TW201905564A - Method for manufacturing liquid crystal display element and display device - Google Patents

Abstract

Provided is a method whereby an alignment control layer effective for uniform horizontal alignment of liquid crystal molecules is formed when an alignment-control-layer-forming monomer added to a liquid crystal composition is polymerized. A liquid crystal display element having a first substrate, a plurality of pixel electrodes formed on the first substrate, a second substrate, a counter electrode formed on the second substrate and facing the pixel electrodes, and a liquid crystal layer sandwiched between the pixel electrodes and the counter electrode, wherein the alignment-control-layer-forming monomer included in the liquid crystal layer is irradiated in a first stage by ultraviolet rays having a specific wavelength and illuminance while being heated and the ultraviolet rays are polarized, and the alignment-control-layer-forming monomer is irradiated in a second stage by non-polarized ultraviolet rays having a specific wavelength and illuminance without being heated.

Description

Liquid crystal display element manufacturing method and display device

The invention relates to a method for manufacturing a horizontal alignment type liquid crystal display element. In particular, it relates to a method for manufacturing a liquid crystal display element using a liquid crystal composition containing an alignment control layer having an aromatic ester that generates photo Fries rearrangement by light irradiation It is a monomer, and the alignment of liquid crystal molecules can be achieved without using an alignment film such as polyimide by the action of the compound, and the dielectric anisotropy is positive or negative.

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

The liquid crystal display element contains a liquid crystal composition having a nematic phase. This composition has appropriate characteristics. By improving the characteristics of the composition, an AM device having good characteristics can be obtained. The correlation between the two characteristics is summarized in Table 1 below. The characteristics of the composition will be further described based on a commercially available AM device. 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 approximately 70 ° C or higher, and the preferred lower limit temperature of the nematic phase is approximately -10 ° C or lower. The viscosity of the composition is related to the response time of the device. In order to display a dynamic image with a component, it is preferable that the response time is short. The ideal response time is less than 1 millisecond. Therefore, it is preferable that the viscosity of the composition is small. More preferably, the viscosity is low at low temperatures.

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

In an AM element having a TN mode, a composition having positive dielectric anisotropy is used. In an AM element having a VA mode, a composition having negative dielectric anisotropy is used. In an AM element having an IPS mode or an FFS mode, a composition having positive or negative dielectric anisotropy is used. A polymer sustained alignment (PSA; polymer sustained alignment) type AM device uses a composition having positive or negative dielectric anisotropy. In a polymer sustained alignment (PSA) type liquid crystal display element, a liquid crystal composition containing a polymer is used. First, the composition to which a small amount of polymerizable compound is added is injected into the device. Next, while applying a voltage between the substrates of the element, the composition was irradiated with ultraviolet rays. The polymerizable compound is polymerized to form a polymer network structure in the composition. In this composition, a polymer can be used to control the alignment of liquid crystal molecules, so the response time of the element is shortened and the afterimage of the image is improved. Such an effect of a polymer can be expected in an element 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 substantially horizontal direction with respect to the main surface of the substrate when no voltage is applied. In order to achieve such alignment control of liquid crystal molecules, alignment films such as polyimide have been used. In recent years, the narrowing of the frame of liquid crystal panels has progressed, the width of the adhesion between the alignment film and the sealant has become narrower and the strength of the adhesion has been weakened, and there may be peeling from the interface between the alignment film and the sealant. In order to prevent such a problem, a method of not using an existing alignment film such as polyimide is proposed. (Patent Document 1 to Patent Document 4) On the other hand, in the VA mode, a PSA type liquid crystal display element in which an alignment film is not formed in advance has also been proposed. This technology does not use existing polyimide and other alignment films, so it is not easy to obtain a uniform vertical alignment. In order to solve such a problem, there has been proposed a method of performing ultraviolet exposure to the polymerizable compound contained in the liquid crystal composition multiple times by changing the intensity or wavelength. (Patent Literature 5 to Patent Literature 6) [Prior Art Literature] [Patent Literature]

[Patent Document 1] International Publication No. 2015/146369 [Patent Document 2] International Publication No. 2017/057162 [Patent Document 3] Japanese Patent Laid-Open No. 2015-64465 [Patent Document 4] Japanese Patent Laid-Open No. 2015-125151 Publication [Patent Document 5] Japanese Patent Laid-Open No. 2005-181582 [Patent Document 6] US Patent Publication 2010/053527

[Problem to be Solved by the Invention] The object of the present invention is to provide a liquid crystal composition containing a horizontal alignment control agent in the manufacture of a horizontal alignment type liquid crystal display element in which an alignment film such as polyimide is not formed in advance. The ultraviolet exposure step of the object further adds an ultraviolet irradiation step, thereby improving the uniformity of the horizontal alignment of the liquid crystal molecules. The following methods are reported: instead of an alignment film such as polyimide, a low-molecular compound having a cinnamate group or polyvinyl cinnamate, a low-molecular compound having a chalcone structure or a polymerizable compound, and a couple A low molecular compound or dendrimer with a nitrogen benzene structure controls the alignment of the liquid crystal (Patent Document 1 and Patent Document 2). In the methods of Patent Document 1 and Patent Document 2, first, the low-molecular compound, polymerizable compound, or polymer is dissolved as an additive in the liquid crystal composition. Next, a thin film containing the additive is formed on the substrate by phase-separating the additive. Finally, the substrate is irradiated with linear polarized light at a temperature higher than the upper limit temperature of the liquid crystal composition. When a low-molecular compound or polymer undergoes dimerization or isomerization by the linear polarized light, the molecules are arranged in a fixed direction. In this method, by selecting the type of additives, it is possible to manufacture a device in the horizontal alignment mode such as IPS or FFS and a device in the vertical alignment mode such as VA. In this method, it is important that the additive is easily dissolved at a temperature higher than the upper limit temperature of the liquid crystal composition, and when the temperature is returned to room temperature, the compound easily separates from the liquid crystal composition. Among them, it is difficult to ensure the compatibility of the additive and the liquid crystal composition. In the methods of Patent Document 3 and Patent Document 4, a dendrimer having azobenzene as a partial structure is dissolved as an additive in the liquid crystal composition. Next, a thin film of the compound is formed on the substrate by phase-separating the compound. At this time, the liquid crystal composition is vertically aligned with respect to the substrate. Next, linearly polarized light is irradiated without heating the substrate. When the dendrimer is dimerized or isomerized by the linear polarized light, its molecules are aligned in a horizontal direction with respect to the substrate. It can manufacture horizontal alignment mode components like IPS or FFS. In this method, it is also necessary to appropriately combine the dendrimer and the liquid crystal composition to facilitate the dissolution and phase separation of the dendrimer. In the case of using a dendrimer having azobenzene as a partial structure, there is a problem of coloration derived from azobenzene. Patent Document 5 discloses a method in which a liquid crystal display element including a liquid crystal composition having a non-liquid crystal polymerizable compound is exposed to ultraviolet rays three times at different polymerization rates. The liquid crystal alignment applied here is vertical alignment, and is related to the vertical alignment type liquid crystal display element, and there is no hint or description related to the application to the horizontal alignment type liquid crystal display element of the present application. Patent Document 6 discloses a method of exposing a liquid crystal display element including a liquid crystal composition having a plurality of polymerizable compounds having different ultraviolet absorption peak wavelengths to each other, and performing ultraviolet exposure in a second wavelength range different from each other. The liquid crystal alignment applied here is vertical alignment, and is related to the vertical alignment type liquid crystal display element, and there is no hint or description related to the application to the horizontal alignment type liquid crystal display element of the present application. [Means to solve the problem]

The present invention has found that the following liquid crystal composition is polymerized by exposure to ultraviolet light under specific conditions, thereby solving the above-mentioned problems, and completed the present invention. The liquid crystal composition contains light generated by ultraviolet irradiation. The alignment control layer of the Frisian rearranged aromatic ester forms a monomer and has positive or negative dielectric anisotropy. The present invention includes the following aspects and the like.

[1] A method for manufacturing a horizontal alignment type liquid crystal display element, wherein the horizontal alignment type liquid crystal display element sandwiches a liquid crystal layer between a pair of substrates arranged oppositely and bonded via a sealant, and the pair of substrates There is an alignment control layer for controlling alignment of liquid crystal molecules with the liquid crystal layer, the liquid crystal layer contains a liquid crystal composition; and in the method of manufacturing the horizontal alignment type liquid crystal display element, the liquid crystal composition contains liquid crystal The compound has a positive or negative dielectric anisotropy, has a transition temperature T _NI from a nematic phase to an isotropic phase, and contains at least one type of photo-Frisian rearrangement, photo isomerization, photo 2 The alignment control layer forming monomer of either polymerization or photolysis is used as the first additive; the liquid crystal layer is maintained at a temperature range above T _NI and the illuminance of the liquid crystal layer is 2 mW / cm ² to 200 mW / The range of cm ^{2 and} the range of exposure of 1 J / cm ² to 15 J / cm ² polarized light is irradiated to the first ultraviolet light having a peak at 280 nm to 340 nm; second, the liquid crystal layer is kept at room temperature (25 ℃) to T _NI temperature range, irradiated from 330 nm to 400 in the range of illuminance of 1 mW / cm ² to 200 mW / cm ² and exposure of 1 J / cm ² to 15 J / cm ² The second ultraviolet light having a peak in nm; the alignment control layer is formed by polymerizing the alignment control layer forming monomer.

[2] The method for manufacturing a horizontally-aligned liquid crystal display element according to [1], wherein the first additive according to [1] is an aromatic ester having photo-Frisian rearrangement by light irradiation The alignment control layer represented by formula (A) forms a monomer, In formula (A), P ¹⁰ and P ²⁰ independently represent a polymerizable group; Sp ¹⁰ and Sp ^{20 are} independently a single bond or an alkylene group having 1 to 12 carbon atoms, and at least one hydrogen of the alkylene group may be fluorinated Or hydroxy substituted, at least one -CH ₂ -may be substituted by -O-, -COO-, -OCO-, or formula (Q-1), at least one -CH ₂ -CH ₂ -may be substituted by -CH = CH- or -C≡C- substitution; in formula (Q-1), M ¹⁰ , M ²⁰ , and M ^{30 are} independently hydrogen, fluorine, alkyl having 1 to 5 carbons, or at least one hydrogen is substituted with fluorine or chlorine Alkyl group with carbon number 1 to 5; Sp ¹¹ is a single bond or an alkylene group with carbon number 1 to 12, at least one hydrogen of the alkyl group can be substituted by fluorine or hydroxyl, and at least one -CH ₂ -can be substituted by -O -, -COO-, or -OCO-, at least one -CH ₂ -CH ₂ -may be substituted by -CH = CH- or -C≡C-; Z ¹⁰ , Z ²⁰ and Z ^{30 are} independently single bonds, -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-, -CONH-, -NHCO-,-(CH ₂ ) _4- , -CH ₂ CH ₂ -or -CF ₂ CF _2- ; A ¹⁰ and A ^{30 are} independently 1,4-stretched Phenyl, 1,4-cyclohexyl, pyridine-2,5-diyl, pyrimidine-2,5-diyl, naphthalene-2,6-diyl, naphthalene-1,5-diyl, tetrahydronaphthalene -2,6-diyl, stilbene-2,7-diyl, biphenyl-4,4'-diyl or 1,3-dioxane-2,5-diyl, the 1,4-extended In phenyl, any hydrogen can be substituted by fluorine, chlorine, cyano, hydroxy, methyl acetyl, acetyloxy, acetyl, trifluoroethyl acetyl, difluoromethyl, trifluoromethyl, carbon number 1 Alkyl group up to 5, alkoxy group having 1 to 5 carbons, or P ¹⁰ -Sp ¹⁰ -Z ¹⁰ -substitution, in the stilbene-2,7-diyl group, any hydrogen can be substituted by fluorine, carbon 1 to 5 alkyl substitution, in the biphenyl-4,4'-diyl group, any hydrogen can be substituted by fluorine, difluoromethyl, trifluoromethyl, C 1-5 alkyl, or C 1 Alkoxy substitution to 5; A ²⁰ is 1,4-phenylene, pyridine-2,5-diyl, pyrimidine-2,5-diyl, represented by formula (A20-1), formula (A20- 2) Represented naphthalene-2,6-diyl, naphthalene-1,5-diyl, biphenylene-4,4'-diyl represented by formula (A20-3) or formula (A20-4) Represented 茀 -2,7-diyl, 1,4-Extenyl represented by formula (A20-1), Y ¹⁰ , Y ¹¹ , Y ¹² and Y ¹³ are independently hydrogen, fluorine, chlorine , Cyano, hydroxy, formyl, acetyloxy, acetyl, trifluoroacetyl, difluoromethyl, trifluoromethyl, carbon number An alkyl group of 1 to 5 or an alkoxy group of 1 to 5 carbons, at least one of Y ¹⁰ and Y ¹³ is hydrogen, and in naphthalene-2,6-diyl represented by formula (A20-2), Y ¹⁴ , Y ¹⁵ , Y ¹⁶ , Y ¹⁷ , Y ¹⁸ and Y ¹⁹ are independently hydrogen, fluorine, C 1-5 alkyl or C 1-5 alkoxy, Y ¹⁴ and Y ¹⁹ At least one of them is hydrogen. In the biphenyl-4,4'-diyl group represented by the formula (A20-3), Y ²⁰ , Y ²¹ , Y ²² , Y ²³ , Y ²⁴ , Y ²⁵ , Y ²⁶ and Y ²⁷ are independently hydrogen, fluorine, difluoromethyl, trifluoromethyl, C 1-5 alkyl, or C 1-5 alkoxy, at least one of Y ²⁰ and Y ²⁷ is hydrogen , of formula (A20-4) fluorenyl-2,7-diyl represented ^{by, Y 28, Y 29, Y} 30, Y 31, Y 32 and Y ³³ are each independently hydrogen, fluorine, carbon number 1 to 5 Alkyl group, at least one of Y ²⁸ and Y ³¹ is hydrogen; n ^{10 is} independently an integer from 0 to 3; during ultraviolet irradiation, the liquid crystal layer is maintained at a temperature range from T _NI or more to T _NI + 5 ° C or less, The first ultraviolet light having a peak value of 280 nm to 340 nm is irradiated with polarized light in the range of illuminance ranging from 2 mW / cm ² to 100 mW / cm ² and an exposure amount ranging from 1 J / cm ² to 13 J / cm ² ; Second, keep the liquid crystal layer at room temperature (25 ℃) to a temperature range less than T _NI , with an illuminance in the range of 1 mW / cm ² to 100 mW / cm ² and 1 J / cm ² to 14 J / The range of the exposure amount of cm ² is irradiated with the second ultraviolet ray having a peak value from 330 nm to 400 nm.

[3] The method for manufacturing a horizontal alignment type liquid crystal display element as described in [1], wherein the liquid crystal layer is maintained at T _NI or more to T _NI + 5 ° C under ultraviolet irradiation as described in [1] or [2] The following temperature range, with illuminance in the range of 2 mW / cm ² to 100 mW / cm ² and exposure range of 1 J / cm ² to 11 J / cm ² , polarized light irradiated at 280 nm to 340 nm has The first ultraviolet of the peak; secondly, the liquid crystal layer is maintained at a temperature range of room temperature (25 ° C) to 45 ° C or less, with an illuminance in the range of 1 mW / cm ² to 50 mW / cm ² and 1 J / cm The range of the exposure amount of ² to 14 J / cm ² is irradiated to the second ultraviolet ray having a peak in 330 nm to 400 nm.

