WO2014133154A1

WO2014133154A1 - Liquid crystal display element, liquid crystal alignment film, and liquid crystal alignment treatment agent

Info

Publication number: WO2014133154A1
Application number: PCT/JP2014/055138
Authority: WO
Inventors: 徳俊三木; 耕平後藤; 雅章片山; 幸司巴; 奈穂菊池; 保坂　和義
Original assignee: 日産化学工業株式会社
Priority date: 2013-03-01
Filing date: 2014-02-28
Publication date: 2014-09-04
Also published as: TW201504282A; CN105164580A; KR102196272B1; JP6459959B2; TWI662061B; CN105164580B; JPWO2014133154A1; KR20150123881A

Abstract

Provided is a liquid crystal display element that has a high liquid crystal vertical alignment property, high adhesion between a liquid crystal layer and a liquid crystal vertical alignment film, and favorable optical characteristics, in particular favorable transparency when voltage is not applied and favorable scattering when voltage is applied. Also provided are a liquid crystal alignment film and a liquid crystal alignment treatment agent for use in said element. The liquid crystal display element comprises a liquid crystal layer between a pair of substrates provided with electrodes, and a liquid crystal composition disposed between the pair of substrates, the liquid crystal composition containing a polymerizable compound that is polymerized by active energy rays and/or heat. Furthermore, at least one of the substrates has a liquid crystal alignment film that has a specific structure and vertically aligns liquid crystals. The liquid crystal display element is obtained by hardening the liquid crystal composition to form a hardened composite of liquid crystals and of the polymerizable compound while all or part of the liquid crystal composition exhibits liquid crystal properties.

Description

Liquid crystal display element, liquid crystal alignment film, and liquid crystal alignment treatment agent

The present invention relates to a transmission / scattering type liquid crystal display element that is transparent when no voltage is applied and is in a scattering state when a voltage is applied, a liquid crystal alignment film used therefor, and a liquid crystal alignment treatment agent for forming the liquid crystal alignment film. is there.

A TN (Twisted Nematic) mode has been put to practical use as a liquid crystal display element using a liquid crystal material. In this mode, light is switched using the optical rotation characteristics of the liquid crystal, and when used as a liquid crystal display element, it is necessary to use a polarizing plate. However, the use efficiency of light becomes low by using a polarizing plate.
As a liquid crystal display element having a high light utilization efficiency without using a polarizing plate, there is a liquid crystal display element that switches between a liquid crystal transmission state (also referred to as a transparent state) and a scattering state. A liquid crystal using a dispersive liquid crystal (PDLC (Polymer Dispersed Liquid Crystal)) or a polymer network liquid crystal (PNLC (Polymer Network Liquid Crystal)) is known.

A liquid crystal display element using these includes a liquid crystal layer between a pair of substrates provided with electrodes, and a polymerizable compound that is polymerized by at least one of active energy rays and heat between the pair of substrates. The liquid crystal composition is disposed, and the liquid crystal composition is cured in a state where a part or the whole of the liquid crystal composition exhibits liquid crystallinity, and is manufactured through a process of forming a cured product composite of liquid crystal and a polymerizable compound It is a liquid crystal display element. And this liquid crystal display element controls the permeation | transmission state and scattering state of a liquid crystal by application of a voltage.

As a conventional liquid crystal display element using PDLC or PNLC, liquid crystal molecules are in a random direction when no voltage is applied, and thus becomes clouded (scattered). There is known a normal type element that is transmitted and becomes a transmission state. However, in a normal type element, it is necessary to always apply a voltage in order to obtain a transmissive state. Therefore, in applications that are often used in a transparent state, for example, when used in a window glass, power consumption is low. large.
A reverse type element has been reported that is in a transmission state when no voltage is applied to a normal type element and in a scattering state when a voltage is applied (see Patent Documents 1 and 2).

Japanese Patent No. 2885116 Japanese Patent No. 4132424

In the reverse type element, since the liquid crystal must be aligned vertically, a liquid crystal alignment film (also referred to as a vertical liquid crystal alignment film) that aligns the liquid crystal vertically is used. At that time, since the vertical liquid crystal alignment film is a highly hydrophobic film, the adhesion between the liquid crystal layer and the liquid crystal alignment film is lowered. Therefore, a large amount of a polymerizable compound (also referred to as a curing agent) for improving the adhesion between the liquid crystal layer and the liquid crystal alignment film must be introduced into the liquid crystal composition used for the reverse type element. However, when a large amount of the polymerizable compound is introduced, the vertical alignment of the liquid crystal is hindered, and there is a problem that transparency when no voltage is applied and scattering characteristics when a voltage is applied are greatly deteriorated. Therefore, the liquid crystal alignment film used for the reverse element needs to have a high vertical alignment property of the liquid crystal.

Therefore, an object of the present invention is to provide a liquid crystal display element having the above-described characteristics. That is, the present invention is a liquid crystal display element, which has high liquid crystal vertical alignment, good optical characteristics, that is, good transparency when no voltage is applied and good scattering characteristics when a voltage is applied. An object of the present invention is to provide a liquid crystal display element having high adhesion between the liquid crystal alignment film and the vertical liquid crystal alignment film. In addition, it aims at providing the liquid crystal aligning film and liquid-crystal aligning agent which are used for the said liquid crystal display element.

As a result of intensive studies, the present inventor has achieved that the liquid crystal display element using a vertical liquid crystal alignment film obtained from a liquid crystal alignment treatment agent containing a polymer having a side chain having a specific structure achieves the above object. The present invention has been found to be extremely effective.

That is, the present invention has the following gist.
(1) A liquid crystal composition including a polymerizable compound having a liquid crystal layer between a pair of substrates provided with electrodes and polymerized by at least one of active energy rays and heat is disposed between the pair of substrates, In addition, at least one of the substrates has a liquid crystal alignment film that vertically aligns the liquid crystal, and the liquid crystal composition is cured in a state where a part or the whole of the liquid crystal composition exhibits liquid crystallinity, and the liquid crystal and the polymerizable compound are cured. A liquid crystal display element obtained by forming a compound composite, wherein the liquid crystal alignment film is a liquid crystal alignment film obtained from a liquid crystal alignment treatment agent containing a polymer having a structure represented by the following formula [1] Display element.

(Y ¹ represents a single bond, — (CH ₂ ) _a — (a is an integer of 1 to 15), —O—, —CH ₂ O—, —COO— or OCO—, and Y ² represents a single bond. Or (CH ₂ ) _b — (b is an integer of 1 to 15), Y ³ is a single bond, — (CH ₂ ) _c — (c is an integer of 1 to 15), —O—, —CH ₂ O—, —COO— or —OCO—, wherein Y ⁴ is a divalent cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring and a heterocyclic ring, or having 17 to 51 carbon atoms having a steroid skeleton Represents a divalent organic group, and an arbitrary hydrogen atom on the cyclic group is an alkyl group having 1 to 3 carbon atoms, an alkoxyl group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a carbon number It may be substituted with 1-3 fluorine-containing alkoxyl group or a fluorine atom, Y ⁵ benzene A divalent cyclic group selected from the group consisting of a cyclohexane ring and a heterocyclic ring, wherein any hydrogen atom on these cyclic groups is an alkyl group having 1 to 3 carbon atoms, an alkoxyl group having 1 to 3 carbon atoms, It may be substituted with a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxyl group having 1 to 3 carbon atoms, or a fluorine atom, n represents an integer of 0 to 4, and Y ⁶ represents 1 to 18 carbon atoms. Or a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxyl group having 1 to 18 carbon atoms, or a fluorine-containing alkoxyl group having 1 to 18 carbon atoms).

(2) The liquid crystal alignment treatment agent includes at least one polymer selected from the group consisting of acrylic polymer, methacrylic polymer, novolac resin, polyhydroxystyrene, polyimide precursor, polyimide, polyamide, polyester, cellulose, and polysiloxane. The liquid crystal display element according to the above (1), which is a liquid crystal aligning agent.
(3) The liquid crystal aligning agent is at least one polymer selected from the group consisting of a polyimide precursor and a polyimide obtained by using a diamine compound having a side chain of the formula [1] as a part of the raw material. The liquid crystal display element according to (2), which is a liquid crystal alignment treatment agent.
(4) The diamine compound according to (3), wherein the diamine compound is at least one polymer selected from the group consisting of a polyimide precursor obtained by using a diamine compound represented by the following formula [1a] and a polyimide. Liquid crystal display element.

(Y ¹ to Y ⁶ are as defined in the above formula [1]. M represents an integer of 1 to 4).

(5) The liquid crystal aligning agent is at least one polymer selected from the group consisting of a polyimide precursor and a polyimide obtained by using a tetracarboxylic acid component represented by the following formula [2] as a part of the raw material. The liquid crystal display element according to any one of the above (2) to (4), which is a liquid crystal alignment treatment agent containing

(Z ¹ represents a structure selected from the group consisting of the following formulas [2a] to [2j]).

(Z ² to Z ⁵ represent a hydrogen atom, a methyl group, a chlorine atom or a benzene ring, and may be the same or different, and in the formula [2g], Z ⁶ and Z ⁷ represent a hydrogen atom or a methyl group. Each may be the same or different).

(6) The liquid crystal aligning agent is a polysiloxane obtained by polycondensation of an alkoxysilane represented by the following formula [A1], represented by the formula [A1] and the following formula [A2] or formula [A3]. Polysiloxane obtained by polycondensation of alkoxysilane containing any one of alkoxysilanes or polycondensation obtained by polycondensation of alkoxysilanes represented by formula [A1], formula [A2] and formula [A3] The liquid crystal display element according to the above (2), which is a liquid crystal aligning agent containing siloxane.

(A ¹ represents the structure represented by the formula [1], A ² represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, A ³ represents an alkyl group having 1 to 5 carbon atoms, m Represents an integer of 1 or 2, n represents an integer of 0 to 2, and p represents an integer of 0 to 3, where m + n + p represents an integer of 4.

(B ¹ represents an organic group having 2 to 12 carbon atoms having a vinyl group, an epoxy group, an amino group, a mercapto group, an isocyanate group, a methacryl group, an acrylic group, a ureido group or a cinnamoyl group, and B ² represents a hydrogen atom or An alkyl group having 1 to 5 carbon atoms, B ³ represents an alkyl group having 1 to 5 carbon atoms, m represents an integer of 1 or 2, n represents an integer of 0 to 2, and p represents 0 to 3 represents an integer of 3 (where m + n + p represents an integer of 4).

(D ¹ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, D ² represents an alkyl group having 1 to 5 carbon atoms, and n represents an integer of 0 to 3).

(7) The liquid crystal display element according to any one of (1) to (6), wherein the liquid crystal alignment treatment agent contains a compound represented by the following formula [6].

(X ¹ represents at least one structure selected from the group consisting of the structures represented by the following formulas [6a-1] to [6a-7]. X ² represents a single bond, —CH ₂ —, —O—. , —NH—, —N (CH ₃ ) —, —CONH—, —NHCO—, —CH ₂ O—, —OCH ₂ —, —COO—, —OCO—, —CON (CH ₃ ) — and —N At least one linking group selected from the group consisting of (CH ₃ ) CO—, wherein X ³ is an alkylene group having 1 to 20 carbon atoms, — (CH ₂ —CH ₂ —O) _p — (p is 1 to Selected from the group consisting of organic groups having a benzene ring or a cyclohexane ring having 6 to 20 carbon atoms, and — (CH ₂ —O—) _q — (q represents an integer of 1 to 10) It indicates at least one kind that time, any -CH 2 in the alkylene group _-. group, - OO -, - OCO -, - CONH-, NHCO -, - CO -, - S -, - SO 2 -, - CF 2 -, - C (CF 3) 2 -, - Si (CH 3) 2 -, The hydrogen atom bonded to any carbon atom may be replaced by —OSi (CH ₃ ) ₂ — or —Si (CH ₃ ) ₂ O—, and the hydroxyl group (OH group), carboxyl group (COOH group) X ⁴ represents a single bond, at least one linking group selected from the group consisting of —CH ₂ —, —OCH ₂ — and —O—CH ₂ —CH ₂ —. X ⁵ represents at least one structure selected from the group consisting of structures represented by the following formulas [6b-1] to [6b-8], n represents an integer of 1 to 3, and m represents 1 Represents an integer of ~ 3.)

(A ¹ represents a hydrogen atom or an alkylene group having 1 to 5 carbon atoms. A ² , A ³ , A ⁵ , A ⁶ and A ⁹ each independently represents a hydrogen atom or an alkylene group having 1 to 3 carbon atoms. A ⁴ , A ⁷ and A ⁸ each independently represents an alkylene group having 1 to 3 carbon atoms.)

(B ¹ represents a hydrogen atom or a benzene ring. B ² represents at least one cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring and a heterocyclic ring. B ³ represents an alkylene having 1 to 12 carbon atoms. And at least one selected from the group consisting of a group, a fluorine-containing alkylene group having 1 to 12 carbon atoms, an alkoxyl group having 1 to 12 carbon atoms, and a fluorine-containing alkoxyl group having 1 to 12 carbon atoms.)

(8) The liquid crystal display device according to any one of the above (1) to (7), wherein the polymer having the structure represented by the formula [1] has a weight average molecular weight of 10,000 to 150,000.
(9) The liquid crystal display element according to any one of (1) to (8), wherein the substrate of the liquid crystal display element is a glass substrate or a plastic substrate.
(10) A liquid crystal alignment film used for the liquid crystal display device according to any one of (1) to (9).
(11) A liquid crystal alignment treatment agent for forming the liquid crystal alignment film according to (10).

According to the present invention, by using a vertical liquid crystal alignment film obtained from a liquid crystal alignment treatment agent containing a polymer having a side chain of a specific structure, the liquid crystal has high vertical alignment properties and good optical characteristics, that is, no voltage marking It is possible to provide a liquid crystal display element that has excellent transparency when applied and scattering characteristics when a voltage is applied, and has high adhesion between the liquid crystal layer and the vertical liquid crystal alignment film. In particular, the liquid crystal display element of the present invention can be suitably used for a reverse element that is in a transmissive state when no voltage is applied and is in a scattering state when a voltage is applied. The liquid crystal display element of the present invention is advantageously used as a liquid crystal display for display purposes, a light control window for controlling transmission and blocking of light, an optical shutter element, and the like.

The specific side chain structure represented by the formula [1] used in the liquid crystal display device of the present invention has a divalent group having 17 to 25 carbon atoms having a benzene ring, cyclohexyl ring or heterocyclic ring, or a steroid skeleton in the side chain portion. It has an organic group. The side chain structure of these rings and organic groups shows a rigid structure as compared with the side chain structure of long-chain alkyl groups, which is a conventional technique for vertically aligning liquid crystals. As a result, the reverse type device using the vertical liquid crystal alignment film having a specific side chain structure obtains a higher and more stable liquid crystal vertical alignment than the conventional long type alkyl group side chain structure reverse type device. be able to.
In addition, the specific side chain structure can obtain high vertical alignment even when the amount of side chain introduced is small compared to the side chain structure of a conventional long chain alkyl group. Therefore, a reverse element using a vertical liquid crystal alignment film having a specific side chain structure has high adhesion between the liquid crystal layer and the vertical liquid crystal alignment film.

From the above points, the liquid crystal display element of the present invention using a vertical liquid crystal alignment film obtained from a liquid crystal alignment treatment agent containing a polymer having a specific side chain structure has high liquid crystal vertical alignment properties, good optical characteristics, That is, it is possible to obtain a liquid crystal display element that has good transparency when no voltage is applied and good scattering characteristics when a voltage is applied, and has high adhesion between the liquid crystal layer and the vertical liquid crystal alignment film.

<Liquid crystal display element>
The liquid crystal display element of the present invention has a liquid crystal layer between a pair of substrates provided with electrodes, and includes a polymerizable compound that is polymerized by at least one of active energy rays and heat between the pair of substrates. The liquid crystal composition is disposed in a state where at least one of the substrates has a liquid crystal alignment film that aligns the liquid crystal vertically and part or all of the liquid crystal composition exhibits liquid crystallinity. The liquid crystal display device is a liquid crystal display device formed by forming a cured product composite of a liquid crystal and a polymerizable compound, and can be suitably used for a reverse type device that is in a transmission state when no voltage is applied and in a scattering state when a voltage is applied.

<LCD>
As the liquid crystal used in the present invention, a nematic liquid crystal or a smectic liquid crystal can be used. Among these, those having negative dielectric anisotropy are preferable. Further, in terms of low voltage driving and scattering characteristics of the element, those having a large dielectric anisotropy and a large refractive index anisotropy are preferable. Furthermore, in order to drive a liquid crystal display element as an active element such as a TFT (Thin Film Transistor), it is required that the liquid crystal has a high electric resistance and a high voltage holding ratio (VHR). For this reason, it is preferable to use a fluorine-based or chlorine-based liquid crystal that has high electrical resistance and does not lower VHR by active energy rays such as ultraviolet rays.

In the liquid crystal display element, a dichroic dye can be dissolved in a liquid crystal composition to form a guest-host type element. In this case, an element is obtained that is transparent when no voltage is applied and absorbs (scatters) when a voltage is applied. Further, in the liquid crystal display element, the direction of the director of the liquid crystal changes by 90 degrees depending on the presence or absence of voltage application. Therefore, by using the difference in the light absorption characteristics of the dichroic dye, a high contrast can be obtained as compared with a conventional guest-host type device that switches between random alignment and vertical alignment. A guest-host type element in which a dichroic dye is dissolved is colored when the liquid crystal is aligned in the horizontal direction, and is opaque only in a scattering state. Therefore, as the voltage is applied, it is possible to obtain an element that switches from colorless and transparent when no voltage is applied to a colored opaque and colored transparent state.
<Polymerizable compound>

The liquid crystal composition of the present invention contains a polymerizable compound that is polymerized by at least one of active energy rays such as ultraviolet rays and heat. The polymerizable compound contained in the liquid crystal composition is a polymerizable compound that is polymerized by at least one of active energy rays such as ultraviolet rays and heat. At that time, polymerization may proceed in any reaction form, and a cured product composite of liquid crystal and a polymerizable compound may be formed. Specific reaction modes of polymerization include radical polymerization, cationic polymerization, anionic polymerization, or polyaddition reaction.
The polymerizable compound may be any compound as long as it dissolves in the liquid crystal. However, when the polymerizable compound is dissolved in the liquid crystal, it is necessary that a temperature at which a part or the whole of the liquid crystal composition exhibits a liquid crystal phase exists. Even when a part of the liquid crystal composition exhibits a liquid crystal phase, it is sufficient that the liquid crystal display element is confirmed with the naked eye and almost uniform transparency and scattering characteristics are obtained throughout the element.

When the reaction form of the polymerizable compound is radical polymerization, the following radical type polymerizable compound can be used.
For example, 2-ethylhexyl acrylate, butyl ethyl acrylate, butoxyethyl acrylate, 2-cyanoethyl acrylate, benzyl acrylate, cyclohexyl acrylate, 2-hydroxypropyl acrylate, 2-ethoxyethyl acrylate, N, N-diethylaminoethyl acrylate, N, N— Dimethylaminoethyl acrylate, dicyclopentanyl acrylate, dicyclopentenyl acrylate, glycidyl acrylate, tetrahydrofurfuryl acrylate, isobornyl acrylate, isodecyl acrylate, lauryl acrylate, morpholine acrylate, phenoxyethyl acrylate, phenoxydiethylene glycol acrylate, 2,2, 2-trifluoroethyl acrylate, 2, , 3,3,3-pentafluoropropyl acrylate, 2,2,3,3-tetrafluoropropyl acrylate, 2,2,3,4,4,4-hexafluorobutyl acrylate, 2-ethylhexyl methacrylate, butylethyl methacrylate , Butoxyethyl methacrylate, 2-cyanoethyl methacrylate, benzyl methacrylate, cyclohexyl methacrylate, 2-hydroxypropyl methacrylate, 2-ethoxyethyl acrylate, N, N-diethylaminoethyl methacrylate, N, N-dimethylaminoethyl methacrylate, dicyclopentanyl methacrylate , Dicyclopentenyl methacrylate, glycidyl methacrylate, tetrahydrofurfuryl methacrylate, isobornyl methacrylate, isodecyl Tacrylate, lauryl methacrylate, morpholine methacrylate, phenoxyethyl methacrylate, phenoxydiethylene glycol methacrylate, 2,2,2-trifluoroethyl methacrylate, 2,2,3,3-tetrafluoropropyl methacrylate, 2,2,3,4,4 4-hexafluorobutyl methacrylate, 4,4′-biphenyl diacrylate, diethylstilbestrol diacrylate, 1,4-bisacryloyloxybenzene, 4,4′-bisacryloyloxydiphenyl ether, 4,4′-bisacryloyloxy Diphenylmethane, 3,9- [1,1-dimethyl-2-acryloyloxyethyl] -2,4,8,10-tetraspiro [5,5] undecane, α, α'-bis [4-acryloyloxy Enyl] -1,4-diisopropylbenzene, 1,4-bisacryloyloxytetrafluorobenzene, 4,4′-bisacryloyloxyoctafluorobiphenyl, diethylene glycol acrylate, 1,4-butanediol diacrylate, 1,3-butylene Glycol diacrylate, dicyclopentanyl diacrylate, glycerol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, tetraethylene glycol diacrylate, trimethylolpropane triacrylate, pentaerythritol tetraacrylate, pentaerythritol Triacrylate, ditrimethylolpropane tetraacrylate, dipentaerythritol hexaacrylate, dipentaeryth Tall monohydroxypentaacrylate, 4,4′-diaacryloyloxystilbene, 4,4′-diaacryloyloxydimethylstilbene, 4,4′-diaacryloyloxydiethylstilbene, 4,4′-diaacryloyloxydipropylstilbene, 4,4′-diacryloyloxydibutylstilbene, 4,4′-diaacryloyloxydipentylstilbene, 4,4′-diaacryloyloxydihexylstilbene, 4,4′-diacryloyloxydifluorostilbene, 2,2,3 3,4,4-hexafluoropentanediol-1,5-diacrylate, 1,1,2,2,3,3-hexafluoropropyl-1,3-diacrylate, diethylene glycol dimethacrylate, 1,4-butane Diol dimethacrylate, 1,3 -Butylene glycol dimethacrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol dimethacrylate, tetraethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, pentaerythritol tetramethacrylate, pentaerythritol trimethacrylate, ditrimethylolpropane tetramethacrylate, And monomers and oligomers such as dipentaerythritol hexamethacrylate, dipentaerythritol monohydroxypentamethacrylate, 2,2,3,3,4,4-hexafluoropentanediol-1,5-dimethacrylate.
Among them, it is preferable to use a polyfunctional radical-type polymerizable compound having three or more functional groups for the purpose of enhancing the scattering characteristics when a voltage is applied.

