CN106462011B

CN106462011B - Liquid crystal display element, liquid crystal alignment film, and liquid crystal alignment treatment agent

Info

Publication number: CN106462011B
Application number: CN201580027656.5A
Authority: CN
Inventors: 三木徳俊; 大村浩之; 桥本淳; 保坂和義
Original assignee: Nissan Chemical Corp
Current assignee: Nissan Chemical Corp
Priority date: 2014-03-27
Filing date: 2015-03-24
Publication date: 2021-11-12
Anticipated expiration: 2035-03-24
Also published as: WO2015146987A1; CN106462011A; TWI735408B; KR102345961B1; TW201602242A; JPWO2015146987A1; JP6575510B2; KR20160138184A

Abstract

A liquid crystal display element having a liquid crystal layer between a pair of substrates having electrodes, wherein a liquid crystal composition containing a polymerizable compound that is polymerized by at least one of an active energy ray and heat is disposed between the pair of substrates, at least one of the substrates is provided with a liquid crystal alignment film that vertically aligns liquid crystal, and the liquid crystal composition is cured in a state in which a part or all of the liquid crystal composition exhibits liquid crystallinity to form a cured product composite of the liquid crystal and the polymerizable compound, thereby obtaining the liquid crystal display element, wherein the liquid crystal alignment film contains a liquid crystal alignment film obtained from a liquid crystal alignment treatment agent containing a liquid crystal alignment film represented by the following formula [1]]A solvent represented by the formula [2-1] and containing a compound having a structure selected from the group consisting of]And formula [2-2]Polymers of at least 1 structure of the group consisting of the structures shown. Formula [1](S¹And S²Represents an alkyl group having 1 to 4 carbon atoms. ) Formula [2-1](Y¹、Y²、Y³Represents a single bond or the like, Y⁴、Y⁵Represents a benzene ring or the like, n represents 0 to 4, Y⁶Represents an alkyl group having 1 to 18 carbon atoms. ) Formula [2-2]](Y⁷Represents a single bond or the like, Y⁸Represents an alkyl group having 8 to 22 carbon atoms, etc. )

Description

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

Technical Field

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

Background

As a liquid crystal display element using a liquid crystal material, a TN (Twisted Nematic) mode has been put to practical use. In this mode, light is switched by utilizing the optical rotation characteristics of liquid crystal, and a polarizing plate is used as a liquid crystal display element. However, the use efficiency of light becomes low due to the use of the polarizing plate.

As a Liquid crystal display element having high light use efficiency without using a polarizing plate, there is a Liquid crystal display element that switches between a transmissive state (also referred to as a transparent state) and a scattering state of Liquid crystal, and generally, a Liquid crystal display element using polymer Dispersed Liquid crystal (also referred to as pdlc (polymer Dispersed Liquid crystal) or polymer Network Liquid crystal (pnlc) is known.

A liquid crystal display element using these elements is manufactured by a process including a step of forming a liquid crystal layer between a pair of substrates having electrodes, the process including: a liquid crystal composition containing a polymerizable compound that is polymerized by at least one of an active energy ray and heat is disposed between the pair of substrates, and the liquid crystal composition is cured in a state in which a part or all of the liquid crystal composition exhibits liquid crystallinity, thereby forming a cured product composite of a liquid crystal and the polymerizable compound. The liquid crystal display element controls the transmission state and the scattering state of the liquid crystal by application of a voltage.

In a conventional liquid crystal display element using PDLC or PNLC, liquid crystal molecules are oriented in random directions when no voltage is applied, and therefore, the liquid crystal display element is in a white turbid (scattering) state, and the liquid crystal molecules are aligned in the electric field direction when a voltage is applied, and light is transmitted through the liquid crystal display element, thereby assuming a transmissive state (also referred to as a normal type element). However, since this standard type element requires a constant voltage application in order to obtain a transmissive state, power consumption increases when the element is used in many applications such as a window glass or the like in which the element is used in a transparent state.

As for the standard type element, a liquid crystal display element (also referred to as a reverse type element) using PDLC which exhibits a transmissive state when no voltage is applied and a scattering state when a voltage is applied has been reported (for example, see patent documents 1 and 2).

Documents of the prior art

Patent document

Patent document 1: japanese patent No. 2885116

Patent document 2: japanese patent No. 4132424

Disclosure of Invention

Problems to be solved by the invention

The reverse type element uses a liquid crystal alignment film (also referred to as a vertical liquid crystal alignment film) for vertically aligning liquid crystal. In this case, since the vertical liquid crystal alignment film has high hydrophobicity, the adhesion between the liquid crystal layer and the liquid crystal alignment film is low. Therefore, it is necessary to introduce 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 into the liquid crystal composition used for the reverse type cell. However, when a large amount of the polymerizable compound is introduced, the vertical alignment of the liquid crystal is impaired, and the transparency when no voltage is applied and the scattering property when a voltage is applied are significantly reduced. Therefore, a liquid crystal alignment film used in a reverse cell needs to have high liquid crystal vertical alignment properties.

As a liquid crystal alignment film mainly used at present, an organic film made of a polyimide polymer, which has excellent durability and is suitable for controlling a pretilt angle of liquid crystal, can be used. The polyimide polymer is polyamic acid as a polyimide precursor and/or polyimide obtained by imidizing polyamic acid, and the liquid crystal alignment film is produced from a liquid crystal alignment treatment agent using these polymers. Since the solvents of the liquid crystal aligning agent using the polyimide-based polymer have low solubility in solvents, highly polar solvents such as N-methyl-2-pyrrolidone (also referred to as NMP) are used. These highly polar solvents have a high boiling point, and for example, NMP has a boiling point of 200 ℃. Therefore, in order to produce a liquid crystal alignment film using a liquid crystal alignment treatment agent using NMP as a solvent, it is necessary to perform firing at a high temperature of about 200 ℃ near the boiling point of NMP in order to eliminate NMP remaining in the liquid crystal alignment film.

On the other hand, when a plastic substrate having low heat resistance and being thin and light is used as a substrate of a liquid crystal display element, the baking for producing a liquid crystal alignment film needs to be performed at a lower temperature. Similarly, it is also required to reduce the energy consumption in the production of the liquid crystal display element by lowering the firing temperature.

In addition, the liquid crystal display element is required to have high coating film uniformity of the liquid crystal alignment film. That is, it is necessary to eliminate coating defects such as shrinkage and pinholes, and coating unevenness. When the coating uniformity of the liquid crystal alignment film is low, the coating film is poor, and the coating film unevenness becomes a display defect or display unevenness, which degrades the display characteristics of the liquid crystal display element. Therefore, it is necessary to provide the liquid crystal aligning agent with high wetting and diffusing properties with respect to a glass substrate or a plastic substrate, which is a substrate of the liquid crystal display element.

The present invention aims to provide a liquid crystal display element which has high vertical alignment of liquid crystal, can obtain good optical characteristics, has high adhesion between a liquid crystal layer and a vertical liquid crystal alignment film, has high coating film uniformity of the vertical liquid crystal alignment film, and is less likely to cause alignment defects associated with coating film defects such as shrinkage and pinholes.

Further, it is an object of the present invention to provide a liquid crystal alignment treatment agent which can be fired at a low temperature when a vertical liquid crystal alignment film used for a liquid crystal display element is produced.

Means for solving the problems

The inventors of the present invention conducted extensive studies and found that: the present inventors have found that a liquid crystal display element using a vertical liquid crystal alignment film obtained from a liquid crystal alignment treatment agent containing a solvent having a specific structure and a polymer having a side chain having a specific structure is extremely effective for achieving the above object, and completed the present invention. That is, the present invention has the following gist.

(1) A liquid crystal display element having a liquid crystal layer between a pair of substrates provided with electrodes, a liquid crystal composition containing a polymerizable compound that is polymerized by at least one of an active energy ray and heat is disposed between the pair of substrates, and at least one of the substrates is provided with a liquid crystal alignment film that vertically aligns liquid crystal, curing the liquid crystal composition in a state in which a part or all of the liquid crystal composition exhibits liquid crystallinity to form a cured product composite of the liquid crystal and the polymerizable compound, thereby obtaining the liquid crystal display element, wherein the liquid crystal alignment film comprises a liquid crystal alignment film obtained from a liquid crystal alignment treatment agent comprising a solvent represented by the following formula [1], and comprises a polymer having at least 1 structure selected from the group consisting of the structures represented by the following formulae [2-1] and [2-2 ].

(S¹And S²Each independently represents an alkyl group having 1 to 4 carbon atoms. )

(Y¹Represents a group selected from a single bond, - (CH)₂)_a- (a represents an integer of 1 to 15), -O-, -CH₂At least 1 of O-, -COO-and-OCO-; y is²Represents a single bond or- (CH)₂)_b- (b represents an integer of 1 to 15); y is³Represents a group selected from a single bond, - (CH)₂)_c- (c represents an integer of 1 to 15), -O-, -CH₂At least 1 of O-, -COO-and-OCO-; y is⁴At least 1 cyclic group selected from a benzene ring, a cyclohexane ring and a heterocyclic ring or a C17-51 organic group having a steroid skeleton, wherein any hydrogen atom in the cyclic group is optionally substituted by a C1-3 alkyl group, a C1-3 alkoxy group, a C1-3 fluoroalkyl group, a C1-3 fluoroalkoxy group or a fluorine atom; y is⁵Represents a benzene ring selected fromAt least 1 cyclic group in cyclohexane ring and hetero ring, any hydrogen atom on the cyclic group is optionally substituted by C1-3 alkyl, C1-3 alkoxy, C1-3 fluorine-containing alkyl, C1-3 fluorine-containing alkoxy or fluorine atom; n represents an integer of 0 to 4; y is⁶Represents at least 1 kind selected from alkyl with 1-18 carbon atoms, fluorine-containing alkyl with 1-18 carbon atoms, alkoxy with 1-18 carbon atoms and fluorine-containing alkoxy with 1-18 carbon atoms. )

-Y⁷-Y⁸ [2-2]

(Y⁷Represents a group selected from a single bond, -O-, -CH₂O-、-CONH-、-NHCO-、-CON(CH₃)-、-N(CH₃) At least 1 bonding group selected from CO-, -COO-and-OCO-; y is⁸Represents an alkyl group having 8 to 22 carbon atoms or a fluoroalkyl group having 6 to 18 carbon atoms. )

(2) The liquid crystal display element according to the above (1), wherein the solvent represented by the above formula [1] is at least 1 solvent selected from the group consisting of 2-butanone, 3-pentanone, 4-methyl-2-pentanone, and 2, 6-dimethyl-4-heptanone.

(3) The liquid crystal display element according to the above (1) or (2), wherein the polymer is at least 1 polymer selected from the group consisting of an acrylic polymer, a methacrylic polymer, a novolac resin, polyhydroxystyrene, a polyimide precursor, polyimide, polyamide, polyester, cellulose, and polysiloxane.

(4) The liquid crystal display element according to the item (3), wherein the polymer is at least 1 polymer selected from the group consisting of a polyimide precursor and a polyimide obtained by using a diamine having at least 1 side chain selected from the group consisting of structures represented by the formulae [2-1] and [2-2] as a part of raw materials.

(5) The liquid crystal display element according to the item (4), wherein the diamine is a diamine represented by the following formula [2 ].

(Y represents at least 1 structure selected from the group consisting of the structures represented by the formulae [2-1] and [2-2 ]; and n represents an integer of 1 to 4.)

(6) The liquid crystal display element according to any one of the above (3) to (5), wherein the polymer is at least 1 polymer selected from the group consisting of a polyimide precursor and a polyimide obtained by using a second diamine represented by the following formula [3] as a part of raw materials.

(X is at least 1 selected from the following structures represented by formulas [3a ] to [3d ], and m represents an integer of 1 to 4.)

-(CH₂)_a-OH [3a]

-(CH₂)_b-COOH [3b]

(formula [3a ]]Wherein a represents an integer of 0 to 4; formula [3b]Wherein b represents an integer of 0 to 4; formula [3c]In, X¹And X²Each independently represents a C1-12 hydrocarbon group; formula [3d]In, X³Represents an alkyl group having 1 to 5 carbon atoms. )

(7) The liquid crystal display element according to any one of the above (3) to (6), wherein the polymer is at least 1 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 [4] as a part of raw materials.

(Z represents at least 1 type selected from the structures represented by the following formulas [4a ] to [4k ])

(formula [4a ]]In, Z¹～Z⁴Each independently represents a hydrogen atom, a methyl group, a chlorine atom or a benzene ring; formula [4g ]]In, Z⁵And Z⁶Each independently represents a hydrogen atom or a methyl group. )

(8) The liquid crystal display element according to the above (3), wherein the polymer is at least 1 kind of polysiloxane selected from the following polysiloxanes: a polysiloxane obtained by condensation polymerization of an alkoxysilane represented by the following formula [ A1 ]; a polysiloxane obtained by polycondensing an alkoxysilane represented by the following formula [ A1] with an alkoxysilane containing any of the alkoxysilanes represented by the following formula [ A2] or formula [ A3 ]; and a polysiloxane obtained by polycondensing the alkoxysilanes represented by the formulae [ A1] and [ A2] and [ A3 ].

(A¹)_mSi(A²)_n(OA³)_p [A1]

(A¹Is selected from the group consisting of the foregoing formulas [2-1]]And formula [2-2]At least 1 structure from the group consisting of the structures shown; a. the²Represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms; a. the³Represents 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; p represents an integer of 0 to 3. Wherein m + n + p represents an integer of 4. )

(B¹)_mSi(B²)_n(OB³)_p [A2]

(B¹An organic group having 2 to 12 carbon atoms and containing at least 1 selected from a vinyl group, an epoxy group, an amino group, a mercapto group, an isocyanate group, a methacryloyl group, an acryloyl group, a ureido group and a cinnamoyl group; b is²Represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms; b is³Represents 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; p represents an integer of 0 to 3. Wherein m + n + p represents an integer of 4. )

(D¹)_nSi(OD²)_4-n [A3]

(D¹Represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms; d²Represents an alkyl group having 1 to 5 carbon atoms; n represents an integer of 0 to 3. )

(9) The liquid crystal display element according to any one of the above (1) to (8), wherein the liquid crystal alignment treatment agent contains at least 1 solvent selected from the group consisting of N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, and γ -butyrolactone.

