Polymer-dispersed liquid crystal elements and their manufacturing methods

Abstract

This invention provides a polymer-dispersed liquid crystal element comprising a liquid crystal alignment film exhibiting high light transmittance in a high-transmittance state and high adhesion between the polymer liquid crystal layer and the substrate. The polymer-dispersed liquid crystal element comprises: One of the opposing configurations is a pair of substrates. Electrodes respectively disposed on the facing surfaces of the aforementioned pair of substrates. A dimming layer containing a polymer phase and a liquid crystal phase, disposed between the aforementioned pair of substrates, and A liquid crystal alignment film formed on at least one electrode configuration surface of the aforementioned pair of substrates, The aforementioned dimming layer is formed by the polymerization of a dimming layer forming material. The aforementioned dimming layer forming material contains liquid crystal components and polymeric compound components. The aforementioned liquid crystal alignment film is formed from a liquid crystal alignment agent containing the following component (A). In equation (1), the meaning of each symbol is as defined in the instruction manual. In equation (2), the meaning of each symbol is as defined in the instruction manual.

Description

[Technical Field]

[0001] This invention relates to polymer-dispersed liquid crystal elements and their manufacturing methods. [Previous Technology]

[0002] Polymer-dispersed liquid crystal elements do not require a polarizing plate, so compared with conventional liquid crystal display elements using polarizing plates in TN, STN, IPS or VA modes, they have the advantage of being able to display brighter images. The element structure is also simple, so they are used in light shutter applications such as dimming glass, and segmented display applications such as clocks.

[0003] Several types of polymer-dispersed liquid crystal elements have been proposed, such as: the type called NCAP (Nematic Curvilinear Aligned Phase) (Patent Document 1), the type called PDLC (Polymer Dispersed Liquid Crystal) (Patent Document 2, Patent Document 3), the type called PNLC (Polymer Network Liquid Crystal) (Patent Document 4), and polymer-stabilized cholesteric texture (PSCT) using cholesteric liquid crystal, etc.

[0004] Liquid crystal elements using PDLC and PNLC are being actively researched. It is known that there are normal mode polymer-dispersed liquid crystal elements (Patent Document 5) where the liquid crystals are in a random white (light scattering) state when no voltage is applied, and align with the electric field and transmit light when a voltage is applied, becoming a transmission state; and reverse mode polymer-dispersed liquid crystal elements (Patent Document 6) where the liquid crystals are in a transmission state when no voltage is applied and scatter when a voltage is applied. For dimming applications, dimming elements with the following structure have been explored: a polymer liquid crystal layer containing liquid crystal molecules encapsulated in a polymer is used as the dimming layer, and the dimming layer is sandwiched between a pair of glass substrates and plastic substrates with transparent electrodes formed by transparent conductive films on both sides; sometimes a liquid crystal alignment film for aligning the liquid crystal molecules is also formed on the surface of the transparent electrodes. [Prior Art Documents] [Patent Documents]

[0005] [Patent Document 1] Japanese Patent Application Publication No. 58-501631 [Patent Document 2] Japanese Patent Application Publication No. 2-15236 [Patent Document 3] Japanese Patent Application Publication No. 63-271233 [Patent Document 4] Japanese Patent Application Publication No. 1-198725 [Patent Document 5] International Publication 2020 / 184420 [Patent Document 6] International Publication 2014 / 133154 [Summary of the Invention]

[0006] [The problem the invention aims to solve]

[0007] In recent years, dimming elements using the aforementioned polymer liquid crystal layers have been studied for their high light transmittance, leading to applications in automotive sunroofs, display windows capable of showing text and patterns, and smart windows that are expected to block infrared light. In these applications, the ability to block the view is required in the light scattering state, while ensuring a sufficient view in the transmission state. Therefore, for dimming elements using PDLC and PNLC, there is a greater need to maximize light transmittance in the transmission state than has been the case to date. If the adhesion between the polymer liquid crystal layer and the substrate in the dimming element is low, the light scattering properties will change over time, potentially resulting in the loss of the ability to block the view. Therefore, a liquid crystal alignment film with high adhesion between the polymer liquid crystal layer and the substrate is sought.

[0008] This invention was developed to solve the above-mentioned problems, and its object is to provide a polymer-dispersed liquid crystal element having a liquid crystal alignment film with high light transmittance in the transmission state and high adhesion between the polymer liquid crystal layer and the substrate. Furthermore, this invention provides a liquid crystal alignment agent for the liquid crystal alignment film with high light transmittance in the transmission state and high adhesion between the polymer liquid crystal layer and the substrate, and the liquid crystal alignment film. [Solution to the Problems]

[0009] In order to achieve the above-mentioned problem, the inventors of this case have made great efforts to study and found that polymeric dispersion liquid crystals containing the following components are effective in achieving the above-mentioned objective, and thus completed the present invention.

[0010] The present invention is based on the following: A polymer-dispersed liquid crystal element comprising: a pair of substrates arranged opposite to each other; electrodes disposed on mutually facing surfaces of the pair of substrates; a dimming layer disposed between the pair of substrates and containing a polymer phase and a liquid crystal phase; and a liquid crystal alignment film formed on at least one electrode surface of the pair of substrates, wherein the dimming layer is formed by polymerization of a dimming layer forming material, the dimming layer forming material containing a liquid crystal composition and a polymeric compound component; and the liquid crystal alignment film is formed by a liquid crystal alignment agent containing the following component (A); (A) component: at least one polymer (A) selected from the group consisting of a polyimide precursor obtained by reacting a diamine component containing a diamine (1) represented by formula (1) and a diamine (2) represented by formula (2) with a tetracarboxylic acid component, and a polyimide consisting of a polyimide of the same. [Chemical 1] In the formula, X1 represents a single bond, -(CH2)a- (a is an integer from 1 to 15), -CONH-, -NHCO-, -CON(CH3)-, -NH-, -O-, -COO-, -OCO-, -CH2-OCO-, -OCH2-, or -((CH2)a1-A1)m1- (a1 is an integer from 1 to 15, A1 represents an oxygen atom or -COO-, m1 is an integer from 1 to 2, when m1 is 2, multiple a1 and A1 have the above definitions independently), G1 represents a divalent aromatic hydrocarbon group selected from 6 to 12 carbon atoms, a divalent alicyclic hydrocarbon group selected from 4 to 8 carbon atoms, and a divalent cyclic group of steroid skeleton. Any hydrogen atom on the cyclic group can also be replaced by an alkyl group with 1 to 3 carbon atoms, an alkoxy group with 1 to 3 carbon atoms, a fluorinated alkyl group with 1 to 3 carbon atoms, a fluorinated alkoxy group with 1 to 3 carbon atoms, or a fluorine atom. When m is an integer from 1 to 4, and m is 2 or more, multiple X1 and G1 can be independently defined as described above. R1 represents a fluorine atom, an alkyl group containing fluorine atoms with 1 to 10 carbon atoms, an alkoxy group containing fluorine atoms with 1 to 10 carbon atoms, an alkyl group with 3 to 10 carbon atoms, an alkoxy group with 3 to 10 carbon atoms, or an alkoxyalkyl group with 3 to 10 carbon atoms. X represents a single bond, -O-, -NH-, -O-(CH2)m2-O-, -C(CH3)2-, -CO-, -COO-, -CONH-, -(CH2)m2-, -SO2-, -OC(CH3)2-, -CO-(CH2)m2-, -NH-(CH2)m2-, -NH-(CH2)m2-NH-, -SO2-(CH2)m2-, -SO2-(CH2)m2-SO2-, -CONH-(CH2)m2-, -CONH-(CH2)m2-NHCO-, or -COO-(CH2)m2-OCO-, where m2 is an integer from 1 to 8, and i and j are each an integer of 0 or 1. When i is 1 and j is 0, the two R0s independently have the above definitions. [Chemical Formula 2] In this formula, Y represents a divalent group, R represents a hydrogen atom or a methyl group, and m is an integer from 4 to 20. [Effects of the Invention]

[0011] According to the present invention, a liquid crystal alignment agent that provides a liquid crystal alignment film with high light transmittance in the transmission state and high adhesion between the polymer liquid crystal layer and the substrate, a liquid crystal alignment film obtained from the liquid crystal alignment agent, and a polymer-dispersed liquid crystal element having the liquid crystal alignment film can be obtained. The mechanism by which the present invention achieves the above-mentioned effects may not be clear, and it is believed that one of the reasons is as described below. That is, the alignment film forming material of the present invention, by having 4 or more alkyl carbons in the polymer component (A) containing formula (2), has high hydrophobicity, and the polymeric unsaturated bond sites are easily present at the alignment film interface, it is believed that higher adhesion can be obtained. Furthermore, by increasing the distance between the main chain of the polymer component (A) and the polymeric unsaturated bond sites of formula (2), it is believed that crosslinking with the polymer liquid crystal layer will proceed with better efficiency, and higher adhesion will be obtained.

Implementation Method

[0013] In this specification, halogen atoms may include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms. Also, in this specification, Boc represents a third butoxycarbonyl group.

[0014] <Polymer Dispersed Liquid Crystal Element> FIG1 is a schematic cross-sectional view showing an example of a liquid crystal element of the present invention. The liquid crystal element (100) includes: a pair of substrates composed of a first substrate (11) and a second substrate (17); transparent electrodes (12) and (16) respectively disposed on the mutually facing surfaces of the pair of substrates; liquid crystal alignment films (13) and (15) formed on the surfaces of the transparent electrodes; and a dimming layer (14) disposed between the first substrate (11) and the second substrate (17). The dimming layer (14) is a layer that has the function of changing transparency in response to the applied state of the electric field caused by the transparent electrodes (12) and (16). The dimming layer (14) is formed of a polymer dispersed liquid crystal with a polymer liquid crystal composite containing a polymer phase and a liquid crystal phase as an essential component. The above-mentioned polymer-dispersed liquid crystals are not particularly limited, such as: liquid crystal droplets dispersed in a transparent polymer material (PDLC), polymer network liquid crystals (PNLC) in which a polymer resin network is formed in a continuous layer of liquid crystal molecules, and polymer-stabilized cholesteric liquid crystals (PSCT) using cholesteric liquid crystal molecules, etc. The following explanation of the dimming layer (14) is based on the above-mentioned PDLC formation example.

[0015] The liquid crystal element illustrated in Figure 1 switches between a light-transmitting state (hereinafter also referred to as a low-haze state (the state with the lowest haze value)) and a light-scattering non-transmitting state (hereinafter also referred to as a high-haze state (the state with the highest haze value)) by changing the voltage applied to the dimming layer (14) and by applying an electric field. In the high-haze state, the haze value of the liquid crystal element (100) of the present invention is preferably 85% or more. In the low-haze state, the haze value of the liquid crystal element (100) of the present invention is preferably 20% or less. The haze value mentioned above is the haze value measured for the entire liquid crystal element (100) of the present invention, and is measured in accordance with ISO 14782 (JIS K7136・2000). The measuring equipment used is, for example, a GAZEGARD II transmittance haze meter (Toyo Seiki Co., Ltd.). A better form of the liquid crystal element is a normal-mode polymer dispersion liquid crystal element that is in a cloudy (light scattering) state when no voltage is applied and transmits light when voltage is applied, or a reverse-mode polymer dispersion liquid crystal element that is in a transmittance state when no voltage is applied and scatters light when voltage is applied.

[0016] Regarding the thickness of the dimming layer (14), considering the viewpoint of controlling the arrangement of liquid crystal materials and ideally exhibiting the dimming effect, 1 to 30 μm is better, 1 to 20 μm is better, and 1 to 15 μm is even better.

[0017] The first substrate (11) and the second substrate (17) are not particularly limited as long as they function as supports for the transparent electrode, and transparent film materials can be ideally used. The aforementioned transparent film material is not particularly limited, and flexible transparent film materials can be used. The aforementioned transparent film material can ideally be, for example, polyester resins such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), acrylic resins such as polymethyl methacrylate (PMMA), polyolefin resins such as polypropylene (PP), cellulose resins such as triacetyl cellulose (TCA), cyclic olefin polymers (COP), and polycarbonate (PC) resins. Among these, considering strength, heat resistance, and transparency, PET is preferable.

[0018] Furthermore, the thickness of the first substrate (11) and the second substrate (17) is not particularly limited, but from the viewpoint of having the strength to function ideally as a substrate, 20 to 300 μm is preferred, and 50 to 150 μm is even more preferred.

[0019] The transparent electrodes (12) and (16) are not particularly limited as long as they can apply a substantially uniform electric field to the dimming layer (14), and ideally, transparent conductive materials that are transparent to the sensing system can be used. The materials constituting the above transparent electrodes include, for example, metal oxides such as ITO (Indium Tin Oxide), IZO (Indium Zinc Oxide), AZO (Aluminum-doped Zinc Oxide), GZO (Gallium-doped Zinc Oxide), ATO (Antimony Tin Oxide), and ZNO (Zinc Oxide). In addition, conductive polymer films, silver nanowires, carbon nanotubes, silver-containing alloys, and other materials can also be used.

[0020] Liquid crystal alignment films (13) and (15) are formed on the respective electrode surfaces of the first substrate (11) and the second substrate (17). The liquid crystal alignment films (13) and (15) are organic thin films that regulate the alignment orientation of liquid crystal molecules in the dimming layer (14). In this embodiment, they are liquid crystal alignment films formed from a liquid crystal alignment agent containing the above-mentioned component (A). Furthermore, it is sufficient to provide liquid crystal alignment films (13) and (15) on at least one of the pair of substrates, but from the viewpoint of alignment stability, it is better to provide them on both substrates.

[0021] The dimming layer (14) is formed by polymerizing a dimming layer forming material containing liquid crystal components and polymeric compound components in a space surrounded by a sealant (not shown) disposed between a pair of substrates and between the pair of substrates in a manner that surrounds the outer edge of the electrode arrangement surface.

[0022] (Liquid Crystal Alignment Agent) Next, the liquid crystal alignment agent used to form the liquid crystal alignment films (13) and (15) will be described. The liquid crystal alignment agent contains the above-mentioned component (A) as a polymer component.

[0023] The divalent cyclic group in G1 of formula (1) above can be, for example, a monocyclic aromatic hydrocarbon group such as benzene; a condensed polycyclic aromatic hydrocarbon group formed by the condensation of two or more monocyclic aromatic hydrocarbon groups such as naphthalene and anthracene; a monocyclic alicyclic hydrocarbon group such as cyclobutane ring, cyclopentane ring, and cyclohexane ring. Furthermore, structures with a steroid skeleton can include structures containing cholesteryl, cholesterol, or lanostane groups. More ideal examples of R1 in R0 of formula (1) above can include -CnH2n+1 (n is an integer from 3 to 10), -O-CnH2n+1 (n is an integer from 3 to 10), or groups in which one or all of the hydrogen atoms of such alkyl or alkoxy groups are replaced by fluorine atoms.

[0024] A more ideal example of the above diamine (1) can be listed as the diamine represented by the following formulas (d1-1) to (d1-12). [Chemical 3][Chemical 4] Xv1 to Xv4, Xp1 to Xp8 each independently represent -(CH2)a- (a is an integer from 1 to 15), -CONH-, -NHCO-, -CON(CH3)-, -NH-, -O-, -CH2O-, -CH2-OCO-, -COO-, or -OCO-, XV5 to XV6, Xs1 to Xs4 each independently represent -O-, -CH2O-, -OCH2-, -COO-, or -OCO-. Xa to Xf are synonyms with X in formula (1), and Rv1 to Rv4, R1a to R1h are synonyms with R1 in formula (1).

[0025] Regarding the diamine (1) mentioned above, from the viewpoint of ideally obtaining the effects of the present invention, it is preferable that the diamine component used in the synthesis of polymer (A) is 5 to 90 mol% out of 100 mol%. Among them, 10 to 90 mol% is more ideal. 15 to 90 mol% is particularly ideal.