Specifically, trimethylolpropane triacrylate, pentaerythritol tetraacrylate, pentaerythritol triacrylate, ditrimethylolpropane tetraacrylate, dipentaerythritol hexaacrylate, dipentaerythritol monohydroxypentaacrylate, trimethylolpropane trimethacrylate, penta Examples thereof include monomers and oligomers such as erythritol tetramethacrylate, pentaerythritol trimethacrylate, ditrimethylolpropane tetramethacrylate, dipentaerythritol hexamethacrylate, dipentaerythritol monohydroxypentamethacrylate.
The radical type polymerizable compound may be used alone or in combination of two or more depending on the optical characteristics of the liquid crystal display element and the adhesion characteristics between the liquid crystal layer and the vertical liquid crystal alignment film.

Furthermore, when the reaction type of the polymerizable compound is radical polymerization, a radical initiator that generates radicals by ultraviolet rays can be introduced into the liquid crystal composition.
Specifically, tert-butylperoxy-iso-butrate, 2,5-dimethyl-2,5-bis (benzoyldioxy) hexane, 1,4-bis [α- (tert-butyldioxy) -iso-propoxy Benzene, di-tert-butyl peroxide, 2,5-dimethyl-2,5-bis (tert-butyldioxy) hexene hydroperoxide, α- (iso-propylphenyl) -iso-propyl hydroperoxide, 2,5- Dimethylhexane, tert-butyl hydroperoxide, 1,1-bis (tert-butyldioxy) -3,3,5-trimethylcyclohexane, butyl-4,4-bis (tert-butyldioxy) valerate, cyclohexanone Peroxide, 2,2 ', 5,5'-tetra (tert-butylperoxide Xoxycarbonyl) benzophenone, 3,3 ′, 4,4′-tetra (tert-butylperoxycarbonyl) benzophenone, 3,3 ′, 4,4′-tetra (tert-amylperoxycarbonyl) benzophenone, 3,3 ′, 4,4′-tetra (tert-hexylperoxycarbonyl) benzophenone, 3,3′-bis (tert-butylperoxycarbonyl) -4,4′-dicarboxybenzophenone, tert-butylperoxybenzoate, di-tert-butyldi Organic peroxides such as peroxyisophthalate, quinones such as 9,10-anthraquinone, 1-chloroanthraquinone, 2-chloroanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, benzoin methyl, benzoin ethyl ether, and benzoin derivatives such as α-methylbenzoin and α-phenylbenzoin.

When the reaction form of the polymerizable compound is cationic polymerization or anionic polymerization, the following ionic type polymerizable compounds can be used.
Specifically, it is a compound having at least one cross-linking group selected from the group consisting of a hydroxyl group, a hydroxyalkyl group, and a lower alkoxyalkyl group.
For example, a melamine derivative, a benzoguanamine derivative or glycoluril in which a hydrogen atom of an amino group is substituted with a methylol group, an alkoxymethyl group or both can be used. The melamine derivative or benzoguanamine derivative may be an oligomer. These preferably have an average of 3 or more and less than 6 methylol groups or alkoxymethyl groups per one triazine ring.

Examples of such melamine derivatives and benzoguanamine derivatives include MX-750, which is an average of 3.7 substituted methoxymethyl groups per triazine ring, and an average of 5. methoxymethyl groups per triazine ring. Eight-substituted MW-30 (manufactured by Sanwa Chemical Co., Ltd.), Cymel 300, 301, 303, 350, 370, 771, 325, 327, 703, 712 and other methoxymethylated melamine, Cymel 235, Of methoxymethylated butoxymethylated melamine such as 236, 238, 212, 253, 254, butoxymethylated melamine such as Cymel 506, 508, carboxyl group-containing methoxymethylated isobutoxymethylated melamine such as Cymel 1141, Cymel 1123 Methoxymethylated etoxy Methylated benzoguanamine, methoxymethylated butoxymethylated benzoguanamine such as Cymel 1123-10, butoxymethylated benzoguanamine such as Cymel 1128, carboxyl group-containing methoxymethylated ethoxymethylated benzoguanamine such as Cymel 1125-80 Cytec Co., Ltd.). Examples of glycoluril include butoxymethylated glycoluril such as Cymel 1170, methylolated glycoluril such as Cymel 1172, and the like.

Examples of the benzene having a hydroxyl group or an alkoxyl group or a phenolic compound include 1,3,5-tris (methoxymethoxy) benzene, 1,2,4-tris (isopropoxymethoxy) benzene, and 1,4-bis. (Sec-butoxymethoxy) benzene, 2,6-dihydroxymethyl-p-tert-butylphenol and the like.

In addition, as the ionic polymerizable compound, a compound having an epoxy group and an isocyanate group and having a crosslinking group can also be used. Specifically, bisphenolacetone glycidyl ether, phenol novolac epoxy resin, cresol novolac epoxy resin, triglycidyl isocyanurate, tetraglycidylaminodiphenylene, tetraglycidyl-m-xylenediamine, tetraglycidyl-1,3-bis (aminoethyl) ) Cyclohexane, tetraphenyl glycidyl ether ethane, triphenyl glycidyl ether ethane, bisphenol hexafluoroacetodiglycidyl ether, 1,3-bis (1- (2,3-epoxypropoxy) -1-trifluoromethyl-2,2, 2-trifluoromethyl) benzene, 4,4-bis (2,3-epoxypropoxy) octafluorobiphenyl, triglycidyl-p-aminophenol, tetraglycidylme Xylenediamine, 2- (4- (2,3-epoxypropoxy) phenyl) -2- (4- (1,1-bis (4- (2,3-epoxypropoxy) phenyl) ethyl) phenyl) propane, , 3-Bis (4- (1- (4- (2,3-epoxypropoxy) phenyl) -1- (4- (1- (4- (2,3-epoxypropoxyphenyl) -1-methylethyl) Phenyl) ethyl) phenoxy) -2-propanol and the like.
The ionic polymerizable compounds may be used alone or in combination of two or more depending on the optical properties and the adhesion properties between the liquid crystal layer and the vertical liquid crystal alignment film.

Furthermore, when the reaction mode of the polymerizable compound is cationic polymerization or anionic polymerization, an ion initiator that generates an acid or a base by ultraviolet rays can be introduced into the liquid crystal composition.
Specifically, triazine compounds, acetophenone derivative compounds, disulfone compounds, diazomethane compounds, sulfonic acid derivative compounds, diaryl iodonium salts, triaryl sulfonium salts, triaryl phosphonium salts, iron arene complexes, and the like can be used. However, it is not limited to these. More specifically, for example, diphenyl iodonium chloride, diphenyl iodonium trifluoromethanesulfonate, diphenyl iodonium mesylate, diphenyl iodonium tosylate, diphenyl iodonium bromide, diphenyl iodonium tetrafluoroborate, diphenyl iodonium hexafluoroantimonate, diphenyl iodonium hexafluoroarsenate. Bis (p-tert-butylphenyl) iodonium hexafluorophosphate, bis (p-tert-butylphenyl) iodonium mesylate, bis (p-tert-butylphenyl) iodonium tosylate, bis (p-tert-butylphenyl) ) Iodonium trifluoromethanesulfonate, bis (p-tert-butylphenol) L) iodonium tetrafluoroborate, bis (p-tert-butylphenyl) iodonium chloride, bis (p-chlorophenyl) iodonium chloride, bis (p-chlorophenyl) iodonium tetrafluoroborate, triphenylsulfonium chloride, triphenylsulfonium bromide, triphenyl (P-methoxyphenyl) sulfonium tetrafluoroborate, tri (p-methoxyphenyl) sulfonium hexafluorophosphonate, tri (p-ethoxyphenyl) sulfonium tetrafluoroborate, triphenylphosphonium chloride, triphenylphosphonium bromide, tri (p-methoxy Phenyl) phosphonium tetrafluoroborate, tri (p-methoxyphenyl) phosphonium hexafluorophos Sulfonates, or tri (p- ethoxyphenyl) phosphonium tetrafluoroborate and the like.
Also, bis [[(2-nitrobenzyl) oxy] carbonylhexane-1,6-diamine], nitrobenzylcyclohexyl carbamate, di (methoxybenzyl) hexamethylene dicarbamate, bis [[(2-nitrobenzyl) Oxy] carbonylhexane-1,6-diamine], nitrobenzyl cyclohexyl carbamate or di (methoxybenzyl) hexamethylene dicarbamate.
Among the above polymerizable compounds, in the present invention, a radical type polymerizable compound is preferably used from the viewpoint of the optical characteristics of the liquid crystal display element.

The amount of the polymerizable compound introduced into the liquid crystal composition is not particularly limited, but when the amount of the polymerizable compound introduced is large, the polymerizable compound does not dissolve in the liquid crystal, or the temperature at which the liquid crystal composition exhibits a liquid crystal phase. Or the change between the transparent state and the scattering state of the element becomes small, and the optical characteristics deteriorate. In addition, when the amount of the polymerizable compound introduced is small, the curability of the liquid crystal layer is lowered, and further, the adhesion between the liquid crystal layer and the vertical liquid crystal alignment film is lowered, and the alignment of the liquid crystal against mechanical external pressure is reduced. Is easily disturbed. Therefore, the introduction amount of the polymerizable compound is preferably 1 to 50 parts by mass with respect to 100 parts by mass of the liquid crystal, and more preferably 5 to 40 parts by mass. Particularly preferred is 11 to 30 parts by mass.
Further, the introduction amount of the radical initiator and the ionic initiator that promote the reaction of the polymerizable compound is not particularly limited, but is preferably 0.01 to 10 parts by mass with respect to 100 parts by mass of the liquid crystal. However, 0.05 to 5 parts by mass is preferable. Particularly preferred is 0.05 to 3 parts by mass.

<Specific polymer>
The liquid crystal display element of the present invention has a vertical liquid crystal alignment film that vertically aligns liquid crystal on at least one of the substrates. The vertical liquid crystal alignment film in that case is obtained from the liquid-crystal aligning agent containing the specific polymer which has a specific side chain structure shown by following formula [1].

In the formula [1], Y ¹ represents a single bond, — (CH ₂ ) _a — (a is an integer of 1 to 15), —O—, —CH ₂ O—, —COO— or —OCO—. . Among these, from the viewpoint of availability of raw materials and ease of synthesis, a single bond, — (CH ₂ ) _a — (a is an integer of 1 to 15), —O—, —CH ₂ O— or —COO. -Is preferred. More preferred is a single bond, — (CH ₂ ) _a — (a is an integer of 1 to 10), —O—, —CH ₂ O— or —COO—.
In the formula [1], Y ² represents a single bond or — (CH ₂ ) _b — (b is an integer of 1 to 15). Among these, a single bond or (CH ₂ ) _b — (b is an integer of 1 to 10) is preferable.
In the formula [1], Y ³ represents a single bond, — (CH ₂ ) _c — (c is an integer of 1 to 15), —O—, —CH ₂ O—, —COO— or —OCO—. . Of these, a single bond, — (CH ₂ ) _c — (c is an integer of 1 to 15), —O—, —CH ₂ O— or —COO— is preferable from the viewpoint of ease of synthesis. More preferred is a single bond, — (CH ₂ ) _c — (c is an integer of 1 to 10), —O—, —CH ₂ O— or —COO—.

In the formula [1], Y ⁴ is a divalent cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring and a heterocyclic ring, and any hydrogen atom of these cyclic groups is an alkyl having 1 to 3 carbon atoms. Group, an alkoxyl group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxyl group having 1 to 3 carbon atoms, or a fluorine atom. Furthermore, Y ⁴ may be a divalent organic group selected from the group consisting of organic groups having 17 to 51 carbon atoms having a steroid skeleton. Among these, an organic group having 17 to 51 carbon atoms having a benzene ring, a cyclohexane ring or a steroid skeleton is preferable from the viewpoint of ease of synthesis.
In formula [1], Y ⁵ represents a divalent cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring and a heterocyclic ring, and any hydrogen atom on these cyclic groups is an alkyl having 1 to 3 carbon atoms. Group, an alkoxyl group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxyl group having 1 to 3 carbon atoms, or a fluorine atom. Of these, a benzene ring or a cyclohexane ring is preferable.

In the formula [1], n represents an integer of 0 to 4. Among these, 0 to 3 are preferable from the viewpoint of availability of raw materials and ease of synthesis. More preferred is 0-2.
In the formula [1], Y ⁶ represents an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxyl group having 1 to 18 carbon atoms, or a fluorine-containing alkoxyl group having 1 to 18 carbon atoms. . Of these, an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 10 carbon atoms, an alkoxyl group having 1 to 18 carbon atoms, or a fluorine-containing alkoxyl group having 1 to 10 carbon atoms is preferable. More preferably, it is an alkyl group having 1 to 12 carbon atoms or an alkoxyl group having 1 to 12 carbon atoms. Particularly preferred is an alkyl group having 1 to 9 carbon atoms or an alkoxyl group having 1 to 9 carbon atoms.

As a preferable combination of Y ¹ , Y ² , Y ³ , Y ⁴ , Y ⁵ , Y ⁶ and n in the formula [1], pages 13 to 34 of International Publication No. WO2011 / 132751 (published 2011.10.27). The same combinations as (2-1) to (2-629) listed in Tables 6 to 47 of the above are listed. It should be noted that Y1 to Y6 in each table of the International Publication are respectively replaced with Y ¹ to Y ⁶ of the present invention. In addition, the organic groups having 12 to 25 carbon atoms having a steroid skeleton in (2-605) to (2-629) listed in the tables of International Publications all have 17 to 17 carbon atoms having a steroid skeleton. It shall be read as 51 organic groups.

The specific polymer having the specific side chain structure is not particularly limited, but from the group consisting of acrylic polymer, methacrylic polymer, novolac resin, polyhydroxystyrene, polyimide precursor, polyimide, polyamide, polyester, cellulose and polysiloxane. It is preferably at least one polymer selected. Among these, a polyimide precursor, polyimide or polysiloxane is preferable.
When a polyimide precursor or polyimide (also collectively referred to as a polyimide polymer) is used for the specific polymer, they are a polyimide precursor or polyimide obtained by reacting a diamine component and a tetracarboxylic acid component. Is preferred.

The polyimide precursor has a structure represented by the following formula [A].

(R ¹ is a tetravalent organic group, R ² is a divalent organic group, A ¹ and A ² represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and each may be the same or different. A ³ and A ^{4 each} represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or an acetyl group, which may be the same or different, and n represents a positive integer).

The diamine component is a diamine compound having two primary or secondary amino groups in the molecule, and the tetracarboxylic acid component is a tetracarboxylic acid compound, tetracarboxylic dianhydride, or tetracarboxylic acid dihalide compound. , Tetracarboxylic acid dialkyl ester compounds or tetracarboxylic acid dialkyl ester dihalide compounds.
The polyimide polymer can be obtained relatively easily by using a tetracarboxylic dianhydride represented by the following formula [B] and a diamine compound represented by the following formula [C] as raw materials. Polyamic acid comprising the structural formula of the repeating unit represented by the formula [D] or polyimide obtained by imidizing the polyamic acid is preferred.

(R ¹ and R ² have the same meaning as defined in formula [A].)

(R ¹ and R ² have the same meaning as defined in formula [A].)
In addition, the polymer of the formula [D] obtained above by the usual synthesis method is added to the alkyl group having 1 to 8 carbon atoms of A ¹ and A ^{2 represented by} the formula [A] and the formula [A]. It is also possible to introduce an alkyl group having 1 to 5 carbon atoms or an acetyl group of A ³ and A ⁴ shown.

As a method for introducing the upper specific side chain structure into the polyimide polymer, it is preferable to use a diamine compound having a specific side chain structure as a part of the raw material. In particular, it is preferable to use a diamine compound represented by the following formula [1a] (also referred to as a specific side chain diamine compound).

In the formula [1a], Y ¹ represents a single bond, — (CH ₂ ) _a — (a is an integer of 1 to 15), —O—, —CH ₂ O—, —COO— or —OCO—. . Among these, from the viewpoint of availability of raw materials and ease of synthesis, a single bond, — (CH ₂ ) _a — (a is an integer of 1 to 15), —O—, —CH ₂ O— or —COO. -Is preferred. More preferred is a single bond, — (CH ₂ ) _a — (a is an integer of 1 to 10), —O—, —CH ₂ O— or —COO—.
In the formula [1a], Y ² represents a single bond or — (CH ₂ ) _b — (b is an integer of 1 to 15). Among these, a single bond or (CH ₂ ) _b — (b is an integer of 1 to 10) is preferable.
In the formula [1a], Y ³ represents a single bond, — (CH ₂ ) _c — (c is an integer of 1 to 15), —O—, —CH ₂ O—, —COO— or —OCO—. . Of these, a single bond, — (CH ₂ ) _c — (c is an integer of 1 to 15), —O—, —CH ₂ O— or —COO— is preferable from the viewpoint of ease of synthesis. More preferred is a single bond, — (CH ₂ ) _c — (c is an integer of 1 to 10), —O—, —CH ₂ O— or —COO—.

In the formula [1a], Y ⁴ is a divalent cyclic group selected from a benzene ring, a cyclohexane ring or a heterocyclic ring, and an arbitrary hydrogen atom of these cyclic groups is an alkyl group having 1 to 3 carbon atoms, carbon It may be substituted with an alkoxyl group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxyl group having 1 to 3 carbon atoms, or a fluorine atom. Furthermore, Y ⁴ may be a divalent organic group selected from organic groups having 17 to 51 carbon atoms and having a steroid skeleton. Among these, an organic group having 17 to 51 carbon atoms having a benzene ring, a cyclohexane ring or a steroid skeleton is preferable from the viewpoint of ease of synthesis.
In the formula [1a], Y ⁵ represents a divalent cyclic group selected from a benzene ring, a cyclohexane ring or a heterocyclic ring, and any hydrogen atom on these cyclic groups is an alkyl group having 1 to 3 carbon atoms, carbon It may be substituted with an alkoxyl group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxyl group having 1 to 3 carbon atoms, or a fluorine atom. Of these, a benzene ring or a cyclohexane ring is preferable.

In the formula [1a], n represents an integer of 0 to 4. Among these, 0 to 3 are preferable from the viewpoint of availability of raw materials and ease of synthesis. More preferred is 0-2.
In the formula [1a], Y ⁶ represents an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxyl group having 1 to 18 carbon atoms, or a fluorine-containing alkoxyl group having 1 to 18 carbon atoms. . Of these, an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 10 carbon atoms, an alkoxyl group having 1 to 18 carbon atoms, or a fluorine-containing alkoxyl group having 1 to 10 carbon atoms is preferable. More preferably, it is an alkyl group having 1 to 12 carbon atoms or an alkoxyl group having 1 to 12 carbon atoms. Particularly preferred is an alkyl group having 1 to 9 carbon atoms or an alkoxyl group having 1 to 9 carbon atoms.

Preferable combinations of Y ¹ , Y ² , Y ³ , Y ⁴ , Y ⁵ , Y ⁶ and n in the formula [1a] include pages 13 to 34 of International Publication No. WO2011 / 132751 (published 2011.10.20). The same combinations as (2-1) to (2-629) listed in Tables 6 to 47 of the above are listed. It should be noted that Y ¹ to Y ⁶ in each table of the International Publication are respectively replaced with Y ¹ to Y ⁶ of the present invention.
In addition, any of the organic groups having 12 to 25 carbon atoms having a steroid skeleton in (2-605) to (2-629) listed in the tables of International Publications each has a carbon number having a steroid skeleton of the present invention. It shall be read as 17 to 51 organic groups.

Among them, (2-25) to (2-96), (2-145) to (2-168), (2-217) to (2-240), (2-268) to (2-315) , (2-364) to (2-387), (2-436) to (2-483), or (2-603) to (2-615) are preferred. Particularly preferred combinations are (2-49) to (2-96), (2-145) to (2-168), (2-217) to (2-240), (2-603) to (2- 606), (2-607) to (2-609), (2-611), (2-612) or (2-624).
In the formula [1a], m is an integer of 1 to 4. Preferably, 1.

Specific examples include structures represented by the following formulas [1a-1] to [1a-31].

(R ¹ represents —O—, —OCH ₂ —, —CH ₂ O—, —COOCH ₂ — or —CH ₂ OCO—, and R ² represents a linear or branched alkyl group having 1 to 22 carbon atoms, A linear or branched alkoxyl group having 1 to 22 carbon atoms, a linear or branched fluorine-containing alkyl group or fluorine-containing alkoxyl group having 1 to 22 carbon atoms.)

(R ³ represents —COO—, —OCO—, —CONH—, —NHCO—, —COOCH ₂ —, —CH ₂ OCO—, —CH ₂ O—, —OCH ₂ — or —CH ₂ —, R ⁴ is a linear or branched alkyl group having 1 to 22 carbon atoms, a linear or branched alkoxyl group having 1 to 22 carbon atoms, a linear or branched fluorine-containing alkyl group having 1 to 22 carbon atoms, or This is a fluorine-containing alkoxyl group.)

(R ⁵ is —COO—, —OCO—, —CONH—, —NHCO—, —COOCH ₂ —, —CH ₂ OCO—, —CH ₂ O—, —OCH ₂ —, —CH ₂ —, —O — Represents — or —NH—, and R ⁶ represents a fluorine group, a cyano group, a trifluoromethane group, a nitro group, an azo group, a formyl group, an acetyl group, an acetoxy group or a hydroxyl group.