(10) The liquid crystal display element according to any one of the above (1) to (9), wherein the liquid crystal alignment treatment agent contains at least 1 solvent selected from the group consisting of 1-hexanol, cyclohexanol, 1, 2-ethylene glycol, 1, 2-propylene glycol, propylene glycol monobutyl ether, ethylene glycol monobutyl ether, and dipropylene glycol dimethyl ether.

(11) The liquid crystal display element according to any one of the above (1) to (10), wherein the liquid crystal alignment treatment agent contains at least 1 kind of solvent selected from the group consisting of cyclopentanone, cyclohexanone, and solvents represented by the following formulae [ S1] to [ S3 ].

(formula [ S1]]In, T¹Represents an alkyl group having 1 to 3 carbon atoms; formula [ S2]In, T²Represents an alkyl group having 1 to 3 carbon atoms; formula [ S3]In, T³Represents an alkyl group having 1 to 4 carbon atoms. )

(12) The liquid crystal display element according to any one of the above (1) to (11), wherein the liquid crystal alignment treatment agent contains at least 1 kind of generator selected from the group consisting of a photoradical generator, a photoacid generator and a photobase generator.

(13) The liquid crystal display element according to any one of the above (1) to (12), wherein the liquid crystal alignment treatment agent contains at least 1 compound selected from the group consisting of compounds having structures represented by the following formulae [ M1] to [ M8 ].

(formula [ M4)]In, W¹Represents a hydrogen atom or a benzene ring; formula [ M7]In, W²Represents at least 1 cyclic group selected from a benzene ring, a cyclohexane ring and a heterocycle; w³Represents 1 kind selected from alkyl with 1-18 carbon atoms, fluorine-containing alkyl with 1-18 carbon atoms, alkoxy with 1-18 carbon atoms and fluorine-containing alkoxy with 1-18 carbon atoms. )

(14) The liquid crystal display element according to any one of the above (1) to (13), wherein the liquid crystal alignment treatment agent comprises a compound having 2 or more substituents selected from the group consisting of an epoxy group, an isocyanate group, an oxetanyl group, a cyclocarbonate group, a hydroxyl group, a hydroxyalkyl group and a lower alkoxyalkyl group.

(15) The liquid crystal display element according to any one of the above (1) to (14), wherein the substrate is a plastic substrate.

(16) A liquid crystal alignment film for use in the liquid crystal display element according to any one of (1) to (15) above.

(17) A liquid crystal aligning agent for use in forming the liquid crystal alignment film according to (16) above.

ADVANTAGEOUS EFFECTS OF INVENTION

The liquid crystal display element of the present invention is a liquid crystal display element which uses a vertical alignment film obtained from a liquid crystal alignment treatment agent containing a solvent having a specific structure and a polymer having a side chain having a specific structure, has high vertical alignment properties of liquid crystal, can obtain good optical characteristics, has high adhesion between a liquid crystal layer and the vertical liquid crystal alignment film, and is less likely to cause alignment defects due to coating film defects such as shrinkage and pinholes, and is particularly suitable for a reverse type element which exhibits a transmissive state when no voltage is applied and exhibits a scattering state when a voltage is applied, and can be used as a liquid crystal display for the purpose of presentation, and a light control window, a light shutter element, and the like for controlling light transmission and light blocking.

Further, since firing at the time of producing a vertical liquid crystal alignment film can be performed at a low temperature, a plastic substrate can be used as the substrate.

Detailed Description

The present invention is a liquid crystal display element obtained by disposing a liquid crystal composition containing a polymerizable compound that is polymerized by at least one of an active energy ray and heat between a pair of substrates having electrodes, and further, by providing at least one substrate with a liquid crystal alignment film that vertically aligns liquid crystal, curing the liquid crystal composition in a state where a part or all of the liquid crystal composition exhibits liquid crystallinity to form a cured product composite of the liquid crystal and the polymerizable compound, wherein the liquid crystal display element is obtained by the liquid crystal alignment film containing a liquid crystal alignment treatment agent that contains a solvent (also referred to as a specific solvent) represented by the above formula [1] and contains a liquid crystal having a structure selected from the group consisting of structures (also collectively referred to as specific side chain structures) represented by the above formulae [2-1] and [2-2] (also referred to as specific side chain structures) Polymers of at least 1 structure in the group (also referred to as specific polymers).

The liquid crystal display element of the present invention is mainly applicable to a reverse type element which exhibits a transmissive state when no voltage is applied and exhibits a scattering state when a voltage is applied.

The specific solvent used in the present invention has a lower boiling point than a solvent used in a conventional liquid crystal alignment agent, for example, NMP, and therefore, the firing step in the production of a liquid crystal alignment film can be performed at a low temperature.

Further, since the viscosity of the specific solvent as a solvent is low, when the liquid crystal alignment treatment agent using the specific solvent is applied to a substrate, the wetting and diffusing properties of the liquid crystal alignment treatment agent are increased, and a liquid crystal alignment film having excellent coating film uniformity can be obtained. In particular, since a liquid crystal alignment film used in a reverse cell needs to have improved vertical alignment properties of liquid crystal, it is necessary to introduce a large amount of hydrophobic side chain groups into a polymer used as a liquid crystal alignment treatment agent for producing the liquid crystal alignment film. Therefore, the liquid crystal aligning agent used for producing the present device is likely to have low wetting and diffusing properties, but this can be improved by using the specific solvent of the present invention.

In a specific side chain structure, in the structure of the formula [2-1], the side chain site has: a benzene ring, a cyclohexane ring, a heterocycle or a C17-51 organic group having a steroid skeleton. Since the side chain structures of these rings and organic groups exhibit a rigid structure, a reverse type cell using a vertical liquid crystal alignment film having a specific side chain structure represented by the formula [2-1] can obtain a high and stable liquid crystal vertical alignment property.

From the above-described viewpoint, by using a vertical alignment film obtained from a liquid crystal alignment treatment agent containing a solvent having a specific structure and a polymer having a specific side chain structure, a liquid crystal display element having high vertical alignment of liquid crystal, excellent optical characteristics, and high adhesion between a liquid crystal layer and the vertical liquid crystal alignment film can be obtained.

Further, by using the liquid crystal aligning agent of the present invention, a liquid crystal display element can be obtained in which the coating film of the vertical liquid crystal alignment film has high uniformity and alignment defects due to coating film defects such as shrinkage and pinholes are less likely to occur.

The liquid crystal display element of the present invention is particularly suitable for a retroreflective element which exhibits a transmissive state when no voltage is applied and a scattering state when a voltage is applied, and can be used as a liquid crystal display for the purpose of presentation, a light control window for controlling light transmission and isolation, a shutter element, and the like. In addition, since firing in the production of a vertical liquid crystal alignment film can be performed at a low temperature, a plastic substrate can be used as the substrate.

< liquid Crystal display element >

The liquid crystal display element of the present invention is manufactured by including a liquid crystal layer between a pair of substrates having electrodes and by performing the following steps: the liquid crystal display element is preferably used for a converse-type element which exhibits a transmissive state when no voltage is applied and a scattering state when a voltage is applied, wherein a liquid crystal composition containing a polymerizable compound which is polymerized by at least one of an active energy ray and heat is disposed between the pair of substrates, and at least one of the substrates is provided with a liquid crystal alignment film which vertically aligns liquid crystal, and the liquid crystal composition is cured in a state in which a part or all of the liquid crystal composition exhibits liquid crystallinity to form a cured product composite of liquid crystal and the polymerizable compound.

< specific solvent >

The specific solvent is represented by the following formula [1 ].

S¹And S²Each independently represents an alkyl group having 1 to 4 carbon atoms.

As the formula [1], at least 1 selected from 2-butanone, 3-pentanone, 4-methyl-2-pentanone, and 2, 6-dimethyl-4-heptanone is preferable.

The specific solvent may be used in a mixture of 1 or 2 or more depending on the solubility of the specific polymer, the vertical alignment property of the liquid crystal when the liquid crystal alignment film is formed, and the optical characteristics of the liquid crystal display element.

< specific side chain Structure >

The liquid crystal display element of the present invention has a vertical liquid crystal alignment film for vertically aligning liquid crystal on at least one substrate. The vertical liquid crystal alignment film is obtained from a liquid crystal alignment treatment agent containing a specific polymer having a structure represented by the following formula [2-1] or formula [2-2 ].

Y¹Represents a group selected from a single bond, - (CH)₂)_a- (a is an integer of 1 to 15), -O-, -CH₂At least 1 of O-, -COO-and-OCO-. Among them, a single bond, - (CH) is preferable from the viewpoint of raw material availability and ease of synthesis₂)_a- (a is an integer of 1 to 15), -O-, -CH₂O-or-COO-. More preferably a single bond, - (CH)₂)_a- (a is an integer of 1 to 10), -O-, -CH₂O-or-COO-.

Y²Represents a single bond or- (CH)₂)_b- (b represents an integer of 1 to 15). Among them, preferred is a single bond or- (CH)₂)_b- (b represents an integer of 1 to 10).

Y³Represents a group selected from a single bond, - (CH)₂)_c- (c represents an integer of 1 to 15), -O-, -CH₂At least 1 of O-, -COO-and-OCO-. Wherein, the slave isFrom the viewpoint of ease of formation, a single bond, - (CH) is preferred₂)_c- (c represents an integer of 1 to 15), -O-, -CH₂O-or-COO-. More preferably a single bond, - (CH)₂)_c- (c represents an integer of 1 to 10), -O-, -CH₂O-or-COO-.

Y⁴Represents at least 1 cyclic group selected from a benzene ring, a cyclohexane ring and a heterocycle, and any hydrogen atom on the cyclic groups is optionally substituted by an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxy group having 1 to 3 carbon atoms or a fluorine atom. Further, Y⁴The organic group may be a 2-valent organic group selected from organic groups having 17 to 51 carbon atoms and having a steroid skeleton. Among them, preferred are benzene rings, cyclohexane rings, or organic groups having 17 to 51 carbon atoms and having a steroid skeleton, from the viewpoint of ease of synthesis.

Y⁵Represents at least 1 cyclic group selected from a benzene ring, a cyclohexane ring and a heterocycle, and any hydrogen atom on the cyclic groups is optionally substituted by an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxy group having 1 to 3 carbon atoms or a fluorine atom. Among them, preferred is a benzene ring or a cyclohexane ring.

n represents an integer of 0 to 4. Among them, from the viewpoint of raw material availability and ease of synthesis, 0 to 3 is preferable. More preferably 0 to 2.

Y⁶Represents 1 kind selected from alkyl with 1-18 carbon atoms, fluorine-containing alkyl with 1-18 carbon atoms, alkoxy with 1-18 carbon atoms and fluorine-containing alkoxy with 1-18 carbon atoms. Among them, preferred is an alkyl group having 1 to 18 carbon atoms, a fluorinated alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 18 carbon atoms or a fluorinated alkoxy group having 1 to 10 carbon atoms. More preferably an alkyl group having 1 to 12 carbon atoms or an alkoxy group having 1 to 12 carbon atoms, particularly preferably an alkyl group having 1 to 9 carbon atoms or an alkoxy group having 1 to 9 carbon atoms.

As formula [2-1]Y in (1)¹、Y²、Y³、Y⁴、Y⁵、Y⁶Preferable combinations with n include groups similar to (2-1) to (2-629) described in tables 6 to 47 on pages 13 to 34 of International publication WO2011/132751 (2011.10.27)And (6) mixing. In the tables of International publication, Y in the present invention¹～Y⁶Are shown as Y1-Y6, but Y1-Y6 are understood to be Y¹～Y⁶. In addition, (2-605) to (2-629) described in each table of the international publication, the organic group having 17 to 51 carbon atoms of the steroid skeleton in the present invention is shown as the organic group having 12 to 25 carbon atoms of the steroid skeleton, but the organic group having 12 to 25 carbon atoms of the steroid skeleton can be understood as the organic group having 17 to 51 carbon atoms of the steroid skeleton.

-Y⁷-Y⁸ [2-2]

Y⁷Represents a group selected from a single bond, -O-, -CH₂O-、-CONH-、-NHCO-、-CON(CH₃)-、-N(CH₃) At least 1 bonding group selected from CO-, -COO-and-OCO-. Among them, a single bond, -O-, -CH is preferable₂O-、-CONH-、-CON(CH₃) -or-COO-. More preferably a single bond, -O-, -CONH-or-COO-.

Y⁸Represents an alkyl group having 8 to 22 carbon atoms or a fluoroalkyl group having 6 to 18 carbon atoms. Among them, preferred is an alkyl group having 8 to 18 carbon atoms.

The specific side chain structure is preferably a specific side chain structure represented by the above formula [2-1] in view of obtaining a high and stable liquid crystal vertical alignment property.

< specific Polymer >

The specific polymer having a specific side chain structure is not particularly limited, and is preferably at least 1 polymer selected from the group consisting of an acrylic polymer, a methacrylic polymer, a novolac resin, polyhydroxystyrene, a polyimide precursor, polyimide, polyamide, polyester, cellulose, and polysiloxane. Among them, polyimide precursors, polyimides, or polysiloxanes are preferable.

When a polyimide precursor or a polyimide (also collectively referred to as a polyimide-based polymer) is used as the specific polymer of the present invention, it is preferably a polyimide precursor or a polyimide obtained by reacting a diamine component with a tetracarboxylic acid component.

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

(R¹Is a 4-valent organic group; r²Is a 2-valent organic group; a. the¹And A²Represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, which may be the same or different; a. the³And A⁴Represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or an acetyl group, and may be the same or different; n represents a positive integer. )

The diamine component is a diamine having 2 primary or secondary amino groups in the molecule, and examples of the tetracarboxylic acid component include a tetracarboxylic acid compound, a tetracarboxylic acid dianhydride, a tetracarboxylic acid dihalide compound, a tetracarboxylic acid dialkyl ester compound, or a tetracarboxylic acid dialkyl ester dihalide compound.

The polyimide polymer of the present invention is preferably a polyamic acid having a structural formula including a repeating unit represented by the following formula [ D ] or a polyimide obtained by imidizing the polyamic acid, because the polyimide polymer can be obtained relatively easily from a tetracarboxylic dianhydride represented by the following formula [ B ] and a diamine represented by the following formula [ C ]. Among these, in the specific polyimide-based polymer of the present invention, polyimide is preferably used from the viewpoint of physical stability and chemical stability of the vertical liquid crystal alignment film.

