
In order to evaluate the uniformity of the horizontal alignment, the light transmission intensity when the angle between the alignment direction of the liquid crystal molecules and the transmission axis of the polarizer of the polarizing microscope is 0 degree, and the light transmission intensity when the angle is 45 degrees The ratio was calculated to be about 670 according to the above equation.

[Comparative Example 1]
A composition was prepared in the same manner as in Example 1 except that the compound (1-12) in Example 1 was not added, and a gap (cell) between two glass substrates was placed via a 3.2 μm spacer and a sealant. This composition was injected at 90 ° C. (above the upper limit temperature of the nematic phase) into an IPS device having no alignment film whose gap was set to 3.2 μm. As the 3.2 μm spacer, Hayabes 3DS-XD manufactured by Hayakawa Rubber Co., Ltd. was used. While maintaining the composition at 90 ° C., first ultraviolet irradiation was performed under the same conditions as in Example 1 to perform a horizontal alignment treatment of the device.
When the uniformity of horizontal alignment was observed in the same manner as in Example 1, light leakage due to alignment defects was observed, and the liquid crystal compound was not aligned.

[Comparative Example 2]
A composition was prepared in the same manner as in Example 1 except that the compound (1-12) in Example 1 was changed to the following compound (R-1). The transition temperature of the composition from a nematic phase to an isotropic phase was about 79 ° C. Next, this composition was added at 90 ° C. (nematic phase) to an IPS device having no alignment film in which a distance (cell gap) between two glass substrates was set to 3.2 μm via a 3.2 μm spacer and a sealant. ). As the 3.2 μm spacer, Hayabeads 3DS-XD manufactured by Hayakawa Rubber Co., Ltd. was used. While maintaining the composition at 90 ° C., the first ultraviolet irradiation was performed under the same conditions as in Example 1 except that the irradiation amount of the ultraviolet light was set to 11 J / cm ² , thereby performing a horizontal alignment treatment of the device.
When the uniformity of horizontal alignment was observed in the same manner as in Example 1, a large number of light leaks due to alignment defects were observed, and it was found that the liquid crystal compound was randomly aligned.

[Comparative Example 3]
A composition was prepared in the same manner as in Example 1, except that the compound (1-12) in Example 1 was changed to the following compound (R-2). The transition temperature of the composition from a nematic phase to an isotropic phase was about 86 ° C. Next, this composition was added at 90 ° C. (nematic phase) to an IPS device having no alignment film in which a distance (cell gap) between two glass substrates was set to 3.2 μm via a 3.2 μm spacer and a sealant. ). As the 3.2 μm spacer, Hayabeads 3DS-XD manufactured by Hayakawa Rubber Co., Ltd. was used. While maintaining the composition at 90 ° C., the first ultraviolet irradiation was performed under the same conditions as in Example 1 except that the irradiation amount of the ultraviolet light was set to 11 J / cm ² , thereby performing a horizontal alignment treatment of the device.
When the uniformity of the horizontal alignment was observed in the same manner as in Example 1, no light leakage was observed and the dark field was maintained. On the other hand, the element was rotated on a horizontal rotating stage of a polarizing microscope, and the angle between the transmission axis of the polarizer of the polarizing microscope and the orientation direction of the liquid crystal molecules was changed from 0 degree. The intensity of light passing through the analyzer did not change even when the angle between the transmission axis of the polarizer of the polarizing microscope and the orientation direction of the liquid crystal molecules was changed. In the device obtained as described above, the liquid crystal molecules were oriented in a direction substantially perpendicular to the main surface of the substrate of the device, and it was determined to be “vertical alignment”.

