Liquid crystal display element

Abstract

Provided is a liquid crystal display element in which adhesion between a liquid crystal layer and an electrode can be increased, and it is possible to suppress the occurrence of bubbles or separation in the element and a decrease in optical characteristics even in a harsh environment in which the element is exposed to high temperature / high humidity or light irradiation for a long time.　A liquid crystal display element having a liquid crystal layer obtained by curing, with ultraviolet irradiation, a liquid crystal composition including a liquid crystal and a polymerizable composition positioned between a pair of substrates provided with an electrode, and furthermore, a transmission / scatter-type liquid crystal display element that is in a scattering state when a voltage is not applied, and that is in a transmitting state when a voltage is applied, the liquid crystal display element being characterized in that the polymerizable composition includes one or more compounds having the structure represented by formula [1A]. (In the formula, * represents a bond.)

Description

[Technical Field]

[0001] The present invention relates to a transmissive / scattering liquid crystal display element. [Background technology]

[0002] The TN (Twisted Nematic) mode is a type of LCD device that has been put to practical use. This mode utilizes the optical rotatory properties of liquid crystals to switch light, so a polarizer is required. The use of a polarizer reduces the efficiency of light utilization. Liquid crystal display elements that do not use polarizers include elements that switch between a transmissive state (also called a transparent state) and a scattering state of the liquid crystal. Generally, elements that use polymer dispersed liquid crystal (PDLC) or polymer network liquid crystal (PNLC) are known.

[0003] In these liquid crystal display elements, a liquid crystal composition containing a polymerizable compound that is polymerized by ultraviolet light is placed between a pair of substrates equipped with electrodes, and the liquid crystal composition is cured by irradiation with ultraviolet light to form a composite of the liquid crystal and a cured product of the polymerizable compound (e.g., a polymer network). In these liquid crystal display elements, the scattering state and transmission state of the liquid crystal are controlled by applying a voltage.

[0004] Among liquid crystal display elements using PDLC or PNLC, there are those in which the liquid crystals are randomly oriented when no voltage is applied, resulting in a cloudy (scattered) state, but when voltage is applied, the liquid crystals align in the direction of the electric field, allowing light to pass through and resulting in a transmissive state (also known as normal-type elements). In this case, because the liquid crystals are random when no voltage is applied, there is no need for a liquid crystal alignment film or alignment treatment to align the liquid crystals in one direction. Therefore, in this liquid crystal display element, the electrodes and the liquid crystal layer (a composite of the above-mentioned liquid crystal and a cured product of a polymerizable compound) are in direct contact with each other (see Patent Documents 1 and 2). On the other hand, a liquid crystal display element (also called a reverse type element) using PDLC, which is in a transmissive state when no voltage is applied and in a scattering state when a voltage is applied, has also been proposed (see Patent Documents 3 and 4). [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent No. 3552328 [Patent Document 2] Japanese Patent No. 4630954 [Patent Document 3] Japanese Patent No. 2885116 [Patent Document 4] Japanese Patent No. 4132424 Summary of the Invention [Problem to be solved by the invention]

[0006] The polymerizable compound in the liquid crystal composition serves to form a polymer network to obtain desired optical properties and to enhance adhesion between the liquid crystal layer and the electrodes. However, because liquid crystal display elements use inorganic electrodes such as ITO (indium tin oxide), compatibility with organic polymerizable compounds, i.e., adhesion, tends to be poor. Poor adhesion can lead to peeling of the element, the generation of bubbles, and even deterioration of the optical properties in the scattering and transparent states due to long-term use, especially in harsh environments such as high temperature and humidity or exposure to light.

[0007] In view of the above, the present invention aims to provide a liquid crystal display element that improves adhesion between the liquid crystal layer and the electrodes, and can suppress peeling of the element, the generation of bubbles, and deterioration of optical properties even in harsh environments such as exposure to high temperature, high humidity, and light irradiation for long periods of time. [Means for solving the problem]

[0008] The present inventors have conducted extensive research to achieve the above object, and as a result have completed the present invention, which has the following gist. That is, the liquid crystal display element has a liquid crystal layer formed by irradiating a liquid crystal composition containing a liquid crystal and a polymerizable composition disposed between a pair of substrates equipped with electrodes with ultraviolet light to harden the liquid crystal layer, and further, the liquid crystal display element is a transmission-scattering type liquid crystal display element that is in a scattering state when no voltage is applied and in a transparent state when voltage is applied, characterized in that the polymerizable composition contains one or more compounds (also referred to as specific polymerizable compounds) having a structure (also referred to as specific structure) represented by the following formula [1A]: [ka] (* indicates a bond.) [Effects of the Invention]

[0009] According to the present invention, a liquid crystal display element can be obtained that can enhance the adhesion between the liquid crystal layer and the electrodes, and can suppress peeling of the element, the generation of bubbles, and the deterioration of optical properties even in harsh environments such as exposure to high temperature and humidity and light irradiation for long periods of time. Therefore, the liquid crystal display element of the present invention can be used for liquid crystal displays for display purposes, light control windows and optical shutter elements that control the blocking and transmission of light, etc. The mechanism by which the liquid crystal display device having the above-mentioned excellent characteristics can be obtained according to the present invention is not entirely clear, but is presumed to be as follows. The liquid crystal composition of the present invention includes a polymerizable composition containing a liquid crystal and a polymerizable compound having a specific structure. The two isopropylidene groups (-C(CH3)2-) in the specific structure reduce cure shrinkage during the curing process due to the intermolecular excluded volume effect. This prevents distortion and voids from occurring between the liquid crystal layer and the substrate, resulting in a highly reliable device. Furthermore, because cure shrinkage is small, the pores in the polymer network (areas where liquid crystal exists) do not collapse and can remain of uniform size, allowing the liquid crystal to be driven uniformly with or without the application of voltage. Furthermore, the ester bond (-OC(=O)-) in the specific structure interacts with the ITO substrate, thereby enhancing the adhesion between the liquid crystal layer and the substrate. DETAILED DESCRIPTION OF THE INVENTION

[0010] <Liquid Crystal Composition> The liquid crystal composition includes a polymerizable composition containing a liquid crystal and a specific polymerizable compound. The liquid crystal may be a nematic liquid crystal, a smectic liquid crystal, or a cholesteric liquid crystal. Of these, a liquid crystal having a positive dielectric anisotropy is used for a normal-type element, and a liquid crystal having a negative dielectric anisotropy is used for a reverse-type element. For the normal-type element of the present invention, a liquid crystal having a positive dielectric anisotropy is preferred. Furthermore, from the viewpoints of low-voltage operation and scattering characteristics, a liquid crystal having a large dielectric anisotropy and a large refractive index anisotropy is preferred. Furthermore, a mixture of two or more types of liquid crystals may be used depending on the physical property values ​​of the phase transition temperature, dielectric anisotropy, and refractive index anisotropy.