[0026] In formula (2), Y is preferably a divalent organic group represented by the base "*1-Y1-(Y2-Y3)n-*2" (n is an integer from 0 to 3. *1 represents an atomic bond with the benzene ring, and *2 represents an atomic bond with -CH2-). In the above base "*1-Y1-(Y2-Y3)n-*2", Y1 and Y3 represent a single bond, -O-, -NH-, -N(CH3)-, -CONH-, -NHCO-, -CO-N(CH3)-, -N(CH3)-CO-, -COO-, or -OCO-. However, when n is 0, Y1 represents a group other than a single bond. Y2 represents a divalent organogroup selected from the group consisting of alkyl groups with 1 to 20 carbon atoms, benzene rings, the group "-CH=CH-Ph-" (Ph represents the benzene ring), cyclohexane rings, and heterocycles. Any hydrogen atom in these divalent organogroups may be substituted by a halogen atom, an alkyl group with 1 to 3 carbon atoms, an alkoxy group with 1 to 3 carbon atoms, an alkyl group with 1 to 3 carbon atoms containing a fluorine atom, or an alkoxy group with 1 to 3 carbon atoms containing a fluorine atom. However, when Y2 represents an alkyl group, Y3 represents a group other than a single bond. When n is 2 or more, multiple Y2 and Y3 groups can each independently have the above definitions. Ideal examples of Y in equation (2) above can be listed as single bond, -O-, -NH-, -N(CH3)-, -CONH-, -NHCO-, -CO-N(CH3)-, -N(CH3)-CO-, -COO-, -OCO-, and the structures represented by equations (2Y-1) to (2Y-10).

[0027] [Chemical 5][Chemical 6] m is an integer from 1 to 20. *1 represents an atomic bond with a benzene ring, and *2 represents an atomic bond with an alkyl group.

[0028] Regarding the diamine (2) mentioned above, from the viewpoint of ideally obtaining the effects of the present invention, it is preferable that the diamine component used in the synthesis of polymer (A) is 10-95 mol% out of 100 mol%. Among them, 10-90 mol% is more ideal. 10-85 mol% is particularly ideal.

[0029] The diamines that can be used in the synthesis of the above-mentioned polymer (A) may also be diamines other than the above-mentioned diamine (1) and diamine (2) (hereinafter also referred to as other diamines). The following diamines are examples of the above-mentioned other diamines. From the viewpoint of ideally obtaining the effect of the present invention, it is more preferable for the diamine component used in the synthesis of polymer (A) to be 1 to 30 mol%, more preferable for 5 to 30 mol%, and most preferably 5 to 25 mol%. The total amount of the above-mentioned diamine (1) and diamine (2) used may be 99 mol% or less, or 95 mol% or less, of the diamine component used in the synthesis of polymer (A). Furthermore, the total amount of the above-mentioned diamine (1) and diamine (2) used may be 70 mol% or more, or 75 mol% or more, of the diamine component used in the synthesis of polymer (A).

[0030] p-phenylenediamine, 2,3,5,6-tetramethyl-p-phenylenediamine, 2,5-dimethyl-p-phenylenediamine, m-diamine, 2,4-dimethyl-m-phenylenediamine, 2,5-diaminotoluene, 2,6-diaminotoluene, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 3,3'-dihydroxy-4,4'-diaminobiphenyl, 2,2'-difluoro-4,4'-diaminobiphenyl, 3,3'-difluoro-4,4'-diaminobiphenyl, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 3,3'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 3,4' -Diaminobiphenyl, 4,4'-Diaminobiphenyl, 3,3'-Diaminobiphenyl, 2,2'-Diaminobiphenyl, 2,3'-Diaminobiphenyl, bis(4-aminophenoxy)methane, 1,2-bis(4-aminophenyl)ethane, 1,2-bis(4-aminophenoxy)ethane, 1,3-bis(3-aminophenyl)propane, 1,3-bis(3-aminophenoxy)propane, 1,4-bis(4-aminophenyl)butane, 1,4-bis(4-aminophenoxy)butane, 1,4-bis(4-amino-2-methylphenoxy)butane, 1,4-bis(3-aminophenyl)butane, bis(3,5-diethyl-4-aminophenyl)methane, 1,5-bis(4-aminophenoxy)pentane, 1,5-bis(3-aminophenyl) 1,6-bis(4-aminophenoxy)hexane, 1,6-bis(3-aminophenoxy)hexane, 1,7-bis(4-aminophenoxy)heptane, 1,7-bis(3-aminophenoxy)heptane, 1,8-bis(4-aminophenoxy)octane, 1,8-bis(3-aminophenoxy)octane, 1,9-bis(4-aminophenoxy)nonane, 1,9-bis(3-aminophenoxy)nonane, 1,10-bis(4-aminophenoxy)decane, 1,10-bis(3-aminophenoxy)decane, 1,11-bis(4-aminophenoxy)undecane, 1,11-bis(3-aminophenoxy)undecane, 1,12-bis(4-aminophenoxy)dodecane, 1,12-bis(3-aminophenoxy)pentane, Dodecane, 4-[2-[2-(4-aminophenoxy)ethoxy]ethoxy]aniline, 1,4-bis(4-aminophenyl)benzene, 1,3-bis(4-aminophenyl)benzene, 4,4'-bis(4-aminophenoxy)biphenyl, 4,4'-bis(4-aminophenoxy)diphenyl ether, 1,4-bis[4-(4-aminophenoxy)phenoxy]benzene, 1,2-bis(6-amino-2-naphthyl)ethane, 1,2-bis(6-amino-2-naphthyl)ethane, 6-[2-(4-aminophenoxy)ethoxy]-2-naphthylamine, 4'-[2-(4-aminophenoxy)ethoxy]-[1,1'-biphenyl]-4-amine, 1,4-bis[2-(4-aminophenyl)ethyl]succinate, 1,6-Bis[2-(4-aminophenyl)ethyl] adipate, 1,4-epoxyphenylbis(4-aminobenzoate), 1,4-epoxyphenylbis(3-aminobenzoate), 1,3-epoxyphenylbis(4-aminobenzoate), 1,3-epoxyphenylbis(3-aminobenzoate), bis(4-aminophenyl) terephthalate, bis(3-aminophenyl) terephthalate, bis(4-aminophenyl) isophthalate, bis(3-aminophenyl) isophthalate (hereinafter, these diamines are collectively referred to as diamines (Ar)); diamines with photoalignment groups such as 4,4'-diaminoazobenzene or diaminodiphenylacetylene; 2-(2,4-diaminophenoxy) methacrylate Diamines such as ethyl ester and 2,4-diamino-N,N-diallyl aniline with photopolymerizable groups other than those in formula (2) at the end; diamines such as 1-(4-(2-(2,4-diaminophenoxy)ethoxy)phenyl)-2-hydroxy-2-methylpropanone and 2-(4-(2-hydroxy-2-methylpropionic acid)phenoxy)ethyl-3,5-diaminobenzoate with free radical polymerization initiator function; diamines such as 4,4'-diaminobenzonitrile aniline with amide bonds; diamines such as 1,3-bis(4-aminophenyl)urea, 1,3-bis(4-aminobenzyl)urea, and 1,3-bis(4-aminophenylethyl)urea with urea bonds; 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether Benzene ether, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2-bis(3-aminophenyl)hexafluoropropane, 2,2-bis(3-amino-4-methylphenyl)hexafluoropropane, 2,2-bis(4-aminophenyl)propane, 2,2-bis(3-aminophenyl)propane, 2,2-bis(3-amino-4-methylphenyl)propane, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane Phenylacetone, 1,4-bis(4-aminobenzyl)benzene; 2,6-diaminopyridine, 3,4-diaminopyridine, 2,4-diaminopyrimidine, 3,6-diaminocarbazole, N-methyl-3,6-diaminocarbazole, 1,4-bis-(4-aminophenyl)-piperazine, 3,6-diaminoacridine, N-ethyl-3,6-diaminocarbazole, N-phenyl-3 6-Diaminocarbazole, N-(3-(1H-imidazol-1-yl)propyl-3,5-diaminobenzylamine, 4-[4-[(4-aminophenoxy)methyl]-4,5-dihydro-4-methyl-2-azolyl]aniline, or a heterocyclic diamine represented by formulas (z-1) to (z-13), or 4,4'-diaminodiphenylamine, 4,Diamines with a diphenylamine structure, such as 4'-diaminodiphenyl-N-methylamine, N,N'-bis(4-aminophenyl)-benzidine, N,N'-bis(4-aminophenyl)-N,N'-dimethylbenzidine, or N,N'-bis(4-aminophenyl)-N,N'-dimethyl-1,4-phenylenediamine, are representative of diamines with at least one nitrogen-containing structure (hereinafter also referred to as specific nitrogen-containing structures) selected from the group consisting of nitrogen-containing heterocycles, secondary amine groups, and tertiary amine groups (but without an amine group bonded to a protecting group that is removed and replaced by a hydrogen atom upon heating); 2,4-diamine 3,5-Diaminophenol, 3,5-Diaminobenzyl alcohol, 2,4-Diaminobenzyl alcohol, 4,6-Diaminoresorcinol; 2,4-Diaminobenzoic acid, 2,5-Diaminobenzoic acid, 3,5-Diaminobenzoic acid, 4,4'-Diaminobiphenyl-3-carboxylic acid, 4,4'-Diaminodiphenylmethane-3-carboxylic acid, 4,4'-Diaminodiphenylethane-3-carboxylic acid, 4,4'-Diaminobiphenyl-3,3'-dicarboxylic acid, 4,4'-Diaminobiphenyl-2,2'-dicarboxylic acid, 3,3'-Diaminobiphenyl-4,4'-dicarboxylic acid, 3,3'-Diaminobiphenyl -2,4'-dicarboxylic acid, 4,4'-diaminodiphenylmethane-3,3'-dicarboxylic acid, 1,2-bis(3-carboxyl-4-aminophenyl)ethane, 4,4'-diaminodiphenyl ether-3,3'-dicarboxylic acid and other diamines having a carboxyl group; 4-(2-(methylamino)ethyl)aniline, 4-(2-aminoethyl)aniline, 1-(4-aminophenyl)-1,3,3-trimethyl-1H-dihydroindene-5-amine, 1-(4-aminophenyl)-2,3-dihydro-1,3,3-trimethyl-1H-indene-6-amine; and the following formulas (5-1) to (5-6) and others having a carboxyl group "-N(D)- "(D indicates a protecting group that is removed and replaced by a hydrogen atom upon heating, preferably a tert-butoxycarbonyl group.)" Diamines containing siloxane bonds, such as 1,3-bis(3-aminopropyl)-tetramethyldisiloxane; diamines with two amino groups bonded to a base, such as m-xylene diamine, 1,3-propane diamine, tetramethylene diamine, pentamethylene diamine, hexamethylene diamine, 1,3-bis(aminomethyl)cyclohexane, 1,4-diaminocyclohexane, 4,4'-methylenebis(cyclohexylamine), and any of the formulas (Y-1) to (Y-167) disclosed in International Publication No. 2018 / 117239.

[0031] [Chemical 7]

[0032] [Chemical 8]

[0033] [Chemical 9]

[0034] Among the other diamines mentioned above, the diamine (Ar) and the diamine with the above-mentioned photopolymerizable group at the end are preferred.

[0035] Examples of tetracarboxylic acid components that can be used in the synthesis of the above polymer (A) include acyclic aliphatic tetracarboxylic dianhydrides, alicyclic tetracarboxylic dianhydrides, aromatic tetracarboxylic dianhydrides, or their derivatives. It is preferable that the tetracarboxylic dianhydride or its derivatives contain at least one substructure selected from the group consisting of a benzene ring, a cyclobutane ring, a cyclopentane ring, and a cyclohexane ring. It is even more desirable that the tetracarboxylic dianhydride or its derivatives contain at least one substructure selected from the group consisting of a cyclobutane ring, a cyclopentane ring, and a cyclohexane ring. Furthermore, aromatic tetracarboxylic dianhydrides refer to acid dianhydrides obtained by intramolecularly dehydrating four carboxyl groups, including at least one carboxyl group bonded by an aromatic ring. However, it is not necessary for it to consist solely of an aromatic ring structure; a portion of it may also have a chain hydrocarbon structure or an alicyclic structure. Acyclic aliphatic tetracarboxylic dianhydrides are acid dianhydrides obtained by intramolecularly dehydrating four carboxyl groups bonded by a chain hydrocarbon structure. However, it is not necessary to be composed solely of a chain hydrocarbon structure; a portion of it may also possess an alicyclic structure, an aromatic ring structure, or heteroatoms such as oxygen atoms. Alicyclic tetracarboxylic dianhydrides are acid dianhydrides obtained by intramolecularly dehydrating four carboxyl groups, including at least one carboxyl group bonded by the alicyclic structure. However, none of these four carboxyl groups are bonded to an aromatic ring. Furthermore, it is not necessary to be composed solely of an alicyclic structure; a portion of it may also possess a chain hydrocarbon structure or an aromatic ring structure.

[0036] The tetracarboxylic acid components that can be used in the synthesis of polymer (A) preferably include the following tetracarboxylic dianhydrides or their derivatives (hereinafter collectively referred to as specific tetracarboxylic acid derivatives). Furthermore, examples of the aforementioned tetracarboxylic dianhydride derivatives include tetracarboxylic acid dihalides, tetracarboxylic acid dialkyl esters, or tetracarboxylic acid dialkyl ester dihalides, etc. One of the aforementioned tetracarboxylic dianhydrides or their derivatives may be used alone, or two or more may be used in combination.

[0037] Acyclic aliphatic tetracarboxylic anhydrides such as 1,2,3,4-butanetetracarboxylic anhydride; 1,2,3,4-cyclobutanetetracarboxylic anhydride, 1,2-dimethyl-1,2,3,4-cyclobutanetetracarboxylic anhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic anhydride, 1,3-dichloro-1,2,3,4-cyclobutanetetracarboxylic anhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic anhydride, 1,3-difluoro-1,2,3,4 -Cyclobutanetetracarboxylic dianhydride, 1,3-bis(trifluoromethyl)-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 3,3',4,4'-dicyclohexyltetracarboxylic dianhydride, 2,3,5-tricarboxylatedcyclopentylacetic acid dianhydride, 5-(2,5-disideloxytetrahydrofuran-3-yl)-3a,4,5,9b-tetrahydronaphtho[1,2-c]furan-1,3-dione, 5-(2,5 -di-side-oxytetrahydrofuran-3-yl)-8-methyl-3a,4,5,9b-tetrahydronaphtho[1,2-c]furan-1,3-dione, 2,4,6,8-tetracarboxylic acid bicyclo[3.3.0]octane-2:4,6:8-dianhydride and other alicyclic tetracarboxylic anhydrides; benzopyrene dianhydride, 3,3',4,4'-diphenyl ketone tetracarboxylic anhydride, 3,3',4,4'-diphenyl ketone tetracarboxylic anhydride, 1,4,5,8-naphthalene tetracarboxylic anhydride, 2,3,6,7-naphthalene tetracarboxylic acid Aromatic tetracarboxylic anhydrides such as dianhydrides, 3,3',4,4'-diphenyl ether tetracarboxylic anhydride, 3,3',4,4'-perfluoroisopropylidene phthalic anhydride, 3,3',4,4'-biphenyltetracarboxylic anhydride, 2,2',3,3'-biphenyltetracarboxylic anhydride, ethylene glycol dipremetyltricarboxylic anhydride, 4,4'-(hexafluoroisopropylidene)phthalic anhydride, and 4,4'-carbonyl phthalic anhydride; in addition, tetracarboxylic anhydrides as described in Japanese Patent Application Publication No. 2010-97188, etc.

[0038] Ideal examples of the aforementioned specific tetracarboxylic acid derivatives include 1,2,3,4-butanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, and 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride. 1,3-Difluoro-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-bis(trifluoromethyl)-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 3,3',4,4'-dicyclohexyltetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic acid dianhydride, 5-(2,5-disideloxy) Tetrahydrofuran-3-yl)-3a,4,5,9b-tetrahydronaphtho[1,2-c]furan-1,3-dione, 5-(2,5-disideloxytetrahydrofuran-3-yl)-8-methyl-3a,4,5,9b-tetrahydronaphtho[1,2-c]furan-1,3-dione, 2,4,6,8-tetracarboxylic acid bicyclo[3.3.0]octane-2:4,6:8-dianhydride, benzopyrenic acid Dihydric anhydride, 3,3',4,4'-diphenylketone tetracarboxylic anhydride, 3,3',4,4'-diphenylphenone tetracarboxylic anhydride, 1,4,5,8-naphthalene tetracarboxylic anhydride, 2,3,6,7-naphthalene tetracarboxylic anhydride, 3,3',4,4'-diphenyl ether tetracarboxylic anhydride, 3,3',4,4'-biphenyl tetracarboxylic anhydride, 2,2',3,3'-biphenyl tetracarboxylic anhydride, or derivatives thereof.