[Comparative Example 4]
A composition was prepared in the same manner as in Example 1 except that the compound (1-12) in Example 1 was changed to the following compound (R-3). The transition temperature from the nematic phase to the isotropic phase of this composition was about 84 ° C. Next, this composition was added at 90 ° C. (nematic phase) to an IPS device having no alignment film in which a distance (cell gap) between two glass substrates was set to 3.2 μm via a 3.2 μm spacer and a sealant. ). As the 3.2 μm spacer, Hayabeads 3DS-XD manufactured by Hayakawa Rubber Co., Ltd. was used. While maintaining the composition at 90 ° C., the first ultraviolet irradiation was performed under the same conditions as in Example 1 except that the irradiation amount of the ultraviolet light was set to 11 J / cm ² , thereby performing a horizontal alignment treatment of the device.
When the uniformity of horizontal alignment was observed in the same manner as in Example 1, a large number of light leaks due to alignment defects were observed, and it was found that the liquid crystal compound was randomly aligned.

The devices of Examples 1 to 3 had almost no light leakage, so the transmittance ratio was large, and the uniformity of horizontal alignment was high. On the other hand, in the device of Comparative Example 1, no alignment control layer was formed because no alignment control monomer was contained, and the liquid crystal compound was not aligned. In addition, in the devices of Comparative Examples 2 and 4, the added polymerizable compound contained an α-methoxymethyl diacrylate structure, but did not have an aromatic ester structure. It did not function as a horizontal alignment control layer. The device of Comparative Example 3 has an aromatic ester structure, but does not have an α-methoxymethyl diacrylate structure, so that interaction with the substrate hardly occurs, and it is presumed that it was difficult to induce horizontal alignment. Is done. From this fact, when a polymerizable compound containing an α-alkoxyalkyl acrylate group is used in a structure that induces photo-Fries rearrangement, photo-dimerization, or photo-isomerization due to polarized ultraviolet irradiation, the function of controlling the horizontal alignment of liquid crystal molecules can be exhibited. You can see that there is. Similar effects can be expected by using other liquid crystal compositions (for example, compositions (M2) to (M8)) and other first additives. Similar effects can be expected even when the first additive and the second additive are used in combination. Further, in the embodiment, only the first ultraviolet irradiation is performed. However, a similar effect can be expected when the second ultraviolet irradiation is performed.
By using the liquid crystal display element of the present invention, it is considered that the uniformity of the horizontal alignment of the liquid crystal compound can be sufficiently ensured even in a conventional system having no alignment film on at least one side or a system not having both sides. Can be Similar effects can be obtained when the dielectric anisotropy of the liquid crystal composition is positive or negative. Further, since the first additive and the second additive are consumed for forming the alignment control layer by the irradiation of polarized ultraviolet light, it is considered that the first additive and the second additive hardly affect the dielectric anisotropy of the liquid crystal composition. Therefore, it can be concluded that the liquid crystal display device of the present invention has a uniform horizontal alignment. In this element, since light leakage is prevented, it can be said that characteristics such as contrast are excellent.

  The liquid crystal display device manufactured by the method of the present invention can be used for a liquid crystal monitor, a liquid crystal television, electronic paper, a light control device using a polymer dispersion mode, and the like.

Claims (17)

A liquid crystal layer is sandwiched between a pair of substrates arranged opposite to each other,
An alignment control layer for controlling alignment of liquid crystal molecules between the pair of substrates and the liquid crystal layer,
The liquid crystal layer is formed from a liquid crystal composition,
The liquid crystal composition comprises at least one liquid crystal compound and, as a first additive, at least one of photo-Fries rearrangement, photo-isomerization, photo-dimerization, and photo-decomposition by light irradiation, which is represented by formula (1). Containing an orientation control layer forming monomer that produces
The horizontal alignment type liquid crystal display device, wherein the alignment control layer contains a polymer obtained by polymerizing the first additive.