(R ⁷ is a linear or branched alkyl group having 3 to 12 carbon atoms, and the cis-trans isomerism of 1,4-cyclohexylene is a trans isomer.)

(R ⁸ is a linear or branched alkyl group having 3 to 12 carbon atoms, and the cis-trans isomerism of 1,4-cyclohexylene is a trans isomer.)

(A ₄ is a linear or branched alkyl group having 3 to 20 carbon atoms which may be substituted with a fluorine atom, and A ₃ is a 1,4-cyclohexylene group or a 1,4-phenylene group. , A ₂ is an oxygen atom or —COO— * (where a bond with “*” is bonded to A ₃ ), and A ₁ is an oxygen atom or —COO— * (note that “*” is attached). Bond is bonded to (CH ₂ ) a ₂ ). A ₁ is an integer of 0 or 1, a ₂ is an integer of 2 to 10, and a ₃ is an integer of 0 or 1. )

Of the above formulas [1a-1] to [1a-31], particularly preferred diamine compounds have the structures [1a-1] to [1a-6], [1a-9] to [1a-13]. ] Or formula [1a-22] to formula [1a-31].

In the present invention, these specific side chain type diamine compounds are contained in an amount of 10 mol% or more and 80 mol% or less of the entire diamine component from the viewpoint of the vertical alignment of the liquid crystal and the adhesion between the liquid crystal layer and the vertical liquid crystal alignment film. Preferably there is. More preferably, it is 10 mol% or more and 70 mol% or less.
The specific side chain type diamine compound described above depends on the solubility of the polyimide polymer in the solvent, the vertical alignment of the liquid crystal when the vertical liquid crystal alignment film is formed, and the characteristics such as the optical characteristics of the liquid crystal display element. One type or a mixture of two or more types can be used.

As the diamine component for producing the polyimide polymer, a diamine compound represented by the following formula [2] is also preferably used.

In the formula [2], X represents a substituent having a structure selected from the group consisting of the following formula [2a], formula [2b], formula [2c] and formula [2d]. m represents an integer of 1 to 4.

In the formula [2a], a represents an integer of 0 to 4. Especially, the integer of 0 or 1 is preferable from the point of the acquisition of a raw material or the ease of a synthesis | combination. b represents an integer of 0 to 4. Especially, the integer of 0 or 1 is preferable from the point of the availability of a raw material or the ease of a synthesis | combination. In the formula [2c], X ¹ and X ² each independently represent a hydrocarbon group having 1 to 12 carbon atoms. In the formula [2d], X ³ represents an alkyl group having 1 to 5 carbon atoms.

Specific examples of the diamine compound represented by the formula [2] are shown below, but are not limited to these examples.
That is, examples of the diamine compound represented by the formula [2] include 2,4-dimethyl-m-phenylenediamine, 2,6-diaminotoluene, 2,4-diaminophenol, 3,5-diaminophenol, 3,5- In addition to diaminobenzyl alcohol, 2,4-diaminobenzyl alcohol, 4,6-diaminoresorcinol, 2,4-diaminobenzoic acid, 2,5-diaminobenzoic acid, 3,5-diaminobenzoic acid, the following formula [ Examples thereof include diamine compounds having structures represented by 2-1] to [2-6].

Among them, 2,4-diaminophenol, 3,5-diaminophenol, 3,5-diaminobenzyl alcohol, 2,4-diaminobenzyl alcohol, 4,6-diaminoresorcinol, 2,4-diaminobenzoic acid, 2, Preference is given to 5-diaminobenzoic acid, 3,5-diaminobenzoic acid, diamine compounds of the formula [2-1], formula [2-2] or formula [2-3]. Particularly preferably, 2,4-diaminophenol, 3,5-diaminophenol, 3,5-diaminobenzyl alcohol, 3,5-diaminobenzoic acid, represented by formula [2-1] or formula [2-2] It is a diamine compound.

The diamine compound represented by the formula [2] has properties such as solubility of a polyimide polymer in a solvent, vertical alignment of liquid crystal when a vertical liquid crystal alignment film is formed, and optical characteristics of a liquid crystal display element. Depending on the situation, one kind or a mixture of two or more kinds can be used.

In order to produce the said polyimide-type polymer, diamine compounds other than the diamine compound shown by Formula [1a] and Formula [2] (it is also called another diamine compound) can also be used as a diamine compound. Specific examples of other diamine compounds are shown below, but are not limited to these examples.
For example, m-phenylenediamine, p-phenylenediamine, 4,4′-diaminobiphenyl, 3,3′-dimethyl-4,4′-diaminobiphenyl, 3,3′-dimethoxy-4,4′-diaminobiphenyl, 3,3′-dihydroxy-4,4′-diaminobiphenyl, 3,3′-dicarboxy-4,4′-diaminobiphenyl, 3,3′-difluoro-4,4′-diaminobiphenyl, 3,3 ′ -Trifluoromethyl-4,4'-diaminobiphenyl, 3,4'-diaminobiphenyl, 3,3'-diaminobiphenyl, 2,2'-diaminobiphenyl, 2,3'-diaminobiphenyl, 4,4'- Diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 2,2'-diaminodiphenylmethane, 2,3'-diaminodiph Nylmethane, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 2,2'-diaminodiphenyl ether, 2,3'-diaminodiphenyl ether, 4,4'-sulfonyldianiline 3,3′-sulfonyldianiline, bis (4-aminophenyl) silane, bis (3-aminophenyl) silane, dimethyl-bis (4-aminophenyl) silane, dimethyl-bis (3-aminophenyl) silane, 4,4'-thiodianiline, 3,3'-thiodianiline, 4,4'-diaminodiphenylamine, 3,3'-diaminodiphenylamine, 3,4'-diaminodiphenylamine, 2,2'-diaminodiphenylamine, 2,3 ' -Diaminodiphenylamine, N-methyl (4,4'-diaminodi Phenyl) amine, N-methyl (3,3′-diaminodiphenyl) amine, N-methyl (3,4′-diaminodiphenyl) amine, N-methyl (2,2′-diaminodiphenyl) amine, N-methyl ( 2,3′-diaminodiphenyl) amine, 4,4′-diaminobenzophenone, 3,3′-diaminobenzophenone, 3,4′-diaminobenzophenone, 1,4-diaminonaphthalene, 2,2′-diaminobenzophenone, 2, , 3'-diaminobenzophenone, 1,5-diaminonaphthalene, 1,6-diaminonaphthalene, 1,7-diaminonaphthalene, 1,8-diaminonaphthalene, 2,5-diaminonaphthalene, 2,6 diaminonaphthalene, 2, 7-diaminonaphthalene, 2,8-diaminonaphthalene, 1,2-bis (4-aminophenyl) ethane 1,2-bis (3-aminophenyl) ethane, 1,3-bis (4-aminophenyl) propane, 1,3-bis (3-aminophenyl) propane, 1,4-bis (4aminophenyl) butane 1,4-bis (3-aminophenyl) butane, bis (3,5-diethyl-4-aminophenyl) methane, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4- Aminophenoxy) benzene, 1,4-bis (4-aminophenyl) benzene, 1,3-bis (4-aminophenyl) benzene, 1,4-bis (4-aminobenzyl) benzene, 1,3-bis ( 4-Aminophenoxy) benzene, 4,4 ′-[1,4-phenylenebis (methylene)] dianiline, 4,4 ′-[1,3-phenylenebis (methylene)] dianiline, 3,4 ′-[1 , 4-F Nylenebis (methylene)] dianiline, 3,4 ′-[1,3-phenylenebis (methylene)] dianiline, 3,3 ′-[1,4-phenylenebis (methylene)] dianiline, 3,3 ′-[1 , 3-phenylenebis (methylene)] dianiline, 1,4-phenylenebis [(4-aminophenyl) methanone], 1,4-phenylenebis [(3-aminophenyl) methanone], 1,3-phenylenebis [ (4-aminophenyl) methanone], 1,3-phenylenebis [(3-aminophenyl) methanone], 1,4-phenylenebis (4-aminobenzoate), 1,4-phenylenebis (3-aminobenzoate) 1,3-phenylenebis (4-aminobenzoate), 1,3-phenylenebis (3-aminobenzoate), bis (4-aminophenoxy) Terephthalate, bis (3-aminophenyl) terephthalate, bis (4-aminophenyl) isophthalate, bis (3-aminophenyl) isophthalate, N, N ′-(1,4-phenylene) bis (4-amino) Benzamide), N, N ′-(1,3-phenylene) bis (4-aminobenzamide), N, N ′-(1,4-phenylene) bis (3-aminobenzamide), N, N ′-(1 , 3-phenylene) bis (3-aminobenzamide), N, N′-bis (4-aminophenyl) terephthalamide, N, N′-bis (3-aminophenyl) terephthalamide, N, N′-bis ( 4-aminophenyl) isophthalamide, N, N′-bis (3-aminophenyl) isophthalamide, 9,10-bis (4-aminophenyl) anthracene, 4,4′- (4-aminophenoxy) diphenylsulfone, 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) hexafluoro Propane, 2,2′-bis (4-aminophenyl) propane, 2,2′-bis (3-aminophenyl) propane, 2,2′-bis (3-amino-4-methylphenyl) propane, 1, 3-bis (4-aminophenoxy) propane, 1,3-bis (3-aminophenoxy) propane, 1,4-bis (4-aminophenoxy) butane, 1,4-bi Sus (3-aminophenoxy) butane, 1,5-bis (4-aminophenoxy) pentane, 1,5-bis (3-aminophenoxy) pentane, 1,6-bis (4-aminophenoxy) hexane, , 6-Bis (3-aminophenoxy) hexane, 1,7-bis (4-aminophenoxy) heptane, 1,7- (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) Ndecane, 1,12-bis (4-aminophenoxy) dodecane, 1,12-bis (3-aminophenoxy) dodecane, bis (4-aminocyclohexyl) methane, bis (4-amino-3-methylcyclohexyl) methane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, , 10-diaminodecane, 1,11-diaminoundecane or 1,12-diaminododecane.

Other examples of the diamine compound include those having an alkyl group, a fluorine-containing alkyl group or a heterocyclic ring in the side chain of the diamine compound.
Specifically, diamine compounds represented by the following formulas [DA1] to [DA13] can be exemplified.

(A ¹ represents an alkyl group having 1 to 22 carbon atoms or a fluorine-containing alkyl group.)

(In formula [DA5] to [DA10], A ¹ represents —COO—, —OCO—, —CONH—, —NHCO—, —CH ₂ —, —O—, —CO— or —NH—, A ² represents a linear or branched alkyl group having 1 to 22 carbon atoms or a linear or branched fluorine-containing alkyl group having 1 to 22 carbon atoms.

(P represents an integer of 1 to 10)

As the other diamine compounds, diamine compounds represented by the following formulas [DA12] to [DA17] can also be used.

(In formula [DA14], m represents an integer of 0 to 3, and in formula [DA17], n represents an integer of 1 to 5).

In addition, diamine compounds represented by the following formulas [DA18] to [DA21] can also be used as long as the effects of the present invention are not impaired.

(In the formula [DA18], A ¹ is a single bond, —CH ₂ —, —C ₂ H ₄ —, —C (CH ₃ ) ₂ —, —CF ₂ —, —C (CF ₃ ) ₂ —, —O —, —CO—, —NH—, —N (CH ₃ ) —, —CONH—, —NHCO—, —CH ₂ O—, —OCH ₂ —, —COO—, —OCO—, —CON (CH ₃ ) — Or —N (CH ₃ ) CO—, each of m ¹ and m ² represents an integer of 0 to 4, and m ¹ + m ² represents an integer of 1 to 4, and in the formula [DA19], m ³ and m ⁴ each represent an integer of 1 to 5, and in formula [DA20], A ² represents a linear or branched alkyl group having 1 to 5 carbon atoms, m ⁵ represents an integer of 1 to 5, [DA21] in, ^{A 3} is a single _{_{_{bond, -CH 2 -, - C 2}}} H 4 -, - C (CH 3) 2 -, - CF 2 -, - C (CF 3) 2 - _{-O -, - CO -, -} NH -, - N (CH 3) -, - CONH -, - NHCO -, - CH 2 O -, - OCH 2 -, - COO -, - OCO -, - CON ( CH ₃ ) — or —N (CH ₃ ) CO—, and m ⁶ represents an integer of 1 to 4.

Furthermore, a diamine compound represented by the following formula [DA22] can also be used as long as the effects of the present invention are not impaired.

(A ¹ is —O—, —NH—, —N (CH ₃ ) —, —CONH—, —NHCO—, —CH ₂ O—, —OCO—, —CON (CH ₃ ) — and —N (CH ₃ ) A divalent organic group selected from the group consisting of CO—, and A ² is a single bond, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, a non-aromatic cyclic hydrocarbon group or an aromatic hydrocarbon group. A ³ is a single bond, —O—, —NH—, —N (CH ₃ ) —, —CONH—, —NHCO—, —COO—, —OCO—, —CON (CH ₃ ) —, — N (CH ₃ ) CO— or —O (CH ₂ ) _m — (m is an integer of 1 to 5), A ⁴ is a nitrogen-containing aromatic heterocyclic ring, and n is an integer of 1 to 4 .)
In addition, as other diamine compounds, diamine compounds represented by the following formulas [DA23] and [DA24] can also be used.

The above-mentioned other diamine compound is one kind depending on the solubility of the polyimide polymer in the solvent, the vertical alignment of the liquid crystal when the vertical liquid crystal alignment film is formed, and the characteristics such as the optical characteristics of the liquid crystal display element. Alternatively, two or more types can be mixed and used.
Examples of the tetracarboxylic acid component for producing the polyimide polymer include tetracarboxylic dianhydride represented by the following formula [3] and tetracarboxylic acid, tetracarboxylic acid dihalide compound, tetracarboxylic acid derivative thereof, tetra It is preferable to use a carboxylic acid dialkyl ester compound or a tetracarboxylic acid dialkyl ester dihalide compound (all are collectively referred to as a specific tetracarboxylic acid component).

(Z ¹ is a group having a structure selected from the following formulas [3a] to [3j].)

In the formula [3a], Z ² to Z ⁵ represent a hydrogen atom, a methyl group, a chlorine atom or a benzene ring, and may be the same or different.
In the formula [3g], Z ⁶ and Z ⁷ represent a hydrogen atom or a methyl group, and may be the same or different.
In the structure represented by the formula [3] which is the specific tetracarboxylic acid component, Z ¹ represents the formula [3a], the formula [ 3c], Formula [3d], Formula [3e], Formula [3f], or Formula [3g] is preferable. More preferred is a structure represented by formula [3a], formula [3e], formula [3f] or formula [3g], and particularly preferred is formula [3e], formula [3f] or formula [3g]. It is.

The specific tetracarboxylic acid component is preferably 1 mol% or more of the total tetracarboxylic acid component. More preferred is 5 mol% or more, and particularly preferred is 10 mol% or more.
Moreover, when using the specific tetracarboxylic acid component of the structure of Formula [3e], Formula [3f], or Formula [3g], the usage-amount is made into 20 mol% or more of the whole tetracarboxylic acid component, and it is desired. An effect is obtained. Preferably, it is 30 mol% or more. Further, all of the tetracarboxylic acid component may be a tetracarboxylic acid component having a structure of the formula [3e], the formula [3f], or the formula [3g].
As long as the effects of the present invention are not impaired, other tetracarboxylic acid components other than the specific tetracarboxylic acid component can be used for the polyimide polymer.
Examples of other tetracarboxylic acid components include the following tetracarboxylic acid compounds, tetracarboxylic dianhydrides, dicarboxylic acid dihalide compounds, dicarboxylic acid dialkyl ester compounds, and dialkyl ester dihalide compounds.

That is, other tetracarboxylic acid components include pyromellitic acid, 2,3,6,7-naphthalenetetracarboxylic acid, 1,2,5,6-naphthalenetetracarboxylic acid, 1,4,5,8-naphthalene. Tetracarboxylic acid, 2,3,6,7-anthracenetetracarboxylic acid, 1,2,5,6-anthracenetetracarboxylic acid, 3,3 ′, 4,4′-biphenyltetracarboxylic acid, 2,3,3 ', 4'-biphenyltetracarboxylic acid, bis (3,4-dicarboxyphenyl) ether, 3,3', 4,4'-benzophenonetetracarboxylic acid, bis (3,4-dicarboxyphenyl) sulfone, bis (3,4-dicarboxyphenyl) methane, 2,2-bis (3,4-dicarboxyphenyl) propane, 1,1,1,3,3,3-hexafluoro 2,2-bis (3,4-dicarboxyphenyl) propane, bis (3,4-dicarboxyphenyl) dimethylsilane, bis (3,4-dicarboxyphenyl) diphenylsilane, 2,3,4,5- Pyridinetetracarboxylic acid, 2,6-bis (3,4-dicarboxyphenyl) pyridine, 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic acid, 3,4,9,10-perylenetetracarboxylic acid or 1,3-diphenyl-1,2,3,4-cyclobutanetetracarboxylic acid.

The specific tetracarboxylic acid component and other tetracarboxylic acid components include solubility of the polyimide polymer in the solvent, vertical alignment of the liquid crystal when the vertical liquid crystal alignment film is formed, and optical characteristics of the liquid crystal display element. Depending on the characteristics, one kind or a mixture of two or more kinds can be used.
The method for synthesizing the polyimide polymer is not particularly limited. Usually, it is obtained by reacting a diamine component and a tetracarboxylic acid component. Generally, at least one tetracarboxylic acid component selected from the group consisting of tetracarboxylic acids and derivatives thereof is reacted with a diamine component consisting of one or more diamine compounds to obtain a polyamic acid. Specifically, a method of obtaining polyamic acid by polycondensation of tetracarboxylic dianhydride and primary or secondary diamine compound, dehydration polycondensation reaction of tetracarboxylic acid and primary or secondary diamine compound A method of obtaining a polyamic acid by using a polycarboxylic acid dihalide and a primary or secondary diamine compound is used.

To obtain the polyamic acid alkyl ester, a method of polycondensing a tetracarboxylic acid obtained by dialkyl esterifying a carboxylic acid group with a primary or secondary diamine compound, a dicarboxylic acid dihalide obtained by dialkyl esterifying a carboxylic acid group and a primary Alternatively, a method of polycondensation with a secondary diamine compound or a method of converting a carboxyl group of a polyamic acid into an ester is used.
In order to obtain polyimide, a method is used in which the polyamic acid or polyamic acid alkyl ester is cyclized to form polyimide.

The reaction between the diamine component and the tetracarboxylic acid component is usually carried out in a solvent with the diamine component and the tetracarboxylic acid component. The solvent used at that time is not particularly limited as long as the produced polyimide precursor is dissolved. Although the specific example of the solvent used for reaction below is given, it is not limited to these examples.
For example, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone or γ-butyrolactone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, 1,3-dimethyl-imidazolidinone, methyl ethyl ketone, Examples include cyclohexanone, cyclopentanone, and 4-hydroxy-4-methyl-2-pentanone.
These may be used alone or in combination. Further, even a solvent that does not dissolve the polyimide precursor may be used by mixing with the above solvent as long as the generated polyimide precursor does not precipitate. Further, since water in the solvent inhibits the polymerization reaction and further causes hydrolysis of the produced polyimide precursor, it is preferable to use a dehydrated and dried solvent.

When the diamine component and the tetracarboxylic acid component are reacted in a solvent, the solution in which the diamine component is dispersed or dissolved in the solvent is stirred, and the tetracarboxylic acid component is added as it is or dispersed or dissolved in the solvent. Methods, conversely, a method of adding a diamine component to a solution in which a tetracarboxylic acid component is dispersed or dissolved in a solvent, a method of alternately adding a diamine component and a tetracarboxylic acid component, etc., and any of these methods May be used. In addition, when reacting using a plurality of diamine components or tetracarboxylic acid components, they may be reacted in a premixed state, individually or sequentially, or further individually reacted low molecular weight substances. May be mixed and reacted to form a polymer. The polymerization temperature at that time can be selected from −20 to 150 ° C., preferably −5 to 100 ° C. The reaction can be carried out at any concentration, but if the concentration is too low, it is difficult to obtain a high molecular weight polymer, and if the concentration is too high, the viscosity of the reaction solution becomes too high and uniform stirring is difficult. It becomes. Therefore, it is preferably 1 to 50% by mass, more preferably 5 to 30% by mass. The initial reaction can be carried out at a high concentration, and then a solvent can be added.

In the polymerization reaction of the polyimide precursor, the ratio of the total number of moles of the diamine component to the total number of moles of the tetracarboxylic acid component is preferably 0.8 to 1.2. Similar to a normal polycondensation reaction, the molecular weight of the polyimide precursor produced increases as the molar ratio approaches 1.0.
Polyimide is a polyimide obtained by ring closure of the polyimide precursor, and in this polyimide, the ring closure rate (also referred to as imidation rate) of the amic acid group does not necessarily need to be 100%, depending on the application and purpose. Can be adjusted arbitrarily.
Examples of the method for imidizing the polyimide precursor include thermal imidization in which the polyimide precursor solution is heated as it is or catalyst imidization in which a catalyst is added to the polyimide precursor solution.
The temperature at which the polyimide precursor is thermally imidized in the solution is 100 to 400 ° C., preferably 120 to 250 ° C., and it is preferable to carry out while removing water generated by the imidation reaction from the system.

The catalyst imidation of the polyimide precursor can be performed by adding a basic catalyst and an acid anhydride to the polyimide precursor solution and stirring at -20 to 250 ° C, preferably 0 to 180 ° C. The amount of the basic catalyst is 0.5 to 30 mol times, preferably 2 to 20 mol times of the amic acid group, and the amount of the acid anhydride is 1 to 50 mol times, preferably 3 to 30 mol of the amido acid group. Is double. Examples of the basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine, and trioctylamine. Among them, pyridine is preferable because it has an appropriate basicity for proceeding with the reaction. Examples of the acid anhydride include acetic anhydride, trimellitic anhydride, pyromellitic anhydride, and the like. Among them, use of acetic anhydride is preferable because purification after completion of the reaction is facilitated. The imidization rate by catalytic imidation can be controlled by adjusting the amount of catalyst, reaction temperature, and reaction time.