(R¹And R²And formula [ A]Are defined in the same way. )

(R¹And R²And formula [ A]Are defined in the same way. )

In addition, the compounds obtained above can also be prepared by a general synthesis methodFormula [ D ]]Into the polymer of the formula [ A ]]Shown as A¹And A²An alkyl group having 1 to 8 carbon atoms and the formula [ A]Shown as A³And A⁴An alkyl group or acetyl group having 1 to 5 carbon atoms.

As a method for introducing a specific side chain structure into a polyimide-based polymer, a diamine having a specific side chain structure is preferably used as a part of the raw material. Particularly preferred is a diamine represented by the following formula [2] (also referred to as a specific side chain type diamine).

Y is a structure represented by the above formula [2-1] or formula [2-2 ]. Among them, the structure represented by the formula [2-1] is preferable in that a high and stable vertical alignment property of liquid crystal can be obtained. n represents an integer of 1 to 4. Among them, the integer 1 is preferable.

As the specific side chain type diamine, a diamine represented by the following formula [2-1a ] is preferably used from the viewpoint that a high and stable liquid crystal vertical alignment property can be obtained.

Y³Represents a group selected from a single bond, - (CH)₂)_c- (c represents an integer of 1 to 15), -O-, -CH₂O-、At least 1 of-COO-and-OCO-. Among them, a single bond, - (CH) is preferable from the viewpoint of ease of synthesis₂)_c- (c represents an integer of 1 to 15), -O-, -CH₂O-or-COO-. More preferably a single bond, - (CH)₂)_c- (c represents an integer of 1 to 10), -O-, -CH₂O-or-COO-.

As formula [2-1a ]]Y in (1)¹、Y²、Y³、Y⁴、Y⁵、Y⁶Preferable combinations with n include tables on pages 13 to 34 of International publication WO2011/132751 (published 2011.10.27)6 to (2-1) to (2-629) in Table 47. In the tables of International publication, Y in the present invention¹～Y⁶Are shown as Y1-Y6, but Y1-Y6 are understood to be Y¹～Y⁶. In addition, (2-605) to (2-629) described in each table of the international publication, the organic group having 17 to 51 carbon atoms of the steroid skeleton in the present invention is shown as the organic group having 12 to 25 carbon atoms of the steroid skeleton, but the organic group having 12 to 25 carbon atoms of the steroid skeleton can be understood as the organic group having 17 to 51 carbon atoms of the steroid skeleton.

Among them, preferred is a combination of (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). 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).

m is an integer of 1 to 4. Preferably the integer 1.

More specifically, diamines represented by the following formulas [2a-1] to [2a-31] are exemplified.

(R¹Each independently represents a group selected from-O-, -OCH₂-、-CH₂O-、-COOCH₂-and-CH₂At least 1 bonding group of OCO-; r²Each independently represents a linear or branched alkyl group having 1 to 22 carbon atoms, a linear or branched alkoxy group having 1 to 22 carbon atoms, a linear or branched fluoroalkyl group having 1 to 22 carbon atoms, or a linear or branched fluoroalkoxy group having 1 to 22 carbon atoms. )

(R³Each independently represents a group selected from-COO-, -OCO-, -CONH-, -NHCO-, -COOCH₂-、-CH₂OCO-、-CH₂O-、-OCH₂-and-CH₂-at least 1 bonding group; r⁴Each independently represents a linear or branched alkyl group having 1 to 22 carbon atoms, a linear or branched alkoxy group having 1 to 22 carbon atoms, a linear or branched fluoroalkyl group having 1 to 22 carbon atoms, or a linear or branched fluoroalkoxy group having 1 to 22 carbon atoms. )

(R⁵Each independently represents a group selected from-COO-, -OCO-, -CONH-, -NHCO-, -COOCH₂-、-CH₂OCO-、-CH₂O-、-OCH₂-、-CH₂At least 1 bonding group of-O-and-NH-; r⁶Each independently represents at least 1 selected from the group consisting of a fluoro group, a cyano group, a trifluoromethyl group, a nitro group, an azo group, a formyl group, an acetyl group, an acetoxy group, and a hydroxyl group. )

(R⁷Each independently represents a linear or branched alkyl group having 3 to 12 carbon atoms, and the cis-trans isomers of the 1, 4-cyclohexylidene group each represent a trans isomer. )

(R⁸Each independently represents a linear or branched alkyl group having 3 to 12 carbon atoms, and the cis-trans isomers of the 1, 4-cyclohexylidene group each represent a trans isomer. )

(A₄Represents a linear or branched alkyl group having 3 to 20 carbon atoms optionally substituted with a fluorine atom; a. the₃Represents 1, 4-cyclohexylidene or 1,4-a phenylene group; a. the₂Represents an oxygen atom or-COO- (-wherein the bond is attached to A)₃Bonding is performed); a. the₁Represents an oxygen atom or-COO- (-CH-C-) - "(wherein the bond is attached to₂)a₂) Bonding is performed). In addition, a₁Represents an integer of 0 or 1; a is₂Represents an integer of 2 to 10; a is₃Represents an integer of 0 or 1. )

Particularly preferred diamines having a structure are those of the formulae [2a-1] to [2a-6], [2a-9] to [2a-13], and [2a-22] to [2a-31 ].

Further, as the specific side chain type diamine having a specific side chain structure of the above formula [2-2], diamines of the following formulae [2a-32] to [2a-35] are preferably used.

(A¹Each independently represents an alkyl group having 1 to 22 carbon atoms or a fluoroalkyl group having 1 to 22 carbon atoms).

The specific side chain diamine is preferably 10 mol% or more and 80 mol% or less of the diamine component as a whole, from the viewpoint of the liquid crystal vertical alignment property in the liquid crystal display element and the adhesion between the liquid crystal layer and the vertical liquid crystal alignment film. More preferably 10 mol% or more and 70 mol% or less.

The specific side chain type diamine may be used in 1 kind or 2 or more kinds by mixing depending on the solubility of the polyimide-based polymer in a solvent, the liquid crystal vertical alignment property when a vertical liquid crystal alignment film is formed, and the optical characteristics of a liquid crystal display element.

In the present invention, when a polyimide-based polymer is used as the specific polymer, it is preferable that the specific side chain type diamine and a second diamine represented by the following formula [3] are used together as a diamine component in a part of the raw materials.

X represents at least 1 selected from the structures represented by the following formulae [3a ] to [3d ].

-(CH₂)_a-OH [3a]

-(CH₂)_b-COOH [3b]

a represents an integer of 0 to 4. Among them, an integer of 0 or 1 is preferable from the viewpoint of availability of raw materials and ease of synthesis. b represents an integer of 0 to 4. Among them, an integer of 0 or 1 is preferable from the viewpoint of availability of raw materials and ease of synthesis. X¹And X²Each independently represents a C1-12 hydrocarbon group. X³Represents an alkyl group having 1 to 5 carbon atoms.

m represents an integer of 1 to 4. Among them, the integer 1 is preferable.

Specific examples of the second diamine include the following diamines.

Examples thereof include 2, 4-dimethyl-m-phenylenediamine, 2, 6-diaminotoluene, 2, 4-diaminophenol, 3, 5-diaminobenzyl alcohol, 2, 4-diaminobenzyl alcohol, 4, 6-diaminoresorcinol, 2, 4-diaminobenzoic acid, 2, 5-diaminobenzoic acid, and 3, 5-diaminobenzoic acid.

Further, diamines having structures represented by the following formulae [3-1] to [3-6] can be exemplified.

Among the second diamines, it is preferable to use a diamine represented by 2, 4-diaminophenol, 3, 5-diaminobenzyl alcohol, 2, 4-diaminobenzyl alcohol, 4, 6-diaminoresorcinol, 2, 4-diaminobenzoic acid, 2, 5-diaminobenzoic acid, 3, 5-diaminobenzoic acid, formula [3-1], formula [3-2] or formula [3-3 ]. Particularly preferred is 2, 4-diaminophenol, 3, 5-diaminobenzyl alcohol, 3, 5-diaminobenzoic acid, a diamine represented by the formula [3-1] or the formula [3-2 ].

The second diamine may be used in a mixture of 1 or 2 or more depending on the solubility of the polyimide-based polymer of the present invention in a solvent, the vertical alignment property of liquid crystal when a vertical liquid crystal alignment film is formed, and the optical characteristics of the liquid crystal display element of the present invention.

When a polyimide-based polymer is used as the specific polymer, a diamine component other than the specific side chain diamine represented by the formula [2] and the second diamine represented by the formula [3] (also referred to as another diamine) may be used as the diamine component. Specific examples of the other diamines are shown below, but the diamines are not limited to these examples.

That is, there may be mentioned m-phenylenediamine, p-phenylenediamine, 4 ' -diaminobiphenyl, 3 ' -dimethyl-4, 4 ' -diaminobiphenyl, 3 ' -dimethoxy-4, 4 ' -diaminobiphenyl, 3 ' -dihydroxy-4, 4 ' -diaminobiphenyl, 3 ' -dicarboxyl-4, 4 ' -diaminobiphenyl, 3 ' -difluoro-4, 4 ' -diaminobiphenyl, 3 ' -trifluoromethyl-4, 4 ' -diaminobiphenyl, 3 ' -diaminobiphenyl, 2 ' -diaminobiphenyl, 2,3 ' -diaminobiphenyl, 4 ' -diaminodiphenylmethane, 3 ' -diaminodiphenylmethane, 4 ' -diaminodiphenylmethane, 3,4 ' -diaminodiphenylmethane, 2 ' -diaminodiphenylmethane, 2,3 ' -diaminodiphenylmethane, 4 ' -diaminodiphenyl ether, 3 ' -diaminodiphenyl ether, 3,4 ' -diaminodiphenyl ether, 2 ' -diaminodiphenyl ether, 2,3 ' -diaminodiphenyl ether, 4 ' -sulfonyldiphenylamine, 3 ' -sulfonyldiphenylamine, bis (4-aminophenyl) silane, bis (3-aminophenyl) silane, dimethyl-bis (4-aminophenyl) silane, dimethyl-bis (3-aminophenyl) silane, 4 ' -thiodiphenylamine, 3 ' -thiodiphenylamine, 4 ' -diaminodiphenylamine, 3,3 '-diaminodiphenylamine, 3, 4' -diaminodiphenylamine, 2 '-diaminodiphenylamine, 2, 3' -diaminodiphenylamine, N-methyl (4,4 '-diaminodiphenyl) 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' -diaminobenzophenone, 3 '-diaminobenzophenone, 3, 4' -diaminobenzophenone, 1, 4-diaminonaphthalene, 2 '-diaminobenzophenone, 2, 3' -diaminodiphenylamine, and mixtures thereof, 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 (4-aminophenyl) 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 '- [1, 4-phenylenebis (methylene) ] diphenylamine, 4' - [1, 3-phenylenebis (methylene) ] diphenylamine, 3,4 '- [1, 4-phenylenebis (methylene) ] diphenylamine, 3, 4' - [1, 3-phenylenebis (methylene) ] diphenylamine, 3 '- [1, 4-phenylenebis (methylene) ] diphenylamine, 3' - [1, 3-phenylenebis (methylene) ] diphenylamine, 1, 4-phenylenebis [ (4-aminophenyl) ketone ], (a group of, 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-aminophenyl) terephthalate, bis (3-aminophenyl) terephthalate, bis (4-aminophenyl) isophthalate, bis (3-aminophenyl) isophthalate, N' - (1, 4-phenylene) bis (4-aminobenzamide) N, N ' - (1, 3-phenylene) bis (4-aminobenzamide), N ' - (1, 4-phenylene) bis (3-aminobenzamide), N ' - (1, 3-phenylene) bis (3-aminobenzamide), N ' -bis (4-aminophenyl) terephthalamide, N ' -bis (3-aminophenyl) terephthalamide, N ' -bis (4-aminophenyl) isophthalamide, N ' -bis (3-aminophenyl) isophthalamide, 9, 10-bis (4-aminophenyl) anthracene, 4 ' -bis (4-aminophenoxy) diphenylsulfone, 2 ' -bis [4- (4-aminophenoxy) phenyl ] propane, 2,2 ' -bis [4- (4-aminophenoxy) phenyl ] hexafluoropropane, 2 ' -bis (4-aminophenyl) hexafluoropropane, 2 ' -bis (3-amino-4-methylphenyl) hexafluoropropane, 2 ' -bis (4-aminophenyl) propane, 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-bis (3-aminophenoxy) butane, 2 ' -bis (3-aminophenyl) hexafluoropropane, 2 ' -bis (3-amino-4-methylphenyl) hexafluoropropane, 1, 3-bis (4-aminophenoxy) propane, 1, 4-bis (3-aminophenoxy) butane, 2 ' -bis (4-aminophenyl) hexafluoropropane, 2 ' -bis (3-aminophenoxy) propane, 2-propane, 2 ' -bis (4-aminophenyl) propane, 2-bis (3-aminophenoxy) propane, 2-propane, 2 ' -bis (4-amino-phenyl) propane, 2-propane, 2, 1, 5-bis (4-aminophenoxy) pentane, 1, 5-bis (3-aminophenoxy) pentane, 1, 6-bis (4-aminophenoxy) hexane, 1, 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, 6-bis (4-aminophenoxy) heptane, 1, 8-bis (4-aminophenoxy) octane, 1, 8-bis (3-aminophenoxy) nonane, 1, 9-bis (4-aminophenoxy) nonane, 1, 10-bis (4-aminophenoxy) undecane, 1, 5-bis (4-aminophenoxy) decane, 1, 6-bis (3-amino) nonane, 1, 9-bis (4-aminophenoxy) nonane, 1,9, 1,2, 1,6, 1,6, 1,5, or a mixture thereof, and a mixture thereof, 1, 11-bis (3-aminophenoxy) undecane, 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, 1, 10-diaminodecane, 1, 11-diaminoundecane, 1, 12-diaminododecane, and the like.

Further, as the other diamine, diamines represented by the following formulae [ DA1] to [ DA11] can be used.

(in the formula [ DA1], p represents an integer of 1-10.)