[0039] The usage ratio of the above-mentioned specific tetracarboxylic acid derivative is preferably 10 mol% or more relative to 100 mol% of the total tetracarboxylic acid component used, more than 20 mol% is better, and more than 50 mol% is even better.

[0040] One embodiment of the present invention further contains a compound selected from the following formulas A1, A3, A4, A6, or A9 to A12. [Chemical 10]

[0041] One embodiment of the present invention comprises at least one polymer selected from the group consisting of a polyimide precursor obtained by reacting a diamine component containing a compound selected from A1, A3, A4, A6, or A9 to A12 above with a tetracarboxylic acid component, and a polyimide consisting of a amide thereof. Here, ideal examples of the aforementioned tetracarboxylic acid component include compounds of the tetracarboxylic acid component that can be used in the synthesis of the aforementioned polymer (A).

[0042] One embodiment of the present invention comprises a liquid crystal alignment agent containing at least one polymer selected from the group consisting of a polyimide precursor obtained by reacting a diamine component containing a compound selected from A1, A3, A4, A6, or A9 to A12 above with a tetracarboxylic acid component, and a polyimide that is a amide thereof. Organic solvents suitable for preparing the above liquid crystal alignment agent, the specific polyimide precursor, or other components besides the polyimide that is a amide thereof, are applicable to the liquid crystal alignment agent embodiment described below.

[0043] <Manufacturing of Polyimide Precursor and Polyimide> In the polymer (A) of the present invention, the polyimide is a amide of the polyimide precursor (A), obtained by dehydrating and cyclizing the polyimide precursor (A). Specific examples of the above-mentioned polyimide precursor include polyamide acid and polyamide ester.

[0044] (Synthesis of polyamide) The synthesis of polyamide is carried out by reacting a diamine component containing the above-mentioned diamine with a tetracarboxylic acid component containing the above-mentioned tetracarboxylic acid dianhydride or its derivative in an organic solvent.

[0045] Specific examples of the above-mentioned organic solvents include cyclohexanone, cyclopentanone, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, γ-butyrolactone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, and 1,3-dimethyl-2-imidazolidineone. Furthermore, when the polymer has high solvent solubility, methyl ethyl ketone, cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, diethylene glycol monomethyl ether, or diethylene glycol monoethyl ether can be used.

[0046] Polyamide esters can be obtained by known methods such as: [I] reacting polyamide obtained by the above methods with an esterifying agent; [II] reacting tetracarboxylic acid diester with a diamine; [III] reacting tetracarboxylic acid diester dihalide with a diamine.

[0047] Furthermore, polyimide can be obtained by cyclizing (nitroimidizing) the above-mentioned polyimide precursor. Also, the nitroimidization rate referred to in this specification is the ratio of nitroimide groups to the total amount of nitroimide groups and carboxyl groups (or their derivatives) derived from tetracarboxylic dianhydride or its derivatives. The nitroimidization rate is not necessarily 100% and can be adjusted arbitrarily according to the application and purpose.

[0048] <Terminal Modifier> When synthesizing the polyimide precursor and polyimide of the present invention, a tetracarboxylic acid component containing tetracarboxylic dianhydride or its derivative, and a diamine component containing the above-mentioned diamine, and an appropriate terminal modifier may also be used to synthesize a terminal-modified polymer.

[0049] Terminal modifying agents, such as acetic anhydride, maleic anhydride, natriuretic anhydride, phthalic anhydride, itaconic anhydride, cyclohexanedicarboxylic anhydride, 3-hydroxyphthalic anhydride, trimellitic anhydride, 3-(3-trimethoxysilyl)propyl)-3,4-dihydrofuran-2,5-dione, 4,5,6,7-tetrafluoroisobenzofuran-1,3-dione, 4-ethynylphthalic anhydride, etc. Dicarbonate diesters such as di-tert-butyl dicarbonate and diallyl dicarbonate; chlorocarbonyl compounds such as acrylonitrile chloride, methacrylonitrile chloride, and nicotinic acid chloride; monoamine compounds such as aniline, 2-aminophenol, 3-aminophenol, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, cyclohexylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, and n-octylamine; monoisocyanate compounds such as ethyl isocyanate, phenyl isocyanate, naphthyl isocyanate, 2-acryloyloxyethyl isocyanate, and 2-methacryloyloxyethyl isocyanate; and isothiocyanate compounds such as ethyl isothiocyanate and allyl isothiocyanate.

[0050] The proportion of the end-modifying agent used should preferably be 0.01 to 20 moles relative to 100 moles of the total diamine component used, and more preferably 0.01 to 10 moles.

[0051] When considering the strength, workability during film formation, and coating properties of the polyimide precursor and polyimide used in this invention, the weight-average molecular weight (Mw) measured by GPC (Gel Permeation Chromatography) is preferably 5,000 to 1,000,000, more preferably 10,000 to 150,000. Furthermore, the molecular weight distribution (Mw / Mn), expressed as the ratio of Mw to the number-average molecular weight (Mn) of polystyrene measured by GPC, is preferably 15 or less, more preferably 10 or less. Regarding the solution viscosity of the polyimide precursor and polyimide, for example, when prepared as a 10% by mass solution, a solution viscosity of 10 to 800 mPa·s is preferred, and a solution viscosity of 15 to 500 mPa·s is even more preferred. Furthermore, the solution viscosity (mPa·s) refers to the value measured at 25°C using an E-type rotational viscometer for a 10% by mass polymer solution prepared using these polyimide precursors and good solvents for polyimides (e.g., γ-butyrolactone, N-methyl-2-pyrrolidone, etc.).

[0052] (Liquid Crystal Orienting Agent) The liquid crystal orientation agent of the present invention, as described above, contains a polymer (A) as an essential component, preferably dissolved in an organic solvent. The blending ratio of the polymer (A) used in the liquid crystal orientation agent of the present invention is not particularly limited; for example, the content of polymer (A) in the liquid crystal orientation agent is 0.1 to 30% by mass relative to the liquid crystal orientation agent, preferably 1 to 10% by mass.

[0053] The organic solvent contained in the liquid crystal alignment agent is not particularly limited as long as it can dissolve the polymer. Examples include: lactone solvents such as γ-pentanolide and γ-butyrolactone; γ-butyrolactone, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-(n-propyl)-2-pyrrolidone, N-isopropyl-2-pyrrolidone, N-(n-butyl)-2-pyrrolidone, N-(tert-butyl)-2-pyrrolidone, N-(n-pentyl)-2-pyrrolidone, N-methoxypropyl-2- Pyrrolidone, N-ethoxyethyl-2-pyrrolidone, N-methoxybutyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone and other acetylamine solvents; N,N-dimethylformamide, N,N-dimethylacetamide, N,N-dimethyllactamide, 3-methoxy-N,N-dimethylpropaneamide, 3-butoxy-N,N-dimethylpropaneamide and other acetylamine solvents; cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone, 2,6-dimethyl-4-heptanone (diisobutyl ketone), emulsifiers... Methyl lactate, ethyl lactate, n-propyl lactate, n-butyl lactate, isoamyl lactate, n-butyl acetate, propylene glycol monoethyl ether, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, ethyl ethoxypropionate, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monopropyl ether, ethylene glycol monoisopropyl ether, ethylene glycol n-butyl ether (butyl ceroxox), ethylene glycol dimethyl ether, ethylene glycol ethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether Diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monobutyl ether, propylene glycol diacetate, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol dimethyl ether, tripropylene glycol monomethyl ether, isoamyl propionate, isoamyl isobutyrate, diisopropyl ether, diisoamyl ether; carbonate solvents such as ethyl carbonate and propyl carbonate; 1-hexanol, cyclohexanol, 1,2-ethanediol, 2,6-dimethyl-4-heptanol (diisobutylmethanol), etc. These can be used alone or in combination of two or more.

[0054] When the liquid crystal alignment agent of the present invention is used in plastic substrates, the organic solvent used in the liquid crystal alignment agent can be composed of a solvent with a boiling point of 190°C or less at 1 atm. Ideal solvent compositions include cyclohexanone and ethylene glycol monobutyl ether, cyclohexanone and propylene glycol monobutyl ether, cyclopentanone and propylene glycol monobutyl ether, cyclohexanone and diethylene glycol monoethyl ether, cyclopentanone and diethylene glycol monoethyl ether, cyclohexanone and diisobutyl ketone, cyclopentanone and diisobutyl ketone, methyl isobutyl ketone and propylene glycol monobutyl ether, methyl ethyl ketone and propylene glycol monobutyl ether. The solvent composition comprises combinations of cyclohexanone with 4-hydroxy-4-methyl-2-pentanone, cyclopentanone with 4-hydroxy-4-methyl-2-pentanone, cyclohexanone with diethylene glycol diethyl ether, cyclopentanone with diethylene glycol diethyl ether, cyclohexanone with n-butyl acetate, cyclopentanone with n-butyl acetate, 4-hydroxy-4-methyl-2-pentanone with ethylene glycol monobutyl ether, cyclohexanone with propylene glycol diacetate, and cyclopentanone with propylene glycol diacetate. The type and content of such organic solvents can be appropriately selected according to the coating apparatus, coating conditions, and coating environment of the liquid crystal alignment agent.

[0055] The liquid crystal alignment agent of the present invention contains polymer (A) as an essential component, as described above, but may also contain other components as needed. These other components include, for example, polymers other than polymer (A) (hereinafter also referred to as other polymers), at least one crosslinking compound selected from the group consisting of a crosslinking compound (c-1) having at least one substituent selected from ethylene oxide, isocyanate group, oxetyl, cyclic carbonate group, terminal isocyanate group, hydroxyl and alkoxy, and a crosslinking compound (c-2) having a polymerizable unsaturated group, functional silane compounds, metal chelate compounds, curing accelerators, surfactants, antioxidants, sensitizers, preservatives, compounds for adjusting the dielectric constant and resistance of the liquid crystal alignment film, photoradical generators, photoacid generators, photoalkali generators, ultraviolet absorbers, and photostabilizers, etc.

[0056] Other polymers are not particularly limited, such as: polyimide precursors other than polymer (A), polyimide, polysiloxane, polyester, polyamide, polyurea, polyorganosiloxane, cellulose derivatives, polyacetal, polystyrene derivatives, poly(styrene-maleic anhydride) copolymer, poly(isobutylene-maleic anhydride) copolymer, poly(vinyl ether-maleic anhydride) copolymer, poly(styrene-phenylmaleimide) derivatives, etc. Specific examples of poly(styrene-maleic anhydride) copolymers include SMA1000, 2000, 3000 (manufactured by Cray Valley Corporation), and GSM301 (manufactured by GIFUSHELLAC Corporation). Specific examples of poly(isobutylene-maleic anhydride) copolymers include ISOBAM-600 (manufactured by Kuraray Corporation). Specific examples of poly(vinyl ether-maleic anhydride) copolymers include Gantrez AN-139 (methyl vinyl ether maleic anhydride resin, manufactured by ASHLAND Corporation). Furthermore, one or more other polymers may be used. When using other polymers, their usage ratio relative to the total amount of polymers contained in the liquid crystal alignment agent is preferably 50% by mass or less, more preferably 0.1% to 40% by mass, and even more preferably 0.1% to 30% by mass.

[0057] Ideal concrete examples of cross-linked compounds (c-1) and (c-2) can be listed as follows: Ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol diglycidyl ether, 2,2-dibromonepentyl glycol diglycidyl ether, 1,3,5,6-tetracyclooxypropyl-2,4-hexanediol, bisphenol A type epoxy resins such as EPIKOTE828 (manufactured by Mitsubishi Chemical Corporation), bisphenol F type epoxy resins such as EPIKOTE807 (manufactured by Mitsubishi Chemical Corporation), hydrogenated bisphenol A type epoxy resins such as YX-8000 (manufactured by Mitsubishi Chemical Corporation), epoxy resins containing biphenyl backbones such as YX6954BH30 (manufactured by Mitsubishi Chemical Corporation), phenolic varnish type epoxy resins such as EPPN-201 (manufactured by Nippon Kayaku Co., Ltd.), EO CN-102S (manufactured by Nippon Kayaku Co., Ltd.) and other (ortho, meta, para) cresol phenolic varnish epoxy resins, TEPIC (manufactured by Nissan Chemical Co., Ltd.) and other trichloropropyl isocyanate, CELLOXIDE2021P (manufactured by Daicel Chemical Co., Ltd.) and other alicyclic epoxy resins, N,N,N',N'-tetracyclooxypropylmethylenediamine, 1,3-bis(N,N-dicyclooxypropylaminomethyl)cyclohexane, N,N,N',N'-tetracyclooxypropyl-4,4'-diaminodiphenylmethane, tetra(epoxypropoxymethyl)methane and other compounds having two or more ethylene oxide groups; compounds having two or more oxocyclic butyl groups as described in paragraphs

[0170] to

[0175] of WO2011 / 132751; CORONATEAP Stable M, CORONATE 2503, 2515, 2507, 2513, 2555, MILLIONATEMS-50 (all manufactured by Tosoh Corporation), TAKENATE Compounds with capped isocyanate groups, such as B-830, B-815N, B-820NSU, B-842N, B-846N, B-870N, B-874N, and B-882N (all manufactured by Mitsui Chemicals); compounds with hydroxyl and alkoxy groups, such as N,N,N',N'-tetra(2-hydroxyethyl)hexamethylenediamine, 2,2-bis(4-hydroxy-3,5-dihydroxymethylphenyl)propane, 2,2-bis(4-hydroxy-3,5-dimethoxymethylphenyl)propane, and 2,2-bis(4-hydroxy-3,5-dihydroxymethylphenyl)-1,1,1,3,3,3-hexafluoropropane; and compounds represented by the formulas (CL-1) to (CL-5). When using crosslinking compounds (c-1) and (c-2), it is preferable to use 0.1 to 30 parts by mass relative to 100 parts by mass of polymer content contained in the liquid crystal alignment agent, and more preferably 0.1 to 20 parts by mass. [Chemical 11] n2 represents an integer from 1 to 10. m2 represents an integer from 1 to 10.

[0058] Compounds used to adjust dielectric constant and resistance include monoamines such as 3-pyridinemethylamine, which are aromatic heterocyclic compounds containing nitrogen atoms. When using a monoamine with an aromatic heterocyclic compound containing nitrogen atoms, it is preferable to use 0.1 to 30 parts by mass relative to 100 parts by mass of the polymer component contained in the liquid crystal alignment agent, and more preferably 0.1 to 20 parts by mass.

[0059] Ideal specific examples of functional silane compounds include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyldiethoxymethylsilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, 3-ureopropyltrimethoxysilane, 3-ureopropyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-epoxypropoxypropylmethyldimethoxysilane. 3-Epoxypropoxypropyltrimethoxysilane, 3-Epoxypropoxypropylmethyldiethoxysilane, 3-Epoxypropoxypropyltriethoxysilane, p-Styryltrimethoxysilane, 3-Methylpropoxypropylmethyldimethoxysilane, 3-Methylpropoxypropyltrimethoxysilane, 3-Methylpropoxypropylmethyldiethoxysilane, 3-Methylpropoxypropyltriethoxysilane, 3-Propylenepropoxypropyltrimethoxysilane, 3-[3-(trimethoxysilyl)propyl]isocyanurate, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanatepropyltriethoxysilane, etc. When using a functional silane compound, it is preferable to use 0.1 to 30 parts by mass relative to 100 parts by mass of the polymer component contained in the liquid crystal alignment agent, and more preferably 0.1 to 20 parts by mass.

[0060] Specific examples of photoradical generators, photoacid generators, and photoalkali generators can be cited from the compounds described on pages 54 to 56 of International Publication No. 2014 / 171493 (published on October 23, 2014). Among them, considering the adhesion between the liquid crystal layer and the liquid crystal alignment film of the liquid crystal element, it is preferable to use a photoradical generator.