[0011] The content of the liquid crystal in the liquid crystal composition is preferably 40 to 70% by mass, more preferably 40 to 60% by mass, and particularly preferably 50 to 60% by mass, assuming the liquid crystal composition to be 100% by mass.

[0012] In order to operate a liquid crystal display element as an active element such as a TFT (Thin Film Transistor), the liquid crystal is required to have high electrical resistance and a high voltage holding ratio (VHR). For this reason, it is preferable to use fluorine- or chlorine-based liquid crystals, which have high electrical resistance and whose VHR does not decrease when exposed to active energy rays such as ultraviolet rays.

[0013] Furthermore, guest-host type liquid crystal display devices can be fabricated by dissolving dichroic dyes in the liquid crystal composition. In this case, a normal-type device is obtained that absorbs (scatters) light when no voltage is applied and becomes transparent when a voltage is applied. Furthermore, in this device, the direction of the liquid crystal director (orientation direction) changes by 90 degrees depending on whether or not a voltage is applied. Therefore, by utilizing the difference in the absorption properties of the dichroic dye, this device can achieve higher contrast than conventional guest-host type devices that switch between random and vertical alignment. Furthermore, guest-host type devices with dissolved dichroic dyes become colored when the liquid crystal is horizontally aligned and opaque only in the scattering state. Therefore, devices can be obtained that switch from a colored, opaque state when no voltage is applied to a colored, transparent state to a colorless, transparent state as a voltage is applied.

[0014] The polymerizable composition contains a polymerizable compound. The polymerizable compound undergoes a polymerization reaction upon irradiation with ultraviolet light during the production of a liquid crystal display element to form a polymer network (also referred to as a curable resin). Therefore, a polymer obtained by polymerizing the polymerizable compound in advance may be introduced into the liquid crystal composition. However, even in the case of a polymer, it is necessary for the polymer to have a site that undergoes a polymerization reaction upon irradiation with ultraviolet light. From the viewpoint of handling of the liquid crystal composition, i.e., preventing the liquid crystal composition from becoming highly viscous and solubility in the liquid crystal, it is preferable to use a liquid crystal composition containing a polymerizable compound.

[0015] The polymerizable compound is not particularly limited as long as it is soluble in the liquid crystal, but when the polymerizable compound is dissolved in the liquid crystal, a temperature must exist at which a part or the whole of the liquid crystal composition exhibits a liquid crystal phase. Even if a part of the liquid crystal composition exhibits a liquid crystal phase, it is sufficient that the liquid crystal display element is observed with the naked eye and the entire element exhibits substantially uniform transparency and scattering properties.

[0016] The polymerizable compound may be any compound that polymerizes when exposed to ultraviolet light, and the polymerization may proceed by any reaction type to form a curable resin. Specific reaction types include radical polymerization, cationic polymerization, anionic polymerization, and polyaddition reaction. Among these, radical polymerization is preferred as the reaction type of the polymerizable compound from the viewpoint of the optical properties of the liquid crystal display element. In this case, the polymerizable composition contains a specific polymerizable compound.

[0017] The content of the polymerizable composition in the liquid crystal composition is preferably 30 to 60% by mass, more preferably 40 to 60% by mass, and particularly preferably 40 to 50% by mass, assuming the liquid crystal composition to be 100% by mass.

[0018] The specific polymerizable compound is a compound having a structure represented by the above formula [1A], and is preferably a compound represented by the following formula [1a]. [ka] (X 1 and X 2 Each independently represents a structure selected from the following formulas [1-a] to [1-d]. A represents the above formula [1A]. L 1 and L 2 each independently represents a single bond or an alkylene group having 1 to 42 carbon atoms, and any -CH2- in the alkylene group may be replaced by -O-, -CO-, -COO-, -OCO-, -CONH-, -NHCO-, -NH-, a benzene ring or a cyclohexane ring. [ka] (* indicates a bond.) In formula [1a], X 1 , X 2 , A, L 1 and L 2 are as defined above, but the following are particularly preferred: X 1 and X 2 are each independently preferably the above formula [1-a] or formula [1-b]. L 1 and L 2 are each independently preferably a single bond or an alkylene group having 1 to 30 carbon atoms, and any -CH2- in the alkylene group may be replaced by -O-, -CO-, -COO-, -OCO-, -CONH-, -NHCO-, -NH-, a benzene ring or a cyclohexane ring.

[0019] Specific examples of the compound having the structure represented by the above formula [1A] include compounds represented by the following formulas [1a-1] to [1a-3], and it is preferable to use these. [ka] (m and n each independently represent an integer of 0 or more.)

[0020] From the viewpoint of the optical properties of the liquid crystal display element, the proportion of the specific polymerizable compound used is preferably 30 to 100 parts by mass, more preferably 40 to 95 parts by mass, and particularly preferably 40 to 80 parts by mass, per 100 parts by mass of the polymerizable composition. Furthermore, the specific polymerizable compound can be used alone or in combination of two or more types depending on the properties.

[0021] From the viewpoint of adhesion between the liquid crystal layer and the electrode, the polymerizable composition preferably further contains one or more compounds represented by the following formula [2] (also referred to as second specific polymerizable compounds). [ka] (Y 1 represents the following formula [2-a] or formula [2-b]. 2 represents an alkylene group having 2 to 24 carbon atoms, and Y 1 Or, any -CH2- that is not adjacent to O may be substituted with -O-, -CO-, -COO-, -OCO-, -CONH-, -NHCO-, -NH- or -CON(CH3)-. Ym represents an integer of 1 to 2. Yn represents an integer of 1 to 2, provided that Ym+Yn is 3. Y 1 and Y 2If there are multiple Y 1 and Y 2 and each independently have the definition above. [ka] (* indicates a bond.)

[0022] Specific examples of the second specific polymerizable compound include the compounds described on pages 6 to 8 of International Publication No. 2019 / 181882 (published on September 26, 2019).

[0023] More specifically, examples of the second specific polymerizable compound include compounds selected from the group consisting of the following formulae [2a-1] to [2a-3], and it is preferable to use these. [ka]

[0024] X a represents the above formula [2-a] or formula [2-b]. b represents an alkylene group having 2 to 18 carbon atoms, and X of the alkylene group a Or, any -CH2- that is not adjacent to O may be substituted with -O-, -CO-, -COO-, -OCO-, -CONH-, -NHCO-, -NH- or -CON(CH3)-. X c represents -COO- or -OCO-. X d represents an alkylene group having 2 to 12 carbon atoms. p1 represents an integer of 1 or 2. p2 represents an integer of 1 or 2, provided that p1+p2 is 3. p3 represents an integer of 2 to 8. X a , X b , X c , X d If there are multiple p3s, multiple X a , X b , X c , X d and p3 independently of each other have the definitions above.

[0025] More specifically, examples of the second specific polymerizable compound include Phosmer M, Phosmer PE, and Phosmer PP (all manufactured by Unichemical Co., Ltd.), Light Acrylate P-1A(N), and Light Ester P-1M (all manufactured by Kyoeisha Chemical Co., Ltd.), KAYAMER PM-2, and KAYAMER PM-21 (all manufactured by Nippon Kayaku Co., Ltd.).