When recovering the produced polyimide precursor or polyimide from the polyimide precursor or polyimide reaction solution, the reaction solution may be poured into a solvent and precipitated. Examples of the solvent used for precipitation include methanol, ethanol, isopropyl alcohol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, toluene, benzene, and water. The polymer precipitated in the solvent can be collected by filtration, and then dried by normal temperature or reduced pressure at room temperature or by heating. In addition, when the polymer collected by precipitation is redissolved in a solvent and reprecipitation and collection is repeated 2 to 10 times, impurities in the polymer can be reduced. Examples of the solvent at this time include alcohols, ketones, and hydrocarbons, and it is preferable to use three or more kinds of solvents selected from these because purification efficiency is further increased.

The molecular weight of the polyimide polymer is 5 in terms of weight average molecular weight measured by GPC (Gel Permeation Chromatography) method in consideration of the strength of the liquid crystal alignment film obtained therefrom, workability during film formation, and coating properties. It is preferably 000 to 1,000,000, more preferably 10,000 to 150,000.
When polysiloxane is used for the specific polymer, a polysiloxane obtained by polycondensation of an alkoxysilane represented by the following formula [A1], represented by the formula [A1] and the following formula [A2] or formula [A3] Polysiloxane obtained by polycondensation of alkoxysilane containing any one of alkoxysilanes or polycondensation obtained by polycondensation of alkoxysilanes represented by formula [A1], formula [A2] and formula [A3] It is preferably any one of siloxanes (also collectively referred to as polysiloxane polymers).

In Formula [A1], A ¹ represents the structure represented by Formula [1], and preferred combinations of Y ¹ , Y ² , Y ³ , Y ⁴ , Y ⁵ , Y ⁶ and n in Formula [1] The same combinations as (2-1) to (2-629) described in Tables 6 to 47 on pages 13 to 34 of International Publication No. WO2011 / 132751 (published 2011.10.27) can be mentioned. It should be noted that Y1 to Y6 in each table of the International Publication are respectively replaced with Y ¹ to Y ⁶ of the present invention. In addition, any of the organic groups having 12 to 25 carbon atoms having a steroid skeleton in (2-605) to (2-629) listed in the tables of International Publications are all carbons having a steroid skeleton of the present invention. It shall be read as an organic group of formulas 17 to 51.

In the formula [A1], A ² is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. Of these, a hydrogen atom or an alkyl group having 1 to 3 carbon atoms is preferable. A ³ is each an alkyl group having 1 to 5 carbon atoms. Of these, alkyl groups having 1 to 3 carbon atoms are preferred from the viewpoint of polycondensation reactivity. m is an integer of 1 or 2. Among these, 1 is preferable from the viewpoint of synthesis. n is an integer of 0-2. p is an integer of 0 to 3. Among these, an integer of 1 to 3 is preferable from the viewpoint of polycondensation reactivity. More preferably, it is 2 or 3. m + n + p is an integer of 4.

As specific examples of the alkoxysilane represented by the formula [A1], alkoxysilanes represented by the following formulas [A1-1] to [A1-32] may be used.

(R ¹ represents an alkyl group having 1 to 3 carbon atoms, R ² represents an alkyl group having 1 to 3 carbon atoms, m represents 2 or 3, and n represents 0 or 1)

(R ¹ represents an alkyl group having 1 to 3 carbon atoms, R ² represents an alkyl group having 1 to 3 carbon atoms, m represents 2 or 3, n represents 0 or 1, and R ³ represents —O—, —COO—, —OCO—, —CONH—, —NHCO—, —CON (CH ₃ ) —, —N (CH ₃ ) CO—, —OCH ₂ —, —CH ₂ O—, —COOCH ₂ — or —CH ₂ OCO—, wherein R ⁴ represents an alkyl group having 1 to 12 carbon atoms, an alkoxy group, a fluorine-containing alkyl group, or a fluorine-containing alkoxy group.

(R ¹ represents an alkyl group having 1 to 3 carbon atoms, R ² represents an alkyl group having 1 to 3 carbon atoms, m represents 2 or 3, n represents 0 or 1, and R ³ represents —O—, —COO—, —OCO—, —CONH—, —NHCO—, —CON (CH ₃ ) —, —N (CH ₃ ) CO—, —OCH ₂ —, —CH ₂ O—, —COOCH _2- or -CH ₂ OCO-, wherein R ⁴ is an alkyl group having 1 to 12 carbon atoms, alkoxy group fluorine-containing alkyl group, fluorine-containing alkoxy group, fluorine group, cyano group, trifluoromethane group, nitro group, (Azo group, formyl group, acetyl group, acetoxy group or hydroxyl group is shown.)

(R ¹ represents an alkyl group having 1 to 3 carbon atoms, R ² represents an alkyl group having 1 to 3 carbon atoms, m represents 2 or 3, n represents 0 or 1, and B ⁴ represents fluorine. Represents an alkyl group having 3 to 20 carbon atoms which may be substituted with an atom, B ³ represents a 1,4-cyclohexylene group or a 1,4-phenylene group, and B ² represents an oxygen atom or —COO— *. (However, the bond marked with “*” binds to B ³ ), and B ¹ is an oxygen atom or —COO— * (where the bond marked with “*” is (CH ₂ ) a ^2. ). a ¹ represents an integer of 0 or 1, a ² represents an integer of 2 to 10, and a ³ represents an integer of 0 or 1. )

The alkoxysilane represented by the above formula [A1] is used for the solubility of the polysiloxane polymer in the solvent, the vertical alignment of the liquid crystal when the vertical liquid crystal alignment film is formed, and the optical characteristics of the liquid crystal display element. Depending on the characteristics, one type or a mixture of two or more types can be used.
The alkoxysilane represented by the formula [A2] is represented by the following formula [A2].

In the formula [A2], B ¹ is an organic group having 2 to 12 carbon atoms having a vinyl group, an epoxy group, an amino group, a mercapto group, an isocyanate group, a methacryl group, an acrylic group, a ureido group, or a cinnamoyl group. Of these, a vinyl group, an epoxy group, an amino group, a methacryl group, an acrylic group, or a ureido group is preferable from the viewpoint of availability. More preferably, they are a methacryl group, an acryl group, or a ureido group.

In the formula [A2], B ² is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. Of these, a hydrogen atom or an alkyl group having 1 to 3 carbon atoms is preferable. In the formula [A2], B ³ is an alkyl group having 1 to 5 carbon atoms. Of these, alkyl groups having 1 to 3 carbon atoms are preferred from the viewpoint of polycondensation reactivity. In the formula [A2], m is an integer of 1 or 2. Among these, 1 is preferable from the viewpoint of synthesis. In the formula [A2], n is an integer of 0-2. p is an integer of 0 to 3. Among these, an integer of 1 to 3 is preferable from the viewpoint of polycondensation reactivity. More preferably, it is 2 or 3. m + n + p is an integer of 4.

Specific examples of the alkoxysilane represented by the formula [A2] include allyltriethoxysilane, allyltrimethoxysilane, diethoxymethylvinylsilane, dimethoxymethylvinylsilane, triethoxyvinylsilane, vinyltrimethoxysilane, vinyltris (2-methoxyethoxy) Silane, m-styrylethyltriethoxysilane, p-styrylethyltriethoxysilane, m-styrylmethyltriethoxysilane, p-styrylmethyltriethoxysilane, 3- (N-styrylmethyl-2-aminoethylamino) propyltri Methoxysilane, diethoxy (3-glycidyloxypropyl) methylsilane, 3-glycidyloxypropyl (dimethoxy) methylsilane, 3-glycidyloxypropyltrimethoxysilane, 2- (3,4 Epoxycyclohexyl) ethyltrimethoxysilane, 3- (2-aminoethylamino) propyldimethoxymethylsilane, 3- (2-aminoethylamino) propyltriethoxysilane, 3- (2-aminoethylamino) propyltrimethoxysilane, 3-aminopropyldiethoxymethylsilane, 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, trimethoxy [3- (phenylamino) propyl] silane, 3-mercaptopropyl (dimethoxy) methylsilane, (3-mercapto Propyl) triethoxysilane, (3-mercaptopropyl) trimethoxysilane, 3- (triethoxysilyl) propyl isocyanate, 3- (triethoxysilyl) propyl methacrylate, 3- (trimethoxysilyl) ) Propyl methacrylate, 3- (triethoxysilyl) propyl acrylate, 3- (trimethoxysilyl) propyl acrylate, 3- (triethoxysilyl) ethyl methacrylate, 3- (trimethoxysilyl) ethyl methacrylate, 3- (triethoxysilyl) ) Ethyl acrylate, 3- (trimethoxysilyl) ethyl acrylate, 3- (triethoxysilyl) methyl methacrylate, 3- (trimethoxysilyl) methyl methacrylate, 3- (triethoxysilyl) methyl acrylate, 3- (trimethoxysilyl) ) Methyl acrylate, γ-ureidopropyltriethoxysilane, γ-ureidopropyltrimethoxysilane, γ-ureidopropyltripropoxysilane, (R) -N-1-phenylethyl-N′-trie Toxisilylpropylurea, (R) -N-1-phenylethyl-N′-trimethoxysilylpropylurea, bis [3- (trimethoxysilyl) propyl] urea, bis [3- (tripropoxysilyl) propyl] urea 1- [3- (trimethoxysilyl) propyl] urea and the like.

Among them, allyltriethoxysilane, allyltrimethoxysilane, diethoxymethylvinylsilane, dimethoxymethylvinylsilane, triethoxyvinylsilane, vinyltrimethoxysilane, vinyltris (2-methoxyethoxy) silane, 3- (triethoxysilyl) propyl methacrylate, 3- (trimethoxysilyl) propyl acrylate, 3- (trimethoxysilyl) propyl methacrylate, 3-glycidyloxypropyl (dimethoxy) methylsilane, 3-glycidyloxypropyl (diethoxy) methylsilane, 3-glycidyloxypropyltrimethoxysilane or 2 -(3,4-Epoxycyclohexyl) ethyltrimethoxysilane is preferred.
The alkoxysilane represented by the above formula [A2] is used for the solubility of the polysiloxane polymer in the solvent, the vertical alignment of the liquid crystal when the vertical liquid crystal alignment film is formed, and the optical characteristics of the liquid crystal display element. Depending on the characteristics, one kind or a mixture of two or more kinds can be used.

The alkoxysilane represented by the formula [A3] is an alkoxysilane represented by the formula [A3].

(D ¹ is each a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and these may be substituted with a halogen atom, a nitrogen atom, an oxygen atom, or a sulfur atom. An alkyl group having 1 to 3 carbon atoms is preferred, and each D ² is an alkyl group having 1 to 5 carbon atoms, among which an alkyl group having 1 to 3 carbon atoms is preferred from the viewpoint of polycondensation reactivity. ], N is an integer of 0 to 3.)

Specific examples of the alkoxysilane represented by the formula [A3] include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, and ethyltriethoxysilane. , Propyltrimethoxysilane, propyltriethoxysilane, methyltripropoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diethoxydiethylsilane, dibutoxydimethylsilane, (chloromethyl) triethoxysilane, 3-chloropropyldimethoxymethylsilane , 3-chloropropyltriethoxysilane, 2-cyanoethyltriethoxysilane, trimethoxy (3,3,3-trifluoropropyl) silane, hexyltrimethoxy Such as orchids or 3-trimethoxysilylpropyl chloride.

In the formula [A3], examples of the alkoxysilane in which n is 0 include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, and tetrabutoxysilane, and these alkoxysilanes are preferably used.
The alkoxysilane represented by the formula [A3] has properties such as solubility of the polysiloxane polymer in the solvent, vertical alignment of the liquid crystal when the vertical liquid crystal alignment film is formed, and optical characteristics of the liquid crystal display element. Depending on the situation, one kind or a mixture of two or more kinds can be used.

The polysiloxane polymer is a polysiloxane obtained by polycondensation of an alkoxysilane represented by the formula [A1], or an alkoxysilane represented by the formula [A1] and the formula [A2] or the formula [A3]. Any of polysiloxanes obtained by polycondensation of alkoxysilane containing one kind, or polysiloxanes obtained by polycondensation of alkoxysilanes represented by formula [A1], formula [A2] and formula [A3] Or one. That is, a polysiloxane obtained by polycondensation only with an alkoxysilane represented by the formula [A1], a polysiloxane obtained by polycondensation of two types of alkoxysilanes represented by the formulas [A1] and [A2], a formula A polysiloxane obtained by polycondensation of two types of alkoxysilanes represented by [A1] and formula [A3], or three types of alkoxysilanes represented by formula [A1], formula [A2] and formula [A3] Any one of polysiloxanes obtained by polycondensation.

Of these, polysiloxanes obtained by polycondensation of a plurality of types of alkoxysilanes are preferred in terms of polycondensation reactivity and solubility of polysiloxane polymers in solvents. That is, polysiloxane obtained by polycondensation of two types of alkoxysilanes represented by formula [A1] and formula [A2], and polycondensation of two types of alkoxysilanes represented by formula [A1] and formula [A3]. Or a polysiloxane obtained by polycondensation of three types of alkoxysilanes represented by the formulas [A1], [A2] and [A3].

When a plurality of types of alkoxysilanes are used when preparing the polysiloxane-based polymer, the alkoxysilane represented by the formula [A1] is preferably 1 to 40 mol%, more preferably all alkoxysilanes. Is 1-30 mol%. In addition, the alkoxysilane represented by the formula [A2] is preferably 1 to 70 mol%, more preferably 1 to 60 mol% in all alkoxysilanes. Further, the alkoxysilane represented by the formula [A3] is preferably 1 to 99 mol%, more preferably 1 to 80 mol% in all alkoxysilanes.
The method for producing the polysiloxane polymer is not particularly limited. The polysiloxane polymer is obtained by polycondensing an alkoxysilane represented by the formula [A1] in a solvent, by polycondensing an alkoxysilane represented by the formula [A1] and the formula [A2] in a solvent. A method obtained by polycondensing an alkoxysilane represented by the formula [A1] and the formula [A3] in a solvent, and an alkoxy represented by the formula [A1], the formula [A2] and the formula [A3]. Examples thereof include a method obtained by polycondensation of silane in a solvent. The polysiloxane polymer is obtained as a solution obtained by polycondensing these alkoxysilanes and uniformly dissolving in a solvent.

The method for polycondensing the polysiloxane polymer is not particularly limited. For example, a method in which an alkoxysilane is hydrolyzed and polycondensed in an alcohol solvent or a glycol solvent can be mentioned. At that time, the hydrolysis / polycondensation reaction may be partially hydrolyzed or completely hydrolyzed. In the case of complete hydrolysis, theoretically, it is sufficient to add 0.5 times the molar amount of water of all alkoxy groups in the alkoxysilane, but it is possible to add an excessive amount of water more than 0.5 times the molar amount. preferable. In order to obtain a polysiloxane polymer, the amount of water used in the hydrolysis / polycondensation reaction can be appropriately selected according to the purpose, but 0.5 to 0.5% of all alkoxy groups in the alkoxysilane. The molar amount is preferably 2.5 times.

Also, for the purpose of promoting hydrolysis and polycondensation reaction, acidic compounds such as hydrochloric acid, sulfuric acid, nitric acid, acetic acid, formic acid, succinic acid, maleic acid, fumaric acid, alkaline such as ammonia, methylamine, ethylamine, ethanolamine or triethylamine A compound or a catalyst such as a metal salt such as hydrochloric acid, nitric acid, or oxalic acid can be used. In addition, the hydrolysis / polycondensation reaction can be promoted by heating the solution in which the alkoxysilane is dissolved. The heating temperature and heating time in that case can be suitably selected according to the objective. For example, conditions such as heating and stirring at 50 ° C. for 24 hours and then stirring under reflux conditions for 1 hour can be mentioned.

Furthermore, another method for polycondensation includes a method in which a polycondensation reaction is carried out by heating a mixture of alkoxysilane, solvent and oxalic acid. Specifically, after adding oxalic acid to a solvent to prepare a solution of oxalic acid in advance, the alkoxysilane is mixed in a state where the solution is heated. At that time, the amount of oxalic acid used in the above reaction is preferably 0.2 to 2.0 mol with respect to 1 mol of all alkoxy groups in the alkoxysilane. This reaction can be carried out at a solution temperature of 50 to 180 ° C., but is preferably carried out under reflux for several tens of minutes to several tens of hours so that the solvent does not evaporate or volatilize.
In the polycondensation reaction for producing the polysiloxane polymer, when a plurality of alkoxysilanes represented by the formulas [A1], [A2] and [A3] are used, a mixture in which a plurality of types of alkoxysilanes are mixed in advance is used. Even if it reacts using, it may react, adding several types of alkoxysilane sequentially.

The solvent used for the polycondensation reaction of alkoxysilane is not particularly limited as long as it can dissolve alkoxysilane. Moreover, even if it is a solvent in which an alkoxysilane does not melt | dissolve, what is melt | dissolved will be sufficient as long as the polycondensation reaction of an alkoxysilane progresses. As the solvent used for the polycondensation reaction, an alcohol is generally generated by the polycondensation reaction of alkoxysilane, and therefore, an alcohol solvent, a glycol solvent, a glycol ether solvent, or a solvent that is compatible with alcohol is used. Specific examples of the solvent used in such a polycondensation reaction include alcohol solvents such as methanol, ethanol, propanol, butanol or diacetone alcohol, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, hexylene glycol, 1, 3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,2-pentanediol, 1,3-pentanediol, 1,4 -Glucol solvents such as pentanediol, 1,5-pentanediol, 2,4-pentanediol, 2,3-pentanediol or 1,6-hexanediol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethyl Glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dipropyl ether, ethylene glycol dibutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol dimethyl ether , Diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene Glycol ether solvents such as recall monobutyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dipropyl ether or propylene glycol dibutyl ether, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, γ-butyrolactone, Examples thereof include solvents that are compatible with alcohols such as N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, tetramethylurea, hexamethylphosphotriamide, and m-cresol.

Moreover, in this invention, in the case of a polycondensation reaction, these solvents can also be used 1 type or in mixture of 2 or more types.
In the polysiloxane polymer solution obtained by the above method, the concentration of silicon atoms contained in all alkoxysilanes charged as a raw material in terms of SiO ₂ (also referred to as SiO ₂ concentration) is 20% by mass or less. Is preferred. In particular, the content is preferably 5 to 15% by mass. By selecting an arbitrary concentration within this concentration range, the generation of gel in the solution can be suppressed, and a uniform polysiloxane polymer solution can be obtained.
The polysiloxane polymer solution obtained by the above method may be used as it is as a specific polymer, and if necessary, the polysiloxane polymer solution obtained by the above method may be concentrated or a solvent. It can also be used as a specific polymer by diluting by addition or substitution with another solvent.

The solvent used for dilution by adding the solvent (also referred to as an added solvent) may be a solvent used for the polycondensation reaction or other solvents. The additive solvent is not particularly limited as long as the polysiloxane polymer is uniformly dissolved, and one or two or more types can be arbitrarily selected and used. Examples of such an additive solvent include ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, ester solvents such as methyl acetate, ethyl acetate, and ethyl lactate, in addition to the solvent used in the polycondensation reaction.
Furthermore, in the present invention, when a polysiloxane polymer and another polymer are used as the specific polymer, the polysiloxane polymer is polycondensed before mixing the other polymer with the polysiloxane polymer. The alcohol generated during the reaction is preferably distilled off at normal pressure or reduced pressure.

<Liquid crystal alignment agent>
The liquid crystal aligning agent of the present invention is a coating solution for forming a vertical liquid crystal alignment film, and is a coating solution containing a specific polymer having a specific side chain structure represented by the formula [1] and a solvent.
The specific polymer having the specific side chain structure is not particularly limited, but at least selected from acrylic polymer, methacrylic polymer, novolac resin, polyhydroxystyrene, polyimide precursor, polyimide, polyamide, polyester, cellulose, or polysiloxane. One polymer is preferred. Among these, a polyimide precursor, polyimide or polysiloxane is preferable. In addition, one kind or two or more kinds of these polymers can be used as the specific polymer.

All polymer components in the liquid crystal alignment treatment agent may be all specific polymers, or other polymers may be mixed. In that case, the content of the other polymer is 0.5 to 15 parts by mass, preferably 1 to 10 parts by mass with respect to 100 parts by mass of the specific polymer. Examples of the other polymer include the polymer having no specific side chain structure represented by the formula [1].

Content of the solvent in a liquid-crystal aligning agent can be suitably selected from a viewpoint of obtaining the coating method of a liquid-crystal aligning agent, and the target film thickness. Among these, from the viewpoint of forming a uniform vertical liquid crystal alignment film by coating, the content of the solvent in the liquid crystal aligning agent is preferably 50 to 99.9% by mass. Among these, 60 to 99% by mass is preferable, and 65 to 99% by mass is particularly preferable.
The solvent used for the liquid crystal aligning agent is not particularly limited as long as the solvent dissolves the specific polymer. Among them, when the specific polymer is a polyimide precursor, polyimide, polyamide or polyester, or when the solubility in a solvent such as acrylic polymer, methacrylic polymer, novolac resin, polyhydroxystyrene, cellulose, polysiloxane is low, It is preferable to use a solvent (also referred to as solvent A) as shown below.

For example, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, dimethyl sulfoxide, γ-butyrolactone, 1,3-dimethyl-imidazolidinone, methyl ethyl ketone , Cyclohexanone, cyclopentanone or 4-hydroxy-4-methyl-2-pentanone. Of these, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone or γ-butyrolactone is preferably used. These may be used alone or in combination.
When the specific polymer is an acrylic polymer, a methacrylic polymer, a novolac resin, polyhydroxystyrene, cellulose, or polysiloxane, a solvent (also referred to as a solvent B) shown below can be used.