In equation (1),
R ¹ , R ² and R ³ are independently hydrogen or alkyl having 1 to 10 carbons, wherein at least one —CH ₂ — is replaced by —O— or —NH— Well;
n is independently 0, 1 or 2;
a is 0, 1, 2, or 3;
Ring ^{A 1} is cyclohexyl, cyclohexenyl, phenyl, 1-naphthyl, 2-naphthyl, tetrahydropyran-2-yl, tetrahydropyran-3-yl, 1,3-dioxan-2-yl, 1,3-dioxane - 3-yl, pyrimidin-2-yl, pyrimidin-5-yl, pyridin-2-yl, pyridin-3-yl, fluoren-2-yl, fluoren-7-yl, phenanthren-2-yl, phenanthrene-7- Yl, anthracen-2-yl, anthracen-6-yl, perhydrocyclopenta [a] phenanthren-3-yl, perhydrocyclopenta [a] phenanthrene-17-yl, 2,3,4,7,8, 9,10,11,12,13,14,15,16,17-tetradecahydrocyclopenta [a] phenanthrene-3- Or 2,3,4,7,8,9,10,11,12,13,14,15,16,17-tetradecahydrocyclopenta [a] phenanthrene-17-yl,
Ring A ² is 1,4-cyclohexylene, 1,3-cyclohexylene, 1,2-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, 1,3-phenylene, , 2-Phenylene, naphthalene-2,6-diyl, naphthalene-1,4-diyl, decahydronaphthalene-2,6-diyl, decahydronaphthalene-1,4-diyl, 1,2,3,4-tetrahydro Naphthalene-2,6-diyl, 1,2,3,4-tetrahydronaphthalene-1,4-diyl, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, pyrimidine-2, 5-diyl, pyridine-2,5-diyl, cyclopentane-1,3-diyl, cyclopentene-1,3-diyl, fluorene-2,7-diyl, carbazole-2,7-diyl, Enanthrene-2,7-diyl, anthracene-2,6-diyl, anthracene-1,4-diyl, perhydrocyclopenta [a] phenanthrene-3,17-diyl, or 2,3,4,7,8, 9,10,11,12,13,14,15,16,17-tetradecahydrocyclopenta [a] phenanthrene-3,17-diyl,
Ring ^{A 3} 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, pyridine-2,5-diyl, fluorene-2,7- Diyl, phenanthrene-2,7-diyl, anthracene-2,6-diyl, anthracene-1,4-diyl, perhydrocyclopenta [a] phenanthrene-3,17-di Or 2,3,4,7,8,9,10,11,12,13,14,15,16,17-tetradecahydrocyclopenta [a] phenanthrene-3,17-diyl;
Z ¹ and Z ² are each independently a single bond or alkylene having 1 to 10 carbon atoms, wherein at least one —CH ₂ — is —O—, —CO—, —COO—, — OCO -, - CONH -, - NHCO- or -OCOO- may be replaced by at least one - _{(CH 2) 2} - may be replaced by -CH = CH- or -C≡C- , In these groups, at least one hydrogen may be replaced by halogen, but at least one of Z ¹ and Z ² is —COO—, —OCO—, —CH ＝ CHCOO—, —OCOCH ＝ CH—, —CH ＝ CH—, —CH ＝ CHCO—, or —COCH ＝ CH—, and when a is 2 or 3, each Z ² may be different;
Sp ¹ , Sp ² , Sp ³ and Sp ⁴ are each independently a single bond or alkylene having 1 to 10 carbon atoms, wherein at least one —CH ₂ — is —O—, —COO— , —OCO— or —OCOO—, and at least one — (CH ₂ ) ₂ — may be replaced by —CH ＝ CH— or —C≡C—, in these groups: At least one hydrogen may be replaced by fluorine or chlorine;
c, d and e are independently 0, 1, 2, 3 or 4; the sum of c, d and e is 1, 2, 3 or 4;
P ¹ , P ² , P ³ and P ⁴ are each independently a polymerizable group represented by the formula (1P-1);