[0026] The proportion of the second specific polymerizable compound used is preferably 0.01 to 10 parts by mass per 100 parts by mass of the polymerizable composition from the viewpoint of adhesion between the liquid crystal layer and the electrode. It is more preferably 0.01 to 5 parts by mass, and particularly preferably 0.01 to 3 parts by mass. The second specific polymerizable compound can be used alone or in combination of two or more types depending on the properties. When two or more types of the second specific polymerizable compound are used in combination, for example, the polymerizable composition may be a polymerizable composition having a structure in which, in the formula [2], Y 1 and Y 2 is as described above, Ym is 1, and Yn is 2; and in the above formula [2], Y 1 and Y 2 is as described above, and may include a compound [2-2] in which Ym is 2 and Yn is 1. The ratio of the compound [2-1] to the compound [2-2] can be appropriately adjusted using the techniques described in, for example, Japanese Patent Application Laid-Open Nos. 59-141588 and 2007-176806. From the viewpoint of adhesion between the liquid crystal layer and the electrode, the amount of the compound [2-1] used is preferably 20 to 70 parts by mass, more preferably 30 to 60 parts by mass, and particularly preferably 40 to 60 parts by mass, per 100 parts by mass of the second specific polymerizable compound represented by the formula [2]. From the viewpoint of adhesion between the liquid crystal layer and the electrode, the amount of the compound [2-2] used is preferably 20 to 70 parts by mass, more preferably 30 to 60 parts by mass, and particularly preferably 40 to 60 parts by mass, per 100 parts by mass of the second specific polymerizable compound represented by the formula [2].

[0027] Furthermore, in terms of the optical properties of the liquid crystal display device, the polymerizable composition preferably further contains one or more compounds represented by the following formula [3] (also referred to as third specific polymerizable compounds). [ka] (Z 1 represents any structure selected from the following formulas [3-a] to [3-e]. 2 represents a single bond, -O-, -NH-, -N(CH3)-, -CHO-, -CONH-, -NHCO-, -CON(CH3)-, -N(CH3)CO-, -COO- or -OCO-. Z 3 is a single bond or -(CH2) a - (where a is an integer from 1 to 15). Z 4 represents a single bond, -O-, -OCH2-, -COO- or -OCO-. Z 5 represents a divalent cyclic group selected from a benzene ring, a cyclohexane ring, and a heterocycle, or a divalent organic group having a steroid skeleton and having 17 to 51 carbon atoms, and any hydrogen atom on the cyclic group may be substituted with an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxy group having 1 to 3 carbon atoms, or a fluorine atom. Z 6 represents a single bond, -O-, -CH2-, -OCH2-, -CH2O-, -COO- or -OCO-. Z 7 represents a cyclic group selected from a benzene ring, a cyclohexane ring, and a heterocycle, and any hydrogen atom on these cyclic groups may be substituted with an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxy group having 1 to 3 carbon atoms, or a fluorine atom. Z 8 represents an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, or a fluorine-containing alkoxy group having 1 to 18 carbon atoms. Zm represents an integer of 0 to 4. When Zm is 2 or more, Zm Z 7 are each independently defined above.) [ka] (* indicates a bond.)

[0028] Specific examples of the third specific polymerizable compound include the compounds described on pages 8 to 21 of International Publication No. 2019 / 181882 (published on September 26, 2019).

[0029] Specifically, examples of the third specific polymerizable compound include compounds selected from the group consisting of the following formulae [3a-1] to [3a-2], [3a-5] to [3a-6], and [3a-9] to [3a-10], and it is preferable to use these. [ka] (Y a represents -O- or -COO-. b represents an alkyl group having 1 to 12 carbon atoms; q1 represents an integer of 1 to 10; and q2 represents an integer of 1 or 2. [ka] (Y c represents a single bond, -COO- or -OCO-. d represents an alkyl group or alkoxy group having 1 to 12 carbon atoms; q3 represents an integer of 1 to 10; and q4 represents an integer of 1 or 2. [ka] (Y e represents -O- or -COO-. f represents a divalent organic group having a steroid skeleton and having 17 to 51 carbon atoms. g represents an alkyl group having 1 to 12 carbon atoms or an alkenyl group having 2 to 18 carbon atoms. q5 represents an integer of 1 to 10.

[0030] From the viewpoint of the optical properties of the liquid crystal display element, the proportion of the third specific polymerizable compound used is preferably 0.1 to 30 parts by mass, more preferably 0.5 to 20 parts by mass, and particularly preferably 1 to 10 parts by mass, per 100 parts by mass of the polymerizable composition. Furthermore, the third specific polymerizable compound can be used alone or in combination of two or more types depending on the properties.

[0031] The polymerizable composition may further contain a polymerizable compound other than the specific polymerizable compound, the second specific polymerizable compound, and the third specific polymerizable compound.