[4] The method for manufacturing a horizontal alignment type liquid crystal display element according to [2], wherein in the formula (A) described in [2], P ¹⁰ and P ²⁰ independently represent acryloxy, methyl Acryloyloxy, α-fluoroacrylate, trifluoromethacrylate, vinyl, vinyloxy, epoxy; Sp ¹⁰ and Sp ^{20 are} independently single bonds or alkylene having 1 to 12 carbon atoms Group, at least one hydrogen of the alkylene group may be substituted by fluorine or hydroxyl, at least one -CH ₂ -may be substituted by -O-, -COO-, or -OCO-, at least one -CH ₂ -CH ₂ -may be substituted by -CH = CH- or -C≡C- substitution; Z ¹⁰ , Z ²⁰ and Z ^{30 are} independently single bonds, -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-, -CONH-, -NHCO-,-(CH ₂ ) _4- , -CH ₂ CH ₂ -or -CF ₂ CF _2- ; A ¹⁰ and A ^{30 are} independently 1,4-phenylene, 1,4-cyclohexyl, naphthalene-2,6-diyl, naphthalene- 1,5-diyl, stilbene-2,7-diyl, biphenyl-4,4'-diyl, in the 1,4-phenylene, any hydrogen can be through fluorine, cyano, hydroxyl, Acetyloxy, acetyl, trifluoroacetyl, difluoromethyl, trifluoromethyl, C 1-5 alkyl, C 1-5 alkoxy, or P ¹⁰ -Sp ¹⁰ -Z ¹⁰ -substitution, in the stilbene-2,7-diyl group, any hydrogen can be substituted by fluorine or an alkyl group having 1 to 5 carbon atoms, and in the biphenyl-4,4′-diyl group, any Hydrogen may be substituted by fluorine, difluoromethyl, trifluoromethyl, C 1-5 alkyl, or C 1-5 alkoxy; A ²⁰ is represented by formula (A20-1) 1, 4-phenylene, naphthalene-2,6-diyl represented by formula (A20-2), biphenyl-4,4'-diyl represented by formula (A20-3) or formula (A20-4 ) Represented by 茀 -2,7-diyl, 1,4-extenyl represented by formula (A20-1), Y ¹⁰ , Y ¹¹ , Y ¹² and Y ¹³ are independently hydrogen, fluorine , Chlorine, cyano, hydroxy, methyl acetyl, acetyl oxy, ethyl acetyl, trifluoroethyl acetyl, difluoromethyl, trifluoromethyl, C 1-5 alkyl, or C 1 Alkoxy substitution to 5, at least one of Y ¹⁰ and Y ¹³ is hydrogen, and naphthalene-2,6-diyl represented by formula (A20-2), Y ¹⁴ , Y ¹⁵ , Y ¹⁶ , Y ¹⁷ , Y ¹⁸ and Y ¹⁹ are each independently substituted with hydrogen, fluorine, C 1-5 alkyl group, or C 1-5 alkoxy group, at least one of Y ¹⁴ and Y ¹⁹ is hydrogen, formula ( A20-3) represented by biphenyl-4,4'-diyl, Y ²⁰ and Y ^{2 1} , Y ²² , Y ²³ , Y ²⁴ , Y ²⁵ , Y ²⁶ and Y ²⁷ are independently hydrogen, fluorine, difluoromethyl, trifluoromethyl, C 1-5 alkyl, or C Alkoxy substitution of 1 to 5, at least one of Y ²⁰ and Y ²⁷ is hydrogen, in the stilbene-2,7-diyl group represented by formula (A20-4), Y ²⁸ , Y ²⁹ , Y ³⁰ , Y ³¹ , Y ³² and Y ³³ are each independently hydrogen, fluorine, and an alkyl group having 1 to 5 carbon atoms, at least one of Y ²⁸ and Y ³¹ is hydrogen; n ^{10 is} independently an integer of 0 to 3.

[5] The method for manufacturing a horizontal alignment type liquid crystal display element according to any one of [1] to [4], wherein the alignment control layer forming monomer is from formula (A-1) to formula (A-3) ) Expressed by either; In formula (A-1) to formula (A-3), R ^{10 is} independently hydrogen, fluorine, methyl, or trifluoromethyl; R ^{31 is} independently hydrogen or methyl; Sp ¹⁰ and Sp ^{20 are} independently Is a single bond or an alkylene group having 1 to 12 carbon atoms, at least one hydrogen of the alkylene group may be substituted by fluorine or hydroxyl, and at least one -CH ₂ -may be substituted by -O-, -COO-, or -OCO- , At least one -CH ₂ -CH ₂ -may be substituted by -CH = CH- or -C≡C-; Z ¹⁰ , Z ²⁰ and Z ^{30 are} independently single bonds, -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-, -CONH- , -NHCO-,-(CH ₂ ) _4- , -CH ₂ CH ₂ -or -CF ₂ CF _2- ; A ^{20 is} independently 1,4-phenylene and formula represented by formula (A20-1) Biphenyl-4,4'-diyl represented by (A20-3) or stilbene-2,7-diyl represented by formula (A20-4), 1,4 represented by formula (A20-1) -In phenylene, Y ¹⁰ , Y ¹¹ , Y ¹² , and Y ¹³ are independently hydrogen, fluorine, hydroxyl, difluoromethyl, trifluoromethyl, C 1-5 alkyl, or carbon Alkoxy substitution of number 1 to 5, at least one of Y ¹⁰ and Y ¹³ is hydrogen, and in biphenyl-4,4′-diyl represented by formula (A20-3), Y ²⁰ , Y ²¹ , Y ²² , Y ²³ , Y ²⁴ , Y ²⁵ , Y ²⁶ and Y ²⁷ are independently hydrogen, fluorine, difluoromethyl, trifluoromethyl, C 1-5 alkyl, or C 1 to 5 alkoxy substitution, at least one of Y ²⁰ and Y ²⁷ is hydrogen, and in the stilbene-2,7-diyl group represented by formula (A20-4), Y ²⁸ , Y ²⁹ , Y ³⁰ , Y ³¹ , Y ³² and Y ³³ are independently hydrogen, fluorine, and a C 1-5 alkyl group, at least one of Y ²⁸ and Y ³¹ is hydrogen; A ^{30 is} independently 1,4-phenylene, naphthalene-2 , 6-diyl, naphthalene-1,5-diyl, stilbene-2,7-diyl, biphenyl-4,4'-diyl, any hydrogen in the 1,4-phenylene Substituted by fluorine, hydroxy, difluoromethyl, trifluoromethyl, C 1-5 alkyl, or C 1-5 alkoxy, any hydrogen in the stilbene-2,7-diyl It can be substituted with fluorine and alkyl groups with 1 to 5 carbon atoms. In the biphenyl-4,4'-diyl group, any hydrogen can be substituted with fluorine, difluoromethyl, trifluoromethyl, and carbon atoms with 1 to 5 Substituted by an alkyl group, or an alkoxy group having 1 to 5 carbon atoms; L ^{10 is} independently hydrogen, fluorine, difluoromethyl, trifluoromethyl, an alkyl group having 1 to 5 carbon atoms, and 1 to 5 carbon atoms Alkoxy or P ¹⁰ -Sp ¹⁰ -Z ^10- ; n ^{11 is} independently an integer from 0 to 4.

[6] The method for manufacturing a horizontal alignment type liquid crystal display element according to any one of [1] to [5], wherein the alignment control layer is formed when the total amount of liquid crystal compounds is 100 parts by weight The ratio of the monomer is in the range of 0.1 parts by weight to 10.0 parts by weight.

[7] The method for manufacturing a horizontal alignment type liquid crystal display element according to any one of [1] to [6], wherein the liquid crystal composition contains a compound selected from the group consisting of formula (2) to formula (4) At least one compound in the group of In formula (2) to formula (4), R ¹¹ and R ^{12 are} independently an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms, and at least one of the alkyl groups and alkenyl groups is -CH ₂ -May be substituted by -O-, at least one hydrogen may be substituted by fluorine; Ring B ¹ , Ring B ² , Ring B ³ and Ring B ^{4 are} independently 1,4-cyclohexyl, 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} independently single bonds ,-(CH ₂ ) _2- , -CH = CH-, -C≡C-, or -COO-.

[8] The method for manufacturing a horizontal alignment type liquid crystal display element according to any one of [1] to [7], wherein the liquid crystal composition further contains a formula selected from Formula (5) to Formula (7) At least one compound in the group of compounds; In formula (5) to formula (7), R ¹³ is an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms. Among the alkyl groups and alkenyl groups, at least one -CH ₂ -may be passed through -O -Substitution, at least one hydrogen may be substituted by fluorine; X ¹¹ is fluorine, chlorine, -OCF ₃ , -OCHF ₂ , -CF ₃ , -CHF ₂ , -CH ₂ F, -OCF ₂ CHF ₂ or -OCF ₂ CHFCF ₃ ; Ring C ¹ , Ring C ² and Ring C ^{3 are} independently 1,4-cyclohexyl, 1,4-phenylene, tetrahydropyran-2,5-diyl where at least one hydrogen can be substituted with fluorine , 1,3-dioxane-2,5-diyl, or pyrimidine-2,5-diyl; Z ¹⁴ , Z ¹⁵ and Z ^{16 are} independently single bonds,-(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-, -CF = CF-CF ₂ O- or-(CH ₂ ) _4- ; L ¹¹ and L ^{12 are} independently hydrogen or fluorine.

[9] The method for manufacturing a horizontal alignment type liquid crystal display element according to any one of [1] to [8], wherein the liquid crystal composition further contains a group selected from the group consisting of compounds represented by formula (8) At least one compound; In formula (8), R ¹⁴ is an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms. In the alkyl group and the alkenyl group, at least one -CH ₂ -may be substituted with -O-, and at least one Hydrogen can be substituted by fluorine; X ¹² is -C≡N or -C≡CC≡N; Ring D ¹ is 1,4-cyclohexyl, at least one hydrogen can be substituted by fluorine, 1,4-phenylene, tetra Hydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, or pyrimidine-2,5-diyl; Z ¹⁷ is 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.

[10] The method for manufacturing a horizontal alignment type liquid crystal display element according to any one of [1] to [9], wherein the liquid crystal composition further contains a formula selected from formula (9) to formula (15) At least one compound in the group of compounds; In formula (9) to formula (15), R ¹⁵ and R ^{16 are} independently an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms, and at least one -CH ₂ in the alkyl group and alkenyl group -May be substituted with -O-, at least one hydrogen may be substituted with fluorine; R ¹⁷ is hydrogen, fluorine, an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms. One -CH ₂ -may be substituted with -O- and at least one hydrogen may be substituted with fluorine; ring E ¹ , ring E ² , ring E ³ and ring E ^{4 are} independently 1,4-cyclohexyl, 1,4- Cyclohexenyl, 1,4-phenylene, tetrahydropyran-2,5-diyl, or decahydronaphthalene-2,6-diyl substituted with fluorine for at least one hydrogen; ring E ⁵ and Ring E ^{6 is} independently 1,4-cyclohexyl, 1,4-cyclohexenyl, 1,4-phenylene, tetrahydropyran-2,5-diyl, or decahydronaphthalene-2 , 6-diyl; Z ¹⁸ , Z ¹⁹ , Z ²⁰ and Z ^{21 are} 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- ; j, k, m, n, p, q , R and s are independently 0 or 1, the sum of k, m, n and p is 1 or 2, the sum of q, r and s is 0, 1, 2 or 3, and t is 1, 2 or 3.

[11] The method for manufacturing a horizontal alignment type liquid crystal display element according to any one of [1] to [10], wherein the liquid crystal composition further contains a polymerizable compound represented by formula (16α) as a second addition And form an alignment control layer containing a copolymer produced by polymerizing these compounds; In formula (16α), ring F and ring I are independently cyclohexyl, cyclohexenyl, phenyl, 1-naphthyl, 2-naphthyl, tetrahydropyran-2-yl, 1,3-dioxan Alkyl-2-yl, pyrimidin-2-yl, or pyrid-2-yl, in these rings, at least one hydrogen can be fluorine, chlorine, alkyl having 1 to 12 carbons, or at least one hydrogen can be fluorine or chlorine Substituted alkyl groups with 1 to 12 carbon atoms; Ring G is 1,4-cyclohexyl, 1,4-cyclohexenyl, 1,4-phenylene, naphthalene-1,2-diyl, Naphthalene-1,3-diyl, naphthalene-1,4-diyl, naphthalene-1,5-diyl, naphthalene-1,6-diyl, naphthalene-1,7-diyl, naphthalene-1,8 -Diyl, naphthalene-2,3-diyl, naphthalene-2,6-diyl, naphthalene-2,7-diyl, tetrahydropyran-2,5-diyl, 1,3-dioxane -2,5-diyl, pyrimidine-2,5-diyl, or pyridine-2,5-diyl, in these rings, at least one hydrogen can be through fluorine, chlorine, alkyl having 1 to 12 carbons, C 1-12 alkoxy, or at least one hydrogen substituted by fluorine or chlorine, C 1-12 alkyl; Z ²² and Z ^{23 are} independently a single bond or C 1-10 alkylene In the alkylene group, at least one -CH ₂ -may be substituted by -O-, -CO-, -COO-, or -OCO-, and at least one-(CH ₂ ) ₂ -may be substituted by -CH = CH-, -C (CH ₃ ) = CH-, -CH = C (CH ₃ )-, or -C (CH ₃ ) = C (CH ₃ )-, in these groups, at least one hydrogen can be substituted by fluorine or chlorine ; P ¹¹ , P ¹² and P ^{13 are} independently polymerizable groups; Sp ¹¹ , Sp ¹² and Sp ^{13 are} independently a single bond or an alkylene group having 1 to 10 carbon atoms, in which at least one of the alkyl groups is- CH ₂ -may be substituted by -O-, -COO-, -OCO-, or -OCOO-, at least one-(CH ₂ ) ₂ -may be substituted by -CH = CH- or -C≡C-, these radicals In at least one hydrogen may be substituted by fluorine or chlorine; u is 0, 1, or 2; f, g, and h are independently 0, 1, 2, 3, or 4, and the sum of f, g, and h is 2 or more.

[12] The method for manufacturing a horizontal alignment type liquid crystal display element according to [11], wherein in the formula (16α) described in [11], P ¹¹ , P ¹² , and P ^{13 are} independently selected from the formula ( P-1) to the group in the group of polymerizable groups represented by formula (P-5); In formula (P-1) to formula (P-5), M ¹¹ , M ¹² and M ^{13 are} independently hydrogen, fluorine, an alkyl group having 1 to 5 carbon atoms, or carbon in which at least one hydrogen is substituted with fluorine or chlorine Number 1 to 5 alkyl.

[13] The method for manufacturing a horizontal alignment type liquid crystal display element according to any one of [11] to [12], wherein when the total amount of the liquid crystal compound is 100 parts by weight, the first in the liquid crystal composition The ratio of the two additives is in the range of 0.03 parts by weight to 10 parts by weight.

[14] A display device including a horizontal alignment type liquid crystal display element obtained by the manufacturing method according to any one of [1] to [13]; and a backlight.