For example, ethanol, isopropyl alcohol, 1-butanol, 2-butanol, isobutyl alcohol, tert-butyl alcohol, 1-pentanol, 2-pentanol, 3-pentanol, 2-methyl-1-butanol, isopentyl alcohol, tert-pentyl alcohol, 3-methyl-2-butanol, neopentyl alcohol, 1-hexanol, 2-methyl-1-pentanol, 2-methyl-2-pentanol, 2-ethyl-1-butanol, 1-heptanol 2-heptanol, 3-heptanol, 1-octanol, 2-octanol, 2-ethyl-1-hexanol, cyclohexanol, 1-methylcyclohexanol, 2-methylcyclohexanol, 3-methylcyclohexanol, 1,2- Etanji 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,5-pentane Diol, 2-methyl-2,4-pentanediol, 2-ethyl-1,3-hexanediol, dipropyl ether, dibutyl ether, dihexyl ether, dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, 1,2-butoxyethane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dibutyl ether, 2-pentanone, 3-pentanone, 2-hexanone, 2 Heptanone, 4-heptanone, 3-ethoxybutyl acetate, 1-methylpentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, ethylene glycol monoacetate, ethylene glycol diacetate, propylene carbonate, ethylene carbonate 2- (methoxymethoxy) ethanol, ethylene glycol monobutyl ether, ethylene glycol monoisoamyl ether, ethylene glycol monohexyl ether, 2- (hexyloxy) ethanol, furfuryl alcohol, diethylene glycol, propylene glycol, propylene glycol monobutyl ether, 1- (Butoxyethoxy) propanol, propylene glycol monomethyl ether acetate, dipropylene glycol, Dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, tripropylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monoacetate, ethylene glycol dia Cetrate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, 2- (2-ethoxyethoxy) ethyl acetate, diethylene glycol acetate, triethylene glycol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, lactic acid Methyl, ethyl lactate, methyl acetate, ethyl acetate N-butyl acetate, propylene glycol monoethyl ether acetate, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, methyl ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, propyl 3-methoxypropionate, butyl 3-methoxypropionate, methyl lactate, ethyl lactate, n-propyl lactate, n-butyl lactate, isoamyl lactate or the following formula [D1] Examples thereof include a solvent represented by the formula [D3].

(In the formula [D1], D ¹ represents an alkyl group having 1 to 3 carbon atoms, in the formula [D2], D ² represents an alkyl group having 1 to 3 carbon atoms, and in the formula [D3], D ³ represents An alkyl group having 1 to 4 carbon atoms).

Among them, 1-hexanol, cyclohexanol, 1,2-ethanediol, 1,2-propanediol, propylene glycol monobutyl ether, ethylene glycol monobutyl ether or a solvent represented by the formula [D1] to formula [D3] is used. Is preferred.
Since these solvents B can improve the coating properties and surface smoothness of the vertical liquid crystal alignment film when applying the liquid crystal aligning agent, a polyimide precursor, polyimide, polyamide or polyester was used as the specific polymer. In this case, it is preferable to use a mixture with the solvent A. In that case, the solvent B is preferably 1 to 70% by mass of the whole solvent contained in the liquid crystal aligning agent. Among these, 10 to 60% by mass is preferable, and 20 to 60% by mass is more preferable.

The liquid crystal aligning agent preferably contains a compound represented by the following formula [6] (hereinafter referred to as an adhesive compound) for the purpose of enhancing the adhesion between the liquid crystal layer and the vertical liquid crystal alignment film.

In the formula [6], X ¹ represents at least one structure selected from the group consisting of structures represented by the following formulas [6a-1] to [6a-7]. Among these, from the viewpoint of easy production of the adhesive compound of the present invention, the formula [6a-1], the formula [6a-2], the formula [6a-3], the formula [6a-5] or the formula [6a- 6] is preferable. A structure represented by formula [6a-1], formula [6a-3], formula [6a-5] or formula [6a-6] is more preferable.

In the formula [6a-2], A ¹ represents a hydrogen atom or an alkylene group having 1 to 5 carbon atoms. Among these, a hydrogen atom or an alkylene group having 1 to 2 carbon atoms is preferable from the viewpoint of easy production of the adhesive compound. More preferably, they are a hydrogen atom or a methyl group.
In the formula [6a-3], A ² represents a hydrogen atom or an alkylene group having 1 to 3 carbon atoms. Among these, a hydrogen atom or an alkylene group having 1 to 2 carbon atoms is preferable from the viewpoint of easy production of the adhesive compound. More preferably, they are a hydrogen atom or a methyl group.
In the formula [6a-5], A ³ and A ⁵ each independently represents a hydrogen atom or an alkylene group having 1 to 3 carbon atoms. Among these, a hydrogen atom or an alkylene group having 1 to 2 carbon atoms is preferable from the viewpoint of easy production of the adhesive compound. More preferably, they are a hydrogen atom or a methyl group.
In the formula [6a-5], A ⁴ represents an alkylene group having 1 to 3 carbon atoms. Among these, an alkylene group having 1 to 2 carbon atoms is preferable from the viewpoint of easy production of the adhesive compound.
In the formula [6a-6], A ⁶ and A ⁹ each independently represents a hydrogen atom or an alkylene group having 1 to 3 carbon atoms. Among these, a hydrogen atom or an alkylene group having 1 to 2 carbon atoms is preferable from the viewpoint of easy production of the adhesive compound. More preferably, they are a hydrogen atom or a C1-C1 alkylene group (methyl group).
In the formula [6a-6], A ⁷ and A ⁸ each independently represents an alkylene group having 1 to 3 carbon atoms. Among these, an alkylene group having 1 to 2 carbon atoms is preferable from the viewpoint of easy production of the adhesive compound.

In the formula [6], X ² represents a single bond, —CH ₂ —, —O—, —NH—, —N (CH ₃ ) —, —CONH—, —NHCO—, —CH ₂ O—, —OCH ₂ It represents at least one linking group selected from the group consisting of —, —COO—, —OCO—, —CON (CH ₃ ) — and —N (CH ₃ ) CO—. Among these, from the viewpoint of easy synthesis of the adhesive compound, a single bond, —CH ₂ —, —O—, —NH—, —CONH—, —NHCO—, —CH ₂ O—, —OCH ₂ —, —COO—, —OCO—, —CON (CH ₃ ) — or —N (CH ₃ ) CO— is preferred. More preferably, they are a single bond, —CH ₂ —, —O—, —NH—, —CONH—, —CH ₂ O—, —OCH ₂ —, —COO— or —OCO—. Particularly preferred is a single bond, —O—, —CONH—, —OCH ₂ —, —COO— or —OCO—.
In the formula [6], X ³ is an alkylene group having 1 to 20 carbon atoms, — (CH ₂ —CH ₂ —O) _p — (p represents an integer of 1 to 10), — (CH ₂ —O—) _q 1 (q represents an integer of 1 to 10) and at least one selected from the group consisting of organic groups having a benzene ring or a cyclohexane ring having 6 to 20 carbon atoms. In this case, any —CH ₂ — group of the alkylene group is —COO—, —OCO—, —CONH—, NHCO—, —CO—, —S—, —SO ₂ —, —CF ₂ —, — _{_{_{C (CF 3) 2 -,}}} - Si (CH 3) 2 -, - OSi (CH 3) 2 - or -Si _(CH ₃₎ may be replaced by 2 O-, bonded to any carbon atom The hydrogen atom may be replaced by a hydroxyl group (OH group), a carboxyl group (COOH group) or a halogen atom. Among these, from the viewpoint of easy production of the adhesive compound, an alkylene group having 1 to 20 carbon atoms, — (CH ₂ —CH ₂ —O) _p — (p represents an integer of 1 to 10), — ( CH ₂ —O—) _q — (q represents an integer of 1 to 10) or structures represented by the following formulas [6c-1] to [6c-5] are preferable. More preferably, an alkylene group having 1 to 15 carbon atoms, — (CH ₂ —CH ₂ —O) _p — (p represents an integer of 1 to 10), — (CH ₂ —O—) _q — (q is And represents a structure represented by the following formula [6c-1], formula [6c-3], formula [6c-4] or formula [6c-5]. Particularly preferably, an alkylene group having 1 to 15 carbon atoms, — (CH ₂ —CH ₂ —O) _p — (p represents an integer of 1 to 10), Formula [6c-1], Formula [6c-4] Or it is a structure shown by Formula [6c-5].

In the formula [6], X ⁴ represents at least one linking group selected from the group consisting of a single bond, —CH ₂ —, —OCH ₂ —, and O—CH ₂ —CH ₂ —. Among these, a structure represented by a single bond, —CH ₂ — or —OCH ₂ — is preferable from the viewpoint of easy synthesis of the adhesive compound.
In the formula [6], X ⁵ represents at least one structure selected from the group consisting of the structures represented by the following formulas [6b-1] to [6b-8]. Among these, the structure represented by the formula [6b-1], the formula [6b-2] or the formula [6b-6] is preferable from the viewpoint of the ease of synthesis of the adhesive compound. A structure represented by the formula [6b-1] or the formula [6b-2] is more preferable.

In the formula [6b-4], B ¹ represents a hydrogen atom or a benzene ring.
In the formula [6b-8], B ² represents at least one cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring and a heterocyclic ring.
In the formula [6b-8], B ³ represents an alkylene group having 1 to 12 carbon atoms, a fluorine-containing alkylene group having 1 to 12 carbon atoms, an alkoxyl group having 1 to 12 carbon atoms, and a fluorine-containing alkoxyl group having 1 to 12 carbon atoms. At least one selected from the group consisting of
In the formula [6], n represents an integer of 1 to 3. Especially, 1 or 2 is preferable from the point of the ease of the synthesis | combination of an adhesive compound. More preferred is 1.
In the formula [6], m represents an integer of 1 to 3. Especially, 1 or 2 is preferable from the point of the ease of the synthesis | combination of an adhesive compound.

More specific structures of the adhesive compound include the following formulas [6-1a] to [6-3a], formulas [6-1b] to [6-3b], and formulas [6-1c] to [6- 3c] and compounds represented by the formulas [6-1d] to [6-3d].

X ^a in formula [6-1a], X ^{d in} formula [6-2a] and X ^g in formula [6-3a] are each independently a single bond, —O—, —CONH—, — At least one linking group selected from the group consisting of OCH ₂ —, —COO— and —OCO—; Of these, a single bond, —O—, —OCH ₂ — or —OCO— is preferable from the viewpoint of easy production of the adhesive compound. More preferably, it is a single bond, —O— or —OCH ₂ —.
X ^b in formula [6-1a], X ^{e in} formula [6-2a] and X ^h in formula [6-3a] are each independently an alkylene group having 1 to 15 carbon atoms, — (CH ₂ —CH ₂ —O) _p — (p represents an integer of 1 to 10), selected from the group consisting of structures represented by formula [6c-1], formula [6c-4] and formula [6c-5] At least one selected. In this case, any —CH ₂ — group of the alkylene group is —COO—, —OCO—, —CONH—, NHCO—, —CO—, —S—, —SO ₂ —, —CF ₂ —, — _{_{_{C (CF 3) 2 -,}}} - Si (CH 3) 2 -, - OSi (CH 3) 2 - or -Si _(CH ₃₎ may be replaced by 2 O-, bonded to any carbon atom The hydrogen atom may be replaced by a hydroxyl group (OH group), a carboxyl group (COOH group) or a halogen atom.
X ^c in formula [6-1a], X ^{f in} formula [6-2a] and X ⁱ in formula [6-3a] are each independently a single bond, —CH ₂ — and —OCH ₂ —. At least one linking group selected from the group consisting of:
N1 in Formula [6-1a], n2 in Formula [6-2a], and n3 in Formula [6-3a] each independently represent an integer of 1 or 2. Of these, 1 is preferable.
M1 in Formula [6-1a], m2 in Formula [6-2a], and m3 in Formula [6-3a] each independently represent an integer of 1 or 2. Of these, 1 is preferable.

X ^a in formula [6-1b], X ^{d in} formula [6-2b] and X ^g in formula [6-3b] are each independently a single bond, —O—, —CONH—, — At least one linking group selected from the group consisting of OCH ₂ —, —COO— and —OCO—; Of these, a single bond, —O—, —OCH ₂ — or —OCO— is preferable from the viewpoint of easy production of the adhesive compound. More preferably, it is a single bond, —O— or —OCH ₂ —.
X ^b in formula [6-1b], X ^{e in} formula [6-2b], and X ^h in formula [6-3b] are each independently an alkylene group having 1 to 15 carbon atoms, — (CH ₂ —CH ₂ —O) _p — (p represents an integer of 1 to 10), selected from the group consisting of structures represented by formula [6c-1], formula [6c-4] and formula [6c-5] At least one selected. In this case, any —CH ₂ — group of the alkylene group is —COO—, —OCO—, —CONH—, NHCO—, —CO—, —S—, —SO ₂ —, —CF ₂ —, — _{_{_{C (CF 3) 2 -,}}} - Si (CH 3) 2 -, - OSi (CH 3) 2 - or -Si _(CH ₃₎ may be replaced by 2 O-, bonded to any carbon atom The hydrogen atom may be replaced by a hydroxyl group (OH group), a carboxyl group (COOH group) or a halogen atom.
X ^c in formula [6-1b], X ^{f in} formula [6-2b], and X ⁱ in formula [6-3b] are each independently a single bond, —CH ₂ — and —OCH ₂ —. And at least one linking group selected from
A ¹ in Formula [6-1b], A ^{2 in} Formula [6-2b], and A ³ in Formula [6-3b] each independently represent a hydrogen atom or an alkylene group having 1 to 2 carbon atoms. Show. Of these, a hydrogen atom or a methyl group is preferable.
N1 in Formula [6-1b], n2 in Formula [6-2b], and n3 in Formula [6-3b] each independently represent an integer of 1 or 2. Of these, 1 is preferable.
M1 in Formula [6-1b], m2 in Formula [6-2b], and m3 in Formula [6-3b] each independently represent an integer of 1 or 2. Of these, 1 is preferable.

X ^a in formula [6-1c], X ^{d in} formula [6-2c], and X ^g in formula [6-3c] are each independently a single bond, —O—, —CONH—, — At least one linking group selected from the group consisting of OCH ₂ —, —COO— and —OCO—; Of these, a single bond, —O—, —OCH ₂ — or —OCO— is preferable from the viewpoint of easy production of the adhesive compound. More preferably, it is a single bond, —O— or —OCH ₂ —.
X ^b in formula [6-1c], X ^{e in} formula [6-2c], and X ^h in formula [6-3c] are each independently an alkylene group having 1 to 15 carbon atoms, — (CH ₂ —CH ₂ —O) _p — (p represents an integer of 1 to 10), selected from the group consisting of structures represented by formula [6c-1], formula [6c-4] and formula [6c-5] At least one selected. In this case, any —CH ₂ — group of the alkylene group is —COO—, —OCO—, —CONH—, NHCO—, —CO—, —S—, —SO ₂ —, —CF ₂ —, — _{_{_{C (CF 3) 2 -,}}} - Si (CH 3) 2 -, - OSi (CH 3) 2 - or -Si _(CH ₃₎ may be replaced by 2 O-, bonded to any carbon atom The hydrogen atom may be replaced by a hydroxyl group (OH group), a carboxyl group (COOH group) or a halogen atom.
X ^c in formula [6-1c], X ^{f in} formula [6-2c], and X ⁱ in formula [6-3c] are each independently a single bond, —CH ₂ — and —OCH ₂ —. At least one linking group selected from the group consisting of:
A ¹ in Formula [6-1c], A ^{4 in} Formula [6-2c], and A ⁷ in Formula [6-3c] each independently represent a hydrogen atom or an alkylene group having 1 to 2 carbon atoms. Show. Of these, a hydrogen atom or a methyl group is preferable.
A ² in formula [6-1c], A ^{5 in} formula [6-2c], and A ⁸ in formula [6-3c] each independently represent an alkylene group having 1 to 2 carbon atoms.
A ³ in Formula [6-1c], A ^{6 in} Formula [6-2c], and A ⁹ in Formula [6-3c] each independently represent a hydrogen atom or an alkylene group having 1 to 2 carbon atoms. Show. Of these, a hydrogen atom or a methyl group is preferable.
N1 in Formula [6-1c], n2 in Formula [6-2c], and n3 in Formula [6-3c] each independently represent an integer of 1 or 2. Of these, 1 is preferable.
M1 in Formula [6-1c], m2 in Formula [6-2c], and m3 in Formula [6-3c] each independently represent an integer of 1 or 2. Of these, 1 is preferable.

X ^a in formula [6-1d], X ^{d in} formula [6-2d] and X ^g in formula [6-3d] are each independently a single bond, —O—, —CONH—, — At least one linking group selected from the group consisting of OCH ₂ —, —COO— and —OCO—; Of these, a single bond, —O—, —OCH ₂ — or —OCO— is preferable from the viewpoint of easy production of the adhesive compound. More preferably, it is a single bond, —O— or —OCH ₂ —.
X ^b in formula [6-1d], X ^{e in} formula [6-2d], and X ^h in formula [6-3d] are each independently an alkylene group having 1 to 15 carbon atoms, — (CH ₂ —CH ₂ —O) _p — (p represents an integer of 1 to 10), selected from the group consisting of structures represented by formula [6c-1], formula [6c-4] and formula [6c-5] At least one selected. In this case, any —CH ₂ — group of the alkylene group is —COO—, —OCO—, —CONH—, NHCO—, —CO—, —S—, —SO ₂ —, —CF ₂ —, — _{_{_{C (CF 3) 2 -,}}} - Si (CH 3) 2 -, - OSi (CH 3) 2 - or -Si _(CH ₃₎ may be replaced by 2 O-, bonded to any carbon atom The hydrogen atom may be replaced by a hydroxyl group (OH group), a carboxyl group (COOH group) or a halogen atom.
X ^c in formula [6-1d], X ^{f in} formula [6-2d], and X ⁱ in formula [6-3d] are each independently a single bond, —CH ₂ — and —OCH ₂ —. And at least one linking group selected from
A ¹ in Formula [6-1d], A ^{5 in} Formula [6-2d], and A ⁸ in Formula [6-3d] each independently represent a hydrogen atom or an alkylene group having 1 to 2 carbon atoms. Show. Of these, a hydrogen atom or a methyl group is preferable.
A ² in Formula [6-1d], A ^{6 in} Formula [6-2d], and A ⁹ in Formula [6-3d] each independently represent an alkylene group having 1 to 2 carbon atoms.
A ³ in Formula [6-1d], A ^{7 in} Formula [6-2d], and A ¹⁰ in Formula [6-3d] each independently represent an alkylene group having 1 to 2 carbon atoms.
A ⁴ in Formula [6-1d], A ^{8 in} Formula [6-2d], and A ¹¹ in Formula [6-3d] each independently represent a hydrogen atom or an alkylene group having 1 to 2 carbon atoms. Show. Of these, a hydrogen atom or a methyl group is preferable.
N1 in Formula [6-1d], n2 in Formula [6-2d], and n3 in Formula [6-3d] each independently represent an integer of 1 or 2. Of these, 1 is preferable.
M1 in Formula [6-1d], m2 in Formula [6-2d], and m3 in Formula [6-3d] each independently represent an integer of 1 or 2. Of these, 1 is preferable.

As the adhesive compound, it is preferable to use at least one compound selected from the group consisting of compounds represented by the following formulas [6-1] and [6-5].

(In formula [6-4], n represents an integer of 1 to 10, and in formula [6-5], m represents an integer of 1 to 10).
Further, for example, specific examples of the adhesive compound include the following compounds.
Polymerizability of trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, tri (meth) acryloyloxyethoxytrimethylolpropane, glycerin polyglycidyl ether poly (meth) acrylate, etc. Compounds having 3 unsaturated groups in the molecule; ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) Acrylate, polypropylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate Ethylene oxide bisphenol A type di (meth) acrylate, propylene oxide bisphenol type di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, glycerin di (meth) acrylate, pentaerythritol di (meth) acrylate, ethylene Polymerizable unsaturated groups such as glycol diglycidyl ether di (meth) acrylate, diethylene glycol diglycidyl ether di (meth) acrylate, diglycidyl phthalate di (meth) acrylate, and hydroxypivalate neopentyl glycol di (meth) acrylate Compounds having two in the molecule; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, -Phenoxy-2-hydroxypropyl (meth) acrylate, 2- (meth) acryloyloxy-2-hydroxypropyl phthalate, 3-chloro-2-hydroxypropyl (meth) acrylate, glycerin mono (meth) acrylate, 2- (meth) And compounds having one polymerizable unsaturated group in the molecule, such as acryloyloxyethyl phosphate ester and N-methylol (meth) acrylamide.
The said adhesive compound is an example of a compound, It is not limited to these. One type of adhesive compound may be used, or two or more types may be combined.
The content of the adhesive compound in the liquid crystal aligning agent is preferably 0.1 to 150 parts by mass with respect to 100 parts by mass of all polymer components. In order for the crosslinking reaction to proceed and to achieve the desired effect, the amount is more preferably 0.1 to 100 parts by weight, and most preferably 1 to 50 parts by weight, based on 100 parts by weight of all polymer components.

As long as the effects of the present invention are not impaired, the liquid crystal aligning agent is selected from the group consisting of a compound having an epoxy group, an isocyanate group, an oxetane group or a cyclocarbonate group, or a hydroxyl group, a hydroxyalkyl group and a lower alkoxyalkyl group. It is also possible to introduce a compound having at least one kind of substituent (collectively referred to as a crosslinkable compound). In that case, it is necessary to have two or more of these substituents in the crosslinkable compound.