[0032] Specific examples of other polymerizable compounds include 2-ethylhexyl acrylate, 1-butylethyl acrylate, 2-butoxyethyl acrylate, 2-cyanoethyl acrylate, benzyl acrylate, cyclohexyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-ethoxyethyl acrylate, N,N-diethyl-2-aminoethyl acrylate, N,N-dimethyl-2-aminoethyl acrylate, dicyclopentanyl acrylate, dicyclopentenyl acrylate, and glycidyl acrylate. , tetrahydrofurfuryl acrylate, isobornyl acrylate, isodecyl acrylate, lauryl acrylate, 4-acryloylmorpholine, 2-phenoxyethyl acrylate, diethylene glycol acrylate phenyl ether, 2,2,2-trifluoroethyl acrylate, 2,2,3,3,3-pentafluoropropyl acrylate, 2,2,3,3-tetrafluoropropyl acrylate, 2,2,3,4,4,4-hexafluorobutyl acrylate, 2-ethylhexyl methacrylate, 1-butylethyl methacrylate , 2-butoxyethyl methacrylate, 2-cyanoethyl methacrylate, benzyl methacrylate, cyclohexyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2-ethoxyethyl acrylate, N,N-diethyl-2-aminoethyl methacrylate, N,N-dimethyl-2-aminoethyl methacrylate, dicyclopentanyl methacrylate, dicyclopentenyl methacrylate, glycidyl methacrylate, tetrahydrofurfuryl methacrylate, isobornyl methacrylate, isodecaylan, Sil methacrylate, lauryl methacrylate, 4-methacryloylmorpholine, 2-phenoxyethyl methacrylate, diethylene glycol methacrylate phenyl ether, 2,2,2-trifluoroethyl methacrylate, 2,2,3,3-tetrafluoropropyl methacrylate, 2,2,3,4,4,4-hexafluorobutyl methacrylate, 4,4'-biphenyl diacrylate, diethylstilbestrol diacrylate, 1,4-bisacryloyloxybenzene, 4,4'-bisacryloyloxydiphenyl ether, 4,4'-Bisacryloyloxydiphenylmethane, 3,9-bis[1,1-dimethyl-2-acryloyloxyethyl]-2,4,8,10-tetraoxaspiro[5,5]undecane, α,α'-bis[4-acryloyloxyphenyl]-1,4-diisopropylbenzene, 1,4-bisacryloyloxytetrafluorobenzene, 4,4'-bisacryloyloxyoctafluorobiphenyl, diethylene glycol acrylate, 1,4-butanediol diacrylate, 1,3-butylene glycol diacrylate, glycerol diacrylate Acrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, tetraethylene glycol diacrylate, trimethylolpropane triacrylate, pentaerythritol tetraacrylate, pentaerythritol triacrylate, ditrimethylolpropane tetraacrylate, dipentaerythritol hexaacrylate, dipentaerythritol monohydroxypentaacrylate, 4,4'-diacryloyloxystilbene, 4,4'-diacryloyloxydimethylstilbene, 4,4'-di Acryloyloxydiethylstilbene, 4,4'-diacryloyloxydipropylstilbene, 4,4'-diacryloyloxydibutylstilbene, 4,4'-diacryloyloxydipentylstilbene, 4,4'-diacryloyloxydihexylstilbene, 4,4'-diacryloyloxydifluorostilbene, 2,2,3,3,4,4-hexafluoropentanediol-1,5-diacrylate, 1,1,2,2,3,3-hexafluoropropyl-1,3-diacrylate, diethylene glycol dimethacrylate, 1,4 -Butanediol dimethacrylate, 1,3-butylene glycol dimethacrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol dimethacrylate, tetraethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, pentaerythritol tetramethacrylate, pentaerythritol trimethacrylate, ditrimethylolpropane tetramethacrylate, dipentaerythritol hexamethacrylate, dipentaerythritol monohydroxypentamethacrylate, 2,2,3,3,4,4-Hexafluoropentanediol-1,5-dimethacrylate, tricyclodecane dimethanol diacrylate, tricyclodecane dimethanol dimethacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, polypropylene glycol #400 diacrylate, polypropylene glycol #700 diacrylate, dipropylene glycol dimethacrylate, tripropylene glycol dimethacrylate, polypropylene glycol #400 dimethacrylate, polypropylene glycol #700 dimethacrylate, nonylphenol EO modified acrylate, nonylphenol EO modified Examples of monomers and oligomers include methacrylate, polyethylene glycol #200 diacrylate, polyethylene glycol #400 diacrylate, polyethylene glycol #600 diacrylate, polyethylene glycol #200 dimethacrylate, polyethylene glycol #400 dimethacrylate, polyethylene glycol #600 dimethacrylate, ethoxylated bisphenol A diacrylate, propoxylated bisphenol A diacrylate, ethoxylated bisphenol A dimethacrylate, propoxylated bisphenol A dimethacrylate, and ethoxylated pentaerythritol tetraacrylate.

[0033] More specifically, IBXA (manufactured by Osaka Organic Chemical Industry Co., Ltd.), NK Ester A-LEN-10, AM-90G, AM-130G, AMP-20GY, A-SA, S-1800A, 701A, A-200, A-400, A-600, A-1000, A-B1206PE, ABE-300, A-BPE-10, A-BPE-20, A-BPE-30, and A-BPE-4 , A-BPEF, A-BPP-3, A-DCP, A-DOD-N, A-HD-N, A-NOD-N, APG-100, APG-200, APG-400, APG-700, A-P TMG-65, A-9300, A-9300-1CL, A-GLY-9E, A-GLY-20E, A-TMM-3, A-TMM-3L, A-TMM-3LM-N, A-TMPT, AD-TMP, ATM-35E, A-TMMT, A-9550, A-DPH, CB-1, M-90G, M-230G, PHE-1G, S, SA, 1G, 2G, 3G, 4G, 9G, 14G, 23G, BPE-80N, BPE-100, BPE-200, BPE-500, BPE-900, BPE-1300N, DCP, DOD-N, HD-N, NOD-N, N PG, 1206PE, 701, 9G, TMPT (all manufactured by Shin-Nakamura Chemical Co., Ltd.), Aronix M-111, M-120, M-140 (all manufactured by Toagosei Co., Ltd.), Blenmar PDE-100, PDE-200, PDE-400, PDP-400N, ADE-200, ADE-300, ADE-400A and ADP-400 (all manufactured by NOF Corporation). Among these, isobornyl acrylate, isobornyl methacrylate, tricyclodecane dimethanol diacrylate, tricyclodecane dimethanol dimethacrylate, polyethylene glycol #200 diacrylate, polyethylene glycol #400 diacrylate, polyethylene glycol #600 diacrylate, polyethylene glycol #200 dimethacrylate, polyethylene glycol #400 dimethacrylate, polyethylene glycol #600 dimethacrylate, tripropylene glycol diacrylate, polypropylene glycol #400 diacrylate, polypropylene glycol #700 diacrylate, tripropylene glycol dimethacrylate, polypropylene glycol #400 dimethacrylate, polypropylene glycol #700 dimethacrylate, ethoxylated bisphenol A diacrylate, ethoxylated bisphenol A dimethacrylate, nonylphenol EO-modified acrylate, and nonylphenol EO-modified methacrylate are preferred.

[0034] From the viewpoint of adhesion between the liquid crystal layer and the electrode, the polymerizable composition preferably contains a compound containing two or more thiol groups in the molecule. Specifically, trimethylolpropane tris(3-mercaptopropionate), tris-[(3-mercaptopropionyloxy)-ethyl]-isocyanurate, pentaerythritol tetrakis(3-mercaptopropionate), tetraethylene glycol bis(3-mercaptopropionate), dipentaerythritol hexakis(3-mercaptopropionate), trimethylolpropane tris(3-mercaptobutyrate ... Examples of suitable mercaptobutyrates include dipentaerythritol ethane tris(3-mercaptobutyrate), pentaerythritol tetrakis(3-mercaptobutyrate), 1,3,5-tris(3-mercaptobutyryloxyethyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, neopentanetetrathiol, pentaerythritol tetrakis(3-mercaptopropionate), and dipentaerythritol hexakis(3-mercaptopropionate). More specifically, examples include Karenz MTPE1, BD1, NR1, and TPMB (all manufactured by Showa Denko K.K.). Of these, it is preferable to use Karenz MTPE1, BD1, and NR1 (all manufactured by Showa Denko K.K.).