[0061] The above-mentioned ultraviolet absorbers may include inorganic ultraviolet absorbers such as titanium dioxide, cerium oxide, zinc oxide, and iron oxide, as well as organic ultraviolet absorbers such as benzotriazole, triazole, and diphenyl ketone. Among them, triazole ultraviolet absorbers are preferred.

[0062] The above-mentioned light stabilizer, for example, is a hindered amine light stabilizer (HALS). It is preferable that the above-mentioned hindered amine light stabilizer is a hindered amine light stabilizer with a reactive functional group.

[0063] The concentration of solid components in the liquid crystal alignment agent (the proportion of the total mass of components other than the organic solvent in the liquid crystal alignment agent to the total mass of the liquid crystal alignment agent) can be appropriately selected considering viscosity, volatility, etc., and is preferably in the range of 1 to 10% by mass. The ideal range of solid component concentration depends on the method used when coating the liquid crystal alignment agent onto the substrate. For example, when using spin coating, a solid component concentration of 1.5 to 4.5% by mass is particularly preferred. When using printing, a solid component concentration of 3 to 9% by mass is preferably set, thereby making the solution viscosity range of 12 to 50 mPa·s. When using inkjet printing, a solid component concentration of 1 to 5% by mass is preferably set, thereby making the solution viscosity range of 3 to 15 mPa·s.

[0064] (Liquid crystal alignment film, liquid crystal element) The liquid crystal alignment film of the present invention is obtained from the above-mentioned liquid crystal alignment agent. The liquid crystal alignment film of the present invention can be a horizontally aligned or vertically aligned liquid crystal alignment film, but it is suitable for PDLC and PNLC type liquid crystal elements. The liquid crystal element of the present invention includes the above-mentioned liquid crystal alignment film.

[0065] The liquid crystal element of the present invention is a liquid crystal element in which a dimming layer comprising a polymer liquid crystal composite containing a polymer phase and a liquid crystal phase is disposed between a pair of substrates with electrode surfaces arranged opposite each other. The liquid crystal element of the present invention can be manufactured, for example, by a method including the following steps (1) to (4). Furthermore, when the liquid crystal element of the present invention is a guest-subject type dimming element, it can be manufactured by a method in which the liquid crystal composition contains the dye described later. Furthermore, the liquid crystal alignment film can be formed on at least one of the pair of substrates, or on either side or on one side.

[0066] (1) Step of coating a liquid crystal alignment agent on one or both of the substrates of the pair of auxiliary electrodes: The liquid crystal alignment agent of the present invention is coated on at least one electrode arrangement surface of the substrate of the auxiliary electrodes using a suitable coating method such as roller coating, spin coating, printing, inkjet coating, etc. Here, the substrate can be the substrates mentioned above. (2) Step of calcining the coating: After the liquid crystal alignment agent is coated, in order to prevent dripping of the coated alignment agent, it is advisable to perform preheating (pre-baking). The pre-baking temperature is preferably 30 to 150°C, more preferably 40 to 130°C, and even more preferably 50 to 120°C. The pre-baking time is preferably 0.25 to 10 minutes, more preferably 0.5 to 5 minutes, and even more preferably 1 to 5 minutes. A heating (post-baking) step may also be performed. The subsequent baking temperature is preferably 80 to 190°C, and even more preferably 120 to 180°C. The post-baking time is preferably 5–30 minutes, more preferably 5–20 minutes. The film thickness formed in this manner is preferably 1–1000 nm, more preferably 5–1000 nm, and even more ideally 10–1000 nm.

[0067] The coating formed in step (2) above can be used directly as a liquid crystal alignment film, but alignment capability imparting treatment can also be applied to the coating. Alignment capability imparting treatment can include: friction treatment by rubbing the coating in a certain direction with a roller wound with a cloth made of fibers such as nylon, silk, or cotton, and photoalignment treatment by irradiating the coating with polarized or unpolarized radiation.

[0068] In the above-described photoalignment process, the radiation used to irradiate the coating can be, for example, ultraviolet light or visible light containing wavelengths of 150–800 nm. When the radiation is polarized, it can be linearly polarized or partially polarized. Furthermore, when the radiation used is linearly polarized or partially polarized, irradiation can be performed from a direction perpendicular to the substrate surface, from an oblique direction, or a combination thereof. When irradiating unpolarized radiation, the irradiation direction is oblique.

[0069] (3) The steps for preparing the dimming layer forming material are as described above. One of the substrates on which a liquid crystal alignment film is formed is a pair of attached electrodes. The dimming layer forming material is then prepared between the two substrates facing each other. Specifically, the following three methods can be listed. The first method is to arrange the two substrates opposite each other by separating the gap (cell gap) with the liquid crystal alignment film faces facing each other. This method is called vacuum injection. In PDLC type liquid crystal elements and PNLC type liquid crystal elements, the cell gap is preferably 1 to 100 μm, more preferably 2 to 50 μm, and even more preferably 5 to 20 μm. Next, the periphery of the two substrates is bonded together with a sealant. The dimming layer forming material containing liquid crystal composition, polymeric compound components and polymerization initiator as needed is injected into the cell gap separated by the substrate surface and the sealant. After contact with the film surface, the injection hole is sealed.

[0070] Furthermore, the second method is called the ODF (One Drop Fill) method. A sealant, for example, that is UV-curable, is applied to a predetermined location on one of the two substrates on which the liquid crystal alignment film is formed. Then, the aforementioned dimming layer forming material is dropped onto a predetermined number of locations on the surface of the liquid crystal alignment film. Next, the other substrate is bonded together with the liquid crystal alignment film facing each other, pushing the liquid crystal composition to the entire surface of the substrate so that it contacts the film surface. Then, the entire substrate is irradiated with ultraviolet light to harden the sealant.

[0071] Furthermore, the third method is called the roll-to-roll method. Specifically, the above-mentioned dimming layer forming material is coated on the film surface of the first electrode substrate on the side where the transparent conductive film is provided, and then bonded to the film surface of the second glass substrate where the transparent conductive film is provided and the dimming layer forming material are in contact, so as to achieve a uniform thickness. The method of coating the composite composition used in this invention can be implemented by known and conventional methods such as coating machine method, rod coating method, roll coating method, direct photogravure coating method, reverse photogravure coating method, inkjet method, mold coating method, and overlay coating method. In any of the methods, it is advisable to further heat to the temperature at which the liquid crystal composition to be used takes an isotropic phase and then slowly cool to room temperature to remove the flow orientation during liquid crystal filling.

[0072] (Dimming Layer Forming Material) The dimming layer forming material of the present invention contains a liquid crystal composition, a polymerizable compound component, and, if necessary, a polymerization initiator. Furthermore, the dimming layer forming material may also contain, as needed, directional additives, anisotropic dyes, ultraviolet absorbers / photostabilizers, and chain transfer agents. The proportion of the liquid crystal composition in the dimming layer forming material is preferably 40 parts by mass or more, more preferably 50 parts by mass or more, and more preferably 60 parts by mass or more, and preferably 90 parts by mass or less, or 80 parts by mass or less. The content of the polymerizable compound component is preferably 10 parts by mass or more, more preferably 20 parts by mass or more, and preferably 60 parts by mass or less, more preferably 50 parts by mass or less, and more preferably 40 parts by mass or less, and preferably less than 40 parts by mass.

[0073] (Liquid Crystal Composition) Examples of liquid crystal compounds constituting liquid crystal compositions include nematic liquid crystals and smectic liquid crystals, with nematic liquid crystals being more ideal. Examples of suitable nematic liquid crystals include Schiff base-based liquid crystals, azoxy-based liquid crystals, biphenyl-based liquid crystals, phenylcyclohexane-based liquid crystals, ester-based liquid crystals, terphenyl-based liquid crystals, biphenylcyclohexane-based liquid crystals, pyrimidine-based liquid crystals, dialkyl-based liquid crystals, bicyclooctane-based liquid crystals, and cubane-based liquid crystals. Furthermore, cholesterol liquid crystals such as cholesterol chloride, cholesterol nonanoate, and cholesterol carbonate; chiral reagents sold under trade names "C-15" and "CB-15" (manufactured by Merck); and strongly dielectric liquid crystals such as p-decoxybenzyl-p-amino-2-methylbutyl cinnamate may also be added to these liquid crystals. The liquid crystal composition described above can be any of the liquid crystal compositions disclosed in Japanese Patent Application Publication Nos. 2007-009120 and 2011-246411. When used as a normal-mode polymer-dispersed liquid crystal element, the liquid crystal composition is a positive liquid crystal composition exhibiting positive dielectric constant anisotropy (hereinafter also referred to as positive liquid crystal). When used as a reverse-mode polymer-dispersed liquid crystal element, the liquid crystal composition is a negative liquid crystal composition exhibiting negative dielectric constant anisotropy (hereinafter also referred to as negative liquid crystal). Examples of positive liquid crystals include ZLI-2293, ZLI-4792, MLC-2003, MLC-2041, MLC-3019, or MLC-7081 manufactured by Merck. Negative liquid crystals, such as Champagne's Sb-323010, Merck's MLC-6608, MLC-6609, or MLC-6610, etc.

[0074] (Polymerizable Compound Component) In PDLC and PNLC liquid crystal elements, the dimming layer forming material preferably contains a polymerizable compound component. The polymerizable compound constituting the polymerizable compound component is preferably a free radical polymerizable compound (monomer) or its oligomer. Alternatively, polymers in which such monomers have undergone polymerization may be used. Specifically, examples include phosphate compounds containing (meth)acrylic groups, monofunctional (meth)acrylate compounds, difunctional (meth)acrylate compounds, and trifunctional or higher (meth)acrylate compounds. Examples of phosphate ester compounds containing (meth)acrylic groups include 2-(meth)acryloxyethyl acid phosphates (e.g., "LIGHT ESTERP-1M" and "LIGHT ACRYLATEP-1A" manufactured by Kyoeisha Chemical Co., Ltd.), bis(2-(meth)acryloxyethyl) acid phosphates (e.g., "LIGHT ESTERP-2M" and "LIGHT ACRYLATEP-2A" manufactured by Kyoeisha Chemical Co., Ltd., and "KAYAMERPM-21" manufactured by Nippon Kayaku Co., Ltd.), and triacryloxyethyl phosphates (e.g., "Viscoat #3PA" manufactured by Osaka Organic Chemical Industry Co., Ltd.), which are vinyl unsaturated compounds containing phosphate groups with three or more vinyl unsaturated groups. Ideal examples of monofunctional (meth)acrylate compounds include: isoborneol (meth)acrylate, cyclohexyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenoxyethyl (meth)acrylate, and other monofunctional (meth)acrylate compounds with alicyclic structures; 2-hydroxypropyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 5-hydroxypentyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, and some ethoxylated 2-hydroxy(meth)acrylates, which are monofunctional (meth)acrylate compounds with alcoholic hydroxyl groups. (Meth)acrylate compounds; (meth)acrylate glycidyl acrylate, α-ethyl(meth)acrylate glycidyl acrylate, α-n-propyl(meth)acrylate glycidyl acrylate, α-n-butyl(meth)acrylate glycidyl acrylate, (meth)acrylate-3,4-epoxybutyl acrylate, (meth)acrylate-4,5-epoxypentyl acrylate, (meth)acrylate-3,4-epoxybutyl acrylate, (meth)acrylate-6,7-epoxypentyl acrylate, α-ethyl(meth)acrylate-6,7-epoxypentyl acrylate, (meth)acrylate-β-methylepoxypropyl acrylate, (meth)acrylate-3,4-epoxycyclohexyl acrylate, and other monofunctional (meth)acrylate compounds with epoxy groups.Ideal examples of difunctional (meth)acrylate compounds and trifunctional or higher (meth)acrylate compounds include diethylene glycol dimethacrylate, 1,4-butanediol dimethacrylate, 1,3-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol dimethacrylate, tetraethylene glycol dimethacrylate, 4,4'-biphenyl dimethacrylate, dicyclopentyl dimethacrylate, glycerol dimethacrylate, 1,9-nonanediol dimethacrylate, polyethylene glycol dimethacrylate, polypropylene glycol dimethacrylate, and hydroxytrimethylacetic acid-modified neopentyl glycol dimethacrylate (e.g., KAYARAD HX-220, KAYARAD FM400, KAYARAD...). HX-620, etc.), 2,2,3,3,4,4-hexafluoropentanediol-1,5-di(meth)acrylate, 1,1-(bisacryloxymethyl)ethyl isocyanate (e.g., "KARENZ BEI" manufactured by Showa Denko), or difunctional (meth)acrylate compounds with carbamate bonds (e.g., difunctional (meth)acrylate compounds with carbamate bonds and alicyclic structures, such as "EBECRYL 230", "EBECRYL 270", "EBECRYL 4858", "EBECRYL 9270" manufactured by DAICEL ALLNEX), etc.; trimethylolpropane tri(meth)acrylate (e.g., "NK ESTER TMPT" manufactured by Shin-Nakamura Kogyo Co.), neopentyl tertrol tri(meth)acrylate (e.g., "NK ESTER" manufactured by Shin-Nakamura Kogyo Co.), etc. Compounds of methacrylates with three or more functions, such as neopentyl tertetrol tetra(meth)acrylate, ethoxylated neopentyl tertetrol tetraacrylate (e.g., "NK ESTER ATM-35E" manufactured by Shin-Nakamura Kogyo Co., Ltd.), di(trimethylolpropane)tetra(meth)acrylate, dinepentyl tertetrol hexa(meth)acrylate (e.g., "NK ESTER A-DPH" manufactured by Shin-Nakamura Kogyo Co., Ltd.), or dinepentyl tertetrol monohydroxypenta(meth)acrylate, or such oligomers, may also be used. In addition to the compounds described above, monofunctional polymeric compounds, difunctional polymeric compounds, and polyfunctional polymeric compounds described on pages 58-60 of International Publication 2015 / 012368, or compounds described in paragraphs

[0195] -

[0205] of International Publication 2018 / 159302 may also be used.

[0075] Ionic polymeric compounds may also be used. Specifically, examples include melamine derivatives, guanidine derivatives, 1,3,5-tris(methoxymethoxy)benzene, 1,2,4-tris(isopropoxymethoxy)benzene, 1,4-bis(dibutoxymethoxy)benzene, 2,6-dihydroxymethyl-p-tert-butylphenol, and compounds containing epoxy groups or isocyanate groups as described on pages 15-16 of International Publication 2014 / 171493 (published on October 23, 2014).

[0076] When using ionic polymeric compounds, ionic initiators that generate acid or base due to ultraviolet light can be introduced to promote the polymerization reaction. Specifically, ionic initiators described on pages 16-17 of International Publication No. 2014 / 171493 (published on October 23, 2014) can be cited.

[0077] (Polymerization Initiator) In the light-adjusting layer forming material, in order to promote the polymerization reaction of polymerizable compounds, especially to promote the free radical polymerization of polymerizable compounds, it is preferable to introduce a free radical initiator (also called a polymerization initiator) that generates free radicals due to ultraviolet light. Specifically, benzo[a]ene and its alkyl ethers, benzyl ketals, acetophenones, acetophosphine oxides, diphenyl ketones, aminodiphenyl ketones, and the free radical initiators described on pages 13-14 of International Publication No. 2014 / 171493 (published on October 23, 2014) are suitable. Among the aforementioned acetophenones, for example, hydroxyacetophenone, aminoacetophenone, dialkoxyacetophenone, halogenated acetophenone, etc., can be used. Commercially available photopolymerization initiators include, for example, BASF's Irgacure 907 (2-[4-(methylthio)benzoyl]-2-(4-hydroxylinyl)propane), Irgacure 651 (2,2-dimethoxy-2-phenylacetophenone), Irgacure 369 (1-(4-hydroxylinophenyl)-2-(dimethylamino)-2-benzyl-1-butanone), Irgacure 184, or IGM Resins' Omnirad 184 (1-hydroxycyclohexylphenyl ketone). The proportion of the polymerization initiator used should preferably be in the range of 0.01 to 5 parts by weight relative to 100 parts by weight of the light-adjusting layer forming material. The above-mentioned photopolymerization initiators can be used alone or in combination of two or more. Furthermore, free radical initiators can also be used alone or in combination of two or more, depending on their specific characteristics.