This illustration also includes the following items. (A) Further containing at least two additives such as a polymerizable compound, a polymerization initiator, a polymerization inhibitor, an optically active compound, an antioxidant, an ultraviolet absorber, a light stabilizer, a heat stabilizer, and an antifoaming agent The liquid crystal composition. (B) A polymerizable composition prepared by adding a polymerizable compound different from the compound (A) or the compound (16α) to the liquid crystal composition. (C) A polymerizable composition prepared by adding compound (A) and compound (16α) to the liquid crystal composition. (D) A liquid crystal composite prepared by polymerizing a polymerizable composition. (E) A polymer stabilized alignment type element containing the liquid crystal composite. (F) By adding compound (A) and compound (16α), and a polymerizable compound different from compound (A) or compound (16α) to the liquid crystal composition, a polymerizable composition is prepared by using A polymer-stabilized alignment element made of the prepared polymerizable composition. [Effect of invention]

According to the present invention, a horizontal alignment type liquid crystal display element excellent in transmittance characteristics or contrast ratio can be realized by subjecting liquid crystal display elements including a liquid crystal composition containing an alignment control layer forming monomer to mutually different conditions. Furthermore, the manufacturing process of the horizontal alignment type liquid crystal display element does not require an alignment film formation step, and the manufacturing cost of the liquid crystal display element can be reduced.

How to use the terms in this specification is as follows. Sometimes the terms "liquid crystal composition" and "liquid crystal display element" are simply referred to as "composition" and "element", respectively. "Liquid crystal display element" is a general term for liquid crystal display panel and liquid crystal display module. "Liquid crystal compound" is a compound having a nematic phase and a smectic phase equivalent liquid crystal phase, and a liquid crystal phase that does not have a liquid crystal phase but is mixed to the composition for the purpose of adjusting the temperature range, viscosity, dielectric anisotropy and other characteristics of the nematic phase Generic term for compounds in the compound. This compound has, for example, a six-membered ring such as 1,4-cyclohexyl or 1,4-phenylene, and its molecular structure is rod-like. The "polymerizable compound" is a compound added for the purpose of generating a polymer in the composition.

The liquid crystal composition is prepared by mixing multiple liquid crystal compounds. Additives such as optically active compounds, antioxidants, ultraviolet absorbers, dyes, defoamers, polymerizable compounds, polymerization initiators, polymerization inhibitors, and polar compounds are optionally added to the liquid crystal composition. Even when it is convenient to add an additive, the ratio of the liquid crystalline compound is also expressed as a weight percentage (weight%) based on the weight of the liquid crystal composition not containing the additive. The ratio of the additive is represented by a weight percentage (parts by weight) based on the weight of the liquid crystal composition not containing the 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. Sometimes parts per million by weight (ppm) are also used. The ratio of the polymerization initiator is exceptionally expressed based on the weight of the polymerizable compound.

The compound represented by formula (A) is sometimes simply referred to as "compound (A)". The compound (A) refers to a compound represented by formula (A), a mixture of two compounds, or a mixture of three or more compounds. This rule also applies to at least one compound selected from the group of compounds represented by formula (2) and the like. Symbols such as B ¹ , C ¹ , D ¹ , and E ¹ surrounded by hexagons correspond to ring B ¹ , ring C ¹ , ring F, etc., respectively. The hexagon represents a condensed ring such as a six-membered ring such as a cyclohexane ring or a benzene ring, or a naphthalene ring. In formula (A-1), formula (A-2), formula (A-3), and formula (16α), a straight line that traverses one side of the hexagon indicates that any hydrogen on the ring can pass through-(L ¹⁰ ) n ¹¹ -or -Sp ¹ -P ¹ and other groups substituted. Subscripts such as 'f' indicate the number of substituted groups. When the subscript is 0, there is no such substitution. When the subscript 'f' is 2 or more, there are multiple -Sp ¹ -P ¹ on the ring F. The plurality of bases represented by -Sp ¹ -P ¹ may be the same or different. These rules also apply to other formulas. In the expression "ring F and ring G are independently X, Y, or Z", since there are multiple subjects, "independently" is used. When the subject is "ring F", since the subject is singular, "independently" is not used.

The symbol of the terminal group R ¹¹ is used for various component compounds. In these compounds, the two groups represented by any two R ¹¹ may be the same or different. For example, compound R (2) ¹¹ is ethyl and R Compound (3) ¹¹ is ethyl. There are also cases where R ¹¹ of the compound (2) is ethyl and R ¹¹ of the compound (3) is propyl. The rule also applies to other end groups, rings, bonding groups, etc. In formula (8), when i is 2, there are two rings D ¹ . In this compound, the two groups represented by the two rings D ¹ may be the same or different. This rule also applies to any two rings D ¹ when i is greater than 2. This rule also applies to other ring, bond base, etc. signs.

The expression "at least one" A "" means that the number of "A" is arbitrary. The expression "at least one 'A' can be replaced by 'B'" means that when the number of 'A' is one, it means that the position of 'A' is arbitrary, and when the number of 'A' is more than two, those The location can also be selected unlimitedly. This rule also applies to the expression "at least one 'A' is replaced by 'B'". The expression "at least one A may be substituted by B, C, or D" means including at least one A substituted by B, at least one A substituted by C, and at least one A substituted by D, and then including multiple A In the case of substitution by at least two of B, C, and D. For example, at least one -CH _2- (or-(CH ₂ ) _2- ) alkyl group that may be substituted with -O- (or -CH = CH-) includes: alkyl, alkenyl, alkoxy, alkoxy Alkyl, alkoxyalkenyl, alkenyloxyalkyl. Furthermore, the situation where two consecutive -CH ₂ -is replaced by -O- to become -OO- is not good. -CH alkyl group, a methyl moiety (-CH ₂ -H) of ₂ - substituted -O- -OH case also becomes poor.

In the liquid crystal compound, the alkyl group is linear or branched, and does not include a cyclic alkyl group. Straight chain alkyl groups are generally superior to branched alkyl groups. The same applies to terminal groups such as alkoxy groups and alkenyl groups. In order to increase the upper limit temperature of the nematic phase, the stereo configuration related to 1,4-cyclohexyl is trans is better than cis. 2-Fluoro-1,4-phenylene refers to the following two divalent groups. In the chemical formula, fluorine can be left (L) or right (R). This rule also applies to asymmetric divalent groups such as tetrahydropyran-2,5-diyl that are generated by removing two hydrogens from the ring.

In the method for manufacturing a horizontally-aligned liquid crystal display element of the present invention, any one of photo-Frisian rearrangement, photo-isomerization, photo-dimerization, photo-decomposition generated by light irradiation is added to the liquid crystal composition enclosed in the device The alignment control layer of the former forms a single liquid crystal composition. The alignment control layer forming monomer changes its structure in a directional manner by irradiation with polarized light, and thus contributes to the alignment control of liquid crystal molecules. In addition, since it has a polymerizable group, the polymer containing the alignment control layer forming monomer has a role as an alignment control film. The compound having an aromatic ester that generates photo-Frisian rearrangement will be described. The compound having an aromatic ester that generates photo-Frisian rearrangement refers to a compound that absorbs ultraviolet light and the aromatic ester site undergoes free radical cleavage and generates rearrangement to hydroxyketone. In the present invention, it is formula (A) and formula ( A-1) to the compound represented by formula (A-3). The compound represented by formula (A-1), formula (A-2) and formula (A-3) is preferred, and the compound represented by formula (A-1) is more preferred. The compound having an aromatic ester and a polymerizable group is irradiated with ultraviolet light to photodecompose the aromatic ester site, thereby forming free radicals and generating photo-Frisian rearrangement. In the optical Fries rearrangement, the light of the aromatic ester portion is decomposed when polarized ultraviolet light has a polarization direction that is the same as the long axis direction of the aromatic ester portion. After photolysis, re-bonding is performed and hydroxyl groups are generated in the molecule by tautomerization. It is considered that the hydroxyl group causes interaction at the substrate interface, and the alignment control layer forming monomer has anisotropy on the substrate interface side and is easily adsorbed. In addition, since it has a polymerizable group, it is fixed by polymerization. This property can be used to prepare thin films capable of aligning liquid crystal molecules. In order to prepare the thin film, the ultraviolet rays irradiated are suitably linearly polarized light. First, in the liquid crystal composition, the alignment control layer forming monomer is added in the range of 0.1 to 10 parts by weight when the total amount of the liquid crystal compound is 100 parts by weight, and in order to dissolve the alignment control layer forming monomer The composition is heated. This composition was injected into an element having no alignment film. Next, linearly polarized light is irradiated while the element is heated, whereby the alignment control layer forming monomer undergoes photo-Frisian rearrangement and is polymerized. The alignment control layer forming monomers rearranged by the photo-Fris are aligned in a fixed direction, and the thin film formed after polymerization has a function as a liquid crystal alignment film.

The alignment control layer forming monomer is referred to as compound (A) in this specification. Furthermore, when referring to the details of the structure, etc., they are distinguished as compound (A-1), compound (A-2), and compound (A-3) as necessary. In the following, 1. Compound (A), 2. Synthesis of Compound (A), 3. Liquid crystal composition as a composition containing compound (A), 4. Liquid crystal display element as an element containing the composition are described in order .

1. Compound (A) 1-1. Example of Compound (A) and liquid crystal composition using the same

A compound represented by formula (A). In formula (A), formula (A-1) to formula (A-3), P ¹⁰ and P ^{20 are} independently polymerizable groups, preferably acryloyloxy, methacryloyloxy, α -Fluoroacrylate, trifluoromethacrylate, vinyl, vinyloxy, epoxy. Sp ¹⁰ and Sp ^{20 are} independently a single bond or an alkylene group having 1 to 12 carbon atoms, at least one hydrogen of which may be substituted by fluorine or hydroxyl, and at least one -CH ₂ -may be substituted by -O-, -COO -, -OCO-, or formula (Q-1), at least one -CH ₂ -CH ₂ -may be substituted by -CH = CH- or -C≡C-. In formula (Q-1), M ¹⁰ , M ²⁰ , and M ^{30 are} independently hydrogen, fluorine, an alkyl group having 1 to 5 carbon atoms, or an alkyl group having 1 to 5 carbon atoms in which at least one hydrogen is substituted with fluorine or chlorine Group, Sp ¹¹ is a single bond or an alkylene group having 1 to 12 carbon atoms, at least one hydrogen of the alkylene group may be substituted by fluorine or hydroxyl, and at least one -CH ₂ -may be substituted by -O-, -COO-, or -OCO- substitution, at least one -CH ₂ -CH ₂ -may be substituted by -CH = CH- or -C≡C-. Z ¹⁰ , Z ²⁰ and Z ^{30 are} 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-, -CONH-, -NHCO-,-(CH ₂ ) _4- , -CH ₂ CH ₂ -or -CF ₂ CF _2- , Preferably 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-, or -CH ₂ CH _2- . A ¹⁰ and A ^{30 are} independently 1,4-phenylene, 1,4-cyclohexyl, pyridine-2,5-diyl, pyrimidine-2,5-diyl, naphthalene-2,6-diyl , Naphthalene-1,5-diyl, tetrahydronaphthalene-2,6-diyl, stilbene-2,7-diyl, biphenyl-4,4'-diyl or 1,3-dioxane- 2,5-diyl, in the 1,4-phenylene group, any hydrogen can be selected from fluorine, chlorine, cyano, hydroxy, methyl acetyl, acetyloxy, ethyl acetyl, trifluoroethyl acetyl, Difluoromethyl, trifluoromethyl, C 1-5 alkyl, C 1-5 alkoxy, or P ¹⁰ -Sp ¹⁰ -Z ¹⁰ -substituted, the stilbene-2,7-diyl In hydrogen, any hydrogen can be substituted by fluorine or C1-C5 alkyl. In the biphenyl-4,4'-diyl group, any hydrogen can be substituted by fluorine, difluoromethyl, trifluoromethyl, C1-C5 alkyl or C1-C5 alkoxy substitution, preferably 1,4-phenylene, 1,4-cyclohexyl, naphthalene-2,6-diyl, naphthalene -1,5-diyl, stilbene-2,7-diyl, biphenyl-4,4'-diyl, in the 1,4-phenylene, any hydrogen can pass through fluorine, cyano, hydroxyl , Acetyloxy, acetyl, trifluoroacetyl, difluoromethyl, trifluoromethyl, C 1-5 alkyl, or C 1-5 alkoxy substitution, the stilbene- In 2,7-diyl group, any hydrogen can be substituted by fluorine and C 1-5 alkyl group. In this biphenyl-4,4'-diyl group, any hydrogen can be substituted by fluorine or difluoromethyl , Trifluoromethyl, C 1-5 alkyl, or C 1-5 alkoxy substitution. A ^{20 is} independently 1,4-phenylene, pyridine-2,5-diyl, pyrimidine-2,5-diyl represented by formula (A20-1), and naphthalene represented by formula (A20-2) -2,6-diyl, naphthalene-1,5-diyl, biphenyl-4,4'-diyl represented by formula (A20-3) or stilbene-2 represented by formula (A20-4) , 7-diyl, preferably 1,4-phenylene represented by formula (A20-1), naphthalene-2,6-diyl represented by formula (A20-2), formula (A20-3) Represented biphenyl-4,4'-diyl or stilbene-2,7-diyl represented by formula (A20-4) is more preferably 1,4-extended represented by formula (A20-1) Phenyl, biphenylene-4,4'-diyl represented by formula (A20-3) or stilbene-2,7-diyl represented by formula (A20-4). In the 1,4-phenylene group represented by the formula (A20-1), Y ¹⁰ , Y ¹¹ , Y ¹² and Y ¹³ are independently hydrogen, fluorine, chlorine, cyano, hydroxy, methylacetyl and acetyl Oxygen, acetyl, trifluoroethyl, difluoromethyl, trifluoromethyl, C 1-5 alkyl, or C 1-5 alkoxy, at least Y ¹⁰ and Y ¹³ One is hydrogen. Preferably, Y ¹⁰ , Y ¹¹ , Y ¹² and Y ¹³ are independently hydrogen, fluorine, chlorine, cyano, hydroxy, methyl acetyl, acetyloxy, acetyl, trifluoroethyl acetyl, difluoro Methyl group, trifluoromethyl group, C 1-5 alkyl group, or C 1-5 alkoxy group, at least one of Y ¹⁰ and Y ¹³ is hydrogen. More preferably, Y ¹⁰ , Y ¹¹ , Y ¹² and Y ¹³ are each independently hydrogen, fluorine, hydroxyl, difluoromethyl, trifluoromethyl, alkyl having 1 to 5 carbons, or carbon having 1 to 5 carbons. Alkoxy, at least one of Y ¹⁰ and Y ¹³ is hydrogen. In the naphthalene-2,6-diyl group represented by the formula (A20-2), Y ¹⁴ , Y ¹⁵ , Y ¹⁶ , Y ¹⁷ , Y ¹⁸ and Y ¹⁹ are independently hydrogen, fluorine, and carbon numbers 1 to 5. An alkyl group or an alkoxy group having 1 to 5 carbon atoms, at least one of Y ¹⁴ and Y ¹⁹ is hydrogen. In the biphenyl-4,4'-diyl group represented by the formula (A20-3), Y ²⁰ , Y ²¹ , Y ²² , Y ²³ , Y ²⁴ , Y ²⁵ , Y ²⁶ and Y ²⁷ are independently hydrogen , Fluorine, difluoromethyl, trifluoromethyl, C 1-5 alkyl, or C 1-5 alkoxy, at least one of Y ²⁰ and Y ²⁷ is hydrogen. In the stilbene-2,7-diyl group represented by the formula (A20-4), Y ²⁸ , Y ²⁹ , Y ³⁰ , Y ³¹ , Y ³² and Y ³³ are independently hydrogen, fluorine, and carbon numbers 1 to 5 Alkyl, at least one of Y ²⁸ and Y ³¹ is hydrogen. n ^{10 is} independently an integer from 0 to 3. In formula (A-1) to formula (A-3), R ¹⁰ is hydrogen, fluorine, or methyl, preferably hydrogen or methyl. R ³¹ is hydrogen or methyl, preferably hydrogen. L ^{10 is} independently hydrogen, fluorine, difluoromethyl, trifluoromethyl, C 1-5 alkyl, or C 1-5 alkoxy, preferably hydrogen, fluorine, trifluoromethyl , An alkyl group having 1 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms. n ^{11 is} independently an integer of 0 to 4, preferably an integer of 0 to 2, and more preferably 0 or 1.