[0035] Furthermore, the polymerizable composition preferably contains a urethane acrylate from the viewpoints of the curability of the liquid crystal layer and the adhesion between the liquid crystal layer and the electrode. Examples of urethane acrylates include aromatic urethane acrylates and aliphatic urethane acrylates. Here, "aromatic urethane acrylate" refers to a urethane acrylate having at least one aromatic group. Furthermore, "aliphatic urethane acrylate" refers to a urethane acrylate having an aliphatic group but no aromatic group. Specific examples of urethane acrylates include EBECRYL 210, 220, 230, 270, 4858, 8402, 8804, 8807, 9270, 4513, 4738, 4740, 8311, 9260, 8701, 4265, 4587, 4666, 8210, 1290, 5129, 8301R, 4501, 2221, 1271, 4859, 8409, 8465, 8809, 8810, 8811, 4101, 4201, 8209, 1291, 8602, 225, KRM 8191, 8667, 8296, 8200, 8904, and 8452 (all manufactured by Daicel-Allnex Co., Ltd.). Among these, from the viewpoint of the transparency of the liquid crystal layer, it is preferable to use aliphatic urethane acrylates such as EBECRYL230, 4858, 8402, 8804, 8807, 9270, 4859, 8465, 8809 and 8811 (all manufactured by Daicel Allnex Co., Ltd.).

[0036] In order to promote radical polymerization of the polymerizable compound, it is preferable to incorporate a radical initiator (also called a photoradical initiator) that generates radicals when exposed to ultraviolet light into the liquid crystal composition.

[0037] Photoradical initiators include 2,2-dimethoxy-1,2-diphenylethan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropionyl)-benzyl]phenyl}-2-methylpropan-1-one, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone, and 2,4,6-trimethylbenzoyl. diphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, 1-[4-(phenylthio)phenyl]octane-1,2-dione 2-(O-benzoyloxime)], 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-ethanone 1-(O-acetyloxime), methylbenzoyl formate, a mixture of oxy-phenyl-acetic acid 2-[2-oxo-2-phenyl-acetoxy-ethoxy]ethyl ester and oxyphenylacetic-2-[2-hydroxy-ethoxy]ethyl ester, and 2-benzyl-2-(dimethylamino)-1-[4-(4-morpholinyl)phenyl]-1-butanone. More specifically, examples of such resins include Omnirad 1173, 184, 127, 2959, 369, 379, 389, 907, 4265, 1000, 651, TPO-H, TPO-L, 819, 819DW, 2022, 2100, 754, OXE-01, OXE-02, OXE-03, OXE-04, BPFlakes, 4MBZFlakes, OMBB, 1601, BMS, ITX, DETX, BBF, EMK, Esacure KIP150, KIP100F, and TZT (all manufactured by IGM Resins).

[0038] Among these, 1-hydroxycyclohexyl phenyl ketone (Omnirad 184 / IGM Resins), 2-hydroxy-2-methyl-1-phenylpropan-1-one (Omnirad 1173 / IGM Resins), 2-benzyl-2-(dimethylamino)-1-[4-(4-morpholinyl)phenyl]-1-butanone (Omnirad 369 / IGM Resins), 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one (Omnirad 907 / IGM Resins), bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide (Omnirad 819 / IGM Resins), 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (Omnirad TPO-H / IGM Resins), Omnirad TPO-L / IGM Resins, etc. It is preferable to use 1-[4-(phenylthio)phenyl]octane-1,2-dione 2-(O-benzoyloxime)](O-acetyloxime) (OmniradOXE01 / IGM Resins) and 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-ethanone 2,1-(O-acetyloxime) (OmniradOXE02 / IGM Resins).

[0039] From the viewpoint of the curability of the liquid crystal layer, the proportion of the photoradical initiator used is preferably 0.01 to 20 parts by mass, more preferably 0.05 to 10 parts by mass, relative to 100 parts by mass of the polymerizable composition. Furthermore, the photoradical initiator may be used alone or in combination of two or more types, depending on the wavelength of the light source used in the curing treatment and the curability of the liquid crystal layer.

[0040] Methods for preparing the liquid crystal composition include a method of mixing liquid crystal and a polymerizable composition containing a specific polymerizable compound together, and a method of mixing a mixture of a specific polymerizable compound and other polymerizable compounds in advance with liquid crystal.

[0041] Among these, in the present invention, a method in which a mixture of the specific polymerizable compound and other polymerizable compounds is mixed in advance and then mixed with the liquid crystal is preferred.

[0042] When preparing the liquid crystal composition, heating may be performed, and the temperature at that time is preferably less than 100°C.

[0043] <Method for manufacturing liquid crystal display element> The substrate used in a liquid crystal display element is not particularly limited as long as it is a highly transparent substrate. In addition to glass substrates, plastic substrates such as acrylic substrates, polycarbonate substrates, and PET (polyethylene terephthalate) substrates, as well as films thereof, can be used. Plastic substrates and films are particularly preferred for use in light-control windows. From the viewpoint of process simplification, it is preferable to use a substrate on which an ITO electrode, an IZO (indium zinc oxide) electrode, an IGZO (indium gallium zinc oxide) electrode, an organic conductive film, or the like for driving liquid crystal is formed. In addition, when a reflective liquid crystal display element is to be produced, a substrate on which a silicon wafer, a metal such as aluminum, or a dielectric multilayer film is formed can be used as the substrate on only one side.

[0044] The method for injecting the liquid crystal composition is not particularly limited, and examples thereof include the following methods. That is, when glass substrates are used as the substrates, a pair of substrates is prepared, and a sealant is applied to the four sides of one substrate, excluding a portion, and then the other substrate is attached with the electrode surface facing inward to produce an empty cell. The liquid crystal composition is then injected under reduced pressure from the area where the sealant is not applied to obtain a liquid crystal composition-injected cell. Furthermore, when plastic substrates or films are used as the substrates, a pair of substrates is prepared, and the liquid crystal composition is dropped onto one substrate by ODF (One Drop Filling) or inkjet printing, and then the other substrate is attached to obtain a liquid crystal composition-injected cell. In the liquid crystal display element of the present invention, the adhesion between the liquid crystal layer and the electrodes is high, so it is not necessary to apply a sealant to the four sides of the substrates.

[0045] The electrode gap (also called the gap) of a liquid crystal display element can be controlled by using spacers or the like. Methods for controlling this include introducing spacers of the desired size into the liquid crystal composition and using substrates with column spacers of the desired size. Furthermore, when plastic or film substrates are used as substrates and the substrates are bonded together by lamination, the gap can also be controlled without introducing spacers.

[0046] The gap size of the liquid crystal display element is preferably 1 to 100 μm, more preferably 1 to 50 μm, and particularly preferably 2 to 30 μm. If the gap is too small, the contrast of the liquid crystal display element will decrease, and if it is too large, the driving voltage of the element will increase.

[0047] A liquid crystal display element is obtained by curing a liquid crystal composition to form a liquid crystal layer. The liquid crystal composition is preferably cured by irradiating the liquid crystal composition-injected cell with ultraviolet light. Examples of the light source for the ultraviolet light irradiation device used in this case include a metal halide lamp and a high-pressure mercury lamp. In this case, the wavelength of the ultraviolet light is preferably 250 to 400 nm, and more preferably 310 to 370 nm. The intensity of ultraviolet light irradiation can be appropriately determined by experiments, etc., and the end point may be determined by the concentration of the unreacted polymerizable compound in the present liquid crystal composition, etc. From the viewpoint of productivity, the intensity of ultraviolet light irradiation is set to 0.1 mW / cm 2 It is preferable that the power is 1 mW / cm or more to complete the polymerization of the polymerizable compound. 2 The intensity of the irradiated light may be higher. Furthermore, during the irradiation of ultraviolet light, a voltage may be applied between the electrodes, or no voltage may be applied between the electrodes.