Examples of the crosslinkable compound having an epoxy group or an isocyanate group include bisphenolacetone glycidyl ether, phenol novolac epoxy resin, cresol novolac epoxy resin, triglycidyl isocyanurate, tetraglycidylaminodiphenylene, tetraglycidyl-m-xylenediamine, tetra Glycidyl-1,3-bis (aminoethyl) cyclohexane, tetraphenyl glycidyl ether ethane, triphenyl glycidyl ether ethane, bisphenol hexafluoroacetodiglycidyl ether, 1,3-bis (1- (2,3-epoxypropoxy)- 1-trifluoromethyl-2,2,2-trifluoromethyl) benzene, 4,4-bis (2,3-epoxypropoxy) octafluorobiphenyl Triglycidyl-p-aminophenol, tetraglycidylmetaxylenediamine, 2- (4- (2,3-epoxypropoxy) phenyl) -2- (4- (1,1-bis (4- (2,3-epoxy) Propoxy) phenyl) ethyl) phenyl) propane or 1,3-bis (4- (1- (4- (2,3-epoxypropoxy) phenyl) -1- (4- (1- (4- (2,3 -Epoxypropoxy) phenyl) -1-methylethyl) phenyl) ethyl) phenoxy) -2-propanol and the like.

The crosslinkable compound having an oxetane group is a crosslinkable compound having at least two oxetane groups represented by the following formula [4].

Specific examples include crosslinkable compounds represented by the formulas [4a] to [4k] described in the paragraphs 58 to 59 of the international publication WO2011 / 132751 (published 2011.10.27).

The crosslinkable compound having a cyclocarbonate group is a crosslinkable compound having at least two cyclocarbonate groups represented by the following formula [5].

Specifically, crosslinkable compounds represented by the formulas [5-1] to [5-42] described in the paragraphs 76 to 82 of the international publication WO2012 / 014898 (published in 2012.2.2) are listed. It is done.

Examples of the crosslinkable compound having at least one substituent selected from the group consisting of a hydroxyl group and an alkoxyl group include an amino resin having a hydroxyl group or an alkoxyl group, such as a melamine resin, a urea resin, a guanamine resin, and a glycoluril. -Formaldehyde resin, succinylamide-formaldehyde resin or ethylene urea-formaldehyde resin. Specifically, a melamine derivative, a benzoguanamine derivative, or glycoluril in which a hydrogen atom of an amino group is substituted with a methylol group, an alkoxymethyl group, or both can be used. The melamine derivative or benzoguanamine derivative can exist as a dimer or a trimer. These preferably have an average of 3 to 6 methylol groups or alkoxymethyl groups per triazine ring.

Examples of the melamine derivative or benzoguanamine derivative include MX-750 in which an average of 3.7 methoxymethyl groups are substituted per triazine ring, and an average of 5.8 methoxymethyl groups per triazine ring. Substituted MW-30 (Sanwa Chemical Co., Ltd.) and Cymel 300, 301, 303, 350, 370, 771, 325, 327, 703, 712 and other methoxymethylated melamines, Cymel 235, 236, 238 , 212, 253, 254, etc., methoxymethylated butoxymethylated melamine, Cymel 506, 508, etc., carboxyl group-containing methoxymethylated isobutoxymethylated melamine, Cymel 1141, methoxy such as Cymel 1123 Methylated ethoxymethyl Benzomethylamine, methoxymethylated butoxymethylated benzoguanamine such as Cymel 1123-10, butoxymethylated benzoguanamine such as Cymel 1128, carboxyl group-containing methoxymethylated ethoxymethylated benzoguanamine such as Cymel 1125-80 (Mitsui Cyanamid) For example). Examples of glycoluril include butoxymethylated glycoluril such as Cymel 1170, methylolated glycoluril such as Cymel 1172, and methoxymethylolated glycoluril such as Powderlink 1174.

Examples of the benzene or phenolic compound having a hydroxyl group or an alkoxyl group include 1,3,5-tris (methoxymethyl) benzene, 1,2,4-tris (isopropoxymethyl) benzene, 1,4-bis ( sec-butoxymethyl) benzene or 2,6-dihydroxymethyl-p-tert-butylphenol.
More specifically, International Publication WO2011 / 132751. (2011.10.27), pages 62 to 66, and crosslinkable compounds represented by the formulas [6-1] to [6-48].

The content of the crosslinkable compound in the liquid crystal aligning agent is preferably 0.1 to 100 parts by mass with respect to 100 parts by mass of all the polymer components. In order for the crosslinking reaction to proceed and to achieve the desired effect, the amount is more preferably 0.1 to 50 parts by weight, and most preferably 1 to 30 parts by weight, based on 100 parts by weight of all polymer components.
In liquid crystal display elements, as a compound that promotes charge transfer in the liquid crystal alignment film and promotes charge release of the element, it is published on pages 69 to 73 of International Publication No. WO2011 / 132751 (published 2011.10.20). Nitrogen-containing heterocyclic amine compounds represented by the formulas [M1] to [M156] can also be added. This amine compound may be added directly to the liquid crystal aligning agent, but it is preferably added after a solution having a concentration of 0.1 to 10% by mass, preferably 1 to 7% by mass with an appropriate solvent. The solvent is not particularly limited as long as it is an organic solvent that dissolves the specific polymer described above.

As the liquid crystal aligning agent, a compound that improves the uniformity of the thickness of the vertical liquid crystal aligning film and the surface smoothness when the liquid crystal aligning agent is applied can be used as long as the effects of the present invention are not impaired. Further, a compound that improves the adhesion between the vertical liquid crystal alignment film and the substrate can be used.
Examples of the compound that improves the film thickness uniformity and surface smoothness of the vertical liquid crystal alignment film include a fluorine-based surfactant, a silicone-based surfactant, and a nonionic surfactant.
Specifically, for example, F-top EF301, EF303, EF352 (above, manufactured by Tochem Products), MegaFuck F171, F173, R-30 (above, manufactured by Dainippon Ink, Inc.), Florard FC430, FC431 (above, Sumitomo 3M Limited), Asahi Guard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (above, manufactured by Asahi Glass). The use ratio of these surfactants is preferably 0.01 to 2 parts by mass, more preferably 0.01 to 1 part by mass with respect to 100 parts by mass of all the polymer components contained in the liquid crystal aligning agent. It is.

Specific examples of the compound that improves the adhesion between the vertical liquid crystal alignment film and the substrate include the following functional silane-containing compounds and epoxy group-containing compounds.
For example, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, N-ethoxycarbonyl-3-aminopropyltrimethoxysilane, N-ethoxy Carbonyl-3-aminopropyltriethoxysilane, N-triethoxysilylpropyltriethylenetriamine, N-trimethoxysilylpropyltriethylenetriamine, 10-trimethoxysilyl-1,4,7-triazadecane, 10-tri Toxisilyl-1,4,7-triazadecane, 9-trimethoxysilyl-3,6-diazanonyl acetate, 9-triethoxysilyl-3,6-diazanonyl acetate, N-benzyl-3-aminopropyltrimethoxy Silane, N-benzyl-3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N-bis (oxyethylene) -3-aminopropyl Trimethoxysilane, N-bis (oxyethylene) -3-aminopropyltriethoxysilane, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, poly Lopylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5,6-tetraglycidyl -2,4-hexanediol, N, N, N ′, N ′,-tetraglycidyl-m-xylenediamine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane or N, N, N ′ , N ′,-tetraglycidyl-4,4′-diaminodiphenylmethane and the like.

When using a compound to be adhered to these substrates, it is preferably 0.1 to 30 parts by mass, more preferably 1 to 30 parts by mass with respect to 100 parts by mass of all polymer components contained in the liquid crystal aligning agent. 20 parts by mass. If it is less than 0.1 part by mass, the effect of improving the adhesion cannot be expected, and if it exceeds 30 parts by mass, the storage stability of the liquid crystal aligning agent may be deteriorated.
In addition to the compounds other than the above, the liquid crystal aligning agent includes a dielectric material for changing the electrical properties such as dielectric constant and conductivity of the vertical liquid crystal alignment film, as long as the effects of the present invention are not impaired. A conductive substance may be added.

<Production Method of Vertical Liquid Crystal Alignment Film / Liquid Crystal Display Element>
The substrate used for the liquid crystal display element is not particularly limited as long as it is a highly transparent substrate. In addition to a glass substrate, a plastic substrate such as an acrylic substrate, a polycarbonate substrate, or a PET (polyethylene terephthalate) substrate can be used. When the liquid crystal display element of the present invention is used as a reverse element for a light control window or the like, a plastic substrate is preferable. From the viewpoint of simplification of the process, it is preferable to use a substrate on which an ITO (Indium Tin Oxide) electrode for driving a liquid crystal is formed. In the case of a reflective reverse element, a substrate on which a metal or dielectric multilayer film such as a silicon wafer or aluminum is formed can be used as long as the substrate is only on one side.

In the liquid crystal display element, at least one of the substrates has a vertical liquid crystal alignment film that aligns liquid crystal molecules vertically. This vertical liquid crystal alignment film can be obtained by applying a liquid crystal alignment treatment agent on a substrate and baking it, followed by alignment treatment by rubbing treatment or light irradiation. Further, in the case of a vertical liquid crystal alignment film, it can be used as a vertical liquid crystal alignment film without alignment treatment.
The application method of the liquid crystal alignment treatment agent is not particularly limited, but industrially includes screen printing, offset printing, flexographic printing, ink jet method, dipping method, roll coater method, slit coater method, spinner method, spray method, etc. Depending on the kind of the substrate and the desired thickness of the vertical liquid crystal alignment film, it can be appropriately selected.

After the liquid crystal alignment treatment agent is applied on the substrate, it is preferably 30 to 300 ° C., depending on the solvent used for the liquid crystal alignment treatment agent, by a heating means such as a hot plate, a thermal circulation oven or an IR (infrared) oven. Can evaporate the solvent at a temperature of 30 to 250 ° C. to form a vertical liquid crystal alignment film. The thickness of the vertical liquid crystal alignment film after firing is disadvantageous in terms of power consumption of the liquid crystal display element if it is too thick, and if it is too thin, the reliability of the element may be lowered. Therefore, it is preferably 5 to 300 nm, more preferably 10 to 200 nm.
The liquid crystal composition used for the liquid crystal display element is a liquid crystal composition having at least a liquid crystal and a polymerizable compound. Examples of those other than the liquid crystal and the polymerizable compound include the initiator and a spacer for controlling an electrode gap (also referred to as a gap) of the liquid crystal display element.

Although the injection method of a liquid crystal composition is not specifically limited, For example, the following method is mentioned. That is, when a glass substrate is used as a substrate, a pair of substrates on which a vertical liquid crystal alignment film is formed is prepared, and a sealant is applied to four pieces of one side of the substrate except for a part, and then the vertical liquid crystal alignment film is formed. An empty cell is manufactured by attaching the substrate on the other side so that the surface is on the inside. And the method of obtaining the liquid crystal composition injection cell by injecting the liquid crystal composition under reduced pressure from a place where the sealant is not applied can be mentioned.
Further, when a plastic substrate is used as a substrate, a pair of substrates on which a vertical liquid crystal alignment film is formed is prepared, and a liquid crystal composition is applied on one substrate by an ODF (One Drop Filling) method or an inkjet method. There is a method in which a liquid crystal composition injection cell is obtained by dropping and then bonding the other substrate together.
In the liquid crystal display element of the present invention, since the adhesion between the liquid crystal layer and the vertical liquid crystal alignment film is high, it is not necessary to apply the sealing agent to the four pieces of the substrate.

The gap of the liquid crystal display element can be controlled by a spacer or the like. Examples of the method include a method of introducing a spacer having a target size into the liquid crystal composition described above, and a method of using a substrate having a column spacer of a target size. The size of the gap is preferably 1 to 100 μm, more preferably 2 to 50 μm. Particularly preferred is 3 to 30 μm. If the gap is too small, the contrast of the liquid crystal display element is lowered. If the gap is too large, the driving voltage of the element is increased.

The liquid crystal display element is obtained by curing the liquid crystal composition in a state where a part or the whole of the liquid crystal composition exhibits liquid crystallinity to form a cured product composite of the liquid crystal and the polymerizable compound. The liquid crystal composition is cured by at least one of irradiation with active energy rays and heating the liquid crystal composition injection cell obtained above. Here, ultraviolet rays are suitable as the active energy ray. The ultraviolet light has a wavelength of 250 nm to 400 nm, preferably 310 nm to 370 nm. In the case of heat treatment, the temperature is 40 to 120 ° C., preferably 60 to 80 ° C. Further, both the ultraviolet treatment and the heat treatment may be performed simultaneously, or the heat treatment may be performed after the ultraviolet treatment. Only the ultraviolet treatment is preferable for curing the liquid crystal composition.
The liquid crystal display element in the present invention is a liquid crystal display element used in transportation equipment and transportation machinery such as automobiles, railways and aircrafts, specifically, an optical shutter element used in a light control window and a room mirror for controlling transmission and blocking of light. It can use suitably for.
In particular, as described above, transparency when no voltage is applied and scattering characteristics when voltage is applied are good, so when this element is used for a glass window of a vehicle, when a conventional reverse type element is used. In comparison, the efficiency of taking in light at night is high, and the effect of preventing glare from outside light is also high. Therefore, it is possible to further improve the safety when driving a vehicle and the comfort when riding. Further, when the liquid crystal display element is manufactured using a film substrate and is used by being attached to a glass window of a vehicle, the reliability of the element is higher than that of a conventional reverse type element. That is, poor adhesion and deterioration are less likely to occur due to the low adhesion between the liquid crystal layer and the vertical alignment film.
In addition, the liquid crystal display element can be used for a light guide plate of a display device such as an LCD (Liquid Crystal Display) or an OLED (Organic Light-Emitting Diode) display, or a back plate of a transparent display using these displays. Specifically, when used for the back plate of a transparent display, the transparent display and the liquid crystal display element are combined, and when the screen is displayed on the transparent display, the liquid crystal display element suppresses light from entering from the back side. Can be used for As a result, the liquid crystal display element is in a scattering state in which voltage is applied when performing screen display on a transparent display, and the screen display can be clarified. After the screen display is finished, no voltage is applied to the transparent display element. It becomes a state.

EXAMPLES The present invention will be specifically described below with reference to examples, but is not limited thereto.
"Abbreviations used in synthesis examples, examples and comparative examples"
L1 (liquid crystal): MLC-6608 (Merck)
R1 (polymerizable compound): Compound represented by the following formula [R1] P1 (photoinitiator): Compound represented by the following formula [P1]

A1: 1,3-diamino-4- [4- (trans-4-n-heptylcyclohexyl) phenoxy] benzene A2: 1,3-diamino-4- [4- (trans-4-n-heptylcyclo) Hexyl) phenoxymethyl] benzene A3: 1,3-diamino-4- {4- [trans-4- (trans-4-n-pentylcyclohexyl) cyclohexyl] phenoxy} benzene A4: A4] Diamine

B1: p-phenylenediamine B2: m-phenylenediamine B3: 3,5-diaminobenzoic acid B4: diamine represented by the following formula [B4] B5: 1,3-diamino-4-octadecyloxybenzene (conventional type) Diamine)

C1: 1,2,3,4-cyclobutanetetracarboxylic dianhydride C2: bicyclo [3,3,0] octane-2,4,6,8-tetracarboxylic dianhydride C3: the following formula [C3 ] C4: tetracarboxylic dianhydride represented by the following formula [C4]

D1: Alkoxysilane monomer represented by the following formula [D1] (alkoxysilane monomer having a specific side chain structure)
D2: 3-Methacryloxypropyltrimethoxysilane (alkoxysilane monomer of the formula [A2])
D3: 3-Ureidopropyltriethoxysilane (alkoxysilane monomer of formula [A2])
D4: Tetraethoxysilane (alkoxysilane monomer of formula [A3])
D5: Octadecyltriethoxysilane (conventional alkoxysilane monomer)

M1: Adhesive compound represented by the following formula [M1] M2: Adhesive compound represented by the following formula [M2] M3: Adhesive compound represented by the following formula [M3]

K1: Crosslinkable compound represented by the following formula [K1]

NMP: N-methyl-2-pyrrolidone NEP: N-ethyl-2-pyrrolidone γ-BL: γ-butyrolactone BCS: ethylene glycol monobutyl ether ECS: ethylene glycol monoethyl ether PB: propylene glycol monobutyl ether

"Molecular weight measurement of polyimide precursor and polyimide polymer"
Using a normal temperature gel permeation chromatography (GPC) apparatus (GPC-101) (manufactured by Showa Denko) and a column (KD-803, KD-805, manufactured by Shodex), the measurement was performed as follows.
Column temperature: 50 ° C
Eluent: N, N′-dimethylformamide (as additive, lithium bromide-hydrate (LiBr · H ₂ O) 30 mmol / L (liter), phosphoric acid / anhydrous crystal (o-phosphoric acid) 30 mmol) / L, 10 ml / L of tetrahydrofuran (THF))
Flow rate: 1.0 ml / min Standard sample for preparing a calibration curve: TSK standard polyethylene oxide (molecular weight; about 900,000, 150,000, 100,000 and 30,000) (manufactured by Tosoh Corporation) and polyethylene glycol (molecular weight; about 12,000, 4,000 and 1,000) (manufactured by Polymer Laboratory).

"Measurement of imidization rate of polyimide polymer"
20 mg of polyimide powder was put into an NMR (nuclear magnetic resonance) sample tube (NMR sampling tube standard, φ5 (manufactured by Kusano Kagaku)), and deuterated dimethyl sulfoxide (DMSO-d6, 0.05 mass% TMS (tetramethylsilane)). (Mixed product) (0.53 ml) was added and completely dissolved by applying ultrasonic waves. This solution was measured for proton NMR at 500 MHz with an NMR measuring instrument (JNW-ECA500) (manufactured by JEOL Datum). The imidation rate is determined based on protons derived from structures that do not change before and after imidation as reference protons, and the peak integrated value of these protons and proton peaks derived from NH groups of amic acid that appear in the vicinity of 9.5 ppm to 10.0 ppm. It calculated | required by the following formula | equation using the integrated value.
Imidization rate (%) = (1−α · x / y) × 100
(X is the accumulated proton peak value derived from NH group of amic acid, y is the accumulated peak value of reference proton, α is the reference proton for one NH group proton of amic acid in the case of polyamic acid (imidation rate is 0%) The number ratio.

"Synthesis of polyimide polymers"
<Synthesis Example 1>
C1 (2.96 g, 15.1 mmol), A1 (2.91 g, 7.65 mmol), B2 (0.17 g, 1.57 mmol) and B3 (0.93 g, 6.11 mmol) were converted to NMP (20.9 g). Then, the mixture was reacted at 40 ° C. for 8 hours to obtain a polyamic acid solution (1) having a resin solid content concentration of 25% by mass. The number average molecular weight of this polyamic acid was 27,600, and the weight average molecular weight was 81,000.

<Synthesis Example 2>
C2 (3.83 g, 15.3 mmol), A2 (6.04 g, 15.3 mmol) and B3 (2.33 g, 15.3 mmol) were mixed in NMP (26.3 g) and reacted at 50 ° C. for 2 hours. After that, C1 (2.94 g, 15.0 mmol) and NMP (23.9 g) were added and reacted at 40 ° C. for 6 hours to obtain a polyamic acid solution (2) having a resin solid content concentration of 25 mass%. . The number average molecular weight of this polyamic acid was 18,500, and the weight average molecular weight was 62,400.

<Synthesis Example 3>
After adding NMP to the polyamic acid solution (2) (30.0 g) obtained in Synthesis Example 2 and diluting to 6% by mass, acetic anhydride (3.91 g) and pyridine (2.42 g) were used as imidization catalysts. In addition, the mixture was reacted at 70 ° C. for 2 hours. This reaction solution was put into methanol (460 ml), and the resulting precipitate was separated by filtration. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyimide powder (3). The imidation ratio of this polyimide was 60%, the number average molecular weight was 20,900, and the weight average molecular weight was 58,100.

<Synthesis Example 4>
C2 (2.64 g, 10.6 mmol), A3 (4.56 g, 10.5 mmol), B3 (1.60 g, 10.5 mmol) and B4 (1.07 g, 5.26 mmol) to NMP (21.4 g) After mixing at 80 ° C. for 5 hours, C1 (3.02 g, 15.8 mmol) and NMP (17.7 g) were added and reacted at 40 ° C. for 8 hours. The resin solid content concentration was 25 mass. % Polyamic acid solution was obtained.
After adding NMP to the obtained polyamic acid solution (30.0 g) and diluting to 6% by mass, acetic anhydride (3.88 g) and pyridine (2.41 g) were added as imidization catalysts, and the mixture was stirred at 50 ° C. for 2 hours. Reacted. This reaction solution was put into methanol (460 ml), and the resulting precipitate was separated by filtration. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyimide powder (4). The imidation ratio of this polyimide was 55%, the number average molecular weight was 18,900, and the weight average molecular weight was 52,200.

<Synthesis Example 5>
C2 (2.50 g, 10.0 mmol), A4 (2.96 g, 6.00 mmol), B1 (0.22 g, 2.00 mmol), B3 (1.52 g, 10.0 mmol) and B4 (0.41 g, 2.00 mmol) was mixed in NMP (19.1 g) and reacted at 80 ° C. for 5 hours, and then C1 (1.92 g, 9.80 mmol) and NMP (9.50 g) were added. The reaction was carried out for a time to obtain a polyamic acid solution having a resin solid content concentration of 25% by mass.
After adding NMP to the obtained polyamic acid solution (30.0 g) and diluting to 6% by mass, acetic anhydride (4.02 g) and pyridine (2.49 g) were added as an imidization catalyst, and the mixture was stirred at 50 ° C. for 2 hours. Reacted. This reaction solution was put into methanol (460 ml), and the resulting precipitate was separated by filtration. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyimide powder (5). The imidation ratio of this polyimide was 48%, the number average molecular weight was 15,600, and the weight average molecular weight was 47,300.

<Synthesis Example 6>
C3 (5.45 g, 24.3 mmol), A2 (5.81 g, 14.7 mmol), B3 (1.12 g, 7.36 mmol) and B4 (0.50 g, 2.46 mmol) were added to NMP (38.6 g). Then, the mixture was reacted at 40 ° C. for 10 hours to obtain a polyamic acid solution having a resin solid content concentration of 25% by mass.
After adding NMP to the obtained polyamic acid solution (30.0 g) and diluting to 6% by mass, acetic anhydride (4.00 g) and pyridine (2.48 g) were added as an imidization catalyst, and the mixture was kept at 70 ° C. for 2 hours. Reacted. This reaction solution was put into methanol (460 ml), and the resulting precipitate was separated by filtration. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyimide powder (6). The imidation ratio of this polyimide was 63%, the number average molecular weight was 16,400, and the weight average molecular weight was 46,200.