1-2. Aspect of Compound (A) Compound (A) is characterized by having an aromatic ester site that generates photo-Frisian rearrangement, and a polymerizable group. When the compound (A) generates photo-Frisian rearrangement by irradiation with ultraviolet rays, the polar groups interact with the substrate surface in a non-covalent bonding manner, which is useful. One of the uses is an additive for liquid crystal compositions used in liquid crystal display elements. The compound (A) is added for the purpose of controlling the alignment of liquid crystal molecules. Such an additive preferably has a high solubility in the liquid crystal composition, is chemically stable under the condition of being sealed in the element, and has a large voltage retention rate when used in a liquid crystal display element. The compound (A) fully satisfies such characteristics to a large extent.

The preferred examples of the compound (A) will be described. Preferred alignment control layer forming monomers are compound (A-1-1) to compound (A-1-10), compound (A-2-1), compound (A-2-2) and compound as follows (A-3-1). In the following compounds, n and m are independently 2 to 6, and R ^{10 is} independently hydrogen, methyl, fluorine, or trifluoromethyl. Y ¹⁰ is hydrogen, fluorine, an alkyl group having 1 to 5 carbons, or an alkoxy group having 1 to 5 carbons. Y ²⁰ is hydrogen, fluorine, an alkyl group having 1 to 5 carbons, or an alkoxy group having 1 to 5 carbons.

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

2. Synthesis of Compound (A) The synthesis method of Compound (A) will be described. The compound (A) can be based on International Publication No. 1995/22586, Japanese Patent Laid-Open No. 2005-206579, International Publication No. 2006/049111, "Macromolecules" (26,1244-1247 (1993)), Japanese Patent Laid-Open No. 2003-238491, International Publication No. 2010/133278, Japanese Patent Laid-Open No. 2000-178233, Japanese Patent Laid-Open No. 2012-1623, Japanese Patent Laid-Open No. 2011-227187 Method to synthesize. The alignment control monomer having an α-fluoroacrylate group is synthesized according to the method described in Japanese Patent Laid-Open No. 2005-112850. The alignment control monomer having an α-trifluoromethacrylate group is synthesized according to the method described in Japanese Patent Laid-Open No. 2004-175728. The compound (A) having a diphenylacetylene structure is synthesized in accordance with International Publication No. 2001/053248. A compound that does not describe a synthesis method can be synthesized by appropriately combining known organic synthetic chemistry methods. See "Organic Syntheses" (John Wiley & Sons, Inc), "Organic Reactions" (John Wiley & Sons, Inc), "Comprehensive Organic Synthesis" (Pergamon Press), "New Experimental Chemistry Lecture" (Maruzen) and other books.

3. Liquid crystal composition The liquid crystal composition contains the compound (A) as an alignment control layer forming monomer. The compound (A) has at least an aromatic ester that generates photo-Frisian rearrangement by light irradiation. Examples of compound (A) are compound (A-1), compound (A-2), or compound (A-3). Compound (A) controls the alignment of liquid crystal molecules by having directional isomerization due to light Fries rearrangement by polarized light irradiation and non-covalent bonding with the device substrate . This composition contains the compound (A) as the component A, and further contains a liquid crystal compound selected from the component B, component C, component D, and component E shown below.

The preferable ratio of the compound (A) is about 0.1 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, in order to dissolve it in the liquid crystal composition Medium is about 7 parts by weight or less. A further preferred ratio is in the range of about 0.3 parts by weight to about 7 parts by weight. The optimal ratio is in the range of about 0.3 parts by weight to about 5 parts by weight. When compound (16α) is further added, the preferred ratio is in the range of about 0.3 parts by weight to about 7 parts by weight.

3-1. Component B to component E Component B as a liquid crystal compound is compound (2) to compound (4). Component C is compound (5) to compound (7). Component D is compound (8). Component E is compound (9) to compound (15). The composition may contain other liquid crystal compounds different from the compounds (2) to (15). In preparing the composition, it is preferable to select component B, component C, component D, and component E in consideration of the magnitude of positive or negative dielectric anisotropy and the like. The composition with the components properly selected has a high upper limit temperature, a low lower limit temperature, a small viscosity, an appropriate optical anisotropy (ie, a large optical anisotropy or a small optical anisotropy), a large positive or negative Dielectric anisotropy, large specific resistance, stability to heat or ultraviolet rays, and appropriate elastic constants (ie, large or small elastic constants).

Component B is a compound in which both terminal groups are alkyl or the like. Preferred examples of component B include compound (2-1) to compound (2-11), compound (3-1) to compound (3-19), and compound (4-1) to compound (4-7) . In the compound of component B, R ¹¹ and R ^{12 are} independently an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms. Among the alkyl group or alkenyl group, at least one -CH ₂ -may be passed through -O -Substitution, at least one hydrogen may be substituted by fluorine.

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

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

The component C, which is a liquid crystalline compound, is a compound having fluorine, chlorine, or a group containing fluorine at the right end. Preferred examples of component C include compound (5-1) to compound (5-16), compound (6-1) to compound (6-113), and compound (7-1) to compound (7-61). In the compound of component C, R ¹³ is an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms. In the alkyl group and alkenyl group, at least one -CH ₂ -may be substituted with -O-, and at least one Hydrogen may be substituted by fluorine; X ¹¹ is fluorine, chlorine, -OCF ₃ , -OCHF ₂ , -CF ₃ , -CHF ₂ , -CH ₂ F, -OCF ₂ CHF ₂ , or -OCF ₂ CHFCF ₃ .

The dielectric anisotropy of the component C is positive, and its stability to heat, light, etc. is very excellent. Therefore, it can be used for the preparation of a composition for modes such as IPS, FFS, and OCB. Based on the weight of the liquid crystal composition, the content of component C is suitably in the range of 1% by weight to 99% by weight, preferably in the range of 10% by weight to 97% by weight, and further preferably in the range of 40% by weight to 95% by weight. When component C is added to a composition with 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.

The component D, which is a liquid crystalline compound, is a compound (8) whose right end group is -C≡N or -C≡CC≡N. Preferred examples of component D include compound (8-1) to compound (8-64). In the compound of component D, R ¹⁴ is an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms. In this alkyl group and alkenyl group, at least one -CH ₂ -may be substituted with -O-, and at least one Hydrogen can be substituted by fluorine; -X ¹² is -C≡N or -C≡CC≡N.

The dielectric anisotropy of the component D is positive, and its value is large, so it can be mainly used for the preparation of a composition for TN and other modes. 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.

In the case of preparing a composition for TN and other modes, based on the weight of the liquid crystal composition, the content of component D is suitably in the range of 1% to 99% by weight, preferably in the range of 10% to 97% by weight, Furthermore, it is preferably in the range of 40% by weight to 95% by weight. When component D is added to a composition with 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.

The component E as a liquid crystal compound is compound (9) to compound (15). These compounds, like 2,3-difluoro-1,4-phenylene, have a phenylene substituted in the lateral position with two fluorine or chlorine. Preferred examples of component E include compound (9-1) to compound (9-8), compound (10-1) to compound (10-17), compound (11-1), compound (12-1) to Compound (12-3), Compound (13-1) to Compound (13-11), Compound (14-1) to Compound (14-3), and Compound (15-1) to Compound (15-3). In the compound of component E, R ¹⁵ and R ^{16 are} independently an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms. Among the alkyl groups and alkenyl groups, at least one -CH ₂ -may be passed through -O -Substitution, at least one hydrogen may be substituted by fluorine; R ¹⁷ is hydrogen, fluorine, an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms, and at least one -CH _2- May be substituted by -O-, at least one hydrogen may be substituted by fluorine.

The dielectric anisotropy of component E is negative and large. Component E can be used for the preparation of IPS, VA, PSA and other modes of the composition. As the content of component E is increased, the dielectric anisotropy of the composition becomes negative and becomes larger, but the viscosity becomes larger. Therefore, as long as the required value of the threshold voltage of the element is satisfied, the content is preferably small. Considering that the dielectric anisotropy is about -5, in order to perform sufficient voltage driving, the content is preferably 40% by weight or more.

In component E, compound (9) is a bicyclic compound, so it is mainly effective in reducing viscosity, adjusting optical anisotropy, or increasing dielectric anisotropy. Compound (10) and compound (11) are tricyclic compounds, and therefore have the effects of raising the maximum temperature, increasing optical anisotropy, or increasing dielectric anisotropy. Compounds (12) to (15) have an effect of increasing dielectric anisotropy.

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

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

3-2. Second additive The polymerizable compound (16α), which is the second additive that functions as a reactive monomer, may be added to this composition for the purpose of improving reactivity (polymerization).

In formula (16α), P ¹¹ , P ¹² , and P ^{13 are} independently polymerizable groups. Preferably, P ¹¹ , P ¹² or P ¹³ is a polymerizable group selected from the group represented by formula (P-1) to formula (P-5). More preferably, P ¹¹ , P ¹² or P ¹³ is a radical (P-1), radical (P-2) or radical (P-3). A particularly preferred group (P-1) is -OCO-CH = CH ₂ or -OCO-C (CH ₃ ) = CH ₂ . The wavy line from the base (P-1) to the base (P-5) indicates the part where bonding is performed.

In the groups (P-1) to (P-5), M ¹¹ , M ¹² , and M ^{13 are} independently hydrogen, fluorine, an alkyl group having 1 to 5 carbon atoms, or at least one hydrogen is substituted with fluorine or chlorine C1-C5 alkyl. In order to increase the reactivity, M ¹¹ , M ¹² or M ¹³ are preferably hydrogen or methyl. More preferably, M ¹¹ is methyl, and further preferably M ¹² or M ¹³ is hydrogen.

In formula (16α), Sp ¹¹ , Sp ¹² , and Sp ^{13 are} independently a single bond or an alkylene group having 1 to 10 carbon atoms. In the alkylene group, at least one -CH ₂ -may be passed through -O-,- COO-, -OCO-, or -OCOO-, at least one-(CH ₂ ) ₂ -may be substituted by -CH = CH- or -C≡C-, in these groups, at least one hydrogen may be substituted by fluorine or chlorine Replace. Preferably, Sp ¹¹ , Sp ¹² or Sp ¹³ are single bonds.

In formula (16α), ring F and ring I are independently cyclohexyl, cyclohexenyl, phenyl, 1-naphthyl, 2-naphthyl, tetrahydropyran-2-yl, 1,3-dioxan Alkan-2-yl, pyrimidin-2-yl or pyrid-2-yl, in these rings, at least one hydrogen can be through fluorine or chlorine, C 1-12 alkyl, C 1-12 alkoxy Or, at least one hydrogen is substituted with fluorine or chlorine and a C 1-12 alkyl group. Preferred ring F or ring I is phenyl. Ring G is 1,4-cyclohexyl, 1,4-cyclohexenyl, 1,4-phenylene, naphthalene-1,2-diyl, naphthalene-1,3-diyl, naphthalene-1 , 4-diyl, naphthalene-1,5-diyl, naphthalene-1,6-diyl, naphthalene-1,7-diyl, naphthalene-1,8-diyl, naphthalene-2,3-diyl , Naphthalene-2,6-diyl, naphthalene-2,7-diyl, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, pyrimidine-2, 5-diyl, or pyridine-2,5-diyl, in these rings, at least one hydrogen can be through fluorine, chlorine, C 1-12 alkyl, C 1-12 alkoxy, or at least One hydrogen is substituted with fluorine or chlorine and a C 1-12 alkyl group. Particularly preferred ring G is 1,4-phenylene or 2-fluoro-1,4-phenylene.

In formula (16α), Z ²² and Z ^{23 are} independently a single bond or an alkylene group having 1 to 10 carbon atoms. In this alkylene group, at least one -CH ₂ -may be substituted by -O-, -CO-,- COO- or -OCO- substitution, at least one-(CH ₂ ) ₂ -can be substituted by -CH = CH-, -C (CH ₃ ) = CH-, -CH = C (CH ₃ )-, or -C ( CH ₃ ) = C (CH ₃ ) -substitution, in these groups, at least one hydrogen may be substituted by fluorine or chlorine. Preferably Z ⁷ or Z ⁸ is a single bond,-(CH ₂ ) _2- , -CH ₂ O-, -OCH _2- , -COO-, or -OCO-. Further preferred Z ²² or Z ²³ is a single bond.

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

Preferred second additives are compounds represented by formula (16α-1) to formula (16α-27). In formula (16α-1) to formula (16α-27), P ¹¹ , P ¹² , and P ^{13 are} independently selected from the group of polymerizable groups represented by formula (P-1) to formula (P-3) Groups in the group, here, M ¹¹ , M ¹² , and M ^{13 are} independently hydrogen, fluorine, an alkyl group having 1 to 5 carbon atoms, or an alkyl group having 1 to 5 carbon atoms in which at least one hydrogen is substituted with fluorine or chlorine base; Sp ¹¹ , Sp ¹² , and Sp ^{13 are} independently a single bond or an alkylene group having 1 to 10 carbon atoms, in which at least one -CH ₂ -may be passed through -O-, -COO-, -OCO- , Or -OCOO- substitution, at least one-(CH ₂ ) ₂ -may be substituted by -CH = CH- or -C≡C-, in these groups, at least one hydrogen may be substituted by fluorine or chlorine.

The polymerizable compound such as the first additive or the second additive used in the liquid crystal composition of this case is added to the liquid crystal composition for the purpose of generating a polymer. The compound (A) can be used alone or in combination of two or more. A copolymer can also be formed from compound (A) and compound (16α). The compound (A) is immobilized in a state where the polar group interacts with the substrate surface in a non-covalent bonding manner. Thereby, while the ability of the liquid crystal molecules to align is further improved, the compound (A) is prevented from diffusing into the liquid crystal composition. Compound (A) forms a polymer by polymerization. Since the polymers are aligned, the liquid crystal molecules can be given an appropriate pretilt angle on the substrate surface. The polymer stabilizes the alignment of liquid crystal molecules, thus shortening the response time of the device and improving the afterimage of the image. Preferred examples of the compound (16α) are acrylate compounds, methacrylate compounds, vinyl compounds, vinyloxy compounds, propenyl ether compounds, epoxy compounds (oxirane, oxetane), And vinyl ketone compounds. Further preferred examples are compounds having at least one acryloyloxy group and compounds having at least one methacryloyloxy group. Further preferred examples also include compounds having both acryloyloxy and methacryloyloxy.

3-3. Additives The liquid crystal composition is prepared by a well-known method. For example, the component compounds are mixed and dissolved by heating. Additives may be added to this composition depending on the application. Examples of additives are polymerization initiators, polymerization inhibitors, optically active compounds, antioxidants, ultraviolet absorbers, light stabilizers, heat stabilizers, defoamers, and the like. Such additives are well known to those skilled in the art and are described in the literature.

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

Additional examples of photo-radical polymerization initiators are: 4-methoxyphenyl-2,4-bis (trichloromethyl) triazine, 2- (4-butoxystyryl) -5-tris Chloromethyl-1,3,4-oxadiazole, 9-phenylacridine, 9,10-benzophenazine (9,10-benzophenazine), benzophenone / michler's ketone) mixture, hexaarylbiimidazole / mercaptobenzimidazole mixture, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropane-1-one, benzoyl dimethyl ketal , 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinylpropane-1-one, 2,4-diethylxanthone / p-dimethylaminobenzene Methyl formate mixture, benzophenone / methyltriethanolamine mixture.