[0048] After the ultraviolet irradiation, a heat treatment may be carried out. The temperature at this time is preferably 20 to 120°C, and more preferably 30 to 100°C. [Example]

[0049] The present invention will be described in more detail below with reference to examples, but is not limited to these examples.

[0050] The abbreviations used below are as follows: "Compounds used in liquid crystal compositions" <Specific polymerizable compound> S1: KAYARAD FM-400 (manufactured by Nippon Kayaku Co., Ltd.) (polymerizable compound represented by formula [1a-1]) S2: KAYARAD HX-220 (manufactured by Nippon Kayaku Co., Ltd.) (polymerizable compound represented by formula [1a-2]) <Second specific polymerizable compound> T1: KAYAMER PM-21 (manufactured by Nippon Kayaku Co., Ltd.) (polymerizable compound represented by formula [2]) (Note that the product catalog for KAYAMER PM-21 describes a compound corresponding to the polymerizable compound in formula [2] in which Ym is approximately 1.5 and Yn is approximately 1.5, but these values ​​are average values ​​for multiple compounds.) <Third specific polymerizable compound> U1: A polymerizable compound represented by the following formula [U1] (a polymerizable compound represented by formula [3]) [ka] <Other polymerizable compounds> R1: IBXA (Osaka Organic Chemical Industry Co., Ltd.) (isobornyl acrylate) R2: 2-hydroxyethyl methacrylate (Tokyo Chemical Industry Co., Ltd.) R3: A-200 (Shinnakamura Chemical Co., Ltd.) (polyethylene glycol diacrylate) R4: EBECRYL 9270 (manufactured by Daicel Allnex) (urethane acrylate) R5: Karenz MT PE1 (Showa Denko) (pentaerythritol tetrakis(3-mercaptobutyrate))

[0051] <Photoradical initiator> P1: Omnirad 184 (IGM Resins) <LCD> L1: MLC-3018 (Merck)

[0052] "Preparation of liquid crystal composition" <Preparation of Liquid Crystal Composition (1)> S1 (3.0 g), R1 (1.5 g), R2 (0.2 g), and R5 (0.3 g) were mixed and stirred at 25° C. for 6 hours to prepare a polymerizable composition solution. Then, this polymerizable composition solution (5.0 g), P1 (0.25 g), and L1 (7.5 g) were mixed and stirred at 25° C. for 8 hours to obtain liquid crystal composition (1). <Preparation of Liquid Crystal Composition (2)> S2 (2.5 g), R1 (2.0 g), R2 (0.2 g), and R5 (0.3 g) were mixed and stirred at 25° C. for 6 hours to prepare a polymerizable composition solution. Then, this polymerizable composition solution (5.0 g), P1 (0.25 g), and L1 (6.5 g) were mixed and stirred at 25° C. for 8 hours to obtain liquid crystal composition (2). <Preparation of Liquid Crystal Composition (3)> S1 (1.5 g), S2 (1.5 g), R1 (1.5 g), R2 (0.2 g), and R5 (0.3 g) were mixed and stirred at 25° C. for 6 hours to prepare a polymerizable composition solution. Then, this polymerizable composition solution (5.0 g), P1 (0.25 g), and L1 (7.0 g) were mixed and stirred at 25° C. for 8 hours to obtain liquid crystal composition (3).

[0053] <Preparation of Liquid Crystal Composition (4)> S1 (1.5 g), S2 (1.5 g), R1 (1.5 g), R2 (0.2 g), and R5 (0.3 g) were mixed and stirred at 25° C. for 6 hours to prepare a polymerizable composition solution. Then, this polymerizable composition solution (5.0 g), T1 (0.01 g), P1 (0.25 g), and L1 (7.0 g) were mixed and stirred at 25° C. for 8 hours to obtain liquid crystal composition (4). <Preparation of Liquid Crystal Composition (5)> S1 (1.5 g), S2 (1.5 g), R1 (1.5 g), R2 (0.2 g), and R5 (0.3 g) were mixed and stirred at 25° C. for 6 hours to prepare a polymerizable composition solution. Then, this polymerizable composition solution (5.0 g), T1 (0.01 g), U1 (0.35 g), P1 (0.25 g), and L1 (7.0 g) were mixed and stirred at 25° C. for 8 hours to obtain liquid crystal composition (5). <Preparation of Liquid Crystal Composition (6)> S1 (1.5 g), S2 (1.2 g), R1 (1.5 g), R2 (0.2 g), R4 (0.3 g), and R5 (0.3 g) were mixed and stirred at 25° C. for 6 hours to prepare a polymerizable composition solution. Then, this polymerizable composition solution (5.0 g), T1 (0.01 g), P1 (0.25 g), and L1 (7.0 g) were mixed and stirred at 25° C. for 8 hours to obtain liquid crystal composition (6).

[0054] <Preparation of Liquid Crystal Composition (7)> S1 (2.0 g), S2 (1.0 g), R1 (1.5 g), R4 (0.2 g), and R5 (0.3 g) were mixed and stirred at 25° C. for 6 hours to prepare a polymerizable composition solution. Then, this polymerizable composition solution (5.0 g), T1 (0.02 g), P1 (0.35 g), and L1 (7.0 g) were mixed and stirred at 25° C. for 8 hours to obtain liquid crystal composition (7). <Preparation of Liquid Crystal Composition (8)> R1 (1.5 g), R2 (0.2 g), R3 (3.0 g), and R5 (0.3 g) were mixed and stirred at 25° C. for 6 hours to prepare a polymerizable composition solution. Then, this polymerizable composition solution (5.0 g), P1 (0.25 g), and L1 (7.5 g) were mixed and stirred at 25° C. for 8 hours to obtain liquid crystal composition (8).

[0055] "Fabrication of liquid crystal display elements (glass substrate)" Two glass substrates (length: 100 mm, width: 100 mm, thickness: 0.7 mm) with ITO electrodes were prepared and washed with pure water and IPA (isopropyl alcohol). 15 μm spacers were applied to the ITO surface of one of the substrates. Liquid crystal compositions (1) to (8) were then dropped onto the spacer-coated surface of the substrate by the ODF (One Drop Filling) method. The other substrate was then bonded to the ITO surface, facing each other, to obtain a pre-processed liquid crystal display element. The LCD panel before this treatment was exposed to an illumination of 10 mW / cm 2 The substrate was irradiated with ultraviolet light for 60 seconds using a metal halide lamp with wavelengths of 350 nm or less cut off, thereby obtaining a liquid crystal display element (glass substrate).