[0078] (Orientation additive) An orientation additive added to the dimming layer forming material, such as the compound described in Japanese Patent Application Publication No. 2019-065230

[0049] , or the compound described in paragraphs

[0028] to

[0083] of International Publication No. 2016 / 140278. A more desirable orientation additive is, for example, XR (X represents hydroxyl or (meth)acryloxy, R and RO in formula (1) are synonymous, including ideal state). The amount of orientation additive used in the dimming layer forming material, from the viewpoint of the optical characteristics of the element, is ideally 0.1 to 30 parts by mass relative to 100 parts by mass of the dimming layer forming material, more preferably 0.5 to 30 parts by mass, and even more preferably 1 to 20 parts by mass. Two or more orientation additives may also be used in combination.

[0079] (Anisotropic Dye) Anisotropic dyes (also known as dichroic dyes or dichroic pigments) may also be added to the above-mentioned dimming layer forming material. The term "isotropic dye" refers to a substance that can anisotropically absorb light in at least a portion or all of the wavelength range within the visible light region, for example, 400–700 nm. There are no particular restrictions on the type of anisotropic dye; for example, black dyes or colored dyes can be used. Examples of such anisotropic dyes include various known products disclosed in Japanese Patent Application Publication No. 2007-009120 and Japanese Patent Application Publication No. 2011-246411. The mixing ratio of the anisotropic dye can be, for example, 0.01 to 5 parts by mass relative to 100 parts by mass of the dimming layer forming material, but this ratio can be changed as needed.

[0080] (UV absorber / light stabilizer) The above-mentioned dimming layer forming material may also contain additional UV absorbers and light stabilizers. Specific examples of UV absorbers and light stabilizers can be found in the exemplified compounds described above. The content of the UV absorber is preferably 0.1 to 3 parts by mass relative to 100 parts by mass of the liquid crystal composition, more preferably 0.1 to 2 parts by mass, and even more preferably 0.3 to 1.5 parts by mass. The content of the light stabilizer is preferably 1 to 10 parts by mass relative to 100 parts by mass of the liquid crystal composition, more preferably 2 to 8 parts by mass, and even more preferably 3 to 6 parts by mass.

[0081] (Chain Transfer Agent) The above-mentioned dimming layer forming material may also contain a chain transfer agent. Ideal examples of chain transfer agents are butylene glycol dithiopropionate, butylene glycol dithioglycolate, neopentyl tert-3-mercaptobutyrate, triethylene glycol dithiol, etc. This prevents the degree of crosslinking of the polymer phase from becoming too high, and thereby makes the liquid crystal material more responsive to an electric field, enabling it to be driven with low voltage. The content of the chain transfer agent is ideally 0.05 to 30 parts by mass relative to 100 parts by mass of the polymeric compound component, and more ideally 0.1 to 20 parts by mass.

[0082] (4) The step of polymerizing the dimming layer forming material to form a dimming layer containing a polymer phase and a liquid crystal phase. The method of polymerizing the dimming layer forming material of the present invention can include methods such as irradiation with active energy rays and thermal polymerization. Among these, it is preferable to polymerize the dimming layer forming material by irradiation with ultraviolet light. Furthermore, the method of ultraviolet irradiation can include irradiating one of the substrates of a pair of auxiliary electrodes with ultraviolet light. The light source of the ultraviolet irradiation device used is, for example, a metal halide lamp or a high-pressure mercury lamp. At this time, the wavelength of ultraviolet light is preferably 250 to 400 nm. Among these, 310 to 370 nm is preferred. The intensity of the ultraviolet irradiation light can be appropriately determined by experiments, etc., or its endpoint can be determined according to the concentration of unreacted polymerizable compounds in the liquid crystal composition. It is ideal for the appropriate amount of ultraviolet irradiation light to be 0.05 J / cm2 or more, and more preferably 1.0 J / cm2 or more. Ideally, the intensity of ultraviolet (UV) irradiation should be 1 mW / cm² or higher; however, to ensure complete polymerization of the polymerizable compound, an intensity of 20 mW / cm² or higher is also acceptable. The irradiation time is preferably 1–3600 seconds, more preferably 60–3600 seconds, and even more preferably 60–1800 seconds. Furthermore, the irradiation period can be either with or without a voltage applied between the electrodes.

[0083] Furthermore, ultraviolet treatment and heat treatment can be performed simultaneously, or ultraviolet treatment can be performed followed by heat treatment. The temperature for heat treatment is preferably 20–120°C, more preferably 30–100°C.

[0084] The liquid crystal element of this invention can be ideally used in transportation equipment and machinery such as automobiles, railways, and aircraft. Specifically, it can be ideally used in dimming windows that control light transmission and blocking, and light shutter elements used in interior mirrors. Considering its excellent transparency when no voltage is applied and its good scattering characteristics when voltage is applied, when this liquid crystal element is used in the glass windows of vehicles, compared to conventional reverse-type elements, it has higher efficiency in allowing light to enter at night, and also improves the effect of preventing glare from external light. Therefore, it can further improve the safety of driving vehicles and the comfort of riding in vehicles. Furthermore, when the liquid crystal element is made from a thin-film substrate and attached to the glass windows of vehicles, the reliability of this element is improved compared to conventional reverse-type elements. That is, it is less prone to defects and deterioration caused by low adhesion between the liquid crystal layer and the liquid crystal alignment film. Furthermore, the liquid crystal element of the present invention can also be used in light guide plates of display devices such as LCD (Liquid Crystal Display) and OLED (Organic Light-emitting Diode) displays, and in the backplanes of transparent displays using such displays. Specifically, when used in the backplane of a transparent display, the liquid crystal element of the present invention is aligned with the transparent display, and when an image is displayed on the transparent display, the liquid crystal element of the present invention can suppress light entering from its back side. Therefore, when an image is displayed on the transparent display, the liquid crystal element becomes a scattering state under applied voltage, resulting in a bright image; after the image display ends, it becomes a transparent state without applied voltage. [Example]

[0085] The following examples illustrate the present invention in more detail, but the invention is not limited thereto. The abbreviations of the compounds used and the methods for determining their properties are as follows.

[0086] (Liquid Crystal) Liquid Crystal L1: Sb-323010 (Negative Nematic Liquid Crystal, manufactured by Champagne Company) (Polymerizable Compound) R1: Isoborneol Acrylate (manufactured by Osaka Organic Chemicals Co., Ltd., IBXA) R2: Compound component represented by the following formula [R2] (manufactured by Nippon Kayaku Co., Ltd., KAYARAD HX-220, m and n are integers whose sum of m and n is equal to 2, or a mixture containing multiple compounds.) R3: Compound component represented by the following formula [R3] (manufactured by Nippon Kayaku Co., Ltd., KAYARAD HX-620, m' and n' are integers whose sum of m' and n' is equal to 4, or a mixture containing multiple compounds.) R4: Compound component represented by the following formula [R4] (manufactured by Shin-Nakamura Chemical Co., Ltd., ethoxylated neopentyl terephthalate tetraacrylate, NK ESTER ATM-35E, where a, b, c, and d are integers whose sum equals 35, or can be mixtures containing multiple compounds. R5: Neopentyl tetrakis(3-mercaptobutyrate) (manufactured by Showa Denko, KARENZ MT PE1) R6: Compound represented by formula [R6] R7: Compound represented by formula [R7] (manufactured by Nippon Kayaku Co., Ltd., KAYARAD FM400) R8: EBECRYL 230 (difunctional aliphatic carbamate acrylate) manufactured by DAICEL ALLNEX R9: EBECRYL 4858 (difunctional aliphatic carbamate acrylate) manufactured by DAICEL ALLNEX R10: 1,1-(bisacryloxymethyl)ethyl isocyanate (manufactured by Showa Denko, KARENZ BE1)

[0087] [Chemical 12]

[0088] (Photoradical initiator) P1: 1-Hydroxycyclohexylphenyl ketone (manufactured by IGM Resins, Omnirad 184)

[0089] (Diamine) A1~A13: The diamine represented by the following formula (A1)~(A13) also, A1~A6 and A9~A12 are the diamines mentioned above (2), and A8 is the diamine mentioned above (1).

[0090] [Chemistry 13]

[0091] (Tetracarboxylic dianhydride) B1: 1,2,3,4-Cyclobutanetetracarboxylic dianhydride [Chemical 14] (Additive) [Chemical 15]

[0092] (Solvent) NMP: N-methyl-2-pyrrolidone; BCS: ethylene glycol monobutyl ether; THF: tetrahydrofuran; DMF: N,N-dimethylformamide

[0093] (Reagents) Boc2O: ditert-butyl dicarbonate EDC・HCl: 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride DMAP: 4-dimethylaminopyridine BHT: 2,6-di-tert-butyl-4-methylphenol TFA: trifluoroacetic acid DBU: 1,8-diazabicyclo[5.4.0]undec-7-ene

[0094] [Synthetic Examples of Monomers] A1, A3, A4, A6, A9, A10, A11, and A12 are novel compounds not disclosed in the literature. The synthetic methods are detailed below. A2 was synthesized using the same method as A1. A5 was synthesized according to the synthetic method described in International Publication 2014 / 208609. The products described in the following monomer synthesis examples 1-8 were identified by 1H-NMR analysis (analytical conditions are as follows). Apparatus: BRUKER ADVANCE III-500MHz; Solvent: Deuterated dimethyl sulfoxide (DMSO-d6); Standard: Tetramethylsilane (TMS) (δ 0.0 ppm for 1H).

[0095] <Synthesis Example 1: Synthesis of A1> A1 was synthesized according to the following scheme. [Chemistry 16]

[0096] THF (150 g) was added to 3,5-diaminobenzoic acid (25.0 g, 0.164 mol) and stirred. Boc₂O (78.9 g, 0.361 mol) dissolved in THF (50 g) was added dropwise. After the addition was complete, the mixture was heated and stirred at 65 °C for 19 hours. After the reaction was complete, the mixture was cooled to room temperature (25 °C), and the THF was concentrated. Ethyl acetate (200 g) was added. The mixture was washed twice with 0.2 N hydrochloric acid (200 g) and the organic phase was concentrated. Ethyl acetate (90 g) was added, and the mixture was stirred at room temperature (25 °C). Heptane (180 g) was added and stirred, and the precipitated crystals were filtered. The obtained crystals were dried to obtain Al-1 (yield: 53.3 g, 0.151 mol, 92%). 1H-NMR (500MHz) in DMSO-d6: 12.83 (br, 1H), 9.48 (s, 2H), 7.86 (s, 1H), 7.68 (d, J=1.5Hz, 2H), 1.47 (s, 18H)

[0097] A1-1 (25.0 g, 0.0709 mol) was added to 4-chloro-1-butanol (10.9 g, 0.100 mol), THF (150 g), EDC·HCl (16.3 g, 0.0851 mol), and DMAP (0.870 g, 7.12 mmol), and stirred at room temperature (25 °C) for 17 hours. After the reaction was completed, stirring was stopped, and the reaction solution was concentrated. Ethyl acetate (150 g) was added, and the mixture was washed once with water (150 g), and then washed twice with 10% potassium carbonate aqueous solution (150 g), and the organic phase was concentrated. Ethyl acetate (40 g) was added to the crude product, and the mixture was stirred at room temperature (25 °C) and then heptane (120 g) was added. The mixture was stirred, and the precipitated crystals were filtered. The obtained crystals were dried to obtain Al-2 (yield: 24.0 g, 0.0542 mol, 76% yield). ¹H-NMR (500 MHz) was performed on DMSO-d6: 9.51 (s, 2H), 7.95 (s, 1H), 7.69 (d, J = 2.0 Hz, 2H), 4.28 (t, 2H), 3.71 (t, 2H), 1.87–1.81 (m, 4H), 1.47 (s, 18H).

[0098] Potassium methacrylate (7.40 g, 0.0596 mol), BHT (0.0240 g), potassium iodide (0.900 g, 5.42 mmol), and DMF (144 g) were added to A1-2 (24.0 g, 0.0542 mol) and heated and stirred at 80 °C. After 18 hours, potassium methacrylate (1.35 g, 0.0109 mol) was added again, and the mixture was heated and stirred for another 24 hours. The reaction solution was filtered, and ethyl acetate (150 g) was added to the filtrate. The solution was washed three times with water (150 g). Specialized white egret activated carbon (2.70 g) was added to the obtained organic phase, and the mixture was heated and stirred at 55 °C. The solution was filtered, and the filtrate was concentrated and dried. Ethyl acetate (45 g) was added, and the mixture was heated and stirred at 45 °C to dissolve it. Heptane (135 g) was added while cooling in an ice bath (0 °C). The precipitated crystals were filtered and dried to obtain Al-3 (yield: 25.6 g, 0.0520 mol, 96% yield). ¹H-NMR (500 MHz) at DMSO-d6: 9.50 (s, 2H), 7.93 (s, 1H), 7.70 (d, J = 2.0 Hz, 2H), 6.03 (t, 1H), 5.66 (t, 1H), 4.28 (t, 2H), 4.16 (t, 2H), 1.88 (s, 3H), 1.77 (t, 4H), 1.47 (s, 18H).

[0099] Chloroform (245g) and trifluoroacetic acid (56.7g, 0.497mol) were added to A1-3 (24.5g, 0.0497mol), and the mixture was stirred at room temperature (25℃) for 23 hours. After the reaction was completed, ethyl acetate (250g) was added, and the mixture was washed twice with 10% potassium carbonate aqueous solution (250g) and once with water (250g) to concentrate and dry the organic phase, thereby obtaining A1 (yield: 12.6g, 0.0431mol, yield 87%). 1H-NMR (500MHz), in DMSO-d6: 6.43 (d, J=2.0Hz, 2H), 6.03 (t, 2H), 5.67 (t, 1 H), 4.96 (s, 4H), 4.20 (t, 2H), 4.15 (t, 2H), 1.88 (s, 3H), 1.75-1.73 (m, 4H)

[0100] <Synthesis Example 2: Synthesis of A3> A3 was synthesized according to the following scheme.