The polymerization can be carried out by adding a photo-radical polymerization initiator to the liquid crystal composition and then irradiating ultraviolet rays. However, unreacted polymerization initiators or decomposition products of polymerization initiators may cause display defects such as afterimages of images in the device. To prevent this, the photopolymerization may be carried out without adding a polymerization initiator. The preferred wavelength of the irradiated light will be described later.

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 the polymerization inhibitor are hydroquinone derivatives such as hydroquinone, methylhydroquinone, 4-tributylbutylcatechol, 4-methoxyphenol, phenothiazine, and the like.

The optically active compound has an effect of preventing reverse twisting by giving a liquid crystal molecule a spiral structure to give a desired twist angle. The helical pitch can be adjusted by adding optically active compounds. For the purpose of adjusting the temperature dependence of the spiral pitch, two or more optically active compounds may be added. Preferred examples of the optically active compound include the following compound (Op-1) to compound (Op-18). In the compound (Op-18), ring J is 1,4-cyclohexyl or 1,4-phenylene, and R ²⁸ is an alkyl group having 1 to 10 carbon atoms.

Antioxidants are effective for maintaining a large voltage retention rate. Preferred examples of antioxidants include the following compounds (AO-1) and compounds (AO-2); IRGANOX 415, IRGANOX 565, IRGANOX 1010, IRGANOX 1035, IRGANOX 3114, and IRGANOX 1098 ( Trade name: BASF (BASF) company). The ultraviolet absorber is effective for preventing the lowering of the upper limit temperature. Preferred examples of ultraviolet absorbers are benzophenone derivatives, benzoate derivatives, triazole derivatives and the like. Specific examples include the following compounds (AO-3) and compounds (AO-4); Dinubin (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 (1,4-diazabicyclo [2.2.2] octane, DABCO).

In order to maintain a large voltage retention rate, a light stabilizer such as an amine having steric hindrance is preferred. Preferred examples of the light stabilizer include the following compound (AO-5) and compound (AO-6); TINUVIN 144, TINUVIN 765, and TINUVIN 770DF (trade name: BASF). The heat stabilizer is also effective for maintaining a large voltage retention rate, and a preferred example may include IRGAFOS 168 (trade name: BASF). Defoamers are effective for preventing foaming. Preferred examples of antifoaming agents are dimethyl silicone oil, methyl phenyl silicone oil and the like.

In the compound (AO-1), R ⁴⁰ is a C 1-20 alkyl group, a C 1-20 alkoxy group, -COOR ⁴¹ , or -CH ₂ CH ₂ COOR ⁴¹ , where R ⁴¹ is a carbon Number 1 to 20 alkyl. In compound (AO-2) and compound (AO-5), R ⁴² is an alkyl group having 1 to 20 carbon atoms. In compound (AO-5), R ⁴³ is hydrogen, methyl or O ^･ (oxygen radical), ring K is 1,4-cyclohexyl or 1,4-phenylene, and z is 1, 2, or 3.

4. Liquid crystal display element The liquid crystal composition can be used in a liquid crystal display element having PC, TN, STN, OCB, PSA and other operating modes and driven in an active matrix manner. The composition can also be used in a liquid crystal display device that has operating modes such as PC, TN, STN, OCB, VA, and IPS and is driven by a passive matrix method. These elements can also be applied to any type of reflective type, transmissive type, and semi-transmissive type.

The composition can also be used for nematic curvilinear aligned phase (NCAP) devices made by microencapsulating nematic liquid crystals, and polymer dispersion types made by forming three-dimensional network polymers in liquid crystals Liquid crystal display element (Polymer Dispersed Liquid Crystal Display, PDLCD), and polymer network liquid crystal display element (Polymer Network Liquid Crystal Display, PNLCD). When the total amount of the liquid crystal compound is 100 parts by weight, a PSA mode liquid crystal display element is produced when the addition amount of the polymerizable compound is about 10 parts by weight or less. The PSA mode device can be driven by driving methods such as active matrix and passive matrix. This type of device can also be applied to any type of reflection type, transmission type, and semi-transmission type. By increasing the amount of polymerizable compound added, a polymer dispersed mode element can also be produced.

The alignment film is a film for aligning liquid crystal molecules in a fixed direction. Polyimide films are usually used. In a liquid crystal display element that does not have such an alignment film, a composition containing the compound (A) as an alignment control layer-forming monomer is used. Compound (A) forms a polymer by polymerization. The polymer has the function of an alignment film, so it can be used instead of the alignment film. An example of a method of manufacturing such an element is shown below. An element having two substrates called an array substrate and a color filter substrate is prepared. The substrate does not have an alignment film. At least one of the substrates has an electrode layer. The liquid crystal compound is mixed to prepare a liquid crystal composition. Compound (A) is added to this composition. Add additives as needed. The composition is injected into the device. After heating the element above the transition temperature (T _NI ) from the nematic phase to the isotropic phase of the liquid crystal composition to change the liquid crystal composition to the isotropic phase state, the first stage of polarized ultraviolet irradiation is performed. The polarized light irradiated here is ultraviolet rays having a peak in the range of wavelength 280 nm to wavelength 340 nm. Next, the liquid crystal composition is not heated, and the second stage of light irradiation is performed at room temperature (25 ° C) to a temperature lower than the T _NI temperature. Here, unpolarized ultraviolet rays are preferred. A better unpolarized ultraviolet ray may also have a peak in the wavelength range of 330 nm to 400 nm. The polymerizable compound is reacted by ultraviolet irradiation. Through this two-stage reaction, an alignment control layer that causes liquid crystal molecules to induce uniform horizontal alignment is generated, and a target device is fabricated.

In this sequence, if the liquid crystal layer is maintained at a temperature range above the transition temperature (T _NI ) of each homogeneous phase of the liquid crystal composition and used in the first stage with a peak in the wavelength range of 280 nm to 340 nm When polarized ultraviolet light is irradiated, the aromatic ester portion of the compound (A) undergoes photolysis to form free radicals and undergoes photo-Frisian rearrangement. In the optical Fries rearrangement, the light in the aromatic ester portion is decomposed by polarized ultraviolet rays when the polarization direction is the same as the long axis direction of the aromatic ester portion. After photolysis, re-bonding is performed and hydroxyl groups are generated in the molecule by tautomerization. It is considered that the hydroxyl group causes interaction at the substrate interface, and the alignment control layer forming monomer has anisotropy on the substrate interface side and is easily adsorbed. In addition, since it has a polymerizable group, it is fixed by polymerization. The polymer is an alignment control layer that aligns liquid crystal molecules uniformly. Secondly, if the liquid crystal layer is kept at a room temperature (25 ° C) to a temperature range smaller than T _NI and irradiated in a non-polarized state to the second ultraviolet rays having a peak at a wavelength of 330 nm to a wavelength of 400 nm, the alignment control layer remains The monomeric aromatic esters undergo photofries rearrangement, or unreacted alignment control layer forming monomers polymerize along the alignment control layer. The photo-Fris rearrangement here is generated inside the polymer oriented by the first ultraviolet rays, and therefore it is considered that the rearrangement reaction tends to proceed in the direction in which the anisotropy of the alignment control layer increases. It is considered that the additional polymerization of the unreacted alignment control layer forming monomer also contributes to impart anisotropy to the alignment control layer. Such an increase in the anisotropy of the alignment control layer means that the alignment restricting force acting on the liquid crystal molecules becomes larger. By the effect of such a polymer, the alignment of the liquid crystal molecules is additionally stabilized, so the contrast of the device is improved. Response time is shortened. The afterimage of the image is a malfunction of the liquid crystal molecules, so the afterimage is also improved by the effect of the polymer. Since the polymerization is carried out in such two stages, there are very few unreacted materials. Therefore, an element with a large voltage retention rate can be obtained.

The ultraviolet irradiation of the substrate will be described. In the present invention, ultraviolet rays are irradiated in at least two stages. The preferred illuminance of the first stage ultraviolet light is in the range of about 2 mW / cm ² to about 200 mW / cm ² , and the preferred exposure amount (illuminance (unit: mW / cm ² ) and irradiation time (unit: second) The product) is in the range of 1 J / cm ² to 15 J / cm ² . It is preferable that ultraviolet rays have a peak in the range of 280 nm to 340 nm, and have peaks near 313 nm and 335 nm. This ultraviolet light is sometimes called "first ultraviolet light". By this ultraviolet ray, most of the polymerizable compounds are polymerized. In the first ultraviolet ray, a further optimal illuminance is in the range of about 2 mW / cm ² to about 100 mW / cm ² , and a further optimal exposure amount is in the range of 1 J / cm ² to 13 J / cm ² . A better illuminance is in the range of about 2 mW / cm ² to about 100 mW / cm ² , and a better exposure is in the range of 1 J / cm ² to 11 J / cm ² .

The preferred ultraviolet illuminance in the second stage is in the range of about 1 mW / cm ² to about 200 mW / cm ² , and the preferred exposure amount is in the range of 1 J / cm ² to 15 J / cm ² . A better illuminance is in the range of about 1 mW / cm ² to about 100 mW / cm ² , and a better exposure is in the range of 1 J / cm ² to 14 J / cm ² . Further, the preferable illuminance is in the range of about 1 mW / cm ² to about 50 mW / cm ² , and the more preferable exposure amount is in the range of 1 J / cm ² to 14 J / cm ² . It is preferable that ultraviolet rays have a peak in the range of 330 nm to 400 nm, and have peaks in the vicinity of 335 nm and in the vicinity of 365 nm. Sometimes this ultraviolet is called "second ultraviolet". With this ultraviolet light, additional Frisian rearrangement can be generated. In addition, the unreacted alignment control layer forming monomer (A) may be converted into a polymer.

According to observation with a scanning electron microscope, the alignment control layer is a thin film containing small irregularities. A layer formed by polymerizing the polymerizable compound from the substrate surface was observed. The height of the cross section of the thin film is defined as the thickness of the alignment control layer. The film thickness is about 1 nm to about 100 nm on average, preferably about 5 nm to about 70 nm. When the film thickness is about 5 nm or more, the horizontal alignment characteristics can be maintained, which is preferable. When the film thickness is 100 nm or less, the driving voltage can be appropriately reduced, which is preferable.

In the horizontal alignment type device, when no voltage is applied, the liquid crystal molecules are aligned approximately horizontally with respect to the substrate surface. Generally, in order to horizontally align liquid crystal molecules, a horizontal alignment film such as polyimide is arranged between the color filter substrate and the liquid crystal layer or between the array substrate and the liquid crystal layer. On the other hand, in the horizontal alignment type device of the present invention, such an alignment film is not required on at least one substrate side. In this device, the liquid crystal molecules are aligned horizontally with respect to the substrate by the function of the alignment control layer. The angle (ie, pretilt angle) between the liquid crystal molecules and the substrate is 0 ° or more and 5 ° or less. It is preferably 0 ° or more and 3 ° or less. By combining such horizontal alignment with comb electrodes, a wide viewing angle can be achieved. [Example]

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

Unless otherwise stated, the reaction is carried out under a nitrogen atmosphere. The compound (A) is synthesized in the order shown in Synthesis Examples and the like. The synthesized compounds are identified using methods such as nuclear magnetic resonance (NMR) analysis. The characteristics are measured by the following method.

NMR analysis: DRX-500 manufactured by Bruker BioSpin was used for the measurement. ^In the measurement of ¹ H-NMR, the sample was dissolved in a deuterated solvent such as CDCl _3, and the measurement was carried out at room temperature under the conditions of 500 MHz and a cumulative number of 16 times. Use tetramethylsilane as an internal standard. ^In the measurement of ¹⁹ F-NMR, CFCl _{3 was} used as an internal standard, and the total number of times was 24. In the description of NMR spectroscopy, s refers to singlet, d refers to doublet, t refers to triplet, q refers to quartet, and quin refers to quintet For quintet, sex refers to sext, m refers to multiplet, and br refers to broad.

Gas chromatography analysis: A GC-2010 gas chromatograph manufactured by Shimadzu Corporation was used for the measurement. As the 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. As a carrier gas, helium gas (1 ml / min) was used. The temperature of the sample vaporization chamber is set to 300 ° C, and the temperature of the detector (flame ionization detector (FID)) is 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 gasification chamber. The recorder uses a gas chromatography solution system (GC Solution system) manufactured by Shimadzu Corporation.

High Performance Liquid Chromatography (HPLC) analysis: Prominence (LC-20AD; SPD-20A) manufactured by Shimadzu Corporation was used for the measurement. YMC-Pack ODS-A (length 150 mm, inner diameter 4.6 mm, particle size 5 μm) made by YMC was used for the column. The eluate is used by mixing acetonitrile and water appropriately. As the detector, an ultraviolet (Ultraviolet, UV) detector, a refractive index (Refractive Index, RI) detector, a corona (CORONA) detector, etc. are suitably used. When using a UV detector, set the detection wavelength to 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. As the recorder, C-R7Aplus manufactured by Shimadzu Corporation was used.

Ultraviolet-visible spectroscopic analysis: PharmaSpec UV-1700 manufactured by Shimadzu Corporation was used for the measurement. Set the detection wavelength to 190 nm to 700 nm. The sample was dissolved in acetonitrile to prepare a 0.01 mmol / L solution, and placed in a quartz cell (optical path length 1 cm) for measurement.

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

Measurement method: The characteristics are measured by the following method. Most of these methods are the methods described in the JEITA standard (JEITA · ED-2521B) reviewed or formulated by the Japan Electronics and Information Technology Industries Association (JEITA) or modified from them method. No thin-film transistor (TFT) was installed on the TN element used for measurement.

(1) Phase structure Place the sample on a heating plate (Mettler FP-52 high-temperature stage) equipped with a polarizing microscope melting point measuring device. While heating the sample at a rate of 3 ° C / min, the phase state and its change were observed with a polarizing microscope to determine the type of phase.

(2) Transition temperature (℃) Scanning calorimeter manufactured by PerkinElmer (Diamond) DSC system or high sensitivity differential scanning calorimeter manufactured by SSI Nanotechnology X-DSC7000. The temperature of the sample was raised and lowered at a rate of 3 ° C / minute, and the starting point of the endothermic peak or exothermic peak accompanying the phase change of the sample was determined by extrapolation to determine the transition temperature. The melting point of the compound and the polymerization initiation temperature were also measured using this device. Sometimes the temperature at which the compound transfers from a solid to a smectic phase and a nematic equal liquid crystal phase is simply referred to as "the lower limit temperature of the liquid crystal phase." Sometimes the temperature at which a compound transitions from a liquid crystal phase to a liquid is simply called "transparent point."

The crystal is expressed as C. When distinguishing the types of crystals, they are expressed as C ₁ and C ₂ , respectively. Denote the smectic phase as S and the nematic phase as N. In the smectic phase, when a smectic A phase, a smectic B phase, a smectic C phase, or a smectic F phase is distinguished, they are expressed as S _A , S _B , S _C , or S _{F, respectively} . Denote the liquid (isotropic) as I. The transition temperature is expressed as "C 50.0 N 100.0 I", for example. 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) The upper limit temperature of the nematic phase (T _NI or NI; ° C) The sample is placed on a hot plate equipped with a melting point measuring device of a polarizing microscope, and heated at a rate of 1 ° C / min. The temperature at which a part of the sample changes from a nematic phase to an isotropic liquid is measured. Sometimes the upper limit temperature of the nematic phase is simply referred to as the "upper limit temperature". When the sample is a mixture of a liquid crystalline compound and a mother liquid crystal, it is indicated by the symbol T _NI . When the sample is a mixture of a liquid crystalline compound and a compound such as component B, component C, and component D, the symbol NI is used.