<Synthesis Example 7>
C3 (5.45 g, 24.3 mmol), A4 (3.63 g, 7.37 mmol) and B3 (2.61 g, 17.2 mmol) were mixed in NMP (35.1 g) and reacted at 40 ° C. for 5 hours. Thus, a polyamic acid solution having a resin solid content concentration of 25% by mass was obtained.
After adding NMP to the obtained polyamic acid solution (30.0 g) and diluting to 6% by mass, acetic anhydride (8.00 g) and pyridine (2.48 g) were added as an imidization catalyst, and the mixture was stirred at 50 ° C. for 3 hours. Reacted. This reaction solution was put into methanol (460 ml), and the resulting precipitate was separated by filtration. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyimide powder (7). The imidation ratio of this polyimide was 54%, the number average molecular weight was 16,900, and the weight average molecular weight was 46,300.

<Synthesis Example 8>
C4 (4.59 g, 15.3 mmol), A3 (6.62 g, 15.3 mmol), B3 (1.86 g, 12.2 mmol) and B4 (0.62 g, 3.05 mmol) in NMP (27.6 g) After mixing at 40 ° C. for 8 hours, C1 (2.94 g, 15.0 mmol) and NMP (22.3 g) were added, and the mixture was reacted at 25 ° C. for 10 hours. % Polyamic acid solution was obtained.
After adding NMP to the obtained polyamic acid solution (30.0 g) and diluting to 6% by mass, acetic anhydride (7.24 g) and pyridine (2.24 g) were added as an imidization catalyst and 1. The reaction was allowed for 5 hours. This reaction solution was put into methanol (460 ml), and the resulting precipitate was separated by filtration. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyimide powder (8). The imidation ratio of this polyimide was 70%, the number average molecular weight was 17,100, and the weight average molecular weight was 37,200.

<Synthesis Example 9>
C2 (3.83 g, 15.3 mmol), B3 (2.33 g, 15.3 mmol) and B5 (5.76 g, 15.3 mmol) were mixed in NMP (24.6 g) and reacted at 80 ° C. for 1 hour. After that, C1 (2.94 g, 15.0 mmol) and NMP (20.0 g) were added and reacted at 40 ° C. for 6 hours to obtain a polyamic acid solution (9) having a resin solid content concentration of 25 mass%. . The number average molecular weight of this polyamic acid was 21,500, and the weight average molecular weight was 63,400.

<Synthesis Example 10>
After adding NMP to the polyamic acid solution (9) (30.0 g) obtained in Synthesis Example 9 and diluting to 6% by mass, acetic anhydride (3.93 g) and pyridine (2.43 g) were used as imidization catalysts. In addition, the mixture was reacted at 70 ° C. for 2 hours. This reaction solution was put into methanol (460 ml), and the resulting precipitate was separated by filtration. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyimide powder (10). The imidation ratio of this polyimide was 61%, the number average molecular weight was 18,900, and the weight average molecular weight was 54,100.

<Synthesis Example 11>
C2 (3.25 g, 13.0 mmol), B3 (0.99 g, 6.51 mmol) and B5 (7.35 g, 19.5 mmol) were mixed in NMP (23.3 g) and reacted at 80 ° C. for 5 hours. After that, C1 (2.53 g, 12.9 mmol) and NMP (19.1 g) were added and reacted at 40 ° C. for 6 hours to obtain a polyamic acid solution having a resin solid content concentration of 25 mass%.
After adding NMP to the obtained polyamic acid solution (30.0 g) and diluting to 6% by mass, acetic anhydride (3.52 g) and pyridine (2.18 g) were added as an imidization catalyst, and the mixture was maintained at 70 ° C. for 2 hours. Reacted. This reaction solution was put into methanol (460 ml), and the resulting precipitate was separated by filtration. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyimide powder (11). The imidation ratio of this polyimide was 60%, the number average molecular weight was 19,200, and the weight average molecular weight was 60,100. The polyimide polymer is shown in Table 1.

* 1: Polyamic acid.

"Synthesis of polysiloxane polymers"
<Synthesis Example 12>
In a 200 ml four-necked reaction flask equipped with a thermometer and reflux tube, ECS (28.3 g), D1 (4.10 g), D2 (7.45 g) and D4 (32.5 g) were mixed, A solution of alkoxysilane monomer was prepared. To this solution, ECS (14.2 g), water (10.8 g), and a solution prepared by mixing oxalic acid (0.70 g) as a catalyst were added dropwise at 25 ° C. over 30 minutes, The mixture was further stirred at 25 ° C. for 30 minutes. Then, after heating using an oil bath and refluxing for 30 minutes, a previously prepared mixed solution of a methanol solution (1.20 g) with a D3 content of 92% by mass and ECS (0.90 g) was added. It was. The mixture was further refluxed for 30 minutes and then allowed to cool to obtain a polysiloxane solution (1) having a SiO ₂ equivalent concentration of 12% by mass.

<Synthesis Example 13>
In a 200 ml four-necked reaction flask equipped with a thermometer and reflux tube, ECS (25.4 g), D1 (8.20 g), D2 (19.9 g) and D4 (20.0 g) were mixed, A solution of alkoxysilane monomer was prepared. To this solution, ECS (12.7 g), water (10.8 g), and a solution prepared by mixing oxalic acid (1.10 g) as a catalyst were added dropwise at 25 ° C. over 30 minutes. The mixture was further stirred at 25 ° C. for 30 minutes. Thereafter, the mixture was heated using an oil bath and refluxed for 30 minutes, and a previously prepared mixed solution of a methanol solution (1.20 g) having a D3 content of 92% by mass and ECS (0.90 g) was added. . The mixture was further refluxed for 30 minutes and then allowed to cool to obtain a polysiloxane solution (2) having a SiO ₂ equivalent concentration of 12% by mass.

<Synthesis Example 14>
Prepare a solution of alkoxysilane monomer by mixing ECS (29.2 g), D1 (4.10 g) and D4 (38.8 g) in a 200 ml four-necked reaction flask equipped with a thermometer and reflux tube. did. To this solution, ECS (14.6 g), water (10.8 g), and a solution prepared by mixing oxalic acid (0.50 g) as a catalyst were added dropwise at 25 ° C. over 30 minutes. The mixture was further stirred at 25 ° C. for 30 minutes. Thereafter, the mixture was heated using an oil bath and refluxed for 30 minutes, and a previously prepared mixed solution of a methanol solution (1.20 g) having a D3 content of 92% by mass and ECS (0.90 g) was added. . The mixture was further refluxed for 30 minutes and then allowed to cool to obtain a polysiloxane solution (3) having a SiO ₂ equivalent concentration of 12% by mass.

<Synthesis Example 15>
In a 200 ml four-necked reaction flask equipped with a thermometer and a reflux tube, ECS (28.3 g), D2 (7.45 g), D4 (32.5 g) and D5 (4.07 g) were mixed, A solution of alkoxysilane monomer was prepared. To this solution, a solution prepared by mixing ECS (14.2 g), water (10.8 g), and oxalic acid (0.70 g) as a catalyst was added dropwise at 25 ° C. over 30 minutes, The mixture was further stirred at 25 ° C. for 30 minutes. Then, after heating using an oil bath and refluxing for 30 minutes, a previously prepared mixed solution of a methanol solution (1.20 g) having a D3 content of 92 mass% and ECS (0.90 g) was added. It was. The mixture was further refluxed for 30 minutes and then allowed to cool to obtain a polysiloxane solution (4) having a SiO ₂ equivalent concentration of 12% by mass.
Table 2 shows the polysiloxane polymer (polysiloxane solution).

"Production of liquid crystal composition (1)"
When L1 (11.5 g), R1 (1.73 g) and P1 (0.12 g) were mixed and heated to cool to 25 ° C., a uniform liquid crystal composition (1) exhibiting liquid crystallinity was obtained.
"Production of liquid crystal composition (2)"
L1 (12.0 g), R1 (2.40 g) and P1 (0.12 g) were mixed, and after heating, cooling to 25 ° C. gave a uniform liquid crystal composition (2) exhibiting liquid crystallinity.

"Production of liquid crystal display elements and evaluation of liquid crystal orientation (glass substrate)"
The liquid crystal aligning agent of the Example or comparative example mentioned later was pressure-filtered with the membrane filter with a pore diameter of 1 micrometer, and the liquid crystal display element (reverse type element) was produced. Specifically, this solution was spun onto the ITO surface of a glass substrate with 100 × 100 mm ITO electrodes (length: 100 mm, width: 100 mm, thickness: 0.7 mm) washed with pure water and IPA (isopropyl alcohol). Coating was performed on a hot plate at 100 ° C. for 5 minutes and in a heat circulation type clean oven at 230 ° C. for 30 minutes to obtain an ITO substrate with a vertical liquid crystal alignment film having a film thickness of 100 nm. Two ITO substrates with the obtained vertical liquid crystal alignment film were prepared, and a 6 μm spacer was applied to the vertical liquid crystal alignment film surface of one of the substrates. Thereafter, the liquid crystal composition is dropped by the ODF method onto the surface of the vertical liquid crystal alignment film coated with the spacer of the substrate, and then bonded so that the interface of the vertical liquid crystal alignment film of the other substrate faces. The liquid crystal display element was obtained.

Using a metal halide lamp with an illuminance of 60 mW on the liquid crystal display element before the above treatment, a wavelength of 350 nm or less was cut, and ultraviolet irradiation of 7 J / cm ^{2 in} terms of 365 nm was performed to obtain a liquid crystal display element. The inside of the irradiation device when the liquid crystal display element was irradiated with ultraviolet rays was controlled at 25 ° C.
The liquid crystal orientation was evaluated using this liquid crystal display element. The liquid crystal orientation was observed with a polarizing microscope (ECLIPSE E600WPOL, manufactured by Nikon Corporation) to confirm whether or not the liquid crystal was vertically aligned. Specifically, a liquid crystal in which the liquid crystal is aligned vertically is regarded as excellent in this evaluation (good display in Tables 7 to 10).

"Production of liquid crystal display elements and evaluation of liquid crystal orientation (plastic substrate)"
The liquid crystal aligning agent of the Example or comparative example mentioned later was pressure-filtered with the membrane filter with a pore diameter of 1 micrometer, and the liquid crystal display element was produced. Specifically, this solution was washed with pure water on a 150 × 150 mm ITO (polyethylene terephthalate) substrate with an ITO electrode (length: 150 mm, width: 150 mm, thickness: 0.2 mm) on a bar coater. Then, heat treatment was performed at 100 ° C. for 5 minutes on a hot plate and at 180 ° C. for 1 minute in a heat circulation type clean oven to obtain an ITO substrate with a vertical liquid crystal alignment film having a film thickness of 100 nm. . Two ITO substrates with the obtained vertical liquid crystal alignment film were prepared, and a 6 μm spacer was applied to the vertical liquid crystal alignment film surface of one of the substrates. Thereafter, the liquid crystal composition is dropped by the ODF method onto the surface of the vertical liquid crystal alignment film coated with the spacer of the substrate, and then bonded so that the interface of the vertical liquid crystal alignment film of the other substrate faces. The liquid crystal display element was obtained.
Using a metal halide lamp with an illuminance of 60 mW, the obtained liquid crystal display element before treatment was cut at a wavelength of 350 nm or less, and irradiated with ultraviolet rays at 7 J / cm ^{2 in} terms of 365 nm to obtain a liquid crystal display element. The inside of the irradiation apparatus when irradiating a liquid crystal cell with ultraviolet rays was controlled at 25 ° C.
The liquid crystal orientation was evaluated using this liquid crystal display element. The liquid crystal orientation was observed with a polarizing microscope (ECLIPSE E600WPOL, manufactured by Nikon Corporation) to confirm whether or not the liquid crystal was vertically aligned. Specifically, the liquid crystal aligned vertically was regarded as excellent in evaluation (good display in Tables 7 to 10).

"Evaluation of optical properties (transparency and scattering properties) (glass substrate)"
The liquid crystal display element (glass substrate) was measured by measuring the transmittance in a state where no voltage was applied. Specifically, the transmittance was measured under the conditions of UV-3600 (manufactured by Shimadzu Corporation) as a measuring device, 25 ° C., the glass substrate with the ITO electrode as a reference, and a scan wavelength of 300 to 800 nm. The evaluation was performed at a transmittance of a wavelength of 450 nm, and the higher the transmittance, the better the evaluation (the transmittance values are shown in Tables 7 to 10).
The scattering characteristics at the time of voltage application were performed by applying 40V to the liquid crystal display element by AC driving and visually observing the alignment state of the liquid crystal. Specifically, those in which the element was clouded, that is, those in which scattering characteristics were obtained were regarded as being excellent in evaluation (good display in Tables 7 to 10).

"Evaluation of optical properties (transparency and scattering properties) (plastic substrate)"
Using a liquid crystal display element (plastic substrate), the transmittance was measured by applying no voltage. Specifically, UV-3600 (manufactured by Shimadzu Corporation) was used as a measurement apparatus, and the transmittance was measured under the conditions of 25 ° C., the above-mentioned PET substrate with an ITO electrode as a reference, and a scan wavelength of 300 to 800 nm. Evaluation was performed at a transmittance of a wavelength of 450 nm, and the higher the transmittance, the better the evaluation.
The scattering characteristics at the time of voltage application were performed by applying 40V to the liquid crystal display element by AC driving and visually observing the alignment state of the liquid crystal. Specifically, a device in which the element was clouded, that is, a device having a scattering characteristic, was regarded as excellent in evaluation (good display in Tables 7 to 9).

"Evaluation of adhesion between liquid crystal layer and vertical liquid crystal alignment film (glass substrate)"
The liquid crystal display element was stored in a high-temperature and high-humidity tank having a temperature of 80 ° C. and a humidity of 90% for 24 hours, and the presence or absence of bubbles in the element and peeling of the element were confirmed. At this time, the case where no bubbles were observed in the device and the device was not peeled off (the liquid crystal layer and the vertical liquid crystal alignment film were peeled off) was excellent in this evaluation (Tables 7 to 10). Good display).
Tables 7 to 10 show the results of adhesion between the liquid crystal layer of this liquid crystal display element and the vertical liquid crystal alignment film.

"Evaluation of adhesion between liquid crystal layer and vertical liquid crystal alignment film (plastic substrate)"
The liquid crystal display element was stored in a high-temperature and high-humidity tank having a temperature of 80 ° C. and a humidity of 90% for 24 hours, and the presence or absence of bubbles in the element and peeling of the element were confirmed. At that time, the case where no bubbles were observed in the device and the device was not peeled off (the liquid crystal layer and the vertical liquid crystal alignment film were peeled off) was excellent in this evaluation (Tables 7 to 9). Good display).

<Example 1>
NMP (9.60 g), BCS (9.40 g), M2 (0.15 g) and K1 (0.08 g) were added to the polyamic acid solution (1) (6.00 g) obtained in Synthesis Example 1. The liquid crystal aligning agent (1) was obtained by stirring at 25 ° C. for 5 hours. This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.
Using the liquid crystal aligning agent (1) and the liquid crystal composition (1), preparation of the above-mentioned liquid crystal display element, evaluation of liquid crystal alignment (glass substrate), evaluation of optical properties (glass substrate), and evaluation of adhesion ( Glass substrate).

<Example 2>
NMP (7.50 g) and BCS (12.1 g) were added to the polyamic acid solution (2) (6.20 g) obtained in Synthesis Example 2, and the mixture was stirred at 25 ° C. for 5 hours. 2) was obtained. This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.
Using the liquid crystal aligning agent (2) and the liquid crystal composition (1), production of the above-mentioned liquid crystal display element, evaluation of liquid crystal alignment (glass substrate, plastic substrate), evaluation of optical properties (glass substrate, plastic substrate), and Evaluation of adhesion (glass substrate, plastic substrate) was performed.

<Example 3>
Using the liquid crystal aligning agent (2) and the liquid crystal composition (2) obtained in Example 2, preparation of the above-mentioned liquid crystal display element, evaluation of liquid crystal orientation (glass substrate), evaluation of optical properties (glass substrate) ) And adhesion evaluation (glass substrate).

<Example 4>
NMP (13.4 g) was added to the polyimide powder (3) (1.55 g) obtained in Synthesis Example 3, and dissolved by stirring at 70 ° C. for 24 hours. To this solution, BCS (10.9 g) was added and stirred at 25 ° C. for 5 hours to obtain a liquid crystal aligning agent (3). This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.
Using the liquid crystal aligning agent (3) and the liquid crystal composition (1), preparation of the above-mentioned liquid crystal display element, evaluation of liquid crystal alignment (glass substrate), evaluation of optical properties (glass substrate), and evaluation of adhesion ( Glass substrate).

<Example 5>
Using the liquid crystal aligning agent (3) and the liquid crystal composition (2) obtained in Example 4, preparation of the above-mentioned liquid crystal display element, evaluation of liquid crystal orientation (glass substrate), evaluation of optical properties (glass substrate) ) And adhesion evaluation (glass substrate).

<Example 6>
NEP (14.1 g) was added to the polyimide powder (3) (1.50 g) obtained in Synthesis Example 3, and dissolved by stirring at 70 ° C. for 24 hours. To this solution, PB (9.40 g), M2 (0.45 g) and K1 (0.15 g) were added and stirred at 25 ° C. for 5 hours to obtain a liquid crystal aligning agent (4). This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.
Using the liquid crystal aligning agent (4) and the liquid crystal composition (1), production of the above-mentioned liquid crystal display element, evaluation of liquid crystal alignment (glass substrate, plastic substrate), evaluation of optical properties (glass substrate, plastic substrate), and Evaluation of adhesion (glass substrate, plastic substrate) was performed.

<Example 7>
NEP (11.9 g) was added to the polyimide powder (3) (1.52 g) obtained in Synthesis Example 3, and dissolved by stirring at 70 ° C. for 24 hours. BCS (11.9g) and M1 (0.53g) were added to this solution, and it stirred at 25 degreeC for 5 hours, and obtained the liquid-crystal aligning agent (5). This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.
Using the liquid crystal aligning agent (5) and the liquid crystal composition (2), preparation of the above-mentioned liquid crystal display element, evaluation of liquid crystal alignment (glass substrate), evaluation of optical properties (glass substrate), and evaluation of adhesion ( Glass substrate).

<Example 8>
NEP (15.3 g) was added to the polyimide powder (4) (1.50 g) obtained in Synthesis Example 4, and dissolved by stirring at 70 ° C. for 24 hours. BCS (8.20g) was added to this solution, and it stirred at 25 degreeC for 5 hours, and obtained the liquid-crystal aligning agent (6). This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.
Using the liquid crystal aligning agent (6) and the liquid crystal composition (2), preparation of the liquid crystal display element, evaluation of liquid crystal alignment (glass substrate), evaluation of optical properties (glass substrate), and evaluation of adhesion ( Glass substrate).

<Example 9>
NEP (15.5 g) was added to the polyimide powder (4) (1.52 g) obtained in Synthesis Example 4, and dissolved by stirring at 70 ° C. for 24 hours. To this solution, PB (8.30 g), M2 (0.53 g) and K1 (0.15 g) were added and stirred at 25 ° C. for 5 hours to obtain a liquid crystal aligning agent (7). This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.
Using the liquid crystal aligning agent (7) and the liquid crystal composition (1), preparation of the liquid crystal display element, evaluation of liquid crystal alignment (glass substrate), evaluation of optical properties (glass substrate), and evaluation of adhesion ( Glass substrate).

<Example 10>
To the polyimide powder (4) obtained in Synthesis Example 4 (1.55 g), γ-BL (13.4 g) was added and dissolved by stirring at 70 ° C. for 24 hours. BCS (10.9g) and M3 (0.23g) were added to this solution, and it stirred at 25 degreeC for 5 hours, and obtained the liquid-crystal aligning agent (8). This liquid crystal aligning agent was confirmed to be a uniform solution with no abnormalities such as turbidity and precipitation.
Using the liquid crystal aligning agent (8) and the liquid crystal composition (1), preparation of the above-mentioned liquid crystal display element, evaluation of liquid crystal alignment (glass substrate), evaluation of optical properties (glass substrate), and evaluation of adhesion ( Glass substrate).

<Example 11>
NMP (16.5 g) was added to the polyimide powder (5) (1.50 g) obtained in Synthesis Example 5 and dissolved by stirring at 70 ° C. for 24 hours. BCS (7.10g) and K1 (0.23g) were added to this solution, and it stirred at 25 degreeC for 5 hours, and obtained the liquid-crystal aligning agent (9). This liquid crystal aligning agent was confirmed to be a uniform solution with no abnormalities such as turbidity and precipitation.
Using the liquid crystal aligning agent (9) and the liquid crystal composition (2), production of the above-mentioned liquid crystal display element, evaluation of liquid crystal alignment (glass substrate, plastic substrate), evaluation of optical properties (glass substrate, plastic substrate) And adhesion (glass substrate, plastic substrate) were evaluated.

<Example 12>
NEP (16.5 g) was added to the polyimide powder (5) (1.50 g) obtained in Synthesis Example 5, and dissolved by stirring at 70 ° C. for 24 hours. BCS (7.10g) and M3 (0.08g) were added to this solution, and it stirred at 25 degreeC for 5 hours, and obtained the liquid-crystal aligning agent (10). This liquid crystal aligning agent was confirmed to be a uniform solution with no abnormalities such as turbidity and precipitation.
Using the liquid crystal aligning agent (10) and the liquid crystal composition (1), production of the above-mentioned liquid crystal display element, evaluation of liquid crystal alignment (glass substrate), evaluation of optical properties (glass substrate), and evaluation of adhesion ( Glass substrate).