In the equation (1P-1),
M ⁴¹ and M ⁴² are independently hydrogen, fluorine, alkyl having 1 to 5 carbons, or alkyl having 1 to 5 carbons in which at least one hydrogen is replaced by fluorine or chlorine;
R ⁴¹ is alkyl having 1 to 10 carbons, alkoxy having 1 to 9 carbons, or alkoxyalkyl having 1 to 9 carbons. In these groups, at least one — (CH ₂ ) ₂ — is represented by — CH ＝ CH— or —C≡C—, in which at least one hydrogen may be replaced by fluorine or chlorine, but P ¹ , P ² , P ³ and P ⁴ In at least one formula (1P-1), R ⁴¹ is alkoxyalkyl having 1 to 9 carbons. In equation (1),
R ¹ , R ² and R ³ are each independently hydrogen or alkyl having 1 to 10 carbons;
In the alkyl, at least one of -CH ₂ - may be replaced by -O- or -NH-;
n is independently 0, 1 or 2;
a is 0, 1, 2, or 3;
Ring ^{A 1} is cyclohexyl, phenyl, 1-naphthyl, 2-naphthyl, pyrimidin-2-yl, pyrimidin-5-yl, pyridin-2-yl, pyridin-3-yl, fluoren-2-yl, fluorene -7 -Yl, phenanthren-2-yl, phenanthren-7-yl or anthracen-2-yl, anthracen-6-yl,
Ring ^{A 2} is 1,4-cyclohexylene, cyclohexylene 1,3-cyclohexylene, 1,4-phenylene, 1,3-phenylene, naphthalene-2,6-diyl, naphthalene-1,4-diyl, pyrimidine -2,5-diyl, pyridine-2,5-diyl, fluorene-2,7-diyl, carbazole-2,7-diyl, phenanthrene-2,7-diyl or anthracene-2,6-diyl, anthracene-1 , 4-diyl,
Ring ^{A 3} is 1,4-cyclohexylene, 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, pyrimidine -2,5-diyl, pyridine-2,5-diyl, fluorene-2,7-diyl, phenanthrene-2,7-diyl, anthracene-2,6-diyl or anthracene-1,4-diyl;
Z ¹ and Z ² are each independently a single bond or alkylene having 1 to 10 carbon atoms, wherein at least one —CH ₂ — is —O—, —CO—, —COO—, — OCO -, - CONH -, - NHCO- or -OCOO- may be replaced by at least one - _{(CH 2) 2} - may be replaced by -CH = CH- or -C≡C- , In these groups, at least one hydrogen may be replaced by halogen, but at least one of Z ¹ and Z ² is —COO—, —OCO—, —CH ＝ CHCOO—, —OCOCH ＝ CH—, —CH ＝ CH—, —CH ＝ CHCO—, or —COCH ＝ CH—, and when a is 2 or 3, each Z ² may be different;
Sp ¹ , Sp ² , Sp ³ and Sp ⁴ are each independently a single bond or alkylene having 1 to 10 carbon atoms, wherein at least one —CH ₂ — is —O—, —COO— , —OCO— or —OCOO—, and at least one — (CH ₂ ) ₂ — may be replaced by —CH ＝ CH— or —C≡C—, in these groups: At least one hydrogen may be replaced by fluorine;
c, d and e are independently 0, 1, 2, 3 or 4; the sum of c, d and e is 1, 2, 3 or 4;
P ¹ , P ² , P ³ and P ⁴ are each independently a polymerizable group represented by the formula (1P-1);

In the equation (1P-1),
M ⁴¹ and M ⁴² are independently hydrogen, fluorine, alkyl having 1 to 5 carbons, or alkyl having 1 to 5 carbons in which at least one hydrogen is replaced by fluorine;
R ⁴¹ is alkyl having 1 to 10 carbons, alkoxy having 1 to 9 carbons, or alkoxyalkyl having 1 to 9 carbons. In these groups, at least one — (CH ₂ ) ₂ — is represented by — CH ＝ CH— or —C≡C—, in which at least one hydrogen may be replaced by fluorine, but at least one of P ¹ , P ² , P ³ and P ⁴ The horizontal alignment type liquid crystal display device according to claim 1, wherein in one formula (1P-1), R ⁴¹ is alkoxyalkyl having 1 to 9 carbon atoms.   The ratio of the total amount of the weight of the unit derived from the first additive in the polymer obtained by polymerizing the first additive in the alignment control layer and the weight of the first additive in the liquid crystal layer 3. The horizontal alignment type liquid crystal display device according to claim 1, wherein, when the total amount of the liquid crystal compound is 100 parts by weight, the range is 0.01 to 10 parts by weight. The horizontal liquid crystal display according to claim 1, wherein the liquid crystal composition contains at least one liquid crystal compound selected from the group of compounds represented by Formulas (2) to (4). Alignment type liquid crystal display device.