[0101] [Chemistry 17]

[0102] THF (180 g) was added to 2-(2,4-dinitrophenyl)-ethyl-1-ol (30.0 g, 0.141 mol), followed by nitrogen substitution. Then, 5% palladium on carbon (containing water) (2.40 g) was added, and nitrogen substitution was performed again. The mixture was then placed in a hydrogen-filled gas sampling bag (Tedlar bag) and stirred at room temperature (25 °C) for 52 hours. After the reaction was completed, the palladium on carbon was removed through a membrane filter. The filtrate was then concentrated and dried to obtain A3-1 (yield: 22.8 g, quant). 1H-NMR (500MHz), in DMSO-d6: 6.56 (d, J=8.0Hz, 1H), 5.87 (d, J=2.5Hz, 1H), 5.79 (d d, J=8.0Hz, 1.0Hz, 1H), 4.52(s, 1H), 4.50(s, 4H), 3.49-3.45(m, 2H), 2.45(t, 2H)

[0103] THF (120 g) was added to A3-1 (19.5 g, 0.128 mol), and the mixture was stirred at room temperature (25 °C). Boc2O (61.5 g, 0.282 mol) diluted with THF (40 g) was added dropwise, and the mixture was stirred at room temperature (25 °C) for 21 hours after the addition was complete. To quench excess Boc2O after the reaction, methanol (20 g) and DMAP (0.20 g) were added to the reaction solution, and the mixture was heated and stirred at 50 °C for 1 hour, resulting in approximately 14% byproduct. The organic phase was concentrated and dried to obtain crude A3-2 (purity 86% by mass, yield: 49.1 g, 0.120 mol, 91% yield). 1H-NMR (500MHz), in DMSO-d6: 9.22 (s, 1H), 8.63 (s, 1H), 7.57 (d, J=1.0Hz, 1H), 7.10 (d, J=7.5H z, 1H), 7.03 (d, J=8.5Hz, 1H), 5.01 (t, 1H), 3.57-3.53 (m, 2H), 2.63 (t, 2H), 1.50-1.35 (m, 18H)

[0104] The crude product of A3-2 (86% by mass, 49.1 g, 0.120 mol) was added to 4-((6-(methacryloxy)hexyl)oxy)benzoic acid (46.9 g, 0.153 mol), THF (392 g), EDC·HCl (32.0 g, 0.167 mol), and DMAP (1.70 g, 0.0139 mol), and stirred at room temperature (25 °C) for 29 hours. After the reaction was completed, stirring was stopped, and the reaction solution was concentrated. Ethyl acetate (400 g) was added to it, and the mixture was washed sequentially with water (350 g), saturated sodium bicarbonate aqueous solution (350 g), and water (350 g), and the organic phase was concentrated. Ethyl acetate (260 g) was added to the obtained crude product, and the mixture was heated and stirred at 50 °C until completely dissolved. After cooling in an ice bath (0 °C), heptane (150 g) was added and stirred. The precipitated crystals were filtered and dried to obtain A3-3 (yield: 43.0 g, 0.0671 mol, yield 56%). 1H-NMR (500MHz), in DMSO-d6: 9.28 (s, 1H), 8.59 (s, 1H), 7.86 (d, J=9.0Hz, 2H), 7.49 (s, 1H), 7.16-7.13 (m, 2H), 7.01 (d, J=9.0Hz, 2H), 6.01 (t, 1H), 5.65(t, 1H), 4.32(t, 2H), 4.10(t, 2H), 4.04(t, 2H), 2.94(t, 2H), 1.87(s, 3H), 1.76-1.71(m, 2H), 1.68-1.61(m, 2H), 1.46-1.34(m, 22H)

[0105] Chloroform (429 g) and trifluoroacetic acid (76.3 g, 0.669 mol) were added to A3-3 (42.9 g, 0.0670 mol), and the mixture was stirred at room temperature (25 °C) for 25 hours. After the reaction was complete, ethyl acetate (250 g) was added, and the mixture was extracted with 20% potassium carbonate aqueous solution (250 g). The mixture was washed with dilute hydrochloric acid (a solution of 12N hydrochloric acid (12 mL) diluted with water (240 mL)). After discarding the organic phase, ethyl acetate (250 g) was added again, and the aqueous phase was adjusted to alkalinity (pH=9) with potassium carbonate aqueous solution (potassium carbonate: 30 g, water: 120 g) and extracted again. The organic phase was concentrated and dried to obtain A3 (yield: 25.9 g, 0.0588 mol, yield 88%). 1H-NMR (500MHz), in DMSO-d6: 7.89 (d, J=9.0Hz, 2H), 7.02 (dd, J=7.0Hz, 2.0Hz, 2H ), 6.63 (d, J=8.0Hz, 1H), 6.01 (t, 1H), 5.89 (d, J=2.0Hz, 1H), 5.80-5.78 (m, 1H), 5 .65(t,1H),4.66(br,2H),4.58(br,2H),4.25(t,2H),4.10(t,2H),4.04(t,2H),2 .73(t, 2H), 1.87(s, 3H), 1.74-1.71(m, 2H), 1.65-1.62(m, 2H), 1.48-1.35(m, 4H)

[0106] <Synthesis Example 3: Synthesis of A4> A4 was synthesized according to the following scheme. [Chemistry 18]

[0107] Ethylene glycol (70.5 g, 1.14 mol), THF (320 g), EDC·HCl (26.1 g, 0.136 mol), and DMAP (1.38 g, 0.0113 mol) were added to A1-1 (40.0 g, 0.114 mol), and the mixture was stirred at room temperature (25 °C) for 23 hours. After the reaction was completed, stirring was stopped, and the reaction solution was concentrated. Ethyl acetate (320 g) was added to the solution, and the mixture was washed sequentially with water (300 g), 10% potassium carbonate aqueous solution (300 g), and water (300 g) to concentrate and dry the organic phase, thereby obtaining crude product A4-1 (yield: 47.8 g). ¹H-NMR (500 MHz), at DMSO-d6: 9.52 (t, 2H), 7.88 (s, 1H), 7.73 (s, 2H), 4.87 (t, 1H), 4.27 (t, 2H), 3.69–3.66 (m, 2H), 1.46 (s, 18H)

[0108] The crude product of A4-1 (47.8 g) was added to 4-((6-(methacryloxy)hexyl)oxy)benzoic acid (40.0 g, 0.131 mol), THF (376 g), EDC·HCl (27.3 g, 0.142 mol), and DMAP (1.45 g, 0.0119 mol), and stirred at room temperature (25 °C) for 21 hours. After the reaction was completed, stirring was stopped, and the reaction solution was concentrated. Ethyl acetate (400 g) was added to it, and the mixture was washed once with water (350 g) and twice with saturated sodium bicarbonate aqueous solution (350 g) to concentrate and dry the organic phase to obtain a brown oil. The fraction was purified by silica gel column chromatography using a mixed solvent of heptane / ethyl acetate = 2 / 1 (volume ratio), and the fraction was concentrated and dried to obtain A4-2 (purity 85% by mass, yield: 59.7g, 0.0741mol). 1H-NMR (500MHz), in DMSO-d6: 9.53 (t, 2H), 8.04 (d, J=9.0Hz, 1H), 7.91-7.87 (m, 2H), 7.76 (s, 1H), 7.11 (d, J=9.0Hz, 1H), 7.00 (d, J=9.0Hz, 2H), 6.01 -6.00(m, 1H), 5.65-5.63(m, 1H), 4.59-4.58(m, 2H), 4.10-4.08(m, 2H), 4. 04-4.00(m, 4H), 1.87-1.86(m, 3H), 1.78-1.58(m, 4H), 1.50-1.30(m, 22H)

[0109] Chloroform (597g) and trifluoroacetic acid (99.4g, 0.872mol) were added to A4-2 (85% by mass, 59.7g, 0.0741mol), and the mixture was stirred at room temperature (25℃) for 20 hours. After the reaction was completed, the reaction solution was concentrated. Ethyl acetate (300g) was added, and the mixture was extracted with 20% potassium carbonate aqueous solution (300g). The mixture was then washed with dilute hydrochloric acid (a solution of 12N hydrochloric acid (17mL) diluted with water (280mL)). The mixture was separated into three layers in the separatory funnel (upper layer, middle layer, lower layer). The second layer from the top, i.e., the middle layer, was removed, and ethyl acetate (120g) was added again. The aqueous phase was adjusted to alkaline (pH=9) with potassium carbonate aqueous solution (potassium carbonate: 30g, water: 120g), and the mixture was extracted with ethyl acetate. The organic phase was concentrated and dried to obtain A4 (yield: 31.7 g, 0.0654 mol, yield 88%). 1H-NMR (500MHz), in DMSO-d6: 7.89 (d, J=8.5Hz, 2H), 7.02 (d, J=8.5Hz, 2H), 6.45 (d, J=2.0Hz, 2H), 6.03 (t, 1H), 6.01 (s, 1H), 5.64 (t, 1H) , 4.99 (br, 4H), 4.56-4.47 (m, 4H), 4.09 (t, 2H), 4.04-4.01 (m, 2H), 1.86 (s, 3H), 1.75-1.68 (m, 2H), 1.68-1.60 (m, 2H), 1.48-1.35 (m, 4H)

[0110] <Synthesis Example 4: Synthesis of A6> A6 was synthesized according to the following scheme. [Chemistry 19]

[0111] Dichloromethane (600g), EDC·HCl (22.8g, 0.119mol), and DMAP (1.39g, 0.0114mol) were added to A1-1 (40.0g, 0.114mol) and stirred at room temperature (25°C). 2-Aminoethanol (7.00g, 0.115mol) was added dropwise, and the mixture was stirred at room temperature (25°C). After 30 minutes, precipitation occurred and the stirring became unsatisfactory. Therefore, 400g of dichloromethane was added, and the mixture was stirred for 22 hours. After the reaction was complete, stirring was stopped, the reaction solution was filtered, and the precipitated crystals were collected. Ethyl acetate (540g) was added, and the mixture was washed twice with water (500g) to concentrate and dry the organic phase, yielding A6-1 (yield: 36.1g, 0.0913mol, 80% yield). 1H-NMR (500MHz), in DMSO-d6: 9.41 (s, 2H), 8.15 (t, 1H), 7.67 (s, 1H), 7.46 (d, J =2.0Hz, 2H), 4.69 (t, 1H), 3.50-3.46 (m, 2H), 3.29-3.27 (m, 2H), 1.47 (s, 18H)

[0112] A6-1 (36.0 g, 0.0910 mol) was added to (E)-3-(4-((6-(methacryloxy)hexyl)oxy)phenyl)acrylic acid (31.8 g, 0.0957 mol), THF (288 g), EDC・HCl (19.2 g, 0.100 mol), and DMAP (1.11 g, 9.09 mmol), and stirred at room temperature (25 °C) for 19 hours. After the reaction was completed, stirring was stopped, and the reaction solution was concentrated. Ethyl acetate (400 g) was added, and the mixture was washed sequentially with water (400 g), saturated sodium bicarbonate aqueous solution (400 g), and water (400 g), respectively, and the organic phase was concentrated. Ethyl acetate (160 g) was added, and the mixture was stirred at room temperature (25 °C) to dissolve the crude product. Heptane (250 g) was added while cooling in an ice bath (0 °C) to induce crystallization. The crystals were filtered and dried to obtain A6-2 (yield: 54.1 g, 0.0762 mol, 84% yield). ¹H-NMR (500 MHz) was performed on DMSO-d6: 9.42 (s, 2H), 8.44 (t, 1H), 7.66–7.60 (m, 4H), 7.49 (d, J = 1.5 Hz, 2H), 6.94 (d, J = 9.0 Hz, 2H), 6.46 (d, J = 16.0 Hz, 1H), 6.01 (s, 1H). ,5.65(t,1H),4.24(t,2H),4.23-4.08(m,2H),4.01-3.99(m,2H),3.54-3.50( m, 2H), 1.99 (s, 3H), 1.75-1.69 (m, 2H), 1.68-1.62 (m, 2H), 1.55-1.34 (m, 22H)

[0113] Dichloromethane (540 g) and trifluoroacetic acid (86.9 g, 0.762 mol) were added to A6-2 (54.1 g, 0.0762 mol), and the mixture was stirred at room temperature (25 °C) for 21 hours. After the reaction was completed, the reaction solution was concentrated. Ethyl acetate (500 g) was added, and the mixture was extracted twice with 20% potassium carbonate aqueous solution (400 g). The mixture was washed separately with water (500 g), and the organic phase was concentrated. THF (200 g) was added and stirred at room temperature (25 °C) to dissolve the crude product. Heptane (200 g) was added while cooling in an ice bath at 0 °C to induce crystallization. The crystals were filtered and dried to obtain A6 (yield: 33.7 g, 0.0661 mol, yield 87%). 1H-NMR (500MHz), in DMSO-d6: 8.15 (t, 1H), 7.65-7.60 (m, 3H), 6.95 (d, J=8.5 Hz, 2H), 6.46 (d, J=16.0Hz, 1H), 6.22 (s, 2H), 6.01 (s, 1H), 5.94 (t, 1H), 5.6 5(t, 1H), 4.84(br, 4H), 4.21(t, 2H), 4.10(t, 2H), 4.00(t, 2H), 3.49-3.46( m, 2H), 1.87 (s, 3H), 1.76-1.70 (m, 2H), 1.69-1.61 (m, 2H), 1.49-1.30 (m, 4H)

[0114] <Synthesis Example 5: Synthesis of A9> A9 was synthesized according to the following scheme. [Chemistry 20]

[0115] The synthesis of A9-1 was carried out in the same manner as the synthesis of A6-2, except that (E)-3-(4-((6-(methacryloxy)hexyl)oxy)phenyl)acrylic acid was not used, but 4-((6-(methacryloxy)hexyl)oxy)benzoic acid was used. 1H-NMR (500MHz), in DMSO-d6: δ (ppm) = 9.42 (s, 2H), 8.49 (t, 1H), 7.92 (t, 2H), 7.64 (s, 1H), 7.50 (d, J = 1.5Hz, 2H), 7.01 (t, 2H), 6.01 (s, 1H), 5 .65(s, 1H), 4.31(t, 2H), 4.09(t, 2H), 4.03(t, 2H), 3.60-3.56(m, 2H), 1.86(s, 3H), 1.76-1.69(m, 2H), 1.68-1.61(m, 2H), 1.50-1.32(m, 22H)

[0116] The synthesis of A9 was performed using A9-1 instead of A6-2, otherwise the synthesis was the same as that of A6, yielding A9 (yield: 16.4 g, 0.0339 mol, 80%). ¹H-NMR (500 MHz) in DMSO-d6: δ(ppm) = 8.21 (t, ¹H), 7.91 (d, J = 9.0 Hz, 2H), 7.02 (d, J = 9.0 Hz, 2H), 6.21 (d, J = 2.0 Hz, 2H), 6.01 (t, ¹H), 5.93 (t, ¹H), 5.65 (t, ¹H), 4 .84(br, 4H), 4.30-4.27(m, 2H), 4.11-4.08(m, 2H), 4.05-4.03(m, 2H), 3.55-3. 52(m, 2H), 1.87(s, 3H), 1.76-1.70(m, 2H), 1.69-1.61(m, 2H), 1.49-1.30(m, 4H)

[0117] <Synthesis Example 6: Synthesis of A10> A10 was synthesized according to the following scheme. [Chemistry 21]

[0118] Acetonitrile (MeCN, 30g) and p-toluenesulfonyl chloride (3.25g, 0.0170mol) were added to A1-1 (5.0g, 0.0142mol) and cooled in an ice bath at 0°C. 1-Methylimidazole (3.50g, 0.0426mol) was added dropwise, and the mixture was stirred in an ice bath at 0°C for 3 hours after the addition was complete. After 3 hours, 1.0–1.1 equivalents of 6-(4-hydroxyphenoxy)hexyl methacrylate were added to A1-1, and the mixture was stirred at 25°C for 21 hours. Water (150g) was added to the reaction mixture and stirred to induce crystallization. The crystals were then filtered. Methanol (45g) was added to the obtained crystals, and the mixture was stirred at 25°C to wash the slurry. The filtered crystals were dried to obtain A10-1 (yield: 8.33g, 0.0136mol, 96% yield). 1H-NMR (500MHz), in DMSO-d6: δ (ppm) = 9.59 (s, 2H), 7.94 (s, 1H), 7.88 (d, J = 1.5Hz, 2H), 7.14 (d, J = 9.0Hz, 2H), 6.98 (d, J = 4.5Hz, 2H), 6.02(s, 1H), 5.66(t, 1H), 4.11(t, 2H), 3.98(t, 2H), 1.88(s, 3H), 1.76-1.69(m, 2H), 1.68-1.61(m, 2H), 1.50-1.37(m, 22H)

[0119] Concentrated hydrochloric acid (12N hydrochloric acid, 12mL) and ethyl acetate (EtOAc, 80mL) were added to the above A10-1 (7.7g), and the mixture was heated and stirred at room temperature (25°C) for 18 hours. Stirring was stopped, and 10% potassium carbonate aqueous solution (77g) was added to the reaction mixture. The mixture was stirred at room temperature (25°C) for 1 hour. The precipitate was filtered and dried to obtain A10(a). The filtrate was transferred to a separatory funnel, the 10% potassium carbonate aqueous solution was removed, and the mixture was washed with water (77g × 2 times) and the organic phase was concentrated (crude product a). Ethyl acetate (16g) was added to the obtained crude product a, and the mixture was stirred at room temperature (25°C). The slurry was washed, and the filtered crystals were dried to obtain A10(b). A10(a) and A10(b) were combined to obtain A10. (Yield: 1.30g, 3.15mmol, yield 94%). 1H-NMR (500MHz), in DMSO-d6: δ (ppm) = 7.08 (d, J = 9.0Hz, 2H), 6.95 (d, J = 9.0Hz, 2H), 6.57 (d, J = 2.0Hz, 2H), 6.09 (t, 1H), 6.02 (s, 1H), 5.66(t, 1H), 5.06(br, 4H), 4.11(t, 2H), 3.97(t, 2H), 1.88(s, 3H), 1.76-1.70(m, 2H), 1.69-1.62(m, 2H), 1.49-1.30(m, 4H)

[0120] <Synthesis Example 7: Synthesis of A11> A11 was synthesized according to the following scheme. [Chemistry 22]