(in the formula [ DA4], m represents an integer of 0 to 3; and in the formula [ DA7], n represents an integer of 1 to 5.)

(formula [ DA 8)]In (A)¹Represents a group selected from a single bond, -CH₂-、-C₂H₄-、-C(CH₃)₂-、-CF₂-、-C(CF₃)₂-、-O-、-CO-、-NH-、-N(CH₃)-、-CONH-、-NHCO-、-CH₂O-、-OCH₂-、-COO-、-OCO-、-CON(CH₃) -and-N (CH)₃) At least 1 bonding group in CO-, m¹And m²Each independently represents an integer of 0 to 4, and m¹+m²Represents an integer of 1 to 4; formula [ DA9]M in³And m⁴Each independently represents an integer of 1 to 5; formula [ DA10]In (A)²Represents a linear or branched alkyl group having 1 to 5 carbon atoms, m⁵Represents an integer of 1 to 5; formula [ DA11]In (A)³Represents a group selected from a single bond, -CH₂-、-C₂H₄-、-C(CH₃)₂-、-CF₂-、-C(CF₃)₂-、-O-、-CO-、-NH-、-N(CH₃)-、-CONH-、-NHCO-、-CH₂O-、-OCH₂-、-COO-、-OCO-、-CON(CH₃) -and-N (CH)₃) At least 1 bonding group in CO-, m⁶Represents an integer of 1 to 4. )

Further, as the other diamine, a diamine represented by the following formula [ DA12] may be used within a range not impairing the effects of the present invention.

(A¹Represents a group selected from-O-, -NH-, -N (CH)₃)-、-CONH-、-NHCO-、-CH₂O-、-OCO-、-CON(CH₃) -and-N (CH)₃) At least 1 bonding group in CO-; a. the²Represents at least 1 selected from single bond, aliphatic hydrocarbon group with 1-20 carbon atoms, non-aromatic ring type hydrocarbon group and aromatic hydrocarbon group; a. the³Represents a single bond, -O-, -NH-, -N (CH)₃)-、-CONH-、-NHCO-、-COO-、-OCO-、-CON(CH₃)-、-N(CH₃) CO-and-O (CH)₂)_mAt least 1 bonding group selected from- (m is an integer of 1 to 5); a. the⁴Represents a nitrogen-containing aromatic heterocycle; n represents an integer of 1 to 4. )

Further, as the other diamine, diamines represented by the following formulae [ DA13] and [ DA14] can be used.

The other diamines may be used in a mixture of 1 or 2 or more depending on the solubility of the polyimide-based polymer of the present invention in a solvent, the vertical alignment property of liquid crystal when a vertical liquid crystal alignment film is formed, and the optical characteristics of the liquid crystal display element of the present invention.

When a polyimide-based polymer is used as the specific polymer, it is preferable to use a tetracarboxylic dianhydride represented by the following formula [4], a tetracarboxylic acid dihalide compound, a tetracarboxylic acid dialkyl ester compound or a tetracarboxylic acid dialkyl ester dihalide compound (all of which will be collectively referred to as specific tetracarboxylic acid components) as a tetracarboxylic acid derivative thereof, as a part of the raw materials.

Z represents at least 1 structure selected from the following formulas [4a ] to [4k ].

Z¹～Z⁴Each independently a hydrogen atom, a methyl group, a chlorine atom or a benzene ring. Z⁵And Z⁶Each independently represents a hydrogen atom or a methyl group.

The specific tetracarboxylic acid component is preferably represented by formula [4a ], formula [4c ], formula [4d ], formula [4e ], formula [4f ] or formula [4g ] in terms of ease of synthesis and ease of polymerization reaction in the production of the polymer. More preferably, the compound is represented by the formula [4a ], the formula [4e ], the formula [4f ] or the formula [4g ], and particularly preferably represented by the formula [4e ], the formula [4f ] or the formula [4g ].

The specific tetracarboxylic acid component is preferably 1 mol% or more, more preferably 5 mol% or more, and particularly preferably 10 mol% or more of the total tetracarboxylic acid components.

When a specific tetracarboxylic acid component of formula [4] in which Z is a structure represented by formula [4e ], formula [4f ] or formula [4g ] is used, the amount used is preferably 20 mol% or more of the total tetracarboxylic acid component. More preferably 30 mol% or more. Further, the tetracarboxylic acid component may be a tetracarboxylic acid component having a structure represented by the formula [4e ], the formula [4f ] or the formula [4g ].

In the tetracarboxylic acid component when the polyimide-based polymer is used as the specific polymer, a tetracarboxylic acid component other than the specific tetracarboxylic acid component may be used within a range not impairing the effects of the present invention.

Examples of the other tetracarboxylic acid component include tetracarboxylic acid compounds, tetracarboxylic dianhydrides, dicarboxylic acid dihalide compounds, dicarboxylic acid dialkyl ester compounds, or dialkyl ester dihalide compounds shown below.

Examples of the other tetracarboxylic acid component include pyromellitic acid, 2,3,6, 7-naphthalenetetracarboxylic acid, 1,2,5, 6-naphthalenetetracarboxylic acid, 1,4,5, 8-naphthalenetetracarboxylic 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-bis (3, 4-dicarboxyphenyl) propane, 1,1,1,3,3, 3-hexafluoro-2, 2-bis (3, 4-dicarboxyphenyl) propane, and mixtures thereof, Bis (3, 4-dicarboxyphenyl) dimethylsilane, bis (3, 4-dicarboxyphenyl) diphenylsilane, 2,3,4, 5-pyridinetetracarboxylic acid, 2, 6-bis (3, 4-dicarboxyphenyl) pyridine, 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 the other tetracarboxylic acid components may be used in 1 type or in combination of 2 or more types depending on the solubility of the polyimide-based polymer in a solvent, the vertical alignment property of liquid crystal when a vertical liquid crystal alignment film is formed, and the optical characteristics of a liquid crystal display element.

When a polyimide-based polymer is used as the specific polymer, a method for producing the polyimide-based polymer is not particularly limited, and a method for producing the polyimide-based polymer by reacting a diamine component with a tetracarboxylic acid component is generally known. That is, a method of obtaining a polyamic acid by reacting at least 1 tetracarboxylic acid component selected from the group consisting of tetracarboxylic acids and derivatives thereof with a diamine component containing 1 or more kinds of diamines. More specifically, the polyamic acid may be obtained by a method in which a tetracarboxylic dianhydride is polycondensed with a primary diamine or a secondary diamine, a method in which a tetracarboxylic acid is subjected to a dehydration polycondensation reaction with a primary diamine or a secondary diamine to obtain a polyamic acid, or a method in which a dicarboxylic acid dihalide is subjected to a polycondensation with a primary diamine or a secondary diamine to obtain a polyamic acid.

To obtain polyamic acid alkyl ester, it is possible to use: a method of polycondensing a tetracarboxylic acid obtained by dialkylesterifying a carboxylic acid group with a primary diamine or a secondary diamine, a method of polycondensing a dicarboxylic acid dihalide obtained by dialkylesterifying a carboxylic acid group with a primary diamine or a secondary diamine, or a method of converting a carboxyl group of a polyamic acid into an ester.

In order to obtain polyimide, a method of ring-closing the polyamic acid or polyamic acid alkyl ester to obtain polyimide can be used.

The reaction of the diamine component with the tetracarboxylic acid component is usually carried out in a solvent. The solvent used in this case is not particularly limited as long as it is a specific solvent of the present invention and a solvent that dissolves the polyimide precursor formed. Specific examples of the solvent used in the reaction are shown below, but the solvent is not limited to these examples.

Examples thereof include the specific solvents of the present invention, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone or γ -butyrolactone, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide, 1, 3-dimethylimidazolidinone, cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone, and the like.

They may be used alone or in combination. Further, even if the solvent is a solvent that does not dissolve the polyimide precursor, the solvent may be mixed and used within a range where the produced polyimide precursor does not precipitate. In addition, since the moisture in the solvent inhibits the polymerization reaction and also causes hydrolysis of the polyimide precursor to be produced, 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 following methods may be mentioned: a method of stirring a solution in which a diamine component is dispersed or dissolved in a solvent, and adding a tetracarboxylic acid component as it is or in a solvent; 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, and any of these methods can be used. When a plurality of diamine components or tetracarboxylic acid components are used and reacted, they may be reacted in a state of being mixed in advance, or may be reacted in sequence, or may be reacted alone to produce a low molecular weight material and a polymer by mixing.

The polymerization temperature in this case may be any temperature of-20 to 150 ℃, preferably in the range of-5 to 100 ℃. The reaction may be carried out at any concentration, and when the concentration is too low, it is difficult to obtain a polymer having a high molecular weight, and when the concentration is too high, the viscosity of the reaction solution becomes too high, and uniform stirring is difficult. Therefore, the amount is preferably 1 to 50% by mass, more preferably 5 to 30% by mass. The reaction is carried out at a high concentration in the initial stage, and a solvent may be added thereafter.

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. The closer the molar ratio is to 1.0, the larger the molecular weight of the polyimide precursor to be produced becomes.

When the polyimide precursor is ring-closed, a polyimide can be obtained. The imidization ratio (ring-closing ratio of the amic acid group) of the polyimide is not necessarily required to be 100%, and may be arbitrarily adjusted depending on the application and the purpose.

Examples of the method for imidizing a polyimide precursor include: thermal imidization in which a solution of a polyimide precursor is directly heated, or catalytic imidization in which a catalyst is added to a solution of a polyimide precursor.

The temperature at which the polyimide precursor is thermally imidized in a solution is 100 to 400 ℃, preferably 120 to 250 ℃, and it is preferable that thermal imidization is performed while discharging water generated in the imidization reaction to the outside of the system.

The catalytic imidization of the polyimide precursor can be carried out by adding a basic catalyst and an acid anhydride to a solution of the polyimide precursor and stirring at-20 to 250 ℃, preferably 0 to 180 ℃. The amount of the basic catalyst is 0.5 to 30 times, preferably 2 to 20 times, the amount of the acid anhydride is 1 to 50 times, preferably 3 to 30 times, the amount of the acid amide group. Examples of the basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine, and trioctylamine, and among these, pyridine is preferable because it has a basic property suitable for promoting the reaction. Examples of the acid anhydride include acetic anhydride, trimellitic anhydride, and pyromellitic anhydride, and among these, acetic anhydride is preferable because purification after completion of the reaction is easy. The imidization rate based on the catalytic imidization can be controlled by adjusting the amount of the catalyst, the reaction temperature, and the reaction time.

When the polyimide precursor or polyimide to be produced is recovered from the reaction solution of the polyimide precursor or polyimide, the reaction solution may be put into a solvent to precipitate the polyimide. Examples of the solvent used for precipitation include methanol, ethanol, isopropanol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, toluene, benzene, and water. The polymer obtained by charging a solvent and precipitating the same may be dried at normal temperature under normal pressure or reduced pressure or dried by heating after filtration and recovery. Further, when the operation of dissolving the polymer recovered by precipitation in the solvent again and recovering the polymer by precipitation is repeated 2 to 10 times, impurities in the polymer can be reduced. Examples of the solvent in this case include alcohols, ketones, hydrocarbons and the like, and when 3 or more solvents selected from these are used, the purification efficiency is further improved, which is preferable.

The molecular weight of the polyimide-based polymer is preferably 5000 to 1000000, more preferably 10000 to 150000, in terms of the strength of the vertical liquid crystal alignment film obtained therefrom, the workability in forming the vertical film, and the film coatability, as measured by a Gel Permeation Chromatography (GPC) method.

When a polysiloxane is used as the specific polymer, it is preferably any of a polysiloxane obtained by polycondensing an alkoxysilane represented by the following formula [ a1], a polysiloxane obtained by polycondensing an alkoxysilane represented by the following formula [ a1] and an alkoxysilane containing any of the alkoxysilanes represented by the following formula [ a2] or formula [ A3], or a polysiloxane (also collectively referred to as a polysiloxane-based polymer) obtained by polycondensing an alkoxysilane represented by the formula [ a1] and formula [ a2] and formula [ A3 ].

(A¹)_mSi(A²)_n(OA³)_p [A1]

Formula [ A1]In (A)¹Is selected from the group consisting of the foregoing formulas [2-1]]And formula [2-2]At least 1 structure of the group. Among them, the formula [2-1] is preferable from the viewpoint of obtaining a high and stable liquid crystal vertical alignment]The structure shown.

As formula [2-1]Y in (1)¹、Y²、Y³、Y⁴、Y⁵、Y⁶Preferable combinations with n include combinations similar to (2-1) to (2-629) described in tables 6 to 47 on pages 13 to 3 of International publication WO2011/132751 (published 2011.10.27). In the tables of International publication, Y in the present invention¹～Y⁶Are shown as Y1-Y6, but Y1-Y6 are understood to be Y¹～Y⁶. In additionIn addition, (2-605) to (2-629) described in each table of the international publication, the organic group having 17 to 51 carbon atoms of the steroid skeleton in the present invention is shown as the organic group having 12 to 25 carbon atoms of the steroid skeleton, but the organic group having 12 to 25 carbon atoms of the steroid skeleton can be understood as the organic group having 17 to 51 carbon atoms of the steroid skeleton.

A²Represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. Among them, preferred is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. A. the³Represents an alkyl group having 1 to 5 carbon atoms. Among them, an alkyl group having 1 to 3 carbon atoms is preferable from the viewpoint of the polycondensation reactivity. m represents an integer of 1 or 2. Among them, 1 is preferable from the viewpoint of synthesis. n represents an integer of 0 to 2. p represents an integer of 0 to 3. Among them, from the viewpoint of the polycondensation reactivity, an integer of 1 to 3 is preferable. More preferably 2 or 3. m + n + p represents an integer of 4.

Specific examples of the alkoxysilane of the formula [ A1] having a specific side chain structure of the formula [2-1] include alkoxysilanes of the following formulae [ A1-1] to [ A1-32 ].