In equations (2) to (4),
R ¹¹ and R ¹² are each independently an alkyl having 1 to 10 carbons or an alkenyl having 2 to 10 carbons. In the alkyl and alkenyl, at least one —CH ₂ — is —O—, —COO -Or -OCO- and at least one hydrogen may be replaced by fluorine;
Ring B ¹ , ring B ² , ring B ³ and ring B ⁴ are each independently 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, 2,5-difluoro- 1,4-phenylene or pyrimidine-2,5-diyl;
Z ¹¹ , Z ¹² and Z ¹³ are each independently a single bond, — (CH ₂ ) ₂ —, —CH ＝ CH—, —C≡C—, or —COO—. 5. The liquid crystal composition according to claim 1, wherein the liquid crystal composition further contains at least one liquid crystal compound selected from the group of compounds represented by Formulas (5) to (7). 6. Horizontal alignment type liquid crystal display device.

In equations (5) to (7),
R ¹³ is alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons. In the alkyl and alkenyl, at least one —CH ₂ — may be replaced by —O—, and at least one Hydrogen may be replaced by fluorine;
X ¹¹ is fluorine, _{chlorine, -OCF 3, -OCHF 2, -CF} 3, -CHF 2, be -CH ₂ F, -OCF 2 CHF 2 or -OCF ₂ CHFCF _3;
Ring C ¹ , ring C ² and ring C ³ are independently 1,4-cyclohexylene, 1,4-phenylene wherein at least one hydrogen may be replaced by fluorine, tetrahydropyran-2,5-diyl , 1,3-dioxane-2,5-diyl, or pyrimidine-2,5-diyl;
Z ¹⁴ , Z ¹⁵ and Z ¹⁶ are each independently a single bond,-(CH ₂ ) _2- , -CH = CH-, -CH = CF-, -CF = CF-, -C≡C-,- COO—, —CF ₂ O—, —OCF ₂ —, —CH ₂ O—, —CH ＝ CF—CF ₂ O—, —CFＣＦCF—CF ₂ O— or — (CH ₂ ) ₄ —;
L ¹¹ and L ¹² are independently hydrogen or fluorine. The horizontal liquid crystal display according to any one of claims 1 to 5, wherein the liquid crystal composition further contains at least one liquid crystal compound selected from the group of compounds represented by formula (8). element.

In equation (8),
R ¹⁴ is alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons. In the alkyl and alkenyl, at least one —CH ₂ — may be replaced by —O—, and at least one Hydrogen may be replaced by fluorine;
X ¹² is an -C≡N or -C≡C-C≡N;
Ring D ¹ is independently 1,4-cyclohexylene, 1,4-phenylene in which at least one hydrogen may be replaced by fluorine, tetrahydropyran-2,5-diyl, 1,3-dioxane-2 , 5-diyl, or pyrimidine-2,5-diyl;
Z ¹⁷ are each independently a single _{bond, - (CH 2) 2 -} , - C≡C -, - COO -, - CF 2 O -, - OCF 2 - or _-CH 2 O-;
L ¹³ and L ¹⁴ are independently hydrogen or fluorine;
i is 1, 2, 3 or 4. The liquid crystal composition according to any one of claims 1 to 6, wherein the liquid crystal composition further contains at least one liquid crystal compound selected from the group of compounds represented by Formulas (9) to (21). Horizontal alignment type liquid crystal display device.