[0121] The synthesis of A11-1 was performed using 4-((6-(acryloyloxy)hexyl)oxy)phenyl)acrylic acid instead of (E)-3-(4-((6-(methacryloyloxy)hexyl)oxy)benzoic acid, otherwise the same as the synthesis of A6-2 was performed to obtain A11-1 (yield: 13.9 g, 0.0208 mol, 93%). ¹H-NMR (500 MHz), in DMSO-d6: δ (ppm) = 9.41 (s, 2H), 8.48 (t, 1H), 7.92 (t, 2H), 7.64 (s, 1H), 7.50 (d, J = 1.5 Hz, 2H), 7.02–7.00 (m, 2H), 6.33–6.29 (m, 1H), 6 .19-6.13(m, 1H), 5.93-5.91(m, 1H), 4.32(t, 2H), 4.11(t, 2H), 4.03(t, 2H), 3.60-3.56(m, 2H), 1.76-1.69(m, 2H), 1.68-1.61(m, 2H), 1.50-1.34(m, 22H)

[0122] The synthesis of A11 uses A11-1 instead of A6-2, and is otherwise the same as the synthesis of A6, to obtain A11 (yield: 7.26 g, 0.0155 mol, yield 81%). 1H-NMR (500MHz), in DMSO-d6: δ (ppm) = 8.19 (t, 1H), 7.92 (d, J = 9.0Hz, 2H), 7. 02(d, J=9.0Hz, 2H), 6.33-6.29(m, 1H), 6.21-6.19(m, 2H), 6.18-6.14(m, 1H ), 5.94-5.91(m, 2H), 4.82(br, 4H), 4.29(t, 2H), 4.19(t, 2H), 4.03(t, 2H), 3.55-3.52(m, 2H), 1.76-1.70(m, 2H), 1.69-1.61(m, 2H), 1.49-1.32(m, 4H)

[0123] <Synthesis Example 8: Synthesis of A12> A12 was synthesized according to the following scheme. [Chemistry 23]

[0124] The synthesis of A12-1 was carried out in the same manner as the synthesis of A10-1, except that 6-(4-hydroxyphenoxy)hexyl)methacrylate was used instead of 6-(4-hydroxyphenoxy)hexyl)acrylate, to obtain A12-1 (yield: 7.66 g, 0.0128 mol, yield 90%). 1H-NMR (500MHz), in DMSO-d6: δ (ppm) = 9.60 (s, 2H), 7.94 (s, 1H), 7.88 (d, J = 1.5Hz, 2H), 7.15-7.13 (m, 2H), 6.99-6.97 (m, 2H), 6.34-6. 30(m, 1H), 6.20-6.14(m, 1H), 5.94-5.92(m, 1H), 4.12(t, 2H), 3.97(t, 2H), 1.75-1.70(m, 2H), 1.69-1.62(m, 2H), 1.50-1.38(m, 22H)

[0125] The synthesis of A12 uses A12-1 instead of A10-1, and is otherwise the same as the synthesis of A10, to obtain A12 (yield: 4.56 g, 0.0111 mol, yield 89%). 1H-NMR (500MHz), in DMSO-d6: δ (ppm) = 7.09-7.07 (m, 2H), 6.96-6.95 (m, 2H), 6.57 (d, J = 2.0Hz, 2H), 6.34-6.30 (m, 1H), 6.20-6.15 (m, 1 H), 6.09 (t, 1H), 5.94-5.92 (m, 1H), 5.07 (br, 4H), 4.12 (t, 2H), 3.96 (t, 2H), 1.75-1.71 (m, 2H), 1.70-1.63 (m, 2H), 1.49-1.36 (m, 4H)

[0126] [Synthesis Example of Polyamide Polymer] <Synthesis Example 1> B1 (3.16 g, 16.1 mmol), A1 (1.45 g, 5.0 mmol), and A8 (5.02 g, 11.6 mmol) were mixed in NMP (38.5 g) and reacted at 25 °C for 24 hours to obtain a polyamide solution (1) with a resin solid content concentration of 20.0% by mass.

[0127] <Synthesis Example 2> B1 (3.16 g, 16.1 mmol), A2 (1.59 g, 5.0 mmol), and A8 (5.02 g, 11.6 mmol) were mixed in NMP (39.0 g) and reacted at 25 °C for 24 hours to obtain a polyamide solution (2) with a resin solid content concentration of 20.0% by mass.

[0128] <Synthesis Example 3> B1 (2.91g, 14.9mmol), A3 (1.98g, 4.5mmol), and A8 (4.56g, 10.5mmol) were mixed in NMP (37.8g) and reacted at 25°C for 24 hours to obtain a polyacrylic acid solution (3) with a resin solids concentration of 20.0% by mass. <Synthesis Example 4> B1 (2.91g, 14.9mmol), A4 (2.18g, 4.5mmol), and A8 (4.56g, 10.5mmol) were mixed in NMP (38.6g) and reacted at 25°C for 24 hours to obtain a polyacrylic acid solution (4) with a resin solids concentration of 20.0% by mass. <Synthesis Example 5> B1 (3.03 g, 15.4 mmol), A5 (2.17 g, 4.7 mmol), and A8 (4.72 g, 10.9 mmol) were mixed in NMP (39.6 g) and reacted at 25 °C for 24 hours to obtain a polyamide solution (5) with a resin solid content concentration of 20.0% by mass.

[0129] <Synthesis Example 6> B1 (2.91g, 14.9mmol), A6 (2.29g, 4.5mmol), and A8 (4.56g, 10.5mmol) were mixed in NMP (39.1g) and reacted at 25°C for 24 hours to obtain a polyamide solution (6) with a resin solid content concentration of 20.0% by mass.

[0130] <Synthesis Example 7> B1 (2.91g, 14.9mmol), A6 (0.76g, 1.5mmol), and A8 (5.87g, 13.5mmol) were mixed in NMP (38.2g) and reacted at 25°C for 24 hours to obtain a polyamide solution (7) with a resin solid content concentration of 20.0% by mass.

[0131] <Synthesis Example 8> B1 (3.30 g, 16.8 mmol), A7 (1.35 g, 5.1 mmol), and A8 (5.17 g, 11.9 mmol) were mixed in NMP (39.3 g) and reacted at 25°C for 24 hours to obtain a polyacrylic acid solution (8) with a resin solids concentration of 20.0% by mass. <Synthesis Example 9> B1 (2.91 g, 14.9 mmol), A9 (2.16 g, 4.5 mmol), and A8 (4.56 g, 10.5 mmol) were mixed in NMP (38.6 g) and reacted at 25°C for 24 hours to obtain a polyacrylic acid solution (9) with a resin solids concentration of 20.0% by mass. <Synthesis Example 10> B1 (2.91 g, 14.9 mmol), A13 (0.43 g, 1.5 mmol), A9 (1.45 g, 3.0 mmol), and A8 (4.56 g, 10.5 mmol) were mixed in NMP (37.4 g) and reacted at 25°C for 24 hours to obtain a polyacrylic acid solution (10) with a resin solids concentration of 20.0% by mass. <Synthesis Example 11> B1 (2.91 g, 14.9 mmol), A7 (0.60 g, 2.3 mmol), A9 (1.09 g, 2.3 mmol), and A8 (4.56 g, 10.5 mmol) were mixed in NMP (36.6 g) and reacted at 25°C for 24 hours to obtain a polyacrylic acid solution (11) with a resin solids concentration of 20.0% by mass. <Synthesis Example 12> B1 (2.91 g, 14.9 mmol), A10 (1.86 g, 4.5 mmol), and A8 (4.56 g, 10.5 mmol) were mixed in NMP (37.3 g) and reacted at 25°C for 24 hours to obtain a polyacrylic acid solution (12) with a resin solids concentration of 20.0% by mass. <Synthesis Example 13> B1 (2.91 g, 14.9 mmol), A12 (1.79 g, 4.5 mmol), and A8 (4.56 g, 10.5 mmol) were mixed in NMP (37.6 g) and reacted at 25°C for 24 hours to obtain a polyacrylic acid solution (13) with a resin solids concentration of 20.0% by mass.

[0132] The types and amounts of the tetracarboxylic acid components and diamine components used in the above synthetic examples 1 to 13 are shown in Table 1. In Table 1, the values ​​in parentheses refer to the amount (in mol) of each tetracarboxylic acid component used relative to a total of 100 mol of tetracarboxylic acid components, and the values ​​for the diamine components refer to the amount (in mol) of each diamine component used relative to a total of 100 mol of diamine components.

[0133] [Table 1]

[0134] [Manufacturing of Liquid Crystal Alignment Agent] The following describes an example of manufacturing a liquid crystal alignment agent. This liquid crystal alignment agent is also used in the fabrication and evaluation of liquid crystal elements.

[0135] <Example 1> Cl (0.1g), NMP (14.9g), and BCS (25.0g) were added to the polyacrylic acid solution (1) (10.0g) obtained in Synthesis Example 1, and stirred at 25°C for 2 hours to obtain liquid crystal alignment agent (1). No abnormalities such as turbidity or precipitation were observed in this liquid crystal alignment agent, confirming that it is a homogeneous solution.

[0136] <Examples 2~12, Comparative Example 1> The type of polyacrylic acid solution used was changed to that shown in Table 2. Otherwise, the same operation as in Example 1 was performed to obtain liquid crystal alignment agents (2)~(13). No abnormalities such as turbidity or precipitation were observed in the above liquid crystal alignment agents (2)~(13), and it was confirmed that they were homogeneous solutions.

[0137] [Table 2] Liquid crystal alignment agent Polyamine solution additive solid components (quality%) Solvent (mass %) NMP BCS Example 1 (1) (1) C1(5) 4 46 50 Example 2 (2) (2) C1(5) 4 46 50 Example 3 (3) (3) C1(5) 4 46 50 Example 4 (4) (4) C1(5) 4 46 50 Example 5 (5) (5) C1(5) 4 46 50 Example 6 (6) (6) C1(5) 4 46 50 Example 7 (7) (7) C1(5) 4 46 50 Example 8 (9) (9) C1(5) 4 46 50 Example 9 (10) (10) C1(5) 4 46 50 Example 10 (11) (11) C1(5) 4 46 50 Example 11 (12) (12) C1(5) 4 46 50 Example 12 (13) (13) C1(5) 4 46 50 Comparative Example 1 (8) (8) C1(5) 4 46 50

[0138] In Table 2, the values ​​in parentheses for additives represent the amount (parts by mass) of additives relative to 100 parts by mass of polymer components. The values ​​for solid components represent the amount (mass%) of solid components relative to the total amount of liquid crystal alignment agent excluding solvents. The values ​​for solvents represent the amount (mass%) of each solvent relative to the total amount of liquid crystal alignment agent.

[0139] <Preparation of the dimming layer forming material (A)> R1 (0.90g), R2 (1.50g), R3 (1.50g), R4 (0.30g), R5 (0.30g), and R6 (0.50g) were mixed and stirred at 25°C for 6 hours to prepare a solution of the polymeric compound (A). Then, the prepared solution of the polymeric compound (A), negative nematic liquid crystal (4.1g), and P1 (0.10g) were mixed and stirred at 25°C for 6 hours to obtain the dimming layer forming material (A).

[0140] <Preparation of the dimming layer forming material (B)> R1 (0.80g), R2 (0.60g), R4 (0.30g), R5 (0.30g), R6 (0.40g), R7 (1.2g), R8 (0.9g), R9 (0.3g), R10 (0.1g), S1 (0.1g), and P1 (0.10g) were mixed and stirred at 50°C for 4 hours to prepare a polymerizable compound solution (B). Then, the prepared polymerizable compound solution (B) was mixed with liquid crystal L1 (4.2g) and stirred at 25°C for 6 hours to obtain the dimming layer forming material (B).

[0141] [Fabrication of Liquid Crystal Element and Evaluation of Optical Properties] The liquid crystal alignment agent of the above-described embodiments or comparative examples was pressurized and filtered through a membrane filter with a pore size of 1 μm to fabricate a liquid crystal element. Specifically, this liquid crystal alignment agent was coated onto the ITO surface of a PET substrate (vertical: 150 mm, width: 150 mm, thickness: 0.2 mm) with an ITO electrode, which had been washed with pure water. The substrate was heated at 80°C for 2 minutes on a hot plate and then subjected to a heat treatment at 120°C for 2 minutes in a thermal cycling clean oven to obtain an ITO substrate with a liquid crystal alignment film thickness of 150 nm. Two ITO substrates with liquid crystal alignment films were prepared. A spacer with a thickness of 7.5 μm was coated onto the liquid crystal alignment film surface of one of the substrates. Next, the aforementioned dimming layer forming material (A) or (B) is dropped onto the alignment film surface of the substrate with pre-coated spacers using the ODF method. Then, it is bonded to the substrate with the liquid crystal alignment film interface facing each other, obtaining a liquid crystal element before processing. This unprocessed liquid crystal element is then subjected to ultraviolet irradiation using an ultraviolet light-emitting diode as a light source, with a wavelength of 365 nm, an ultraviolet irradiance of 4 mW, and an irradiation time of 250 seconds. The temperature inside the irradiation device is controlled at 25°C. This yields a liquid crystal element (reverse-type element).

[0142] [Evaluation of Optical Properties (Transparency and Scattering Properties)] The evaluation of transparency without applied voltage was performed by measuring the haze (also known as HAZE) of the liquid crystal element under the condition of no applied voltage. Specifically, a BYK haze-gardi (manufactured by TETSUTANI) was used to measure HAZE. The lower the HAZE, the better the transparency. The evaluation of scattering properties under applied voltage was performed by applying 48V AC drive to the liquid crystal element and measuring HAZE under the same conditions as above. The higher the HAZE, the better the scattering properties. The evaluation results of the optical properties are shown in Table 3.

[0143] [Evaluation of the adhesion between the liquid crystal layer and the alignment film] The fabricated liquid crystal element was placed on a small benchtop testing machine EZ-SX manufactured by Shimadzu Corporation. After fixing the lower substrate to the platform, the end of the upper substrate was fixed, and the upper substrate was stretched upwards. The peel strength (N / 25mm) at which the liquid crystal layer and the alignment film would separate was measured. The higher this value, the better the adhesion. The evaluation results of the adhesion are shown in Table 3. [Table 3] Liquid crystal alignment agent dimming layer forming material Haze (%) Peel strength (N / 25mm) No applied voltage Apply voltage Example 1 (1) (A) 7 93 0.11 Example 2 (2) (A) 7 93 0.18 Example 3 (3) (A) 7 93 0.27 Example 4 (4) (A) 7 93 0.27 Example 5 (5) (A) 7 93 0.28 Example 6 (6) (A) 7 93 0.28 Example 7 (7) (A) 5 93 0.12 Example 8 (9) (B) - 94 0.25 Example 9 (10) (B) 5 96 0.22 Example 10 (11) (B) 5 97 0.22 Example 11 (12) (B) 7 96 0.18 Example 12 (13) (B) 6 96 0.12 Comparative Example 1 (8) (A) 7 93 0.06

[0144] As shown in Table 3, the liquid crystal alignment film obtained by using a liquid crystal alignment agent containing diamines A1-A6, A9-A10, or A12 of the aforementioned diamine (2) exhibits improved adhesion between the liquid crystal layer and the liquid crystal alignment film compared to a liquid crystal alignment film composed of a diamine component that does not contain the aforementioned diamine (2). Furthermore, the liquid crystal alignment film obtained by using a liquid crystal alignment agent containing diamines A1-A6, A9-A10, or A12 of the aforementioned diamine (2) also exhibits good optical properties (transparency and scattering properties).

[0145] Furthermore, the entire contents of the specification, scope of the application, drawings and offer of Japanese Patent Application No. 2021-134039, filed on August 19, 2021, are incorporated herein by reference and are disclosed as a part of the specification of this invention. [Simplified Explanation of the Diagram]

[0012] FIG1 is a schematic cross-sectional view showing an example of the liquid crystal element of the present invention.