(formula [ A1-1)]-formula [ A1-4]In, R¹、R³、R⁵And R⁷Each independently represents an alkyl group having 1 to 3 carbon atoms; r²、R⁴、R⁶And R⁸Each independently represents an alkyl group having 1 to 3 carbon atoms; each m independently represents 2 or 3; each n independently represents 0 or 1. )

(formula [ A1-5)]-formula [ A1-8]In, R¹、R³、R⁵And R⁷Each independently represents an alkyl group having 1 to 3 carbon atoms; r²、R⁴、R⁶And R⁸Each independently represents an alkyl group having 1 to 3 carbon atoms; each m independently represents 2 or 3; n independently of one another represents 0 or1。)

(formula [ A1-9)]-formula [ A1-12]In, R¹、R³、R⁵And R⁷Each independently represents an alkyl group having 1 to 3 carbon atoms; r²、R⁴、R⁶And R⁸Each independently represents an alkyl group having 1 to 3 carbon atoms; each m independently represents 2 or 3; each n independently represents 0 or 1. )

(formula [ A1-13)]-formula [ A1-16]In, R¹、R³、R⁵And R⁷Each independently represents an alkyl group having 1 to 3 carbon atoms; r²、R⁴、R⁶And R⁸Each independently represents an alkyl group having 1 to 3 carbon atoms; each m independently represents 2 or 3; each n independently represents 0 or 1. )

(formula [ A1-17)]And formula [ A1-18]In, R¹And R³Each independently represents an alkyl group having 1 to 3 carbon atoms; r²And R⁴Each independently represents an alkyl group having 1 to 3 carbon atoms; each m independently represents 2 or 3; each n independently represents 0 or 1. )

(formula [ A1-19)]-formula [ A1-22]In, R¹、R⁵、R⁹And R¹³Each independently represents an alkyl group having 1 to 3 carbon atoms; r²、R⁶、R¹⁰And R¹⁴Each independently represents an alkyl group having 1 to 3 carbon atoms; r³、R⁷、R¹¹And R¹⁵Each independently represents a group selected from-O-, -COO-, -OCO-, -CONH-, -NHCO-, -CON (CH)₃)-、-N(CH₃)CO-、-OCH₂-、-CH₂O-、-COOCH₂-and-CH₂At least 1 bonding group of OCO-; r⁴、R⁸、R¹²And R¹⁶Each independently represents an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a fluoroalkyl group having 1 to 12 carbon atoms or a fluoroalkoxy group having 1 to 12 carbon atoms; each m independently represents 2 or 3; each n is independently 0 or 1; formula [ A1-20]-formula [ A1-22]The cis-trans isomers of the 1, 4-cyclohexylidene group in (A) represent trans isomers, respectively. )

(formula [ A1-23)]And formula [ A1-24]In, R¹And R⁵Each independently represents an alkyl group having 1 to 3 carbon atoms; r²And R⁶Each independently represents an alkyl group having 1 to 3 carbon atoms; r³And R⁷Each independently represents a group selected from-O-, -COO-, -OCO-, -CONH-, -NHCO-, -CON (CH)₃)-、-N(CH₃)CO-、-OCH₂-、-CH₂O-、-COOCH₂-and-CH₂At least 1 bonding group of OCO-; r⁴And R⁸Each independently represents at least 1 organic group selected from the group consisting of an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a fluoroalkyl group having 1 to 12 carbon atoms, a fluoroalkoxy group having 1 to 12 carbon atoms, a fluoro group, a cyano group, a trifluoromethyl group, a nitro group, an azo group, a formyl group, an acetyl group, an acetoxy group, and a hydroxyl group; each m independently represents 2 or 3; each n independently represents 0 or 1. )

(formula [ A1-25)]-formula [ A1-28]In, R¹、R⁵、R⁹And R¹³Each independently represents an alkyl group having 1 to 3 carbon atoms; r²、R⁶、R¹⁰And R¹⁴Each independently represents an alkyl group having 1 to 3 carbon atoms; r³、R⁷、R¹¹And R¹⁵Each independently represents a group selected from-O-, -COO-, -OCO-, -CONH-, -NHCO-, -CON (CH)₃)-、-N(CH₃)CO-、-OCH₂-、-CH₂O-、-COOCH₂-and-CH₂At least 1 bonding group of OCO-; r⁴、R⁸、R¹²And R¹⁶Each independently represents an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a fluoroalkyl group having 1 to 12 carbon atoms or a fluoroalkoxy group having 1 to 12 carbon atoms; each m independently represents 2 or 3; n each independently represents 0 or 1; formula [ A1-26]-formula [ A1-28]The cis-trans isomers of the 1, 4-cyclohexylidene group in (A) represent trans isomers, respectively. )

(formula [ A1-29)]-formula [ A1-31]In, R¹、R⁵And R⁹Each independently represents an alkyl group having 1 to 3 carbon atoms; r²、R⁶And R¹⁰Each independently represents an alkyl group having 1 to 3 carbon atoms; r³、R⁷And R¹¹Each independently represents a group selected from-O-, -COO-, -OCO-, -CONH-, -NHCO-, -CON (CH)₃)-、-N(CH₃)CO-、-OCH₂-、-CH₂O-、-COOCH₂-and-CH₂At least 1 bonding group of OCO-; r⁴、R⁸And R¹²Each independently represents an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a fluoroalkyl group having 1 to 12 carbon atoms or a fluoroalkoxy group having 1 to 12 carbon atoms; each m independently represents 2 or 3; n each independently represents 0 or 1; formula [ A1-29]-formula [ A1-31]The cis-trans isomers of the 1, 4-cyclohexylidene group in (A) represent trans isomers, respectively. )

(formula [ A1-32)]In, R¹Represents an alkyl group having 1 to 3 carbon atoms; r²C1-3An alkyl group; m represents 2 or 3; n represents 0 or 1; b is⁴Represents an alkyl group having 3 to 20 carbon atoms optionally substituted with a fluorine atom; b is³Represents 1, 4-cyclohexylene or 1, 4-phenylene; b is²Represents an oxygen atom or-COO- (-wherein the bond is attached to B)³Bonding is performed); b is¹Is oxygen atom or-COO- (-wherein the bond is attached to (CH))₂)a²) Bonding is performed). In addition, a¹Represents an integer of 0 or 1; a is²Represents an integer of 2 to 10; a is³Represents an integer of 0 or 1. )

Among the alkoxysilanes represented by the above-mentioned formulas [ A1-1] to [ A1-32], particularly preferred alkoxysilanes have a structure represented by the formulas [ A1-9] to [ A1-18], [ A1-19] to [ A1-21], [ A1-23] to [ A1-28] or [ A1-32 ].

Specific examples of the alkoxysilane represented by the formula [ A1] having the specific side chain structure represented by the formula [2-2] include the following alkoxysilanes.

That is, octyltrimethoxysilane, octyltriethoxysilane, decyltrimethoxysilane, dodecyltrimethoxysilane, dodecyltriethoxysilane, hexadecyltrimethoxysilane, hexadecyltriethoxysilane, pentyltriethoxysilane, heptadecyltrimethoxysilane, heptadecyltriethoxysilane, octadecyltrimethoxysilane, octadecyltriethoxysilane, nonadecyltrimethoxysilane, nonadecyltriethoxysilane, isooctyltriethoxysilane, phenethyltriethoxysilane, pentafluorophenylpropyltrimethoxysilane, m-styrylethyltrimethoxysilane, p-styrylethyltrimethoxysilane, 1-naphthyltriethoxysilane, 1-naphthyltrimethoxysilane, triethoxy-1H, 1H,2H, 2H-tridecafluorooctylsilane, dodecyltrimethoxysilane, hexadecyltrimethoxysilane, hexadecyltriethoxysilane, heptadecyltriethoxysilane, heptadecyltrimethoxysilane, octadecyltrimethoxysilane, nonadecyltrimethoxysilane, nonadecyltriethoxysilane, isooctyltriethoxysilane, phenethyltriethoxysilane, p-1H, 1H,2H, 2H-tridecafluorooctylsilane, n-octylsilane, and the like, Dimethoxydiphenylsilane, dimethoxymethylphenylsilane, triethoxyphenylsilane, and the like.

The alkoxysilane represented by the formula [ a1] may be used in a mixture of 2 or more types depending on the solubility of the polysiloxane polymer in a solvent, the liquid crystal vertical alignment property when a vertical liquid crystal alignment film is formed, and the optical characteristics of a liquid crystal display element.

(B¹)_mSi(B²)_n(OB³)_p [A2]

Formula [ A2]In (B)¹The organic group has 2 to 12 carbon atoms and at least 1 carbon atom selected from vinyl, epoxy, amino, mercapto, isocyanate, methacryloyl, acryloyl, ureido and cinnamoyl. Among them, from the viewpoint of easy availability, an organic group having 2 to 12 carbon atoms and having a vinyl group, an epoxy group, an amino group, a methacryloyl group, an acryloyl group, or a ureido group is preferable. More preferably an organic group having 2 to 12 carbon atoms and having a methacryloyl group, an acryloyl group or a ureido group.

B²Represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. Among them, preferred is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.

B³Represents an alkyl group having 1 to 5 carbon atoms. Among them, an alkyl group having 1 to 3 carbon atoms is preferable from the viewpoint of the polycondensation reactivity.

m represents an integer of 1 or 2. Among them, 1 is preferable from the viewpoint of synthesis.

n represents an integer of 0 to 2.

p represents an integer of 0 to 3. Among them, from the viewpoint of the polycondensation reactivity, an integer of 1 to 3 is preferable. More preferably 2 or 3.

In the formula [ A2], m + n + p represents an integer of 4.

Specific examples of the alkoxysilane represented by the formula [ A2] in the present invention include the following alkoxysilanes.

That is, there may be mentioned allyltriethoxysilane, allyltrimethoxysilane, diethoxymethylvinylsilane, dimethoxymethylvinylsilane, triethoxysilane, vinyltrimethoxysilane, vinyltris (2-methoxyethoxy) silane, m-styrylethyltriethoxysilane, p-styrylethyltriethoxysilane, m-styrylmethyl-triethoxysilane, p-styrylmethyl-triethoxysilane, 3- (N-styrylmethyl-2-aminoethylamino) propyltrimethoxysilane, 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-mercaptopropyl) triethoxysilane, (3-mercaptopropyl) trimethoxysilane, 3- (triethoxysilyl) propyl isocyanate, 3- (triethoxysilyl) propyl methacrylate, 3- (triethoxysilyl) propyl ester, 3- (aminoethyl) propyl methacrylate, 3- (aminoethyl) propyl ester, 3- (aminoethyl) propyl methyl silane, 3- (aminopropyl) diethoxymethylsilane, 3- (triethoxysilyl) propyl ester, and the like, 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, gamma-ureidopropyl triethoxysilane, gamma-ureidopropyl trimethoxysilane, beta-ureidopropyl triethoxysilane, beta-ureido-methyl acrylate, and the like, Gamma-ureidopropyltripropoxysilane, (R) -N-1-phenylethyl-N '-triethoxysilylpropylurea, (R) -N-1-phenylethyl-N' -trimethoxysilylpropylurea, bis [3- (trimethoxysilyl) propyl ] urea, bis [3- (tripropoxysilyl) propyl ] urea, 1- [3- (trimethoxysilyl) propyl ] urea, and the like.

Wherein, as the alkoxysilane represented by the formula [ A2], preference is given to using allyltriethoxysilane, allyltrimethoxysilane, diethoxymethylvinylsilane, dimethoxymethylvinylsilane, triethoxyvinylsilane, vinyltrimethoxysilane, vinyltris (2-methoxyethoxy) silane, 3- (triethoxysilyl) propyl methacrylate, 3- (trimethoxysilyl) propyl acrylate, 3- (trimethoxysilyl) propyl methacrylate, 3- (trimethoxysilyl) propyl 3-glycidyloxymethylsilane, 3-glycidyloxymethylsilane (diethoxy) methylsilane, 3-glycidyloxytrimethoxysilane or 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane.

The alkoxysilane represented by the formula [ a2] may be used in a mixture of 2 or more types depending on the solubility of the polysiloxane polymer in a solvent, the vertical alignment property of liquid crystal when a vertical liquid crystal alignment film is formed, and the optical characteristics of a liquid crystal display element.

(D¹)_nSi(OD²)_4-n [A3]

Formula [ A3]In (D)¹Represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, which is optionally substituted with a halogen atom, a nitrogen atom, an oxygen atom or a sulfur atom. Among them, preferred is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.

D²Represents an alkyl group having 1 to 5 carbon atoms. Among them, an alkyl group having 1 to 3 carbon atoms is preferable from the viewpoint of the polycondensation reactivity.

n represents an integer of 0 to 3.

Specific examples of the alkoxysilane represented by the formula [ A3] include the following alkoxysilanes.

That is, tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, methyltripropoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diethoxydiethylsilane, dibutoxydimethylsilane, (chloromethyl) triethoxysilane, 3-chloropropyldimethoxymethylsilane, 3-chloropropyltriethoxysilane, 2-cyanoethyltriethoxysilane, trimethoxy (3,3, 3-trifluoropropyl) silane, hexyltrimethoxysilane, 3-trimethoxysilylpropyl chloride and the like can be mentioned.

In the formula [ A3], examples of the alkoxysilane in which n is 0 include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane and tetrabutoxysilane, and the alkoxysilane represented by the formula [ A3] is preferably used.

The alkoxysilane represented by the formula [ a3] can be used by mixing 2 or more types of alkoxysilane depending on the solubility of the polysiloxane polymer of the present invention in a solvent, the vertical alignment property of a liquid crystal when a vertical liquid crystal alignment film is formed, and the optical characteristics of a liquid crystal display element.

When a polysiloxane polymer is used as the specific polymer of the present invention, it is preferably any of a polysiloxane obtained by polycondensing an alkoxysilane represented by the formula [ a1], a polysiloxane obtained by polycondensing an alkoxysilane represented by the formula [ a1] and an alkoxysilane containing any of the alkoxysilanes represented by the formula [ a2] or the formula [ A3], and a polysiloxane obtained by polycondensing an alkoxysilane represented by the formula [ a1] and the formula [ a2] and the formula [ A3 ].

That is, the polysiloxane is any of a polysiloxane obtained by polycondensing only an alkoxysilane represented by the formula [ A1], a polysiloxane obtained by polycondensing two alkoxysilanes represented by the formulae [ A1] and [ A2], a polysiloxane obtained by polycondensing two alkoxysilanes represented by the formulae [ A1] and [ A3], or a polysiloxane obtained by polycondensing three alkoxysilanes represented by the formulae [ A1] and [ A2] and [ A3 ].