In equations (9) to (21),
R ¹⁵ and R ¹⁶ are independently alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, wherein at least one —CH ₂ — is replaced with —O— in the alkyl and alkenyl. And at least one hydrogen may be replaced by fluorine;
R ¹⁷ is hydrogen, fluorine, alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons. In the alkyl and alkenyl, at least one —CH ₂ — may be replaced by —O—. Well, at least one hydrogen may be replaced by fluorine;
Ring E ¹ , ring E ² , ring E ³ and ring E ⁴ are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, wherein at least one hydrogen may be replaced by fluorine, 4-phenylene, tetrahydropyran-2,5-diyl or decahydronaphthalene-2,6-diyl;
Ring E ⁵ and ring E ⁶ are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, tetrahydropyran-2,5-diyl or decahydronaphthalene-2,6 -Diyl;
^{Z 18, Z 19, Z 20} , and ^{Z 21} are each independently a single _{bond, - (CH 2) 2 -} , - COO -, - CH 2 O -, - OCF 2 -, or -OCF ₂ CH ₂ CH ₂ —;
L ¹⁵ and L ¹⁶ are independently fluorine or chlorine;
S ¹¹ is hydrogen or methyl;
X is independently, -CHF- or -CF ₂ - and is;
j, k, m, n, p, q, r, and s are each independently 0 or 1, and the sum of k, m, n, and p is 0, 1, 2, or 3, and q, The sum of r and s is 0, 1, 2 or 3, and t is 1, 2 or 3.   The liquid crystal composition further contains, as a second additive, a polymerizable compound different from the first additive, and the alignment control layer is obtained by polymerizing the first additive and the second additive. The horizontal alignment type liquid crystal display device according to any one of claims 1 to 7, comprising a polymer. The horizontal alignment type liquid crystal display device according to claim 8, wherein the second additive is represented by a formula (16α).

In the equation (16α),
Ring F and Ring I are independently cyclohexyl, cyclohexenyl, phenyl, 1-naphthyl, 2-naphthyl, tetrahydropyran-2-yl, tetrahydropyran-3-yl, 1,3-dioxan-2-yl, 1,3-dioxan-3-yl, pyrimidin-2-yl, pyridin-2-yl, pyrimidin-5-yl, fluoren-2-yl, fluoren-7-yl, phenanthren-2-yl, phenanthrene-7- Yl, anthracen-2-yl, anthracen-6-yl, perhydrocyclopenta [a] phenanthren-3-yl, perhydrocyclopenta [a] phenanthren-17-yl, 2,3,4,7,8, 9,10,11,12,13,14,15,16,17-tetradecahydrocyclopenta [a] phenanthrene-3-i Or 2,3,4,7,8,9,10,11,12,13,14,15,16,17-tetradecahydrocyclopenta [a] phenanthrene-17-yl, in these rings The at least one hydrogen may be replaced by fluorine, chlorine, alkyl having 1 to 12 carbons, or alkyl having 1 to 12 carbons in which at least one hydrogen is replaced by fluorine or chlorine;
Ring G is 1,4-cyclohexylene, 1,3-cyclohexylene, 1,2-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, 1,3-phenylene, 1, 2-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, fluorene-2,7-diyl, carbazole-2,7-diyl, phenanthrene-2,7-diyl, anthracene-2,6-diyl, anthracene-1,4 Diyl, perhydrocyclopenta [a] phenanthrene-3,17-diyl, pyrimidine-2,5-diyl or pyridine-2,5-diyl, in which at least one hydrogen is fluorine, chlorine, Alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, or alkyl having 1 to 12 carbons in which at least one hydrogen is replaced by fluorine or chlorine;
Z ²² and Z ²³ are each independently a single bond or alkylene having 1 to 10 carbons, wherein at least one —CH ₂ — is —O—, —COO—, —OCO— or — may be replaced by -OCOO-, at least one - _{(CH 2) 2} - is, -CH = CH -, - C≡C -, - C (CH 3) = CH -, - CH = C (CH 3 ) - or _{-C (CH 3) = C (} CH 3) - may be replaced by, in these groups, at least one hydrogen may be replaced by fluorine or chlorine;
P ¹¹ , P ¹² and P ¹³ are each independently a polymerizable group, but at least one of Z ²² and Z ²³ has —COO—, —OCO—, —CH ＝ CHCOO—, and —OCOCH = When CH—, —CH ＝ CH—, —CH ＝ CHCO—, or —COCH ＝ CH—, all of P ¹¹ , P ¹² and P ¹³ are not simultaneously represented by the formula (1P-1). ;