(4) lower limit temperature (T _C; ℃) nematic phase A sample having a nematic phase at 0 ℃, -10 ℃, -20 ℃ , a freezer of -30 ℃ and -40 ℃ for 10 days To observe the liquid crystal phase. For example, when the sample is in the state of a nematic phase at -20 ° C and changes to a crystal or a smectic phase at -30 ° C, T _{C is} described as ≦ -20 ° C. Sometimes the lower limit temperature of the nematic phase is simply referred to as "lower limit temperature".

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

(6) Optical anisotropy (refractive index anisotropy; measured at 25 ° C; Δn) Measured using an abbe refractometer with a polarizing plate mounted on the eyepiece using light at a wavelength of 589 nm . After rubbing the surface of the main rod in one direction, drop the sample onto the main rod. The refractive index (n∥) is measured when the direction of polarized light is parallel to the direction of rubbing. The refractive index (n⊥) is measured when the direction of polarized light is perpendicular to the direction of rubbing. The value of optical anisotropy (Δn) is calculated according to the formula of Δn = n∥-n⊥.

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

For samples with positive dielectric anisotropy and negative samples, the method of measuring the characteristics may be different. The measurement method for the dielectric anisotropy timing is described in item (8a) to item (12a). The case where the dielectric anisotropy is negative is described in items (8b) to (12b).

(8a) Viscosity (rotational viscosity; γ1; measured at 25 ° C; mPa · s) positive dielectric anisotropy: according to M. Imai et al. “Molecular Crystals and Liquid Crystals) ”(Vol. 259, 37 (1995)). The sample was placed in a TN device with a twist angle of 0 degrees and a gap (cell gap) of two glass substrates of 5 μm. To this element, a voltage is applied stepwise in the range of 16 V to 19.5 V in units of 0.5 V. After no voltage was applied for 0.2 seconds, it was applied repeatedly under the condition that only one rectangular wave (rectangular pulse; 0.2 seconds) and no voltage (2 seconds) were applied. The peak current and peak time of the transient current generated by this application are measured. From these measured values and the calculation formula (8) on page 40 of the paper by M. Imai et al., The value of the rotational viscosity is obtained. The value of the dielectric anisotropy required for this calculation was obtained by the method described below using an element whose rotational viscosity was measured.

(8b) Viscosity (rotational viscosity; γ1; measured at 25 ° C; mPa · s) Negative dielectric anisotropy: According to M. Imai et al.'S "Molecular Crystals and Liquid Crystals (Molecular Crystals and Liquid Crystals) ”(Vol. 259, 37 (1995)). A sample was placed in a VA element with a distance (cell gap) of two glass substrates of 20 μm. To this element, a voltage is applied stepwise in a range of 39 volts to 50 volts in units of 1 volt. After no voltage was applied for 0.2 seconds, it was applied repeatedly under the condition that only one rectangular wave (rectangular pulse; 0.2 seconds) and no voltage (2 seconds) were applied. The peak current and peak time of the transient current generated by this application are measured. From these measured values and the calculation formula (8) on page 40 of the paper by M. Imai et al., The value of the rotational viscosity is obtained. The dielectric anisotropy required for this calculation uses the value measured in the following dielectric anisotropy term.

(9a) Dielectric anisotropy (Δε; measured at 25 ° C) Positive dielectric anisotropy: In a TN device with a gap (cell gap) of 9 μm and a twist angle of 80 degrees between two glass substrates Put the sample. A sine wave (10 V, 1 kHz) was applied to the device, and the dielectric constant (ε∥) in the long axis direction of the liquid crystal molecule was measured after 2 seconds. A sine wave (0.5 V, 1 kHz) was applied to the device, and the dielectric constant (ε⊥) in the short-axis direction of the liquid crystal molecules was measured after 2 seconds. The value of dielectric anisotropy is calculated according to the formula of Δε = ε∥-ε⊥.

(9b) Dielectric anisotropy (Δε; measured at 25 ° C) Negative dielectric anisotropy: The value of dielectric anisotropy is calculated according to the equation of Δε = ε∥-ε⊥. The dielectric constants (ε∥ and ε⊥) are measured as follows. 1) Determination of dielectric constant (ε∥): Coat octadecyltriethoxysilane (0.16 mL) in ethanol (20 mL) on a sufficiently 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 element with a distance (cell gap) of two glass substrates of 4 μm, and the element was sealed with an adhesive hardened by ultraviolet rays. A sine wave (0.5 V, 1 kHz) was applied to the device, and the dielectric constant (ε∥) in the long axis direction of the liquid crystal molecule was measured after 2 seconds. 2) Measurement of dielectric constant (ε⊥): Apply the polyimide solution on a glass substrate that has been sufficiently cleaned. After calcining the glass substrate, the obtained alignment film was subjected to rubbing treatment. A sample was placed in a TN device with a gap (cell gap) of 9 μm and a twist angle of 80 degrees between two glass substrates. A sine wave (0.5 V, 1 kHz) was applied to the device, and the dielectric constant (ε⊥) in the short-axis direction of the liquid crystal molecules was measured after 2 seconds.

(10a) Elastic constant (K; measured at 25 ° C; pN) Positive dielectric anisotropy: For measurement, an HPR 4284A LCR meter manufactured by Yokogawa Hewlett-Packard Co., Ltd. was used. A sample is placed in a horizontally aligned element with a gap (cell gap) of two glass substrates of 20 μm. A charge of 0 to 20 volts was applied to the device, and the electrostatic capacitance and applied voltage were measured. Using the formula (2.98) and formula (2.101) on page 75 of the “Liquid Crystal Device Manual” (Nikkei Industry News Corporation), fit the measured capacitance (C) to the value of the applied voltage (V) according to formula (2.99 ) To obtain the values of K ₁₁ and K ₃₃ . Next, in the formula (3.18) on page 171, K ₂₂ is calculated using the values of K ₁₁ and K ₃₃ that are obtained first. The elastic constant K is expressed as the average value of K ₁₁ , K ₂₂ and K ₃₃ obtained in this way.

(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 Dongyang Technology Co., Ltd. was used for the measurement. Place the sample in the vertical alignment element with a gap (cell gap) of 20 μm between the two glass substrates. A charge of 20 volts to 0 volts was applied to the device, and the electrostatic capacitance and applied voltage were measured. Using the formula (2.98) and formula (2.101) on page 75 of the "Liquid Crystal Device Manual" (Nikkei Industry News Corporation), the values of the electrostatic capacitance (C) and the applied voltage (V) are fitted and obtained according to formula (2.100) The value of the elastic constant.

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

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

(12a) Response time (τ; measured at 25 ° C; ms) Positive dielectric anisotropy: LCD5100 type luminance meter manufactured by Otsuka Electronics Co., Ltd. was used for the measurement. The light source is a halogen lamp. The low-pass filter is set to 5 kHz. A sample was placed in a normally white mode TN device with a gap (cell gap) of two glass substrates of 5.0 μm and a twist angle of 80 degrees. A rectangular wave (60 Hz, 5 V, 0.5 seconds) was applied to this element. At this time, the element is irradiated with light from the vertical direction, and the amount of light transmitted through the element is measured. When the light amount reaches the maximum, the transmittance is regarded as 100%, and when the light amount is the smallest, the transmittance is regarded as 0%. Rise time (τr: rise time; milliseconds) is the time required for the transmittance to change from 90% to 10%. Fall time (τf: fall time; milliseconds) is the time required for the transmittance to change from 10% to 90%. The response time is expressed by the sum of the rise time and fall time determined in the above manner.

(12b) Response time (τ; measured at 25 ° C; ms) Negative dielectric anisotropy: LCD5100 type luminance meter manufactured by Otsuka Electronics Co., Ltd. was used for measurement. The light source is a halogen lamp. The low-pass filter is set to 5 kHz. A sample was placed in a patterned vertical alignment (PVA) element with a normal black mode (3.2 mm gap between two glass substrates) and a rubbing direction of anti-parallel. The device was sealed with an adhesive hardened by ultraviolet rays. A voltage slightly exceeding the threshold voltage was applied to the device for 1 minute, followed by applying a voltage of 5.6 V while irradiating 23.5 mW / cm ² of ultraviolet light for 8 minutes. A rectangular wave (60 Hz, 10 V, 0.5 seconds) was applied to this element. At this time, the element is irradiated with light from the vertical direction, and the amount of light transmitted through the element is measured. When the light amount reaches the maximum, the transmittance is regarded as 100%, and when the light amount is the smallest, the transmittance is regarded as 0%. Response time is expressed by the time (fall time; millisecond) required for the transmission rate to change from 90% to 10%.

(13) Voltage retention rate The device obtained by polymerizing the polymerizable compound was charged with a pulse voltage (1 V and 60 microseconds) at 60 ° C. The decayed voltage was measured with a high-speed voltmeter in a period of 1.67 seconds, and the area A between the voltage curve and the horizontal axis in a unit cycle was obtained. Area B is the area without attenuation. The voltage retention rate is expressed by the percentage of area A relative to area B.

(14) Illumination For the measurement of ultraviolet illuminance, an ultraviolet illuminance meter manufactured by Ushio (USHIO) Electric Co., Ltd. and UIT-250 (sensors: UVD-S313 and UVD-S365) are used.

(15) Horizontal alignment The obtained element was set on a polarizing microscope, and the element was irradiated with light from below to observe the presence or absence of light leakage. When the liquid crystal molecules are sufficiently aligned and light does not pass through the device, it is determined that the horizontal alignment is "good". When the light passing through the device is observed, it is expressed as "there is an alignment defect".

(16) Pre-tilt angle (degree) Opti-Pro manufactured by Shintech Co., Ltd. was used to measure the pre-tilt angle.

(17) Film thickness The film thickness of the alignment control layer was measured using SEM (scanning electron microscope (SU-70 manufactured by Hitachi High-technologies) Co., Ltd.).

The first additive is selected from the compounds shown below.

The compounds in the composition are based on the definitions of 1) to 5) in Table 2 below, and are represented by symbols. In Table 2, the stereo configuration related to 1,4-cyclohexyl is trans. The number in parentheses after the symbol corresponds to the compound number. The symbol (-) refers to other liquid crystal compounds. The ratio (percentage) of the liquid crystal compound is a weight percentage (% by weight) based on the weight of the liquid crystal composition. Finally, the characteristic values of the liquid crystal composition are summarized. The characteristic is measured according to the method described previously, and the measured value (not extrapolated) is directly recorded.

Table 2 The expression method of the compound using the symbol R- (A ₁ ) -Z ₁ -... Z _n- (A _n ) -R '

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

[Composition (M2)] 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 ℃; Tc <-20 ℃; Δn = 0.108; Δε = 10.4; Vth = 1.35 V; η = 17.8 mPa · s; γ1 = 79.9 mPa · s.

[Composition (M3)] 2-HH-3 (2-1) 9% 3-HH-4 (2-1) 3% 3-HH-V (2-1) 15% 3-HH-V1 (2 -1) 6% 1V2-HH-3 (2-1) 3% V-HB (2F, 3F) -O2 (9-1) 7% V2-BB (2F, 3F) -O2 (9-3) 10 % V-HHB (2F, 3F) -O1 (10-1) 7% V-HHB (2F, 3F) -O2 (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 ℃; Tc ＜ -20 ℃; Δn = 0.100; Δε = -3.4; Vth = 2.25 V

[Example 1] To 100 parts by weight of the composition (M1), a compound (A-1-3-1) was added as an alignment control layer forming monomer at a ratio of 0.5 parts by weight. As an antioxidant, a compound (AO-1) having R ⁴⁰ as a heptyl group (C ₇ H _15- ) was added at a rate of 150 ppm. A liquid crystal element with a comb-shaped electrode (hereinafter referred to as, sometimes Known as IPS components or simply components). While maintaining the liquid crystal layer at 90 ° C, irradiate the device with 10 J / cm ² from the normal direction as the first ultraviolet rays with polarized ultraviolet rays having a peak at wavelength 313 nm, wavelength 335 nm, and wavelength 365 nm (at wavelength 313 nm The illuminance is 3 mW / cm ^2. UIT-150 and UVD-S313 manufactured by Ushio (USHIO) Motor Co., Ltd. are used for measurement). The ultraviolet irradiation lamp is USH-250BY manufactured by Niuwei (USHIO) Electric Co., Ltd. The exposure unit (unit) is ML-251A / B manufactured by Niuwei (USHIO) Motor Co., Ltd. Polarized ultraviolet rays are formed using a wire grid polarizer (ProFlux UVT260A manufactured by Polatechno Co., Ltd.). The IPS device was cooled to room temperature (25 ° C), and while maintaining the liquid crystal layer at room temperature (25 ° C), black light F40T10 manufactured by Eyegraphics Co., Ltd. as the second ultraviolet light was used Peak wavelengths 335 nm and 365 nm), irradiate the element 5.4 J / cm ² from the normal direction in a non-polarized state (no wire grid polarizer is used) (illuminance at a wavelength of 365 nm is 3 mW / cm ^2. Use oxtail (USHIO) UIT-150 and UVD-S365 manufactured by Electric Motor Co., Ltd.) are used to perform horizontal alignment of components. Next, the element formed with the alignment control layer was placed on a polarizing microscope and the alignment state of the liquid crystal was observed. The polarizer and the analyzer of the polarizing microscope are arranged so that their transmission axes are orthogonal to each other. First, install the device in such a way that the alignment direction of the liquid crystal molecules is parallel to the transmission axis of the polarizer of the polarizing microscope, that is, the angle between the alignment direction of the liquid crystal molecules and the transmission axis of the polarizer of the polarizing microscope is 0 degrees. Polarized microscope on a horizontal rotating table. Light is irradiated from the lower side of the element, that is, the polarizer side, and the presence or absence of light passing through the analyzer is observed. Since almost no light passing through the analyzer was observed, the alignment was determined to be "good". In addition, in the same observation, when the light transmitted through the analyzer is observed, the alignment is determined to be "defective". Next, the element is rotated on a horizontal rotating stage of the polarizing microscope, so that the angle formed by the transmission axis of the polarizer of the polarizing microscope and the alignment direction of the liquid crystal molecules changes from 0 degrees. It was confirmed that the intensity of the light transmitted through the analyzer increased as the angle formed by the polarization axis of the polarizing microscope and the alignment direction of the liquid crystal molecules became larger, and was approximately maximum when the angle was 45 degrees. From the above, in the device obtained, the liquid crystal molecules are aligned in a substantially horizontal direction with respect to the main surface of the substrate of the device, and it is determined as “horizontal alignment”. In order to evaluate the uniformity of horizontal alignment, a multimedia display tester made by Yokogawa Electric Co., Ltd. 3298 was used to obtain the angle between the alignment direction of the liquid crystal molecules and the transmission axis of the polarizer of the polarizing microscope at 0 degrees The ratio of the luminance at that time to the luminance at 45 degrees ((light transmission intensity in the light transmission state) / (light transmission intensity in the black state)) was about 1300, which was good. The alignment control layer on the element substrate was observed with a scanning electron microscope. As a result, the film thickness was about 8 nm, and most of the alignment control layer-forming monomer was consumed.