Among these, from the viewpoint of the polycondensation reactivity and the solubility of the polysiloxane polymer in a solvent, a polysiloxane obtained by polycondensing a plurality of alkoxysilanes is preferable. That is, it is preferable to be a polysiloxane obtained by polycondensing two kinds of alkoxysilanes represented by the formula [ A1] and the formula [ A2], a polysiloxane obtained by polycondensing two kinds of alkoxysilanes represented by the formula [ A1] and the formula [ A3], or a polysiloxane obtained by polycondensing three kinds of alkoxysilanes represented by the formula [ A1] and the formula [ A2] and the formula [ A3 ].

When a plurality of alkoxysilanes are used in the production of the polysiloxane polymer, the alkoxysilane represented by the formula [ a1] is preferably 1 to 40 mol%, more preferably 1 to 30 mol%, based on the total alkoxysilanes. The alkoxysilane represented by the formula [ A2] is preferably 1 to 70 mol%, more preferably 1 to 60 mol%, based on the total alkoxysilane. Further, the alkoxysilane represented by the formula [ A3] is preferably 1 to 99 mol%, more preferably 1 to 80 mol%, based on the total alkoxysilane.

The method for producing the polysiloxane polymer used in the present invention is not particularly limited. Examples thereof include: a method of polycondensing an alkoxysilane represented by the formula [ A1] in a solvent, a method of polycondensing an alkoxysilane represented by the formula [ A1] and the formula [ A2] in a solvent, a method of polycondensing an alkoxysilane represented by the formula [ A1] and the formula [ A3] in a solvent, and a method of polycondensing an alkoxysilane represented by the formula [ A1] and the formula [ A2] and the formula [ A3] in a solvent. The polysiloxane polymer of the present invention can be obtained as a solution in which these alkoxysilanes are condensed and uniformly dissolved in a solvent.

The method for polycondensing the polysiloxane polymer is not particularly limited. For example, a method of subjecting alkoxysilane to hydrolysis/polycondensation reaction in a specific solvent, an alcohol-based solvent or a glycol-based solvent of the present invention can be mentioned. In this case, the hydrolysis/polycondensation reaction may be partially hydrolyzed or may be completely hydrolyzed. In the case of conducting complete hydrolysis, water may be theoretically added in an amount of 0.5 times the molar amount of all alkoxy groups in the alkoxysilane, and preferably more than 0.5 times the molar amount of water is added. The amount of water used in the hydrolysis/polycondensation reaction for obtaining the polysiloxane polymer of the present invention can be appropriately selected according to the purpose, and is preferably 0.5 to 2.5 times the molar amount of all alkoxy groups in the alkoxysilane.

In addition, in order to promote the hydrolysis/polycondensation reaction, acidic compounds such as hydrochloric acid, sulfuric acid, nitric acid, acetic acid, formic acid, oxalic acid, maleic acid, fumaric acid, and the like; basic compounds such as ammonia, methylamine, ethylamine, ethanolamine, triethylamine and the like; or a catalyst such as a metal salt of hydrochloric acid, nitric acid, oxalic acid, or the like. Further, the hydrolysis/polycondensation reaction can be promoted by heating the solution in which the alkoxysilane is dissolved. The heating temperature and the heating time at this time can be appropriately selected according to the purpose. For example, the reaction mixture may be heated and stirred at 50 ℃ for 24 hours and then stirred under reflux for 1 hour.

Further, as another method for carrying out the polycondensation, there is a method of heating a mixture of alkoxysilane, a solvent and oxalic acid to carry out the polycondensation reaction. Specifically, the method is a method of adding oxalic acid to a solvent in advance to prepare an oxalic acid solution, and then mixing alkoxysilane in a state of heating the solution. In this case, the amount of oxalic acid used in the reaction is preferably 0.2 to 2.0 moles per 1 mole of all alkoxy groups in the alkoxysilane. The reaction may be carried out at a solution temperature of 50 to 180 ℃, and 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 above-mentioned formulae [ A1], [ A2] and [ A3] are used, a mixture of a plurality of alkoxysilanes mixed in advance may be used for the reaction, or the reaction may be carried out while a plurality of alkoxysilanes are added in order.

The solvent used for the polycondensation reaction of alkoxysilane is not particularly limited as long as it is a specific solvent of the present invention or a solvent in which alkoxysilane is dissolved. In addition, even in the case of a solvent which does not dissolve the alkoxysilane, the alkoxysilane may be dissolved while the polycondensation reaction proceeds. As the solvent used for the polycondensation reaction, in general, an alcohol is produced by the polycondensation reaction of the alkoxysilane, and therefore an alcohol-based solvent, a glycol ether-based solvent, or a solvent having good compatibility with an alcohol can be used.

Specific examples of the solvent used in such a polycondensation reaction include the specific solvents of the present invention; alcohol solvents such as methanol, ethanol, propanol, butanol, and diacetone alcohol; glycol solvents such as ethylene glycol, diethylene glycol, 1, 2-propanediol, dipropylene glycol, hexanediol, 1, 3-propanediol, 1, 2-butanediol, 1, 3-butanediol, 1, 4-butanediol, 2, 3-butanediol, 1, 2-pentanediol, 1, 3-pentanediol, 1, 4-pentanediol, 1, 5-pentanediol, 2, 4-pentanediol, 2, 3-pentanediol, and 1, 6-hexanediol; glycol ether solvents such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene 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 monobutyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dipropyl ether, and propylene glycol dibutyl ether; solvents having good compatibility with alcohols, such as N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, γ -butyrolactone, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide, tetramethylurea, hexamethylphosphoric triamide, and m-cresol.

In the present invention, these solvents may be used in combination of 2 or more in the polycondensation reaction.

With respect to the solution of the polysiloxane polymer obtained by the above-mentioned method, silicon atoms of all alkoxysilanes charged as raw materials are converted to SiO₂Concentration of (also referred to as SiO)₂Reduced concentration) is preferably 20% by mass or less. Among them, it is preferably 5 to 15% by mass. By selecting an arbitrary concentration within this concentration range, the occurrence of gel in the solution can be suppressed, and a uniform solution of the polysiloxane polymer can be obtained.

In the present invention, the solution of the polysiloxane polymer obtained by the above-mentioned method may be used as it is as the specific polymer, or the solution of the polysiloxane polymer obtained by the above-mentioned method may be concentrated, diluted with a solvent, or replaced with another solvent, if necessary, to be used as the specific polymer.

The solvent used for the dilution by adding the solvent (also referred to as an additive solvent) may be a solvent used for the polycondensation reaction or another solvent. The solvent to be added is not particularly limited as long as it is within a range in which the polysiloxane polymer is uniformly dissolved, and 1 or 2 or more kinds thereof can be arbitrarily selected and used. Examples of such an additive solvent include ester solvents such as methyl acetate, ethyl acetate, and ethyl lactate, in addition to the solvents used in the polycondensation reaction.

Further, in the present invention, when the polysiloxane polymer and the other polymers are used as the specific polymer, it is preferable that alcohol generated in the polycondensation reaction of the polysiloxane polymer is distilled off in advance under normal pressure or reduced pressure before the other polymers are mixed with the polysiloxane polymer.

< liquid Crystal alignment treating agent >

The liquid crystal alignment treatment 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 solvent represented by the formula [1] and a specific polymer having at least 1 specific side chain structure selected from the group consisting of the structures represented by the formulae [2-1] and [2-2 ].

As the specific polymer having a specific side chain structure, there is no particular limitation as described above, and at least 1 polymer selected from the group consisting of an acrylic polymer, a methacrylic polymer, a novolac resin, polyhydroxystyrene, a polyimide precursor, polyimide, polyamide, polyester, cellulose, and polysiloxane is preferable. Among them, polyimide precursors, polyimides, or polysiloxanes are preferable, and polyimides or polysiloxanes are particularly preferable. In addition, the specific polymer of the present invention may use 1 or 2 or more of these polymers.

All of the polymer components in the liquid crystal aligning agent of the present invention may be the specific polymer of the present invention, or other polymers other than the specific polymer may be mixed. In this case, the content of the other polymer is 0.5 to 15 parts by mass, preferably 1 to 10 parts by mass, based on 100 parts by mass of the specific polymer of the present invention. As other polymers, there may be mentioned those having no specific side chain structure represented by the above formula [2-1] or the above formula [2-2 ].

The solvent content in the liquid crystal aligning agent of the present invention can be appropriately selected from the viewpoint of the method of applying the liquid crystal aligning agent and the achievement of a desired film thickness. Among them, the solvent content in the liquid crystal alignment treatment agent is preferably 50 to 99.9 mass% from the viewpoint of forming a uniform vertical liquid crystal alignment film by coating. Among them, the amount is preferably 60 to 99% by mass, and particularly preferably 65 to 99% by mass.

The solvent used in the liquid crystal aligning agent of the present invention may be all the specific solvents of the present invention, and it is preferable to use the specific solvents of the present invention in combination with a solvent for dissolving the specific polymer. In this case, when the specific polymer of the present invention is a polyimide precursor, polyimide, polyamide or polyester, or when the solubility of an acrylic polymer, methacrylic polymer, novolac resin, polyhydroxystyrene, cellulose or polysiloxane in a solvent is low, it is preferable to use a solvent (also referred to as a group a solvent) as shown below.

Namely, N-dimethylformamide, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, dimethyl sulfoxide, γ -butyrolactone, 1, 3-dimethyl-imidazolidinone, cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone, and the like. Among them, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone or γ -butyrolactone is preferably used.

Further, they 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, and further when the specific polymer of the present invention is a polyimide precursor, polyimide, polyamide, or polyester and the solubility of the specific polymer in a solvent is high, it is preferable to use a solvent (also referred to as a B-type solvent) as shown below.

Namely, ethanol, isopropanol, 1-butanol, 2-butanol, isobutanol, t-butanol, 1-pentanol, 2-pentanol, 3-pentanol, 2-methyl-1-butanol, isopentanol, t-pentanol, 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-ethyl-1-hexanol, cyclohexanol, 1-methylcyclohexanol, 2-methylcyclohexanol, 3-methylcyclohexanol, 1, 2-ethylene glycol, 1, 2-propylene glycol, 1, 2-propanediol, isobutanol, 3-methyl-1-pentanol, 2-methyl-2-pentanol, 2-methyl-1-pentanol, 2-ethyl-1-hexanol, 3-methyl-cyclohexanol, 1, 2-ethylene glycol, 2-butanol, and the like, 1, 3-propanediol, 1, 2-butanediol, 1, 3-butanediol, 1, 4-butanediol, 2, 3-butanediol, 1, 5-pentanediol, 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, 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, diethylene glycol dimethyl ether, diethylene glycol dibutyl ether, 3-ethoxybutyl acetate, 1-methylpentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, ethylene glycol diacetate, propylene carbonate, ethylene carbonate, 2- (methoxymethoxy) ethanol, propylene glycol dimethyl ether, propylene glycol dimethyl ether, propylene glycol dimethyl ether, propylene glycol dimethyl, Ethylene glycol monobutyl ether, ethylene glycol monoisoamyl ether, ethylene glycol monohexyl ether, 2- (hexyloxy) ethanol, furfuryl alcohol, diethylene glycol, propylene glycol monobutyl ether, 1- (butoxyethoxy) propanol, propylene glycol monomethyl ether acetate, 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, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, 2- (2-ethoxyethoxy) ethyl acetate, diethylene glycol acetate, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether acetate, propylene glycol monoethyl ether, propylene glycol, 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, cyclopentanone, cyclohexanone, or a solvent represented by the following formulae [ S1] to [ S3 ].

(T¹、T²And T³The same meaning as defined in the foregoing. )

Among them, 1-hexanol, cyclohexanol, 1, 2-ethylene glycol, 1, 2-propylene glycol, propylene glycol monobutyl ether, ethylene glycol monobutyl ether, or dipropylene glycol dimethyl ether is preferably used.

Furthermore, cyclopentanone, cyclohexanone, or a solvent represented by the above-mentioned formulas [ S1] to [ S3] is also preferably used.

Since these group B solvents can improve the film coatability and surface smoothness of the vertical liquid crystal alignment film when the liquid crystal alignment treatment agent is applied, when a polyimide precursor, a polyimide, a polyamide or a polyester is used as the specific polymer, it is preferable to use the group B solvent in combination with the group a solvent.

The solvent in the liquid crystal aligning agent of the present invention may be the specific solvent of the present invention, but is preferably 1 to 80% by mass of the entire solvent contained in the liquid crystal aligning agent. More preferably 1 to 70% by mass, and particularly preferably 5 to 60% by mass. Most preferably 5 to 50 mass%.

In the liquid crystal alignment treatment agent of the present invention, at least 1 kind of generating agent (also referred to as a specific generating agent) selected from the group consisting of a photoradical generating agent, a photoacid generating agent and a photobase generating agent is preferably introduced.

The photo radical generator is not particularly limited as long as it is a substance that generates radicals by ultraviolet rays, and examples thereof include the photo radical generators described below.

Namely, t-butylperoxyisobutyrate, 2, 5-dimethyl-2, 5-bis (benzoylperoxy) hexane, 1, 4-bis [ α - (t-butylperoxy) isopropoxy ] benzene, di-t-butyl peroxide, 2, 5-dimethyl-2, 5-bis (t-butylperoxy) hexene hydroperoxide, α - (cumyl) isopropyl hydroperoxide, 2, 5-dimethylhexane, t-butyl hydroperoxide, 1-bis (t-butylperoxy) -3,3, 5-trimethylcyclohexane, butyl-4, 4-bis (t-butylperoxy) valerate, cyclohexanone peroxide, 2 ', 5, 5' -tetrakis (t-butylperoxycarbonyl) benzophenone, 3 ', 4, 4' -tetrakis (t-butylperoxycarbonyl) benzophenone, 2,5 '-bis (t-butylperoxy) hexylene, 1, 5-bis (t-butylperoxy) hexylene, 2', 5,5 '-tetrakis (t-butylperoxy) valerate, 3', 4,4 '-tetrakis (t-butylperoxycarbonyl) benzophenone, 4' -tetrakis (t-butylperoxy) hexylene, Organic peroxides such as 3,3 ', 4, 4' -tetrakis (t-amylperoxycarbonyl) benzophenone, 3 ', 4, 4' -tetrakis (t-hexylperoxycarbonyl) benzophenone, 3 '-bis (t-butylperoxycarbonyl) -4, 4' -dicarboxybenzophenone, t-butyl peroxybenzoate, and di-t-butyl diperoxyiisophthalate; quinones such as 9, 10-anthraquinone, 1-chloroanthraquinone, 2-chloroanthraquinone, octamethylanthraquinone, and 1, 2-benzoanthraquinone; benzoin derivatives such as benzoin methyl ether, benzoin ethyl ether, α -methylbenzoin, and α -phenylbenzoin.