In the equation (1P-1),
M ⁴¹ and M ⁴² are independently hydrogen, fluorine, alkyl having 1 to 5 carbons, or alkyl having 1 to 5 carbons in which at least one hydrogen is replaced by fluorine or chlorine;
R ⁴¹ is alkyl having 1 to 10 carbons, alkoxy having 1 to 9 carbons, or alkoxyalkyl having 1 to 9 carbons. In these groups, at least one — (CH ₂ ) ₂ — is represented by — CH ＝ CH— or —C≡C—, in which at least one hydrogen may be replaced by fluorine or chlorine, but P ¹ , P ² , P ³ and P ⁴ In at least one formula (1P-1), R ⁴¹ is alkoxyalkyl having 1 to 9 carbons;
In the equation (16α),
Sp ¹¹ , Sp ¹² and Sp ¹³ are each independently a single bond or alkylene having 1 to 10 carbon atoms, wherein at least one —CH ₂ — is —O—, —COO—, —OCO - or it may be replaced by -OCOO-, at least one - _{(CH 2) 2} - may be replaced by -CH = CH- or -C≡C-, and in the groups, at least one Hydrogen may be replaced by fluorine or chlorine;
u is 0, 1 or 2;
f, g, and h are each independently 0, 1, 2, 3, or 4, and the sum of f, g, and h is 2 or more.   The weight of the unit derived from the second additive in the polymer obtained by polymerizing the first additive and the second additive in the alignment control layer, and the weight of the second additive in the liquid crystal layer 10. The horizontal alignment type liquid crystal display according to claim 8, wherein the ratio of the total amount of the liquid crystal compound is in the range of 0.03 parts by weight to 10 parts by weight when the total amount of the liquid crystal compound is 100 parts by weight. element. A method for manufacturing a horizontal alignment type liquid crystal display element for manufacturing the horizontal alignment type liquid crystal display element according to claim 1, wherein:
Sandwiching the liquid crystal composition between a pair of substrates,
The liquid crystal composition is maintained in a temperature range equal to or higher than a transition temperature T _NI from a nematic phase to an isotropic phase, and the liquid crystal composition is irradiated with polarized ultraviolet rays, and at least the first additive is polymerized, whereby the alignment is performed. A method for manufacturing a horizontal alignment type liquid crystal display device, comprising a step of forming a control layer. In the step of forming the alignment control layer, the liquid crystal composition is maintained in a temperature range of T _NI or higher and T _NI + 15 ° C. or lower, has a peak in a wavelength range of 300 nm to 400 nm, and has an illuminance of 2 mW / cm. The horizontal alignment type liquid crystal display device according to claim 11, wherein the irradiation is performed by irradiating polarized ultraviolet light in a range of ² to 300 mW / cm ² and an exposure amount of 0.03 J / cm ² to 20 J / cm ^2. Manufacturing method. The step of forming the alignment control layer is performed by irradiating the polarized ultraviolet light, and further adding additional non-polarized ultraviolet light, by keeping the liquid crystal composition in a temperature range of 20 ° C. or more and 45 ° C. or less, to a wavelength of 330 nm to 400 nm. The irradiation is performed by irradiating a light having a peak and an illuminance in a range of 1 mW / cm ² to 50 mW / cm ² and an exposure amount of 1 J / cm ² to 10 J / cm ^2. A method for manufacturing a horizontal alignment type liquid crystal display device. A liquid crystal composition used in the method for producing a horizontal alignment type liquid crystal display device according to claim 11, wherein:
The at least one liquid crystalline compound having a transition temperature T _NI from a nematic phase to an isotropic phase, and a monomer for forming an alignment control layer represented by the formula (1) according to claim 1 as a first additive. A liquid crystal composition comprising: at least one of:   A polymerizable compound used in the method for producing a horizontal alignment type liquid crystal display device according to claim 11, wherein the polymerizable compound is represented by the formula (1) according to claim 1.   Use of the polymerizable compound according to claim 15 as a monomer for forming an alignment control layer.   A display device, comprising: a horizontal alignment type liquid crystal display element according to claim 1; and a backlight.