<Example 13>
NEP (15.3 g) was added to the polyimide powder (5) (1.50 g) obtained in Synthesis Example 5, and dissolved by stirring at 70 ° C. for 24 hours. To this solution, BCS (2.40 g), PB (5.90 g), M2 (0.45 g) and K1 (0.08 g) were added and stirred at 25 ° C. for 5 hours to obtain a liquid crystal aligning agent (11). Got. This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.
Using the liquid crystal aligning agent (11) and the liquid crystal composition (1), production of the above-described liquid crystal display element / evaluation of liquid crystal alignment (glass substrate, plastic substrate), evaluation of optical properties (glass substrate, plastic substrate), and Evaluation of adhesion (glass substrate, plastic substrate) was performed.

<Example 14>
To the polyimide powder (5) obtained in Synthesis Example 5 (1.50 g), γ-BL (17.6 g) was added and dissolved by stirring at 70 ° C. for 24 hours. To this solution, BCS (5.90 g) and M1 (0.60 g) were added and stirred at 25 ° C. for 5 hours to obtain a liquid crystal aligning agent (12). This liquid crystal aligning agent was confirmed to be a uniform solution with no abnormalities such as turbidity and precipitation.
Using the liquid crystal aligning agent (12) and the liquid crystal composition (2), preparation of the above-mentioned liquid crystal display element, evaluation of liquid crystal alignment (glass substrate), evaluation of optical properties (glass substrate), and evaluation of adhesion ( Glass substrate).

<Example 15>
NEP (13.4 g) was added to the polyimide powder (6) (1.55 g) obtained in Synthesis Example 6, and dissolved by stirring at 70 ° C. for 24 hours. To this solution, PB (10.9 g), M2 (0.47 g) and K1 (0.08 g) were added and stirred at 25 ° C. for 5 hours to obtain a liquid crystal aligning agent (13). This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.
Using the liquid crystal aligning agent (13) and the liquid crystal composition (1), preparation of the liquid crystal display element, evaluation of liquid crystal alignment (glass substrate), evaluation of optical properties (glass substrate), and evaluation of adhesion ( Glass substrate).

<Example 16>
NMP (14.4 g) was added to the polyimide powder (6) (1.53 g) obtained in Synthesis Example 6, and dissolved by stirring at 70 ° C. for 24 hours. BCS (9.60 g) and K1 (0.15 g) were added to this solution, and the mixture was stirred at 25 ° C. for 5 hours to obtain a liquid crystal aligning agent (14). This liquid crystal aligning agent was confirmed to be a uniform solution with no turbidity or precipitation.
Using the liquid crystal aligning agent (14) and the liquid crystal composition (2), preparation of the liquid crystal display element, evaluation of liquid crystal alignment (glass substrate), evaluation of optical properties (glass substrate), and evaluation of adhesion ( Glass substrate).

<Example 17>
NEP (15.8 g) was added to the polyimide powder (7) (1.55 g) obtained in Synthesis Example 7 and dissolved by stirring at 70 ° C. for 24 hours. To this solution, PB (8.50 g), M2 (0.39 g) and K1 (0.16 g) were added and stirred at 25 ° C. for 5 hours to obtain a liquid crystal aligning agent (15). This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.
Using the liquid crystal aligning agent (15) and the liquid crystal composition (1), production of the above-mentioned liquid crystal display element, evaluation of liquid crystal alignment (glass substrate, plastic substrate), evaluation of optical properties (glass substrate, plastic substrate), and Evaluation of adhesion (glass substrate, plastic substrate) was performed.

<Example 18>
NMP (16.5 g) was added to the polyimide powder (7) (1.50 g) obtained in Synthesis Example 7, and dissolved by stirring at 70 ° C. for 24 hours. To this solution, BCS (7.10 g), M3 (0.15 g) and K1 (0.08 g) were added and stirred at 25 ° C. for 5 hours to obtain a liquid crystal aligning agent (16). This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.
Using the liquid crystal aligning agent (16) and the liquid crystal composition (1), production of the above-mentioned liquid crystal display element, evaluation of liquid crystal alignment (glass substrate), evaluation of optical properties (glass substrate), and evaluation of adhesion ( Glass substrate).

<Example 19>
Γ-BL (14.6 g) was added to the polyimide powder (8) (1.55 g) obtained in Synthesis Example 8, and dissolved by stirring at 70 ° C. for 24 hours. To this solution, BCS (9.70 g) was added and stirred at 25 ° C. for 5 hours to obtain a liquid crystal aligning agent (17). This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.
Using the liquid crystal aligning agent (17) and the liquid crystal composition (2), preparation of the above-mentioned liquid crystal display element, evaluation of liquid crystal alignment (glass substrate), evaluation of optical properties (glass substrate), and evaluation of adhesion ( Glass substrate).

<Example 20>
NEP (13.0 g) was added to the polyimide powder (8) (1.51 g) obtained in Synthesis Example 8, and dissolved by stirring at 70 ° C. for 24 hours. To this solution, BCS (10.6 g), M2 (0.45 g) and K1 (0.15 g) were added and stirred at 25 ° C. for 5 hours to obtain a liquid crystal aligning agent (18). This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.
Using the liquid crystal aligning agent (18) and the liquid crystal composition (1), preparation of the liquid crystal display element, evaluation of liquid crystal alignment (glass substrate), evaluation of optical properties (glass substrate), and evaluation of adhesion ( Glass substrate).

<Example 21>
ECS (3.70 g) and BCS (11.3 g) were added to the polysiloxane solution (1) (15.0 g) obtained in Synthesis Example 12, and the mixture was stirred at 25 ° C. for 5 hours. 19) was obtained. This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.
Using the liquid crystal aligning agent (19) and the liquid crystal composition (1), production of the above-mentioned liquid crystal display element / evaluation of liquid crystal alignment (glass substrate, plastic substrate), evaluation of optical properties (glass substrate, plastic substrate), And adhesion (glass substrate, plastic substrate) were evaluated.

<Example 22>
Using the liquid crystal aligning agent (19) and the liquid crystal composition (2) obtained in Example 20, preparation of the above-mentioned liquid crystal display element, evaluation of liquid crystal alignment (glass substrate), evaluation of optical properties (glass substrate) ) And adhesion evaluation (glass substrate).

<Example 23>
ECS (10.0 g) and BCS (6.00 g) were added to the polysiloxane solution (2) (16.0 g) obtained in Synthesis Example 13, and the mixture was stirred at 25 ° C. for 5 hours. 20) was obtained. This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.
Using the liquid crystal aligning agent (20) and the liquid crystal composition (1), production of the above-mentioned liquid crystal display element, evaluation of liquid crystal alignment (glass substrate), evaluation of optical properties (glass substrate), and evaluation of adhesion ( Glass substrate).

<Example 24>
Using the liquid crystal aligning agent (20) and the liquid crystal composition (2) obtained in Example 23, preparation of the above-mentioned liquid crystal display element, evaluation of liquid crystal alignment (glass substrate), evaluation of optical properties (glass substrate) ) And adhesion evaluation (glass substrate).

<Example 25>
ECS (10.0 g), BCS (6.00 g) and M2 (0.24 g) were added to the polysiloxane solution (2) (10.0 g) obtained by the synthesis method of Synthesis Example 13, and 5 ° C. at 25 ° C. By stirring for a time, a liquid crystal aligning agent (21) was obtained. This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.
Using the liquid crystal aligning agent (21) and the liquid crystal composition (1), preparation of the liquid crystal display element, evaluation of liquid crystal alignment (glass substrate), evaluation of optical properties (glass substrate), and evaluation of adhesion ( Glass substrate).

<Example 26>
ECS (9.70 g) and PB (5.80 g) were added to the polysiloxane solution (3) (15.5 g) obtained in Synthesis Example 14, and the mixture was stirred at 25 ° C. for 5 hours. 22) was obtained. This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.
Using the liquid crystal aligning agent (22) and the liquid crystal composition (1), preparation of the liquid crystal display element, evaluation of liquid crystal alignment (glass substrate), evaluation of optical properties (glass substrate), and evaluation of adhesion ( Glass substrate).

<Example 27>
Using the liquid-crystal aligning agent (22) and liquid-crystal composition (2) obtained in Example 26, preparation of the above-mentioned liquid crystal display element, evaluation of liquid crystal orientation (glass substrate), evaluation of optical characteristics (glass substrate) ) And adhesion evaluation (glass substrate).

<Comparative Example 1>
NMP (7.90 g) and BCS (12.7 g) are added to the polyamic acid solution (9) (6.50 g) having a resin solid content concentration of 25% by mass obtained in Synthesis Example 9, and the mixture is stirred at 25 ° C. for 5 hours. As a result, a liquid crystal aligning agent (23) was obtained. This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.
Using the liquid crystal aligning agent (23) and the liquid crystal composition (1), preparation of the above-mentioned liquid crystal display element, evaluation of liquid crystal alignment (glass substrate), evaluation of optical properties (glass substrate), and evaluation of adhesion ( Glass substrate).

<Comparative example 2>
Using the liquid crystal aligning agent (23) and the liquid crystal composition (2) obtained in Comparative Example 1, preparation of the above-mentioned liquid crystal display element, evaluation of liquid crystal alignment (glass substrate), evaluation of optical properties (glass substrate) ) And adhesion evaluation (glass substrate).

<Comparative Example 3>
NMP (14.6 g) was added to the polyimide powder (10) (1.70 g) obtained in Synthesis Example 10, and dissolved by stirring at 70 ° C. for 24 hours. To this solution, BCS (12.0 g) was added and stirred at 25 ° C. for 5 hours to obtain a liquid crystal aligning agent (24). This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.
Using the liquid crystal aligning agent (24) and the liquid crystal composition (1), preparation of the above-mentioned liquid crystal display element, evaluation of liquid crystal alignment (glass substrate), evaluation of optical properties (glass substrate), and evaluation of adhesion ( Glass substrate).

<Comparative example 4>
Using the liquid crystal aligning agent (24) and the liquid crystal composition (2) obtained in Comparative Example 3, preparation of the above-mentioned liquid crystal display element, evaluation of liquid crystal alignment (glass substrate), evaluation of optical properties (glass substrate) ) And adhesion evaluation (glass substrate).

<Comparative Example 5>
NMP (14.2 g) was added to the polyimide powder (11) (1.65 g) obtained in Synthesis Example 11, and dissolved by stirring at 70 ° C. for 24 hours. BCS (11.6g) was added to this solution, and it stirred at 25 degreeC for 5 hours, and obtained the liquid-crystal aligning agent (25). This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.
Using the liquid crystal aligning agent (25) and the liquid crystal composition (1), preparation of the above-mentioned liquid crystal display element, evaluation of liquid crystal alignment (glass substrate), evaluation of optical properties (glass substrate), and evaluation of adhesion ( Glass substrate).

<Comparative Example 7>
ECS (4.00 g) and BCS (12.0 g) were added to the polysiloxane solution (4) (16.0 g) obtained in Synthesis Example 15, and the mixture was stirred at 25 ° C. for 5 hours. 26) was obtained. This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.
Using the liquid crystal aligning agent (26) and the liquid crystal composition (1), preparation of the above-mentioned liquid crystal display element, evaluation of liquid crystal alignment (glass substrate), evaluation of optical properties (glass substrate), and evaluation of adhesion ( Glass substrate).

<Comparative Example 8>
Using the liquid crystal aligning agent (26) and the liquid crystal composition (2) obtained in Comparative Example 7, preparation of the above-mentioned liquid crystal display element, evaluation of liquid crystal alignment (glass substrate), evaluation of optical properties (glass substrate) ) And adhesion evaluation (glass substrate).

* 1: An alignment defect was observed in the device.
* 2: The liquid crystal was not vertically aligned.
* 3: Since the liquid crystal was not vertically aligned, measurement was not possible.
* 4: Bubbles were observed in the element.
* 5: The element peeled between the liquid crystal layer and the vertical liquid crystal alignment film.

As can be seen from the above, the liquid crystal display elements of the examples have higher liquid crystal vertical alignment than the comparative examples, and good optical characteristics, that is, transparency when no voltage is applied and scattering characteristics when a voltage is applied. Good, and furthermore, the adhesion between the liquid crystal layer and the vertical liquid crystal alignment film is high. In particular, when the content of the polymerizable compound in the liquid crystal composition is large, that is, in the example, even when the liquid crystal composition (2) is used, the vertical alignment of the liquid crystal is high and good optical characteristics, that is, The transparency when no voltage was applied and the scattering characteristics when a voltage was applied were good.
Specifically, a comparison between Examples and Comparative Examples having different side chain structures in the polymer, that is, a comparison between Example 2 and Comparative Example 1, a comparison between Example 4 and Comparative Example 3, and an Example In comparison between No. 21 and Comparative Example 7, in the liquid crystal display element of the comparative example, alignment defects due to insufficient vertical alignment of the liquid crystal were observed and the transmittance when no voltage was applied was also lower than in the example. Further, since the liquid crystal composition (1) having a small content of the polymerizable compound in the liquid crystal composition is used, in the comparative example, the adhesion between the liquid crystal layer and the vertical liquid crystal alignment film is low, and the inside of the high temperature and high humidity tank In the liquid crystal display element, bubbles were observed.

Moreover, the liquid crystal composition (2) having a high content of the polymerizable compound in the liquid crystal composition was used, and only the side chain structure in the polymer was different between the specific side chain structure and the conventional side chain structure. Comparison of Example 3 and Comparative Example 2, Comparison of Example 5 and Comparative Example 4, and Comparison of Example 22 and Comparative Example 8 Although the adhesion between the liquid crystal layer and the vertical liquid crystal alignment film was excellent, the liquid crystal was not aligned vertically.
In addition, when the content of the side chain structure in the polymer is increased by using the conventional side chain structure, that is, in the liquid crystal display elements of Comparative Examples 5 and 6, the vertical alignment property of the liquid crystal and the voltage application Although the transmittance characteristics at the time were excellent, the liquid crystal display element was peeled off due to poor adhesion between the liquid crystal layer and the vertical liquid crystal alignment film when stored in a high temperature and high humidity tank.

The liquid crystal display element of the present invention is useful for a liquid crystal display for display purposes, and further for a light control window, an optical shutter element, etc. for houses, buildings, vehicles, etc. for controlling transmission and blocking of light.
The entire contents of the specification, claims, and abstract of Japanese Patent Application No. 2013-040398 filed on March 1, 2013 are incorporated herein as the disclosure of the specification of the present invention. Is.

Claims

A liquid crystal composition having a liquid crystal layer between a pair of substrates provided with electrodes and including a polymerizable compound that is polymerized by at least one of active energy rays and heat is disposed between the pair of substrates, At least one has a liquid crystal alignment film for vertically aligning liquid crystals, and the liquid crystal composition is cured in a state where a part or the whole of the liquid crystal composition exhibits liquid crystallinity, and a cured product composite of liquid crystal and a polymerizable compound A liquid crystal display element obtained by forming a liquid crystal display element, wherein the liquid crystal alignment film comprises a liquid crystal alignment film obtained from a liquid crystal aligning agent containing a polymer having a structure represented by the following formula [1].

(Y 1 represents a single bond, — (CH 2 ) a — (a is an integer of 1 to 15), —O—, —CH 2 O—, —COO— or OCO—, and Y 2 represents a single bond. Or (CH 2 ) b — (b is an integer of 1 to 15), Y 3 is a single bond, — (CH 2 ) c — (c is an integer of 1 to 15), —O—, —CH 2 O—, —COO— or OCO—, wherein Y 4 is a divalent cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring and a heterocyclic ring, or 2 having 17 to 51 carbon atoms having a steroid skeleton. An arbitrary hydrogen atom on the cyclic group is an alkyl group having 1 to 3 carbon atoms, an alkoxyl group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, or 1 carbon atom may be substituted with a fluorine-containing alkoxyl group or a fluorine atom ~ 3, Y 5 is a benzene ring A divalent cyclic group selected from the group consisting of a cyclohexane ring and a heterocyclic ring, wherein any hydrogen atom on the cyclic group is an alkyl group having 1 to 3 carbon atoms, an alkoxyl group having 1 to 3 carbon atoms, carbon May be substituted with a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxyl group having 1 to 3 carbon atoms, or a fluorine atom, n represents an integer of 0 to 4, and Y 6 has 1 to 18 carbon atoms. An alkyl group, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxyl group having 1 to 18 carbon atoms, or a fluorine-containing alkoxyl group having 1 to 18 carbon atoms).
The liquid crystal aligning agent includes at least one polymer selected from the group consisting of acrylic polymer, methacrylic polymer, novolak resin, polyhydroxystyrene, polyimide precursor, polyimide, polyamide, polyester, cellulose, and polysiloxane. The liquid crystal display element according to claim 1, which is an agent.
Liquid crystal alignment treatment, wherein the liquid crystal alignment treatment agent includes at least one polymer selected from the group consisting of a polyimide precursor obtained by using a diamine compound having a side chain of the formula [1] as part of the raw material and polyimide. The liquid crystal display element according to claim 2, which is an agent.
The liquid crystal display element according to claim 3, wherein the diamine compound is at least one polymer selected from the group consisting of a polyimide precursor obtained by using a diamine compound represented by the following formula [1a] and a polyimide.

(Y 1 to Y 6 are as defined in the above formula [1]. M represents an integer of 1 to 4).
The liquid crystal aligning agent contains at least one polymer selected from the group consisting of a polyimide precursor and a polyimide obtained by using a tetracarboxylic acid component represented by the following formula [2] as a part of the raw material. The liquid crystal display element according to any one of claims 2 to 4, which is an alignment treatment agent.

(Z 1 represents a structure selected from the group consisting of the following formulas [2a] to [2j]).

(Z 2 to Z 5 represent a hydrogen atom, a methyl group, a chlorine atom or a benzene ring, and may be the same or different, and Z 6 and Z 7 represent a hydrogen atom or a methyl group, and each represents the same. Or different.)
The liquid crystal aligning agent is a polysiloxane obtained by polycondensation of an alkoxysilane represented by the following formula [A1], an alkoxysilane represented by the formula [A1] and the following formula [A2] or the formula [A3]. Among polysiloxanes obtained by polycondensation of alkoxysilanes containing any one of them, or polysiloxanes obtained by polycondensation of alkoxysilanes represented by formula [A1], formula [A2] and formula [A3] The liquid crystal display element of Claim 2 which is a liquid-crystal aligning agent containing any one of these.

(A 1 represents the structure represented by the formula [1], A 2 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, A 3 represents an alkyl group having 1 to 5 carbon atoms, m Represents an integer of 1 or 2, n represents an integer of 0 to 2, and p represents an integer of 0 to 3, where m + n + p represents an integer of 4.

(B 1 represents an organic group having 2 to 12 carbon atoms having a vinyl group, an epoxy group, an amino group, a mercapto group, an isocyanate group, a methacryl group, an acrylic group, a ureido group or a cinnamoyl group, and B 2 represents a hydrogen atom or An alkyl group having 1 to 5 carbon atoms, B 3 represents an alkyl group having 1 to 5 carbon atoms, m represents an integer of 1 or 2, n represents an integer of 0 to 2, and p represents 0 to 3 represents an integer of 3 (where m + n + p represents an integer of 4).

(D 1 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, D 2 represents an alkyl group having 1 to 5 carbon atoms, and n represents an integer of 0 to 3).
The liquid crystal display element according to any one of claims 1 to 6, wherein the liquid crystal aligning agent contains a compound represented by the following formula [6].

(X 1 represents at least one structure selected from the group consisting of the structures represented by the following formulas [6a-1] to [6a-7]. X 2 represents a single bond, —CH 2 —, —O—. , —NH—, —N (CH 3 ) —, —CONH—, —NHCO—, —CH 2 O—, —OCH 2 —, —COO—, —OCO—, —CON (CH 3 ) — and —N At least one linking group selected from the group consisting of (CH 3 ) CO—, wherein X 3 is an alkylene group having 1 to 20 carbon atoms, — (CH 2 —CH 2 —O) p — (p is 1 to Selected from the group consisting of organic groups having a benzene ring or a cyclohexane ring having 6 to 20 carbon atoms, and — (CH 2 —O—) q — (q represents an integer of 1 to 10) It indicates at least one kind that time, any -CH 2 in the alkylene group -. group, - OO -, - OCO -, - CONH-, NHCO -, - CO -, - S -, - SO 2 -, - CF 2 -, - C (CF 3) 2 -, - Si (CH 3) 2 -, The hydrogen atom bonded to any carbon atom may be replaced by —OSi (CH 3 ) 2 — or —Si (CH 3 ) 2 O—, and the hydroxyl group (OH group), carboxyl group (COOH group) X 4 represents a single bond, at least one linking group selected from the group consisting of —CH 2 —, —OCH 2 — and —O—CH 2 —CH 2 —. X 5 represents at least one structure selected from the group consisting of structures represented by the following formulas [6b-1] to [6b-8], n represents an integer of 1 to 3, and m represents 1 Represents an integer of ~ 3.)

(A 1 represents a hydrogen atom or an alkylene group having 1 to 5 carbon atoms. A 2 , A 3 , A 5 , A 6 and A 9 each independently represents a hydrogen atom or an alkylene group having 1 to 3 carbon atoms. A 4 , A 7 and A 8 each independently represents an alkylene group having 1 to 3 carbon atoms.)

(B 1 represents a hydrogen atom or a benzene ring. B 2 represents at least one cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring and a heterocyclic ring. B 3 represents an alkylene having 1 to 12 carbon atoms. And at least one selected from the group consisting of a group, a fluorine-containing alkylene group having 1 to 12 carbon atoms, an alkoxyl group having 1 to 12 carbon atoms, and a fluorine-containing alkoxyl group having 1 to 12 carbon atoms.)
The liquid crystal display element according to any one of claims 1 to 7, wherein the polymer having the structure represented by the formula [1] has a weight average molecular weight of 10,000 to 150,000.
The liquid crystal display element according to any one of claims 1 to 8, wherein the substrate of the liquid crystal display element is a glass substrate or a plastic substrate.
10. A liquid crystal alignment film used for the liquid crystal display element according to claim 1.
A liquid crystal alignment treatment agent for forming the liquid crystal alignment film according to claim 10.