Claims

1. A polymer-dispersed liquid crystal element comprising: a pair of substrates arranged opposite to each other; electrodes disposed on mutually facing surfaces of the pair of substrates; a dimming layer disposed between the pair of substrates and containing a polymeric phase and a liquid crystal phase; and a liquid crystal alignment film formed on at least one electrode surface of the pair of substrates, wherein the dimming layer is formed by polymerization of a dimming layer forming material, the dimming layer forming material containing a liquid crystal composition and a polymeric compound component; and the liquid crystal alignment film is formed from a liquid crystal alignment agent containing the following component (A); (A) component: at least one polymer (A) selected from the group consisting of a polyimide precursor obtained by reacting a diamine component containing a diamine (1) represented by formula (1) and a diamine (2) represented by formula (2) with a tetracarboxylic acid component, and a polyimide that is a polyimide derivative thereof. In the formula, X1 represents a single bond, -(CH2)a- (a is an integer from 1 to 15), -CONH-, -NHCO-, -CON(CH3)-, -NH-, -O-, -COO-, -OCO-, -CH2-OCO-, -OCH2-, or -((CH2)a1-A1)m1- (a1 is an integer from 1 to 15, A1 represents an oxygen atom or -COO-, m1 is an integer from 1 to 2, and when m1 is 2, multiple a1 and A1 have the above definitions independently), and G1 represents a divalent aromatic hydrocarbon group selected from 6 to 12 carbon atoms, divalent alicyclic hydrocarbon groups with 4 to 8 carbon atoms, and divalent cyclic groups of steroid skeletons. Any hydrogen atom on the cyclic group can also be replaced by an alkyl group with 1 to 3 carbon atoms, an alkoxy group with 1 to 3 carbon atoms, a fluorinated alkyl group with 1 to 3 carbon atoms, a fluorinated alkoxy group with 1 to 3 carbon atoms, or a fluorine atom. When m is an integer from 1 to 4, and m is 2 or more, multiple X1 and G1 can be independently defined as described above. R1 represents a fluorine atom, an alkyl group containing fluorine atoms with 1 to 10 carbon atoms, an alkoxy group containing fluorine atoms with 1 to 10 carbon atoms, an alkyl group with 3 to 10 carbon atoms, an alkoxy group with 3 to 10 carbon atoms, or an alkoxyalkyl group with 3 to 10 carbon atoms. X represents a single bond, -O-, -NH-, -O-(CH2)m2-O-, -C(CH3)2-, -CO-, -COO-, -CONH-, -(CH2)m2-, -SO2-, -OC(CH3)2-, -CO-(CH2)m2-, -NH-(CH2)m2-, -NH-(CH2)m2-NH-, -SO2-(CH2)m2-, -SO2-(CH2)m2-SO2-, -CONH-(CH2)m2-, -CONH-(CH2)m2-NHCO-, or -COO-(CH2)m2-OCO-, where m2 is an integer from 1 to 8, and i and j are each an integer of 0 or 1. When i is 1 and j is 0, the two R0s independently have the above definitions. In the formula, the Y-series group "*1-Y1-(Y2-Y3)n-*2" represents a divalent organogroup, R represents a hydrogen atom or a methyl group, and m is an integer from 4 to 20;Where n is an integer from 0 to 3, *1 represents an atomic bond with the benzene ring, *2 represents an atomic bond with -CH2-, Y1 represents a single bond, -O-, -NH-, -N(CH3)-, -CONH-, -NHCO-, -CO-N(CH3)-, -N(CH3)-CO-, or -OCO-, and Y3 represents a single bond, -O-, -NH-, -N(CH3)-, -CONH-, -NHCO-, -CO-N(CH3)-, -N(CH3)-CO-, -COO-, or -OCO-. However, when n is 0, Y1 represents -O-, -NH-, -N(CH3)-, -CONH-, -NHCO-, -CO-N(CH3)-, -N(CH3)-CO-, or -OCO-. Y2 represents a divalent organogroup selected from the group consisting of alkyl groups with 1 to 20 carbon atoms, benzene rings, the group "-CH=CH-Ph-" (Ph represents a benzene ring), cyclohexane rings, and heterocycles. Any hydrogen atom in these divalent organogroups may be replaced by a halogen atom, an alkyl group with 1 to 3 carbon atoms, an alkoxy group with 1 to 3 carbon atoms, an alkyl group with 1 to 3 carbon atoms containing a fluorine atom, or an alkoxy group with 1 to 3 carbon atoms containing a fluorine atom. However, when Y2 represents an alkyl group, Y3 represents a group other than a single bond; when n is 2 or more, multiple Y2 and Y3 groups independently possess the above definitions.

2. As in claim 1, a polymer-dispersed liquid crystal element, wherein, The content of the polymeric compound component is 10 parts by mass or more relative to 100 parts by mass of the dimming layer forming material.

3. The polymer-dispersed liquid crystal element as claimed in claim 1 or 2, wherein, In equation (1), R0 represents -CnH2n+1 (n is an integer from 3 to 10) or -O-CnH2n+1 (n is an integer from 3 to 10).

4. The polymer-dispersed liquid crystal element as claimed in claim 1 or 2, wherein, The divalent cyclic group in G1 of formula (1) is a benzene ring, naphthalene ring, anthracene ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, or includes a structure containing cholesteryl, cholesterol or lanosteryl groups.

5. The polymer-dispersed liquid crystal element as claimed in claim 1 or 2, wherein, The diamine (1) represented by formula (1) is the diamine represented by the following formulas (d1-1) to (d1-12), where Xv1 to Xv4 and Xp1 to Xp8 each independently represent -(CH2)a- (a is an integer from 1 to 15), -CONH-, -NHCO-, -CON(CH3)-, -NH-, -O-, -CH2O-, -CH2-OCO-, -COO-, or -OCO-, XV5 to XV6 and Xs1 to Xs4 each independently represent -O-, -CH2O-, -OCH2-, -COO-, or -OCO-, Xa to Xf are synonyms with X in formula (1), and Rv1 to Rv4 and R1a to R1h are synonyms with R1 in formula (1).

6. The polymer-dispersed liquid crystal element as claimed in claim 1 or 2, wherein, In formula (2), Y is selected from any of the following groups of structures: single bond, -O-, -NH-, -N(CH3)-, -CONH-, -NHCO-, -CO-N(CH3)-, -N(CH3)-CO-, -OCO-, and structures represented by formulas (2Y-1) to (2Y-10). m is an integer from 1 to 20. *1 represents an atomic bond with a benzene ring, and *2 represents an atomic bond with an alkyl group.

7. The polymer-dispersed liquid crystal element as claimed in claim 1 or 2, wherein, The tetracarboxylic acid component contains acyclic aliphatic tetracarboxylic dianhydride, alicyclic tetracarboxylic dianhydride, aromatic tetracarboxylic dianhydride, or their derivatives.

8. The polymer-dispersed liquid crystal element as claimed in claim 1 or 2, wherein, The tetracarboxylic acid component contains a tetracarboxylic dianhydride or a derivative thereof having at least one substructure selected from the group consisting of a benzene ring, a cyclobutane ring, a cyclopentane ring, and a cyclohexane ring.

9. The polymer-dispersed liquid crystal element as claimed in claim 1 or 2, wherein, The content of the diamine (1) is 5 to 90 moles of 100 moles of diamine composition, and the content of the diamine (2) is 10 to 95 moles of 100 moles of diamine composition.

10. A liquid crystal alignment agent used in a liquid crystal alignment film forming a polymer-dispersed liquid crystal element, the liquid crystal alignment agent comprising the following (A) component; (A) component: at least one polymer (A) selected from the group consisting of a polyimide precursor obtained by reacting a diamine component containing a diamine (1) represented by formula (1) and a diamine (2) represented by formula (2) with a tetracarboxylic acid component, and polyimides comprising amides thereof. In the formula, X1 represents a single bond, -(CH2)a- (a is an integer from 1 to 15), -CONH-, -NHCO-, -CON(CH3)-, -NH-, -O-, -COO-, -OCO-, -CH2-OCO-, -OCH2-, or -((CH2)a1-A1)m1- (a1 is an integer from 1 to 15, A1 represents an oxygen atom or -COO-, m1 is an integer from 1 to 2, and when m1 is 2, multiple a1 and A1 have the above definitions independently), and G1 represents a divalent aromatic hydrocarbon group selected from 6 to 12 carbon atoms, divalent alicyclic hydrocarbon groups with 4 to 8 carbon atoms, and divalent cyclic groups of steroid skeletons. Any hydrogen atom on the cyclic group can also be replaced by an alkyl group with 1 to 3 carbon atoms, an alkoxy group with 1 to 3 carbon atoms, a fluorinated alkyl group with 1 to 3 carbon atoms, a fluorinated alkoxy group with 1 to 3 carbon atoms, or a fluorine atom. When m is an integer from 1 to 4, and m is 2 or more, multiple X1 and G1 can be independently defined as described above. R1 represents a fluorine atom, an alkyl group containing fluorine atoms with 1 to 10 carbon atoms, an alkoxy group containing fluorine atoms with 1 to 10 carbon atoms, an alkyl group with 3 to 10 carbon atoms, an alkoxy group with 3 to 10 carbon atoms, or an alkoxyalkyl group with 3 to 10 carbon atoms. X represents a single bond, -O-, -NH-, -O-(CH2)m2-O-, -C(CH3)2-, -CO-, -COO-, -CONH-, -(CH2)m2-, -SO2-, -OC(CH3)2-, -CO-(CH2)m2-, -NH-(CH2)m2-, -NH-(CH2)m2-NH-, -SO2-(CH2)m2-, -SO2-(CH2)m2-SO2-, -CONH-(CH2)m2-, -CONH-(CH2)m2-NHCO-, or -COO-(CH2)m2-OCO-, where m2 is an integer from 1 to 8, and i and j are each an integer of 0 or 1. When i is 1 and j is 0, the two R0s independently have the above definitions. In the formula, the Y-series group "*1-Y1-(Y2-Y3)n-*2" represents a divalent organogroup, R represents a hydrogen atom or a methyl group, and m is an integer from 4 to 20;Where n is an integer from 0 to 3, *1 represents an atomic bond with the benzene ring, *2 represents an atomic bond with -CH2-, Y1 represents a single bond, -O-, -NH-, -N(CH3)-, -CONH-, -NHCO-, -CO-N(CH3)-, -N(CH3)-CO-, or -OCO-, and Y3 represents a single bond, -O-, -NH-, -N(CH3)-, -CONH-, -NHCO-, -CO-N(CH3)-, -N(CH3)-CO-, -COO-, or -OCO-. However, when n is 0, Y1 represents -O-, -NH-, -N(CH3)-, -CONH-, -NHCO-, -CO-N(CH3)-, -N(CH3)-CO-, or -OCO-. Y2 represents a divalent organogroup selected from the group consisting of alkyl groups with 1 to 20 carbon atoms, benzene rings, the group "-CH=CH-Ph-" (Ph represents a benzene ring), cyclohexane rings, and heterocycles. Any hydrogen atom in these divalent organogroups may be replaced by a halogen atom, an alkyl group with 1 to 3 carbon atoms, an alkoxy group with 1 to 3 carbon atoms, an alkyl group with 1 to 3 carbon atoms containing a fluorine atom, or an alkoxy group with 1 to 3 carbon atoms containing a fluorine atom. However, when Y2 represents an alkyl group, Y3 represents a group other than a single bond; when n is 2 or more, multiple Y2 and Y3 groups independently possess the above definitions.

11. The liquid crystal alignment agent as claimed in claim 10, wherein, The polymer-dispersed liquid crystal element is a PDLC or PNLC type liquid crystal element.

12. A liquid crystal alignment film formed using a liquid crystal alignment agent as claimed in claim 10 or 11.

13. A method for manufacturing a polymer-dispersed liquid crystal element, comprising the following steps (1) to (4): (1) coating one or both of a pair of substrates with electrode attachments with a liquid crystal alignment agent containing the following component (A); (2) calcining the coating film formed on the substrate of (1); (3) preparing a dimming layer forming material; (4) polymerizing the dimming layer forming material to form a dimming layer containing a polymer phase and a liquid crystal phase; (A) component: selected from at least one polymer (A) in the group consisting of a polyimide precursor obtained by reacting a diamine component containing a diamine (1) represented by formula (1) and a diamine (2) represented by formula (2) with a tetracarboxylic acid component, and a polyimide consisting of a polyimide derivative thereof. In the formula, X1 represents a single bond, -(CH2)a- (a is an integer from 1 to 15), -CONH-, -NHCO-, -CON(CH3)-, -NH-, -O-, -COO-, -OCO-, -CH2-OCO-, -OCH2-, or -((CH2)a1-A1)m1- (a1 is an integer from 1 to 15, A1 represents an oxygen atom or -COO-, m1 is an integer from 1 to 2, and when m1 is 2, multiple a1 and A1 have the above definitions independently), and G1 represents a divalent aromatic hydrocarbon group selected from 6 to 12 carbon atoms, divalent alicyclic hydrocarbon groups with 4 to 8 carbon atoms, and divalent cyclic groups of steroid skeletons. Any hydrogen atom on the cyclic group can also be replaced by an alkyl group with 1 to 3 carbon atoms, an alkoxy group with 1 to 3 carbon atoms, a fluorinated alkyl group with 1 to 3 carbon atoms, a fluorinated alkoxy group with 1 to 3 carbon atoms, or a fluorine atom. When m is an integer from 1 to 4, and m is 2 or more, multiple X1 and G1 can be independently defined as described above. R1 represents a fluorine atom, an alkyl group containing fluorine atoms with 1 to 10 carbon atoms, an alkoxy group containing fluorine atoms with 1 to 10 carbon atoms, an alkyl group with 3 to 10 carbon atoms, an alkoxy group with 3 to 10 carbon atoms, or an alkoxyalkyl group with 3 to 10 carbon atoms. X represents a single bond, -O-, -NH-, -O-(CH2)m2-O-, -C(CH3)2-, -CO-, -COO-, -CONH-, -(CH2)m2-, -SO2-, -OC(CH3)2-, -CO-(CH2)m2-, -NH-(CH2)m2-, -NH-(CH2)m2-NH-, -SO2-(CH2)m2-, -SO2-(CH2)m2-SO2-, -CONH-(CH2)m2-, -CONH-(CH2)m2-NHCO-, or -COO-(CH2)m2-OCO-, where m2 is an integer from 1 to 8, and i and j are each an integer of 0 or 1. When i is 1 and j is 0, the two R0s independently have the above definitions. In the formula, the Y-series group "*1-Y1-(Y2-Y3)n-*2" represents a divalent organogroup, R represents a hydrogen atom or a methyl group, and m is an integer from 4 to 20;Where n is an integer from 0 to 3, *1 represents an atomic bond with the benzene ring, *2 represents an atomic bond with -CH2-, Y1 represents a single bond, -O-, -NH-, -N(CH3)-, -CONH-, -NHCO-, -CO-N(CH3)-, -N(CH3)-CO-, or -OCO-, and Y3 represents a single bond, -O-, -NH-, -N(CH3)-, -CONH-, -NHCO-, -CO-N(CH3)-, -N(CH3)-CO-, -COO-, or -OCO-. However, when n is 0, Y1 represents -O-, -NH-, -N(CH3)-, -CONH-, -NHCO-, -CO-N(CH3)-, -N(CH3)-CO-, or -OCO-. Y2 represents a divalent organogroup selected from the group consisting of alkyl groups with 1 to 20 carbon atoms, benzene rings, the group "-CH=CH-Ph-" (Ph represents a benzene ring), cyclohexane rings, and heterocycles. Any hydrogen atom in these divalent organogroups may be replaced by a halogen atom, an alkyl group with 1 to 3 carbon atoms, an alkoxy group with 1 to 3 carbon atoms, an alkyl group with 1 to 3 carbon atoms containing a fluorine atom, or an alkoxy group with 1 to 3 carbon atoms containing a fluorine atom. However, when Y2 represents an alkyl group, Y3 represents a group other than a single bond; when n is 2 or more, multiple Y2 and Y3 groups independently possess the above definitions.

14. A compound selected from the following formulas A3, A6, A9 or A11.

15. A polymer selected from at least one of the group consisting of a polyimide precursor obtained by reacting a diamine component containing a compound of claim 14 with a tetracarboxylic acid component, and a polyimide consisting of a polyimide thereof.

16. A liquid crystal alignment agent comprising the polymer of claim 15.

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