The photoacid generator and the photobase generator are not particularly limited as long as they generate an acid or a base by ultraviolet rays, and examples thereof include triazine compounds, acetophenone derivative compounds, disulfone (disulfone) compounds, diazomethane compounds, sulfonic acid derivative compounds, diaryl iodonium salts, triarylsulfonium salts, triarylphosphonium salts, and iron arene complexes. More specifically, the following photoacid generators and photobase generators can be mentioned.

Namely, diphenyliodonium chloride, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium methanesulfonate, diphenyliodonium toluenesulfonate, diphenyliodonium bromide, diphenyliodonium tetrafluoroborate, diphenyliodonium hexafluoroantimonate, diphenyliodonium hexafluoroarsenate, bis (4-tert-butylphenyl) iodonium hexafluorophosphate, bis (p-tert-butylphenyl) iodonium methanesulfonate, bis (p-tert-butylphenyl) iodonium toluenesulfonate, bis (p-tert-butylphenyl) iodonium trifluoromethanesulfonate, bis (p-tert-butylphenyl) iodonium tetrafluoroborate, bis (p-tert-butylphenyl) iodine chloride, bis (p-chlorophenyl) iodonium tetrafluoroborate, triphenylsulfonium chloride, triphenylsulfonium bromide, tris (p-methoxyphenyl) sulfonium tetrafluoroborate, tris (p-methoxyphenyl) sulfonium hexafluorophosphate, Tris (p-ethoxyphenyl) sulfonium tetrafluoroborate, triphenylsulfonium chloride, triphenylsulfonium bromide, tris (p-methoxyphenyl) sulfonium tetrafluoroborate, tris (p-methoxyphenyl) sulfonium hexafluorophosphate, tris (p-ethoxyphenyl) sulfonium tetrafluoroborate, bis [ [ (2-nitrobenzyl) oxy ] carbonylhexane-1, 6-diamine ], nitrobenzylcyclohexylcyclohexylcarbamate, bis (methoxybenzyl) hexamethylenedicarbamate, and the like.

Among these, the specific generating agent of the present invention is preferably used from the viewpoint of improving the adhesion between the liquid crystal layer and the vertical liquid crystal alignment film.

The content of the specific initiator in the liquid crystal aligning agent of the present invention is preferably 0.01 to 50 parts by mass per 100 parts by mass of all the polymer components. More preferably 0.01 to 30 parts by mass, and particularly preferably 0.1 to 20 parts by mass.

The specific developer may be used in combination with 2 or more kinds of the specific developer depending on the solubility of the specific developer in a solvent, the vertical alignment property of liquid crystal when the liquid crystal alignment film is formed, and the optical characteristics of the liquid crystal display element.

In the liquid crystal alignment treatment agent of the present invention, for the purpose of improving the adhesion between the liquid crystal layer and the vertical liquid crystal alignment film, it is preferable to introduce at least 1 compound (also referred to as a specific adhesion compound) selected from the group consisting of compounds having structures represented by the following formulae [ M1] to [ M8 ]. In this case, it is preferable that 2 or more structures represented by the formulae [ M1] to [ M8] are present in the compound.

Formula [ M4]In, W¹Represents a hydrogen atom or a benzene ring.

Formula [ M7]In, W²Represents at least 1 cyclic group selected from a benzene ring, a cyclohexane ring and a heterocycle; w³Represents 1 kind selected from alkyl with 1-18 carbon atoms, fluorine-containing alkyl with 1-18 carbon atoms, alkoxy with 1-18 carbon atoms and fluorine-containing alkoxy with 1-18 carbon atoms.

More specifically, the following substances are exemplified.

That is, compounds having 3 polymerizable unsaturated groups in the molecule, such as trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, tris (meth) acryloyloxyethoxy trimethylolpropane, glycerol polyglycidyl ether poly (meth) acrylate, and the like; 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, butanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, ethylene oxide bisphenol A type di (meth) acrylate, compounds having 2 polymerizable unsaturated groups in the molecule, such as propylene oxide bisphenol type di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, glycerol di (meth) acrylate, pentaerythritol di (meth) acrylate, ethylene glycol diglycidyl ether di (meth) acrylate, diethylene glycol diglycidyl ether di (meth) acrylate, phthalic acid diglycidyl ester di (meth) acrylate, and hydroxypivalic acid neopentyl glycol di (meth) acrylate; and compounds having 1 polymerizable unsaturated group in the molecule, such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-phenoxy-2-hydroxypropyl (meth) acrylate, 2- (meth) acryloyloxy-2-hydroxypropyl phthalate, 3-chloro-2-hydroxypropyl (meth) acrylate, glycerol mono (meth) acrylate, 2- (meth) acryloyloxyethyl phosphate, and N-methylol (meth) acrylamide.

Further, a compound represented by the following formula [7A ] can also be used.

(formula [7A ]]In, E¹Represents at least 1 selected from the group consisting of cyclohexane ring, bicyclohexane ring, benzene ring, biphenyl ring, terphenyl ring, naphthalene ring, fluorene ring, anthracene ring and phenanthrene ring, E²Is represented by the following formula [7a ]]Or formula [7b]And n represents an integer of 1 to 4. )

The content of the specific adhesion compound in the liquid crystal aligning agent of the present invention is preferably 0.1 to 150 parts by mass per 100 parts by mass of the total polymer components. In order to perform the crosslinking reaction and exhibit the desired effect, the amount of the crosslinking agent is more preferably 0.1 to 100 parts by mass, particularly preferably 1 to 50 parts by mass, based on 100 parts by mass of the entire polymer component.

The specific adhesion compound may be used in a mixture of 2 or more types depending on the solubility of the specific adhesion compound in a solvent, the vertical alignment property of liquid crystal when a vertical liquid crystal alignment film is formed, and the optical characteristics of the liquid crystal display element.

In the liquid crystal aligning agent of the present invention, a compound having an epoxy group, an isocyanate group, an oxetanyl group or a cyclocarbonate group is preferably introduced within a range in which the effects of the present invention are not impaired; a compound having at least 1 substituent selected from the group consisting of a hydroxyl group, a hydroxyalkyl group and a lower alkoxyalkyl group (also collectively referred to as a specific crosslinkable compound). In this case, it is necessary that 2 or more of these substituents be present in the crosslinkable compound.

Examples of the crosslinkable compound having an epoxy group or an isocyanate group include the following compounds.

Namely, bisphenol acetone glycidyl ether, phenol novolac epoxy resin, cresol novolac epoxy resin, triglycidyl isocyanurate, tetraglycidyl aminobiphenyl, tetraglycidyl m-xylylenediamine, tetraglycidyl-1, 3-bis (aminoethyl) cyclohexane, tetraphenyl glycidyl ether ethane, triphenyl glycidyl ether ethane, bisphenol hexafluoroacetyl diglycidyl ether, 1, 3-bis (1- (2, 3-epoxypropoxy) -1-trifluoromethyl-2, 2, 2-trifluoromethyl) benzene, 4-bis (2, 3-epoxypropoxy) octafluorobiphenyl, triglycidyl p-aminophenol, tetraglycidyl m-xylylenediamine, 2- (4- (2, 3-epoxypropoxy) phenyl) -2- (4- (1, 1-bis (4- (2, 3-epoxypropoxy) phenyl) ethyl) phenyl) propane, 1, 3-bis (4- (1- (4- (2, 3-epoxypropoxy) phenyl) -1-methylethyl) phenyl) ethyl) phenoxy) -2-propanol, and the like.

The crosslinkable compound having an oxetanyl group is a crosslinkable compound having at least 2 oxetanyl groups represented by the following formula [4A ].

Specifically, examples of the crosslinkable compound include crosslinkable compounds represented by the formulae [4a ] to [4k ] described in international publication WO2011/132751(2011.10.27 publication) at pages 58 to 59.

The crosslinkable compound having a cyclocarbonate group is a crosslinkable compound having at least 2 cyclocarbonate groups represented by the following formula [5A ].

Specifically, examples of the crosslinkable compound include crosslinkable compounds represented by the formulae [5-1] to [5-42] described in International publication WO2012/014898 (publication 2012.2.2) on pages 76 to 82.

Examples of the crosslinkable compound having at least 1 substituent selected from the group consisting of a hydroxyl group and an alkoxy group include amino resins having a hydroxyl group or an alkoxy group, such as melamine resin, urea resin, guanamine resin, glycoluril-formaldehyde resin, succinamide-formaldehyde resin, ethyleneurea-formaldehyde resin, and the like. Specifically, a melamine derivative, a benzoguanamine derivative, or glycoluril in which the hydrogen atom of the amino group is substituted with a hydroxymethyl group and/or an alkoxymethyl group can be used. The melamine derivative or benzoguanamine derivative may be present in the form of a dimer or trimer. They preferably have an average of 3 or more and 6 or less hydroxymethyl groups or alkoxymethyl groups per 1 triazine ring.

Examples of such melamine derivatives or benzoguanamine derivatives include commercially available methoxymethylated melamines such as MX-750 substituted with an average of 3.7 methoxymethyl groups per 1 triazine ring, MW-30 substituted with an average of 5.8 methoxymethyl groups per 1 triazine ring (Sanhe chemical Co., Ltd.), CYMEL 300, 301, 303, 350, 370, 771, 325, 327, 703, 712, etc.; methoxymethylated butoxymethylated melamines such as CYMEL 235, 236, 238, 212, 253, 254; butoxymethylated melamines such as CYMEL 506, 508; carboxymethoxymethylated isobutoxymethylated melamines such as CYMEL 1141; methoxymethylated ethoxymethylated benzoguanamine such as CYMEL 1123; methoxymethylated butoxymethylated benzoguanamine such as CYMEL 1123-10; butoxymethylated benzoguanamine such as CYMEL 1128; carboxylmethoxymethylated ethoxymethylated benzoguanamine such as CYMEL 1125-80 (manufactured by Mitsui-Cyanamid Ltd.). Examples of glycolurils include butoxymethylated glycolurils such as CYMEL 1170, hydroxymethylated glycolurils such as CYMEL 1172, and the like; methoxy methylolated glycolurils such as Powder link 1174, and the like.

Examples of the benzene or phenol compound having a hydroxyl group or an alkoxy group include 1,3, 5-tris (methoxymethyl) benzene, 1,2, 4-tris (isopropoxymethyl) benzene, 1, 4-bis (sec-butoxymethyl) benzene, 2, 6-dihydroxymethyl-p-tert-butylphenol, and the like.

More specifically, examples thereof include crosslinkable compounds represented by the formulae [6-1] to [6-48] described in International publication WO2011/132751(2011.10.27 publication) at pages 62 to 66.

The content of the specific crosslinkable compound in the liquid crystal aligning agent of the present invention is preferably 0.1 to 100 parts by mass per 100 parts by mass of the total polymer components. In order to perform the crosslinking reaction and exhibit the desired effect, the amount of the crosslinking agent is more preferably 0.1 to 50 parts by mass, particularly preferably 1 to 40 parts by mass, based on 100 parts by mass of the entire polymer component.

The specific crosslinkable compound may be used in a mixture of 2 or more types depending on the solubility of the specific crosslinkable compound in a solvent, the vertical alignment property of liquid crystal when a vertical liquid crystal alignment film is formed, and the optical characteristics of a liquid crystal display element.

In the liquid crystal display element of the present invention, as a compound that promotes charge transfer in the liquid crystal alignment film and promotes charge removal from the element, a nitrogen-containing heterocyclic amine compound represented by the formulae [ M1] to [ M156] described on pages 69 to 73 of international publication WO2011/132751(2011.10.27 publication) may be added. The amine compound may be added directly to the liquid crystal aligning agent, and is preferably added after being dissolved in an appropriate solvent to a concentration of 0.1 to 10% by mass, preferably 1 to 7% by mass. The solvent is not particularly limited as long as it is an organic solvent that dissolves the above-mentioned specific polymer.

The liquid crystal aligning agent of the present invention may be a compound which improves the film thickness uniformity and surface smoothness of the vertical liquid crystal alignment film when the liquid crystal aligning agent is applied, within a range not impairing the effects of the present invention. Further, a compound or the like which improves the adhesion between the vertical liquid crystal alignment film and the substrate may be used.

Examples of the compound for improving 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. More specifically, for example, Eftop EF301, EF303, and EF352 (manufactured by Tohkem products Corporation); megafac F171, F173, R-30 (see above, DIC Corporation); fluorad FC430 and FC431 (manufactured by Sumitomo 3M Limited); asahiguard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by Asahi glass Co., Ltd.). The amount of the surfactant is preferably 0.01 to 2 parts by mass, more preferably 0.01 to 1 part by mass, per 100 parts by mass of all the polymer components contained in the liquid crystal aligning agent.

Specific examples of the compound for improving the adhesion between the vertical liquid crystal alignment film and the substrate include a functional silane-containing compound and an epoxy-containing compound described below.