[Comparative Example 1] The IPS device without an alignment film was injected at a distance (cell gap) of 3.2 μm between the two glass substrates at 90 ° C (above the upper limit temperature of the nematic phase) by injecting the composition used in Example 1 in. While maintaining the liquid crystal layer at 90 ° C, irradiate the device with 10 J / cm ² from the normal direction as the first ultraviolet rays with polarized ultraviolet rays having a peak at a wavelength of 313 nm, a wavelength of 335 nm, and a wavelength of 365 nm (at a wavelength of 313 nm The illuminance is 3 mW / cm ² ), and only this is used to perform the horizontal alignment of the device. Next, the element on which the alignment control layer was formed was placed on a polarizing microscope, and the alignment state of the liquid crystal was observed in the same manner as in Example 1. Light is irradiated from the lower side of the element, that is, the polarizer side, and the presence or absence of light passing through the analyzer is observed. Since the light passing through the analyzer was slightly observed, the alignment was determined to be "slightly defective". Next, the element was rotated on a horizontal rotating stage of the polarizing microscope to change the angle between the transmission axis of the polarizing microscope's polarizer and the alignment direction of the liquid crystal molecules from 0 degrees. It is "horizontal alignment". In order to evaluate the uniformity of the horizontal alignment, the brightness at an angle of 0 degrees and the brightness at 45 degrees between the alignment direction of the liquid crystal molecules and the transmission axis of the polarizer of the polarizing microscope were obtained by the same method as in Example 1. The result is about 860, which is worse than Example 1. The alignment control layer on the element substrate was observed with a scanning electron microscope. As a result, the film thickness was about 8 nm, and most of the alignment control layer-forming monomer was consumed.

[Comparative Example 2] The IPS element without an alignment film was injected into the two glass substrates at a spacing (cell gap) of 3.2 μm at 90 ° C (above the upper limit temperature of the nematic phase) into the two glass substrates in. While maintaining the liquid crystal layer at 90 ° C, irradiate the device with 10 J / cm ² from the normal direction as the first ultraviolet rays with polarized ultraviolet rays having a peak at a wavelength of 313 nm, a wavelength of 335 nm, and a wavelength of 365 nm (at a wavelength of 313 nm The illuminance is 3 mW / cm ² ). Cool the IPS element to room temperature (25 ° C), and use the same light source as the first ultraviolet to irradiate the element with 5.4 J / cm ² non-polarized light from the normal direction (illuminance of 8 mW / cm ² at a wavelength of 313 nm ) While performing the second stage of exposure and performing the horizontal alignment process of the device. Next, the element on which the alignment control layer was formed was placed on a polarizing microscope, and the alignment state of the liquid crystal was observed in the same manner as in Example 1. Light is irradiated from the lower side of the element, that is, the polarizer side, and the presence or absence of light passing through the analyzer is observed. Since the light passing through the analyzer was slightly observed, the alignment was determined to be "slightly defective". Next, the element was rotated on a horizontal rotating stage of the polarizing microscope to change the angle between the transmission axis of the polarizing microscope's polarizer and the alignment direction of the liquid crystal molecules from 0 degrees. The result showed the same tendency as in Example 1. It is "horizontal alignment". In order to evaluate the uniformity of the horizontal alignment, the brightness at an angle of 0 degrees and the brightness at 45 degrees between the alignment direction of the liquid crystal molecules and the transmission axis of the polarizer of the polarizing microscope were obtained by the same method as in Example 1. The result is about 720, which is worse than Example 1. The alignment control layer on the element substrate was observed with a scanning electron microscope. As a result, the film thickness was about 8 nm, and most of the alignment control layer-forming monomer was consumed.

[Comparative Example 3] The composition used in Example 1 was injected into two glass substrates at an interval (cell gap) of 3.2 μm at 90 ° C (above the upper limit temperature of the nematic phase) and an IPS device without an alignment film in. While maintaining the liquid crystal layer at 90 ° C, irradiate the device with 10 J / cm ² from the normal direction as the first ultraviolet ray of unpolarized ultraviolet light having a peak at wavelength 313 nm, wavelength 335 nm, and wavelength 365 nm (wavelength 313 The illuminance at nm is 8 mW / cm ² ). While maintaining the liquid crystal layer at 90 ° C, use the same light source as the first ultraviolet to irradiate the device with 5.4 J / cm ² polarized light from the normal direction (illumination at a wavelength of 313 nm of 3 mW / cm ² ). At the stage of exposure, horizontal alignment of components is performed. Next, the element on which the alignment control layer was formed was placed on a polarizing microscope, and the alignment state of the liquid crystal was observed in the same manner as in Example 1. Light is irradiated from the lower side of the element, that is, the polarizer side, and the presence or absence of light passing through the analyzer is observed. Since the light passing through the analyzer was slightly observed, the alignment was determined to be "slightly defective". Next, the element was rotated on a horizontal rotating stage of the polarizing microscope to change the angle between the transmission axis of the polarizing microscope's polarizer and the alignment direction of the liquid crystal molecules from 0 degrees. It is "horizontal alignment". In order to evaluate the uniformity of the horizontal alignment, the brightness at an angle of 0 degrees and the brightness at 45 degrees between the alignment direction of the liquid crystal molecules and the transmission axis of the polarizer of the polarizing microscope were obtained by the same method as in Example 1. The result is about 800, which is worse than Example 1. The alignment control layer on the element substrate was observed with a scanning electron microscope. As a result, the film thickness was about 8 nm, and most of the alignment control layer-forming monomer was consumed.

[Example 2] An IPS device was produced in the same manner as in Example 1, except that the compound (A-1-3-4) as the alignment control layer forming monomer was 3 parts by weight. In addition, the first ultraviolet ray and the second ultraviolet ray were irradiated by the same method as in Example 1 to perform horizontal alignment treatment. The uniformity of the alignment of the obtained element was “good” as in Example 1, and was “horizontal alignment”. The uniformity of horizontal alignment was obtained by the same method as in Example 1. As a result, the brightness ratio was about 1,000, which was good. The alignment control layer on the element substrate was observed with a scanning electron microscope. As a result, the film thickness was about 48 nm, and most of the alignment control layer-forming monomer was consumed.

[Example 3] An IPS device was produced by the same method as Example 1 except that the compound (A-1-3-14) as the alignment control layer forming monomer was 3 parts by weight. In addition, the first ultraviolet ray and the second ultraviolet ray were irradiated by the same method as in Example 1 to perform horizontal alignment treatment. The uniformity of the alignment of the obtained element was “good” as in Example 1, and was “horizontal alignment”. The uniformity of the horizontal alignment was obtained by the same method as in Example 1. As a result, the brightness ratio was about 1040, which was good. The alignment control layer on the element substrate was observed with a scanning electron microscope. As a result, the film thickness was about 48 nm, and most of the alignment control layer-forming monomer was consumed.

[Example 4] An IPS device was produced in the same manner as in Example 1, except that the compound (A-2-2-2) as the alignment control layer forming monomer was 0.5 parts by weight. In addition, except that the exposure amount of the first ultraviolet ray was 0.9 J / cm ² , the second ultraviolet ray was irradiated in the same manner as in Example 1 to perform a horizontal alignment process. The uniformity of the alignment of the obtained element was “good” as in Example 1, and was “horizontal alignment”. The horizontal alignment uniformity was obtained by the same method as in Example 1. As a result, the brightness ratio was about 1100, which was good. The alignment control layer on the element substrate was observed with a scanning electron microscope. As a result, the film thickness was about 8 nm, and most of the alignment control layer-forming monomer was consumed.

[Example 5] An IPS device was produced by the same method as Example 4 except that the compound (A-2-2-2) as the alignment control layer forming monomer was 10 parts by weight. In addition, the first ultraviolet ray and the second ultraviolet ray were irradiated by the same method as in Example 1 to perform horizontal alignment treatment. The uniformity of the horizontal alignment of the obtained element has the same tendency as in Example 1.

The element of Example 1 hardly leaked light. On the other hand, in Comparative Examples 1 to 3, light leakage was slightly observed. It is believed that light leakage is caused by insufficient alignment restriction of the alignment control layer. From the observation of the thickness of the alignment control layer, it is considered that the approximate total amount of the alignment control layer forming monomers in Examples and Comparative Examples is converted into a polymer. It is presumed that the reason for the difference in the brightness ratio between the example and the comparative example is that by the second ultraviolet irradiation, the remaining aromatic ester portion in the alignment control layer undergoes photo-Frisian rearrangement, or the unreacted alignment control layer forms a single The body polymerizes along the alignment control layer, so the anisotropy (alignment restricting force) of the alignment control layer becomes high. It is considered that the second ultraviolet irradiation step of the present invention helps to improve the uniformity of horizontal alignment. The same effect can also be obtained when the dielectric anisotropy of the liquid crystal composition is positive. Therefore, it can be concluded that the liquid crystal display element manufactured by the method of the present invention has a uniform horizontal alignment. Since this element prevents light leakage, it can be said to have excellent characteristics such as contrast. [Industry availability]

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

Claims (14)