[0056] "Fabrication of liquid crystal display elements (plastic substrate)" Two PET substrates (length: 150 mm, width: 150 mm, thickness: 0.1 mm) with ITO electrodes were prepared and washed with pure water. A 15 μm spacer was applied to the ITO surface of one of the substrates. The liquid crystal compositions (1) to (8) were then dropped onto the spacer-coated ITO surface of the substrate by the ODF method. The other substrate was then bonded to the other substrate so that the ITO surface faced each other, yielding a pre-processed liquid crystal display element. When dropping the liquid crystal composition and bonding the substrates by the ODF method, a glass substrate was used as a support substrate for the PET substrates with ITO electrodes. The support substrate was then removed before UV irradiation. This untreated liquid crystal display element was irradiated with ultraviolet light in the same manner as in the above "Preparation of liquid crystal display element (glass substrate)" to obtain a liquid crystal display element (plastic substrate).

[0057] "Evaluation of optical properties (scattering properties and transparency)" This evaluation was carried out by measuring the haze (cloudiness) of the liquid crystal display element (glass substrate and plastic substrate) with no applied voltage (0 V) and with an applied voltage (AC drive: 15 to 60 V). The haze was measured using a haze meter (HZ-V3, manufactured by Suga Test Instruments Co., Ltd.) in accordance with JIS K 7136. In this evaluation, the higher the haze in the no-voltage-applied state (0 V), the better the scattering properties, and the lower the haze in the applied voltage state (60 V), the better the transparency. Furthermore, as a stability test for the LCD elements in a high-temperature, high-humidity environment, measurements were also taken after storing them for 24 hours in a thermo-hygrostat chamber at a temperature of 80°C and a humidity of 90% RH. Specifically, the smaller the change in haze after storage in the thermo-hygrostat chamber compared to the initial haze, the better the evaluation. Furthermore, as a stability test for the liquid crystal display element against light irradiation, a tabletop UV curing device (HCT3B28HEX-1) (manufactured by Senlite Co., Ltd.) was used to test the stability of the liquid crystal display element against light irradiation at 5 J / cm2 at a wavelength of 365 nm. 2 Specifically, the smaller the change in haze after UV irradiation compared to the initial haze, the better the evaluation. Table 1 shows the measurement results of haze initially, after storage in a constant temperature and humidity chamber (constant temperature and humidity), and after ultraviolet light irradiation (ultraviolet light).

[0058] "Evaluation of adhesion between liquid crystal layer and electrodes" This evaluation was carried out by storing the liquid crystal display elements (glass substrate and plastic substrate) in a constant temperature and humidity chamber at a temperature of 80°C and a humidity of 90%RH for 24 hours, and checking for peeling and the presence of bubbles in the liquid crystal display elements (as a stability test for liquid crystal display elements in a high-temperature, high-humidity environment). Specifically, elements that did not experience peeling (peel-off between the liquid crystal layer and the resin film, or between the resin film and the electrodes) and elements that did not experience bubbles were rated as excellent in this evaluation (shown as good in the table). In Examples 4 to 7, in addition to the standard test, an enhanced test was also performed in which the samples were stored in a thermo-hygrostat at a temperature of 80° C. and a humidity of 90% RH for 72 hours. The evaluation method was the same as above. In addition, a desktop UV curing device (HCT3B28HEX-1) (manufactured by Senlite) was used to cure the liquid crystal display element at 5 J / cm2 at a wavelength of 365 nm. 2 (As a stability test of the liquid crystal display element against light irradiation.) Specifically, the element was evaluated as excellent if there was no peeling of the element and no air bubbles were generated inside the element (shown as good in the table). Table 2 shows the results (adhesion) of the adhesion between the liquid crystal layer and the electrode initially, after storage in a constant temperature and humidity chamber (constant temperature and humidity), and after ultraviolet light irradiation (ultraviolet light).

[0059] <Examples 1 to 8, Comparative Examples 1 and 2> As shown in Tables 1 and 2 below, using the above liquid crystal compositions (1) to (8), liquid crystal display elements were prepared by the above methods, and their optical properties (scattering properties and transparency) and adhesion between the liquid crystal layer and the electrodes were evaluated. In Examples 1, 3, 8, and Comparative Example 1, glass substrates were used to fabricate and evaluate liquid crystal display elements, while plastic substrates were used in Examples 2, 4, 5, 6, 7, and Comparative Example 2.

[0060] [Table 1]

[0061] [Table 2]

[0062] As described above, the liquid crystal display elements of the examples exhibited better optical properties than the comparative examples, i.e., the change in haze after storage in a constant temperature and humidity chamber and after UV irradiation was smaller compared to the initial state. Furthermore, the liquid crystal display elements exhibited high adhesion between the liquid crystal layer and the electrodes, and no peeling or bubbles were observed in the liquid crystal display elements even after exposure to these harsh environments. In particular, these properties were excellent even when a plastic substrate was used as the substrate for the liquid crystal display element. Specifically, the comparisons under the same conditions were made between Example 1 and Comparative Example 1, and between Example 2 and Comparative Example 2. Furthermore, when the polymerizable composition contained the second specific polymerizable compound in addition to the specific polymerizable compound, fewer bubbles were generated in the liquid crystal display element even after long-term storage in a constant temperature and humidity chamber as in the stress test, compared to when the second specific polymerizable compound was not used. Specifically, this is a comparison between Example 4 and Example 5 under the same conditions. Furthermore, when the polymerizable composition contained a third specific polymerizable compound in addition to the specific polymerizable compound, the haze under voltage application was lower and the driving voltage was also lower than when the third specific polymerizable compound was not used. Specifically, in a comparison between Example 5 and Example 6 under the same conditions, the haze of Example 6 was lower at an applied voltage lower than that of Example 5. In addition, when the polymerizable composition contained urethane acrylate in addition to the specific polymerizable compound, bubbles were not generated in the liquid crystal display element even after long-term storage in a constant temperature and humidity chamber as performed in an stress test, compared to when the polymerizable composition did not contain the specific polymerizable compound. Specifically, this is a comparison between Example 5 and Example 7 under the same conditions. [Industrial Applicability]

[0063] By using a liquid crystal composition containing a polymerizable compound having a specific structure, it is possible to obtain a liquid crystal display element that can improve the adhesion between the liquid crystal layer and the electrodes, and can suppress peeling of the element, the generation of bubbles, and the deterioration of optical properties even in harsh environments such as exposure to high temperature and humidity and light irradiation for long periods of time. The liquid crystal display element of the present invention can be suitably used as a normal-type element that is in a scattering state when no voltage is applied and in a transparent state when a voltage is applied. This element can be used for liquid crystal displays for display purposes, as well as for light control windows and optical shutter elements that control the blocking and transmission of light. A plastic substrate can be used as the substrate of this normal-type element.

[0064] The entire contents of the specification, claims, drawings and abstract of Japanese Patent Application No. 2020-202015, filed on December 4, 2020, are hereby incorporated by reference as part of the disclosure of the specification of the present invention.