A method of manufacturing a horizontal alignment type liquid crystal display element, wherein the horizontal alignment type liquid crystal display element sandwiches a liquid crystal layer between a pair of substrates arranged oppositely and bonded via a sealant, and the pair of substrates and the Between the liquid crystal layers, there is an alignment control layer that controls alignment of liquid crystal molecules, the liquid crystal layer includes a liquid crystal composition; and in the method of manufacturing the horizontal alignment type liquid crystal display element, the liquid crystal composition contains a liquid crystal compound and has Positive or negative dielectric anisotropy, with a transition temperature T _NI from a nematic phase to an isotropic phase, and contains at least one type of photo-Frisian rearrangement, photo-isomerization, photo-dimerization, The alignment control layer forming monomer of any one of photolysis is used as the first additive; the liquid crystal layer is maintained at a temperature range above T _NI , and the illuminance of the liquid crystal layer is 2 mW / cm ² to 200 mW / cm ² Range, and the exposure range of 1 J / cm ² to 15 J / cm ² polarized light is irradiated to the first ultraviolet light having a peak at 280 nm to 340 nm; second, the liquid crystal layer is kept at room temperature (25 ° C) to The temperature range of T _NI is irradiated at 330 nm to 400 nm with an illuminance in the range of 1 mW / cm ² to 200 mW / cm ² and an exposure range of 1 J / cm ² to 15 J / cm ² Peak second ultraviolet rays; forming the alignment control layer by polymerizing the alignment control layer forming monomer. The method for manufacturing a horizontal alignment type liquid crystal display element as described in item 1 of the patent application, wherein the first additive as described in item 1 of the patent application is an aroma having light Fries rearrangement by light irradiation The alignment control layer forming monomer represented by the formula (A) of the family ester, In formula (A), P ¹⁰ and P ²⁰ independently represent a polymerizable group; Sp ¹⁰ and Sp ^{20 are} independently a single bond or an alkylene group having 1 to 12 carbon atoms, and at least one hydrogen of the alkyl group can be passed through Fluorine or hydroxyl substitution, at least one -CH ₂ -may be substituted by -O-, -COO-, -OCO-, or formula (Q-1), at least one -CH ₂ -CH ₂ -may be substituted by -CH = CH- Or -C≡C-; in formula (Q-1), M ¹⁰ , M ²⁰ , and M ^{30 are} independently hydrogen, fluorine, alkyl having 1 to 5 carbons, or at least one hydrogen is substituted with fluorine or chlorine The alkyl group having 1 to 5 carbon atoms; Sp ¹¹ is a single bond or an alkylene group having 1 to 12 carbon atoms, at least one hydrogen of which may be substituted by fluorine or hydroxyl, and at least one -CH ₂ -may be -O-, -COO-, or -OCO- substitution, at least one -CH ₂ -CH ₂ -may be substituted by -CH = CH- or -C≡C-; Z ¹⁰ , Z ²⁰ and Z ^{30 are} independently 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-, -CONH-, -NHCO-,-(CH ₂ ) _4- , -CH ₂ CH ₂ -or -CF ₂ CF _2- ; A ¹⁰ and A ^{30 are} independently 1,4 -Phenylene, 1,4-cyclohexyl, pyridine-2,5-diyl, pyrimidine-2,5-diyl, naphthalene-2,6-diyl, naphthalene-1,5-diyl, tetra Hydronaphthalene-2,6-diyl, stilbene-2,7-diyl, biphenyl-4,4'-diyl or 1,3-dioxane-2,5-diyl, said 1, In the 4-phenylene group, any hydrogen can be substituted by fluorine, chlorine, cyano, hydroxy, methyl acetyl, acetyloxy, acetyl, trifluoroacetyl, difluoromethyl, trifluoromethyl, C 1-5 alkyl group, C 1-5 alkoxy group, or P ¹⁰ -Sp ¹⁰ -Z ¹⁰ -substituted, in the stilbene-2,7-diyl group, any hydrogen can be substituted by fluorine, Substitution of C 1-5 alkyl group, in the biphenyl-4,4'-diyl group, any hydrogen can be substituted by fluorine, difluoromethyl, trifluoromethyl, C 1-5 alkyl group , Or alkoxy substituted with 1 to 5 carbons; A ²⁰ is 1,4-phenylene, pyridine-2,5-diyl, pyrimidine-2,5-diyl represented by formula (A20-1) , Naphthalene-2,6-diyl, naphthalene-1,5-diyl represented by formula (A20-2), biphenylene-4,4'-diyl represented by formula (A20-3) or formula (A20-4) represented by 茀 -2,7-diyl, and 1,4-phenylene represented by formula (A20-1), Y ¹⁰ , Y ¹¹ , Y ¹² and Y ¹³ are independently Hydrogen, fluorine, chlorine, cyano, hydroxyl, methyl acetyl, ethyl oxy, ethyl acetyl, trifluoroethyl acetyl, difluoromethyl, trifluoro A methyl group, an alkyl group having 1 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms, at least one of Y ¹⁰ and Y ¹³ is hydrogen, and naphthalene-2,6- represented by formula (A20-2) In the diyl group, Y ¹⁴ , Y ¹⁵ , Y ¹⁶ , Y ¹⁷ , Y ¹⁸ and Y ¹⁹ are independently hydrogen, fluorine, an alkyl group having 1 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms, Y ^At least one of ¹⁴ and Y ¹⁹ is hydrogen, and in the biphenyl-4,4'-diyl group represented by the formula (A20-3), Y ²⁰ , Y ²¹ , Y ²² , Y ²³ , Y ²⁴ , Y ²⁵ , Y ²⁶ and Y ²⁷ are independently hydrogen, fluorine, difluoromethyl, trifluoromethyl, C 1-5 alkyl, or C 1-5 alkoxy, Y ²⁰ and Y ²⁷ At least one of them is hydrogen, and among the stilbene-2,7-diyl groups represented by the formula (A20-4), Y ²⁸ , Y ²⁹ , Y ³⁰ , Y ³¹ , Y ³² and Y ³³ are independently hydrogen, fluorine, alkyl having 1 to 5, Y ²⁸ and Y ³¹ is at least one of hydrogen; n ¹⁰ is independently an integer of 0 to 3; ultraviolet ray irradiation, the liquid crystal layer is maintained to less than T _NI T _NI + 5 ℃ The following temperature range, with illuminance in the range of 2 mW / cm ² to 100 mW / cm ² and exposure range of 1 J / cm ² to 13 J / cm ² , polarized light irradiated at 280 nm to 340 nm has Peak first ultraviolet; second, keep the liquid crystal layer at room temperature (25 ° C) to a temperature range less than T _NI , with an illuminance in the range of 1 mW / cm ² to 100 mW / cm ² and 1 J / cm The range of the exposure amount of ² to 14 J / cm ² is irradiated to the second ultraviolet ray having a peak in 330 nm to 400 nm. The method for manufacturing a horizontal alignment type liquid crystal display element as described in item 1 of the patent application range, wherein the ultraviolet irradiation as described in item 1 of the patent application range keeps the liquid crystal layer from T _NI or more to T _NI + 5 ° C or less The temperature range of the polarized light has a peak at 280 nm to 340 nm with a range of illuminance of 2 mW / cm ² to 100 mW / cm ² and an exposure amount of 1 J / cm ² to 11 J / cm ² The first ultraviolet ray; Second, keep the liquid crystal layer at a temperature ranging from room temperature (25 ° C) to below 45 ° C, with an illuminance in the range of 1 mW / cm ² to 50 mW / cm ² and 1 J / cm ² The range of the exposure amount to 14 J / cm ² is irradiated to the second ultraviolet rays having a peak in 330 nm to 400 nm. The method for manufacturing a horizontal alignment type liquid crystal display element as described in item 2 of the patent application, wherein in formula (A) as described in item 2 of the patent application, P ¹⁰ and P ²⁰ independently represent an acryloxy group , Methacryloyloxy, α-fluoroacrylate, trifluoromethacrylate, vinyl, vinyloxy, epoxy; Sp ¹⁰ and Sp ^{20 are} independently a single bond or carbon number 1 to 12 Alkylene, at least one hydrogen of the alkylene may be substituted by fluorine or hydroxyl, at least one -CH ₂ -may be substituted by -O-, -COO-, or -OCO-, at least one -CH ₂ -CH ₂ -Can be substituted by -CH = CH- or -C≡C-; Z ¹⁰ , Z ²⁰ and Z ^{30 are} independently single bonds, -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-, -CONH-, -NHCO-,-(CH ₂ ) _4- , -CH ₂ CH ₂ -or -CF ₂ CF _2- ; A ¹⁰ and A ^{30 are} independently 1,4-phenylene, 1,4-cyclohexyl, naphthalene-2,6-di Group, naphthalene-1,5-diyl, stilbene-2,7-diyl, biphenyl-4,4'-diyl, in the 1,4-phenylene group, any hydrogen can be Cyano, hydroxy, acetyloxy, acetyl, trifluoroacetyl, difluoromethyl, trifluoromethyl, C 1-5 alkyl, C 1-5 alkoxy, or P ¹⁰ -Sp ¹⁰ -Z ¹⁰ -substitution, in the stilbene-2,7-diyl group, any hydrogen can be substituted by fluorine or C 1-5 alkyl group, the biphenyl-4,4 ' -In the diyl group, any hydrogen may be substituted with fluorine, difluoromethyl, trifluoromethyl, a C 1-5 alkyl group, or a C 1-5 alkoxy group; A ²⁰ is the formula (A20- 1) 1,4-phenylene represented by, naphthalene-2,6-diyl represented by formula (A20-2), biphenyl-4,4'-bis represented by formula (A20-3) Radical or fluoren-2,7-diyl represented by formula (A20-4), 1,4-extenyl represented by formula (A20-1), Y ¹⁰ , Y ¹¹ , Y ¹² and Y ¹³ are It can independently pass hydrogen, fluorine, chlorine, cyano, hydroxy, methyl acetyl, acetyloxy, ethyl acetyl, trifluoroethyl acetyl, difluoromethyl, trifluoromethyl, carbon number 1 to 5. Alkyl or alkoxy substituted with 1 to 5 carbons, at least one of Y ¹⁰ and Y ¹³ is hydrogen, and naphthalene-2,6-diyl represented by formula (A20-2), Y ¹⁴ and Y ¹⁵ , Y ¹⁶ , Y ¹⁷ , Y ¹⁸ and Y ¹⁹ are each independently substituted with hydrogen, fluorine, alkyl having 1 to 5 carbons or alkoxy having 1 to 5 carbons, at least Y ¹⁴ and Y ¹⁹ One is hydrogen, and biphenyl-4,4'-di expressed by formula (A20-3) In the group, Y ²⁰ , Y ²¹ , Y ²² , Y ²³ , Y ²⁴ , Y ²⁵ , Y ²⁶ and Y ²⁷ can independently pass hydrogen, fluorine, difluoromethyl, trifluoromethyl, carbon number 1 to 5 Substituted by an alkyl group or an alkoxy group having 1 to 5 carbon atoms, at least one of Y ²⁰ and Y ²⁷ is hydrogen, and in the stilbene-2,7-diyl group represented by the formula (A20-4), Y ²⁸ , Y ²⁹ , Y ³⁰ , Y ³¹ , Y ³² and Y ³³ are independently hydrogen, fluorine, and alkyl groups having 1 to 5 carbon atoms, and at least one of Y ²⁸ and Y ³¹ is hydrogen; n ^{10 is} independently 0 to An integer of 3. The method for manufacturing a horizontal alignment type liquid crystal display element according to any one of the first to fourth patent application ranges, wherein the alignment control layer forming monomer is from formula (A-1) to formula (A-3) ) Expressed by either; In formula (A-1) to formula (A-3), R ^{10 is} independently hydrogen, fluorine, methyl, or trifluoromethyl; R ^{31 is} independently hydrogen or methyl; Sp ¹⁰ and Sp ^{20 are} independently Is a single bond or an alkylene group having 1 to 12 carbon atoms, at least one hydrogen of the alkylene group may be substituted by fluorine or hydroxyl, and at least one -CH ₂ -may be substituted by -O-, -COO-, or -OCO- Substitution, at least one -CH ₂ -CH ₂ -may be substituted by -CH = CH- or -C≡C-; Z ¹⁰ , Z ²⁰ and Z ^{30 are} independently single bonds, -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-, -CONH -, -NHCO-,-(CH ₂ ) _4- , -CH ₂ CH ₂ -or -CF ₂ CF _2- ; A ^{20 is} independently 1,4-phenylene represented by formula (A20-1), Biphenylene-4,4'-diyl represented by formula (A20-3) or stilbene-2,7-diyl represented by formula (A20-4), 1, represented by formula (A20-1), In 4-phenylene, Y ¹⁰ , Y ¹¹ , Y ¹² , and Y ¹³ are independently hydrogen, fluorine, hydroxyl, difluoromethyl, trifluoromethyl, C 1-5 alkyl, or Alkoxy substitution of carbon number 1 to 5, at least one of Y ¹⁰ and Y ¹³ is hydrogen, and in the biphenyl-4,4′-diyl group represented by formula (A20-3), Y ²⁰ and Y ²¹ , Y ²² , Y ²³ , Y ²⁴ , Y ²⁵ , Y ²⁶ and Y ²⁷ are independently hydrogen, fluorine, difluoromethyl, trifluoromethyl, C 1-5 alkyl, or C 1 Alkoxy substitution to 5, at least one of Y ²⁰ and Y ²⁷ is hydrogen, and in the stilbene-2,7-diyl group represented by formula (A20-4), Y ²⁸ , Y ²⁹ , Y ³⁰ , Y ³¹ , Y ³² and Y ³³ are independently hydrogen, fluorine, and C 1-5 alkyl groups, at least one of Y ²⁸ and Y ³¹ is hydrogen; A ^{30 is} independently 1,4-phenylene, naphthalene- 2,6-diyl, naphthalene-1,5-diyl, stilbene-2,7-diyl, biphenyl-4,4'-diyl, of the 1,4-phenylene, any Hydrogen may be substituted with fluorine, hydroxyl, difluoromethyl, trifluoromethyl, C 1-5 alkyl, or C 1-5 alkoxy, the stilbene-2,7-diyl group, Any hydrogen may be substituted with fluorine and alkyl groups having 1 to 5 carbon atoms. In the biphenyl-4,4'-diyl group, any hydrogen may be substituted with fluorine, difluoromethyl, trifluoromethyl, carbon Alkyl group with 1 to 5 or alkoxy group with 1 to 5 carbons; L ^{10 is} independently hydrogen, fluorine, difluoromethyl, trifluoromethyl, alkyl with 1 to 5 carbons, and carbon number 1 to 5 alkoxy groups or P ¹⁰ -Sp ¹⁰ -Z ¹⁰ -; N ^{11 is} independently an integer from 0 to 4. The method for manufacturing a horizontal alignment type liquid crystal display element according to any one of claims 1 to 4, wherein the alignment control layer is formed when the total amount of liquid crystal compounds is 100 parts by weight The ratio of the monomer is in the range of 0.1 parts by weight to 10.0 parts by weight. The method for manufacturing a horizontal alignment type liquid crystal display element according to any one of the first to fourth patent application ranges, wherein the liquid crystal composition contains a compound selected from the group consisting of formula (2) to formula (4) At least one compound in the group of In formula (2) to formula (4), R ¹¹ and R ^{12 are} independently an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms, and at least one of the alkyl groups and alkenyl groups is -CH ₂ -May be substituted with -O-, at least one hydrogen may be substituted with fluorine; Ring B ¹ , Ring B ² , Ring B ³ and Ring B ^{4 are} independently 1,4-cyclohexyl, 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} independently single Key,-(CH ₂ ) _2- , -CH = CH-, -C≡C-, or -COO-. The method for manufacturing a horizontal alignment type liquid crystal display element according to any one of the first to fourth patent application ranges, wherein the liquid crystal composition further contains a formula selected from formula (5) to formula (7) At least one compound in the group of compounds; In formula (5) to formula (7), R ¹³ is an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms. Among the alkyl groups and alkenyl groups, at least one -CH ₂ -may be passed through- O-substituted, at least one hydrogen may be substituted with fluorine; X ¹¹ is fluorine, chlorine, -OCF ₃ , -OCHF ₂ , -CF ₃ , -CHF ₂ , -CH ₂ F, -OCF ₂ CHF ₂ or -OCF ₂ CHFCF ₃ ; Ring C ¹ , Ring C ² and Ring C ^{3 are} independently 1,4-cyclohexyl, 1,4-phenylene, tetrahydropyran-2,5-di Group, 1,3-dioxane-2,5-diyl, or pyrimidine-2,5-diyl; Z ¹⁴ , Z ¹⁵ and Z ^{16 are} 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-, -CF = CF-CF ₂ O- or-(CH ₂ ) _4- ; L ¹¹ and L ^{12 are} independently hydrogen or fluorine. The method for manufacturing a horizontal alignment type liquid crystal display element according to any one of the first to fourth patent application ranges, wherein the liquid crystal composition further contains a group selected from the group consisting of compounds represented by formula (8) At least one compound; In formula (8), R ¹⁴ is an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms. In the alkyl group and the alkenyl group, at least one -CH ₂ -may be substituted with -O-, at least One hydrogen may be substituted with fluorine; X ¹² is -C≡N or -C≡CC≡N; Ring D ¹ is 1,4-cyclohexyl, at least one hydrogen may be substituted with fluorine, 1,4-phenylene, Tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, or pyrimidine-2,5-diyl; Z ¹⁷ is 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 method for manufacturing a horizontal alignment type liquid crystal display element according to any one of the first to fourth patent application ranges, wherein the liquid crystal composition further contains a formula selected from formula (9) to formula (15) At least one compound in the group of compounds; In formula (9) to formula (15), R ¹⁵ and R ^{16 are} independently an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms, and of the alkyl group and alkenyl group, at least one -CH ₂ -May be substituted with -O-, at least one hydrogen may be substituted with fluorine; R ¹⁷ is hydrogen, fluorine, an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms. , At least one -CH ₂ -may be substituted by -O-, at least one hydrogen may be substituted by fluorine; ring E ¹ , ring E ² , ring E ³ and ring E ^{4 are} independently 1,4-cyclohexyl, 1, 4-cyclohexenyl, 1,4-phenylene, tetrahydropyran-2,5-diyl or decahydronaphthalene-2,6-diyl substituted with fluorine for at least one hydrogen; ring E ⁵ And ring E ^{6 is} independently 1,4-cyclohexyl, 1,4-cyclohexenyl, 1,4-phenylene, tetrahydropyran-2,5-diyl or decahydronaphthalene-2 , 6-diyl; Z ¹⁸ , Z ¹⁹ , Z ²⁰ and Z ^{21 are} 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- ; j, k, m, n, p, q , R and s are independently 0 or 1, the sum of k, m, n and p is 1 or 2, the sum of q, r and s is 0, 1, 2 or 3, and t is 1, 2 or 3. The method for manufacturing a horizontal alignment type liquid crystal display element according to any one of the first to fourth patent application ranges, wherein the liquid crystal composition further contains a polymerizable compound represented by formula (16α) as a second addition And form an alignment control layer containing a copolymer produced by polymerizing these compounds; In formula (16α), ring F and ring I are independently cyclohexyl, cyclohexenyl, phenyl, 1-naphthyl, 2-naphthyl, tetrahydropyran-2-yl, 1,3-dioxan Alkyl-2-yl, pyrimidin-2-yl, or pyrid-2-yl, in these rings, at least one hydrogen can be fluorine, chlorine, alkyl having 1 to 12 carbons, or at least one hydrogen can be fluorine or chlorine Substituted alkyl groups with 1 to 12 carbon atoms; Ring G is 1,4-cyclohexyl, 1,4-cyclohexenyl, 1,4-phenylene, naphthalene-1,2-diyl, Naphthalene-1,3-diyl, naphthalene-1,4-diyl, naphthalene-1,5-diyl, naphthalene-1,6-diyl, naphthalene-1,7-diyl, naphthalene-1,8 -Diyl, naphthalene-2,3-diyl, naphthalene-2,6-diyl, naphthalene-2,7-diyl, tetrahydropyran-2,5-diyl, 1,3-dioxane -2,5-diyl, pyrimidine-2,5-diyl, or pyridine-2,5-diyl, in these rings, at least one hydrogen can be through fluorine, chlorine, alkyl having 1 to 12 carbons, C 1-12 alkoxy, or at least one hydrogen substituted by fluorine or chlorine, C 1-12 alkyl; Z ²² and Z ^{23 are} independently a single bond or C 1-10 alkylene In the alkylene group, at least one -CH ₂ -may be substituted by -O-, -CO-, -COO-, or -OCO-, and at least one-(CH ₂ ) ₂ -may be substituted by -CH = CH- , -C (CH ₃ ) = CH-, -CH = C (CH ₃ )-, or -C (CH ₃ ) = C (CH ₃ )-, in these groups, at least one hydrogen can be replaced by fluorine or chlorine Substitution; P ¹¹ , P ¹² and P ^{13 are} independently a polymerizable group; Sp ¹¹ , Sp ¹² and Sp ^{13 are} independently a single bond or an alkylene group having 1 to 10 carbon atoms, in the alkylene group, at least One -CH ₂ -may be substituted by -O-, -COO-, -OCO-, or -OCOO-, at least one-(CH ₂ ) ₂ -may be substituted by -CH = CH- or -C≡C-, In these groups, at least one hydrogen may be substituted by fluorine or chlorine; u is 0, 1, or 2; f, g, and h are independently 0, 1, 2, 3, or 4, and the sum of f, g, and h is 2 the above. The method for manufacturing a horizontal alignment type liquid crystal display element as described in item 11 of the patent application scope, wherein in formula (16α) as described in item 11 of the patent application range, P ¹¹ , P ¹² , and P ^{13 are} independently selected Groups in the group of polymerizable groups represented by formula (P-1) to formula (P-5); In formula (P-1) to formula (P-5), M ¹¹ , M ¹² and M ^{13 are} independently hydrogen, fluorine, an alkyl group having 1 to 5 carbon atoms, or carbon in which at least one hydrogen is substituted with fluorine or chlorine Number 1 to 5 alkyl. The method for manufacturing a horizontal alignment type liquid crystal display element as described in item 11 of the patent application range, wherein when the total amount of the liquid crystal compound is 100 parts by weight, the proportion of the second additive in the liquid crystal composition is 0.03 parts by weight Parts to 10 parts by weight. A display device comprising a horizontal alignment type liquid crystal display element obtained by the manufacturing method as described in any one of claims 1 to 13; and a backlight.