Claims

1. A liquid crystal display element having a liquid crystal layer formed by irradiating a liquid crystal composition containing a liquid crystal and a polymerizable composition disposed between a pair of substrates each having an electrode with ultraviolet light to cure the liquid crystal composition, Furthermore, a transmissive scattering type liquid crystal display element that is in a scattering state when no voltage is applied and in a transparent state when a voltage is applied, The polymerizable composition contains two or more compounds having a structure represented by the following formula [1A]: The compound having a structure represented by the following formula [1A] is a compound represented by the following formula [1a]: The two or more compounds having a structure represented by formula [1A] are two or more compounds selected from the following formulas [1a-1] to [1a-3]: A liquid crystal display device characterized in that the content of a compound having a structure represented by the following formula [1A] is 40 to 95 parts by mass in 100 parts by mass of a polymerizable composition: 【Chemistry 1】 (* indicates a bond.) 【Chemistry 2】 (X 1 and X 2 each independently represent a structure selected from the following formulae [1-a] to [1-d]. A represents the formula [1A]. L 1 and L 2 each independently represent a single bond or an alkylene group having 1 to 42 carbon atoms, and any —CH 2 — in the alkylene group may be replaced by —O—, —CO—, —COO—, —OCO—, —CONH—, —NHCO—, —NH—, a benzene ring, or a cyclohexane ring.) 【Transformation 3】 (* indicates a bond.) 【Chemistry 4】 (m and n each independently represent an integer of 0 or more.)

2. 2. The liquid crystal display device according to claim 1, wherein the polymerizable composition further contains one or more compounds represented by the following formula [2]: 【Transformation 5】 (Y １ represents the following formula [2-a] or [2-b]. ２ represents an alkylene group having 2 to 24 carbon atoms, and Y １ or any —CH that is not adjacent to O ２ - represents -O-, -CO-, -COO-, -OCO-, -CONH-, -NHCO-, -NH-, or -CON(CH ３ Ym represents an integer of 1 to 2. Yn represents an integer of 1 to 2. However, Ym+Yn is 3. Y １ and Y ２ If there are multiple Y １ and Y ２ and each independently have the definition above. 【Transformation 6】 (* indicates a bond.)

3. The polymerizable composition is a polymerizable composition having, in the formula [2], Y １ and Y ２ is as claimed in claim 2, Ym is 1, and Yn is 2; and １ and Y ２ and a compound [2-2] in which Ym is 2 and Yn is 1, as defined in claim 2.

4. 4. The liquid crystal display element according to claim 2, wherein the compound represented by formula [2] is at least one selected from the group consisting of the following formulas [2a-1] to [2a-3]: 【Transformation 7】 (X ａ represents the formula [2-a] or [2-b]. ｂ represents an alkylene group having 2 to 18 carbon atoms, and X of the alkylene group ａ or any —CH that is not adjacent to O ２ - represents -O-, -CO-, -COO-, -OCO-, -CONH-, -NHCO-, -NH-, or -CON(CH ３ )- may be substituted. ｃ represents —COO— or —OCO—. ｄ represents an alkylene group having 2 to 12 carbon atoms. p1 represents an integer of 1 or 2. p2 represents an integer of 1 or 2, provided that p1+p2 is 3. p3 represents an integer of 2 to 8. X ａ , X ｂ , X ｃ , X ｄ and when there are a plurality of p3, a plurality of X ａ , X ｂ , X ｃ , X ｄ and p3 independently have the above definitions.

5. 5. The liquid crystal display element according to claim 2, wherein the content of the compound having a structure represented by the formula [2] is 0.01 to 10 parts by mass in 100 parts by mass of the polymerizable composition.

6. 6. The liquid crystal display element according to claim 1, wherein the polymerizable composition further contains one or more compounds represented by the following formula [3]: 【Transformation 8】 (Z １ represents any structure selected from the following formulas [3-a] to [3-e]. ２ is a single bond, -O-, -NH-, -N(CH ３ ) -, -CH ２ O-, -CONH-, -NHCO-, -CON(CH ３ ) -, -N(CH ３ ) represents CO—, —COO—, or —OCO—. ３ is a single bond or -(CH ２ ) ａ - (where a is an integer of 1 to 15). Z ４ is a single bond, -O-, -OCH ２ represents -, -COO- or -OCO-. ５ represents a divalent cyclic group selected from a benzene ring, a cyclohexane ring, and a heterocycle, or a divalent organic group having 17 to 51 carbon atoms and a steroid skeleton, and any hydrogen atom on the cyclic group may be substituted with an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxy group having 1 to 3 carbon atoms, or a fluorine atom. Z ６ is a single bond, -O-, -CH ２ -, -OCH ２ -, -CH ２ represents —O—, —COO—, or —OCO—. ７ represents a cyclic group selected from a benzene ring, a cyclohexane ring, and a heterocycle, and any hydrogen atom on these cyclic groups may be substituted with an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxy group having 1 to 3 carbon atoms, or a fluorine atom. Z ８ represents an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, or a fluorine-containing alkoxy group having 1 to 18 carbon atoms. Zm represents an integer of 0 to 4. When Zm is 2 or more, Zm Z ７ each independently has the definition above. 【Chemistry 9】 (* indicates a bond.)

7. The liquid crystal display element according to claim 6, wherein the compound represented by formula [3] is at least one selected from the group consisting of the following formulas [3a-1] to [3a-2], [3a-5] to [3a-6], and [3a-9] to [3a-10]: 【Chemistry 10】 (Y ａ represents —O— or —COO—. ｂ represents an alkyl group having 1 to 12 carbon atoms; q1 represents an integer of 1 to 10; and q2 represents an integer of 1 or 2. 【Chemistry 11】 (Y ｃ represents a single bond, —COO— or —OCO—. ｄ represents an alkyl group or an alkoxy group having 1 to 12 carbon atoms; q3 represents an integer of 1 to 10; and q4 represents an integer of 1 or 2. 【Chemistry 12】 (Y ｅ represents —O— or —COO—. ｆ represents a divalent organic group having a steroid skeleton and having 17 to 51 carbon atoms. ｇ represents an alkyl group having 1 to 12 carbon atoms or an alkenyl group having 2 to 18 carbon atoms. q5 represents an integer of 1 to 10.

8. 8. The liquid crystal display element according to claim 6, wherein the content of the compound having the structure represented by the formula [3] is 0.1 to 30 parts by mass in 100 parts by mass of the polymerizable composition.

9. 9. The liquid crystal display element according to claim 1, wherein the polymerizable composition further contains one or more kinds of urethane acrylate.

10. 10. The liquid crystal display element according to claim 1, wherein the liquid crystal composition further contains a photoradical initiator.

11. 11. The liquid crystal display element according to claim 1, wherein the substrate of the liquid crystal display element is a glass substrate or a plastic substrate.

12. 12. The liquid crystal display element according to claim 1, which is a normal type element.

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