Examples thereof include 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-ethoxycarbonyl-3-aminopropyltriethoxysilane, N-triethoxysilylpropyltriethylenetriamine, N-trimethoxysilylpropyltriethylenetriamine, 10-trimethoxysilyl-1, 4, 7-triazacyclodecane, 10-triethoxysilyl-1, 4, 7-triazacyclodecane, 9-trimethoxysilyl-3, 6-diazanonylacetate, 9-triethoxysilyl-3, 6-diazanonylacetate, N-benzyl-3-aminopropyltrimethoxysilane, N-benzyl-3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N-bis (oxyethylene) -3-aminopropyltrimethoxysilane, N-bis (oxyethylene) -3-aminopropyltriethoxysilane, ethylene glycol diglycidyl ether, N-bis (oxyethylene) -3-aminopropyltrimethoxysilane, N-bis (oxyethylene) -3-aminopropyltriethoxysilane, N-bis (oxyethylene) -3-aminopropyl-trimethoxysilane, ethylene glycol diglycidyl ether, N-bis (oxyethylene) -3-aminopropyl-trimethoxysilane, N-bis (oxyethylene) -3-aminopropyl-triethoxysilane, N-bis (oxyethylene) -3-glycidylether, N-bis (oxyethylene) -2-bis (oxyethylene) triethoxysilane, N-bis (oxyethylene) ether, and (oxyethylene) ether, Polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1, 6-hexanediol diglycidyl ether, glycerol diglycidyl ether, 2-dibromoneopentyl glycol diglycidyl ether, 1,3,5, 6-tetraglycidyl-2, 4-hexanediol, N ', -tetraglycidyl-m-xylylenediamine, 1, 3-bis (N, N-diglycidylaminomethyl) cyclohexane, N ', -tetraglycidyl-4, 4 ' -diaminodiphenylmethane, and the like.

When a compound for bonding the liquid crystal alignment film to the substrate is used, the amount is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass, per 100 parts by mass of all the polymer components contained in the liquid crystal alignment agent. If the amount is less than 0.1 part by mass, the effect of improving adhesion cannot be expected, and if the amount is more than 30 parts by mass, the storage stability of the liquid crystal aligning agent may be deteriorated. In the liquid crystal alignment treatment agent of the present invention, a dielectric material or a conductive material for changing electric characteristics such as a dielectric constant and conductivity of the vertical liquid crystal alignment film may be added in addition to the above-mentioned compounds within a range not to impair the effects of the present invention.

< liquid Crystal composition >

As the liquid crystal in the liquid crystal composition used in the liquid crystal display element of the present invention, nematic liquid crystal or smectic liquid crystal can be used. Among them, the liquid crystal display element of the present invention preferably has negative dielectric anisotropy. In addition, from the viewpoint of low-voltage driving and scattering characteristics of the liquid crystal display element of the present invention, an element having a large anisotropy of dielectric constant and a large anisotropy of refractive index is preferable. Further, in order to drive the liquid crystal display element of the present invention as an active element such as a TFT (Thin Film Transistor), the liquid crystal is required to have high resistance and high voltage holding ratio (also referred to as VHR). Therefore, fluorine-based or chlorine-based liquid crystals having high resistance and whose VHR is not lowered by active energy rays such as ultraviolet rays are preferably used as the liquid crystals. In addition, the liquid crystal used in the liquid crystal display element of the present invention is preferably a liquid crystal having a large birefringence (Δ n).

The liquid crystal display element of the present invention may be a guest-host type element obtained by dissolving a dichroic dye in a liquid crystal composition. In this case, an element which is transparent when no voltage is applied and which absorbs (scatters) when a voltage is applied can be obtained. In the liquid crystal display element of the present invention, the orientation direction of the liquid crystal changes by 90 degrees depending on whether or not a voltage is applied. Therefore, the liquid crystal display element of the present invention can obtain a high contrast ratio by utilizing the difference in light absorption characteristics of the dichroic dye, as compared with a conventional guest-host type element in which switching is performed between random alignment and vertical alignment. In addition, the guest-host type element in which the dichroic dye is dissolved becomes colored when the liquid crystal is aligned in the horizontal direction, and becomes opaque only in the scattering state. Therefore, an element which switches from colorless transparency when no voltage is applied to a colored opaque state or a colored transparent state with the application of a voltage can be obtained.

The liquid crystal composition of the liquid crystal display element of the present invention contains a polymerizable compound that is polymerized by at least one of an active energy ray such as ultraviolet light and heat. In this case, the polymerization may be carried out in any reaction form to form a cured product composite of the liquid crystal and the polymerizable compound. Specific polymerization forms include radical polymerization, cationic polymerization, anionic polymerization, and addition polymerization.

The polymerizable compound of the present invention may be any compound as long as it is dissolved in a liquid crystal. In particular, when the polymerizable compound is dissolved in the liquid crystal, it is necessary to have a temperature at which a part or all of the liquid crystal composition of the present invention exhibits a liquid crystal phase. Even when a part of the liquid crystal composition exhibits a liquid crystal phase, the liquid crystal display element of the present invention can be visually confirmed to obtain substantially uniform transparency and scattering characteristics throughout the entire element.

The reactive form of the polymerizable compound is radical polymerization, and the following radical polymerizable compounds can be used.

Namely, 2-ethylhexyl acrylate, butyl ethyl acrylate, butoxyethyl acrylate, 2-cyanoethyl acrylate, benzyl acrylate, cyclohexyl acrylate, 2-hydroxypropyl acrylate, 2-ethoxyethyl acrylate, N-diethylaminoethyl acrylate, N-dimethylaminoethyl acrylate, dicyclopentyl acrylate, dicyclopentenyl acrylate, glycidyl acrylate, tetrahydrofurfuryl acrylate, isobornyl acrylate, isodecyl acrylate, lauryl acrylate, morpholinyl acrylate, phenoxyethyl acrylate, phenoxydiethylene glycol acrylate, 2,2, 2-trifluoroethyl acrylate, 2,2,3,3, 3-pentafluoropropyl acrylate, 2,2,3, 3-tetrafluoropropyl acrylate, 2,2,3,4,4, 4-hexafluorobutyl methacrylate, 2-ethylhexyl methacrylate, butyl ethyl methacrylate, butoxyethyl methacrylate, 2-cyanoethyl methacrylate, benzyl methacrylate, cyclohexyl methacrylate, 2-hydroxypropyl methacrylate, 2-ethoxyethyl acrylate, N-diethylaminoethyl methacrylate, N-dimethylaminoethyl methacrylate, dicyclopentyl methacrylate, dicyclopentenyl methacrylate, glycidyl methacrylate, tetrahydrofurfuryl methacrylate, isobornyl methacrylate, isodecyl methacrylate, lauryl methacrylate, morpholinyl methacrylate, phenoxyethyl methacrylate, phenoxydiethylene glycol methacrylate, 2-methacrylic acid, 2, 2-trifluoroethyl ester, 2,3, 3-tetrafluoropropyl methacrylate, 2,3,4,4, 4-hexafluorobutyl methacrylate, 4,4 ' -biphenyl diacrylate, diethylstilbestrol diacrylate, 1, 4-bisacryloxybenzene, 4,4 ' -bisacryloxydiphenyl ether, 4,4 ' -bisacryloxydiphenylmethane, 3,9- [1, 1-dimethyl-2-acryloyloxyethyl ] -2,4,8, 10-tetraoxaspiro [5,5] undecane, α ' -bis [ 4-acryloyloxyphenyl ] -1, 4-diisopropylbenzene, 1, 4-bisacryloxy tetrafluorobenzene, 4,4 ' -bisacryloxy octafluorobiphenyl, Diethylene glycol acrylate, 1, 4-butanediol diacrylate, 1, 3-butanediol 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, dipentaerythritol monohydroxypentaacrylate, 4 ' -diacryloyloxystilbene, 4 ' -diacryloyloxydimethylstilbene, 4 ' -diacryloyloxydiethylstilbene, 4 ' -diacryloyloxydiprostylstilbene, 4 ' -diacryloyloxydipropylstilbene, 4 ' -diacryloyloxydibutylstilbene, 4 ' -diacryloyloxydiphenylstilbene, 4,4 '-diacryloyloxydihexylstilbene, 4, 4' -diacryloyloxydifluorstilbene, 2,2,3,3,4, 4-hexafluoropentanediol-1, 5-diacrylate, 1,2,2,3, 3-hexafluoropropyl-1, 3-diacrylate, diethylene glycol dimethacrylate, 1, 4-butanediol dimethacrylate, 1, 3-butanediol dimethacrylate, 1, 6-hexanediol dimethacrylate, neopentyl glycol dimethacrylate, tetraethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, pentaerythritol tetramethacrylate, pentaerythritol trimethacrylate, ditrimethylolpropane tetramethacrylate, dipentaerythritol hexamethacrylate, dipentaerythritol monohydroxypentamethacrylate or 2, monomers and oligomers such as 2,3,3,4, 4-hexafluoropentanediol-1, 5-dimethacrylate.

Among these, in the liquid crystal display element of the present invention, in order to improve scattering characteristics when a voltage is applied, a polyfunctional radical polymerizable compound having 3 or more functional groups is preferably used.

Specific examples thereof include monomers and oligomers such as trimethylolpropane triacrylate, pentaerythritol tetraacrylate, pentaerythritol triacrylate, ditrimethylolpropane tetraacrylate, dipentaerythritol hexaacrylate, dipentaerythritol monohydroxypentaacrylate, trimethylolpropane trimethacrylate, pentaerythritol tetramethacrylate, pentaerythritol trimethacrylate, ditrimethylolpropane tetramethacrylate, dipentaerythritol hexamethacrylate or dipentaerythritol monohydroxypentamethacrylate.

The radical polymerizable compound may be used in a mixture of 2 or more types depending on the optical characteristics of the liquid crystal display element and the adhesion between the liquid crystal layer and the vertical liquid crystal alignment film.

Further, when the reactive form of the polymerizable compound is radical polymerization, a radical initiator that generates radicals by ultraviolet rays may be introduced into the liquid crystal composition.

Specific examples thereof include t-butylperoxyisobutyrate, 2, 5-dimethyl-2, 5-bis (benzoylperoxy) hexane, 1, 4-bis [ α - (t-butylperoxy) isopropoxy ] benzene, di-t-butyl peroxide, 2, 5-dimethyl-2, 5-bis (t-butylperoxy) hexylene peroxide, α - (isopropylphenyl) isopropyl peroxide, 2, 5-dimethylhexane, t-butyl peroxide, 1-bis (t-butylperoxy) -3,3, 5-trimethylcyclohexane, butyl-4, 4-bis (t-butylperoxy) valerate, cyclohexanone peroxide, 2 ', 5,5 ' -tetrakis (t-butylperoxycarbonyl) benzophenone, 3 ', organic peroxides such as 4,4 ' -tetrakis (t-butylperoxycarbonyl) benzophenone, 3 ', 4,4 ' -tetrakis (t-amylperoxycarbonyl) benzophenone, 3 ', 4,4 ' -tetrakis (t-hexylperoxycarbonyl) benzophenone, 3 ' -bis (t-butylperoxycarbonyl) -4,4 ' -dicarboxybenzophenone, t-butylperoxybenzoate, and di-t-butylperoxyisophthalate; quinones such as 9, 10-anthraquinone, 1-chloroanthraquinone, 2-chloroanthraquinone, octamethylanthraquinone, and 1, 2-benzoanthraquinone; benzoin derivatives such as benzoin methyl ether, benzoin ethyl ether, α -methylbenzoin, and α -phenylbenzoin.

When the reactive form of the polymerizable compound is cationic polymerization or anionic polymerization, the following ionic polymerizable compounds can be used.

That is, the compound has at least 1 kind of crosslinking-forming group selected from the group consisting of a hydroxyl group, a hydroxyalkyl group, and a lower alkoxyalkyl group. Specifically, the hydrogen atom of the amino group is substituted with a hydroxymethyl group and/or an alkoxymethyl group to obtain a melamine derivative, a benzoguanamine derivative, or glycoluril. The melamine derivative or benzoguanamine derivative may be an oligomer. They preferably have an average of 3 or more and less than 6 hydroxymethyl groups or alkoxymethyl groups per 1 triazine ring.

Examples of such melamine derivatives and benzoguanamine derivatives include commercially available methoxymethylated melamines such as MX-750 substituted with an average of 3.7 methoxymethyl groups per 1 triazine ring, MW-30 substituted with an average of 5.8 methoxymethyl groups per 1 triazine ring (Sanhe chemical Co., Ltd.), CYMEL 300, 301, 303, 350, 370, 771, 325, 327, 703 and 712; methoxymethylated butoxymethylated melamines such as CYMEL 235, 236, 238, 212, 253, 254; butoxymethylated melamines such as CYMEL 506, 508; carboxymethoxymethylated isobutoxymethylated melamines such as CYMEL 1141; methoxymethylated ethoxymethylated benzoguanamine such as CYMEL 1123; methoxymethylated butoxymethylated benzoguanamine such as CYMEL 1123-10; butoxymethylated benzoguanamine such as CYMEL 1128; carboxymethoxymethylated ethoxymethylated benzoguanamine such as CYMEL 1125-80 (manufactured by Mitsui-Cytec Ltd.).

Examples of glycolurils include butoxymethylated glycoluril such as CYMEL 1170, and hydroxymethylated glycoluril such as CYMEL 1172.

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

As the ionic polymerizable compound of the present invention, a compound containing an epoxy group or an isocyanate group and having a crosslinking-forming group can also be used. Specific examples thereof include bisphenol acetone glycidyl ether, phenol novolac epoxy resin, cresol novolac epoxy resin, triglycidyl isocyanurate, tetraglycidyl aminobiphenyl, tetraglycidyl m-xylylenediamine, tetraglycidyl-1, 3-bis (aminoethyl) cyclohexane, tetraphenyl glycidyl ether ethane, triphenyl glycidyl ether ethane, bisphenol hexafluoroacetyl diglycidyl ether, 1, 3-bis (1- (2, 3-epoxypropoxy) -1-trifluoromethyl-2, 2, 2-trifluoromethyl) benzene, 4-bis (2, 3-epoxypropoxy) octafluorobiphenyl, triglycidyl p-aminophenol, tetraglycidyl m-xylylenediamine, 2- (4- (2, 3-epoxypropoxy) phenyl) -2- (4- (1, 1-bis (4- (2, 3-epoxypropoxy) phenyl) ethyl) phenyl) propane, 1, 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 compound may be used in a mixture of 2 or more types depending on the optical characteristics of the liquid crystal display element and the adhesion between the liquid crystal layer and the vertical liquid crystal alignment film.

Further, when the reactive form of the polymerizable compound is cationic polymerization or anionic polymerization, an ionic initiator that generates an acid or a base by ultraviolet rays may be introduced into the liquid crystal composition.

Specifically, triazine compounds, acetophenone derivative compounds, disulfone compounds, diazomethane compounds, sulfonic acid derivative compounds, diaryliodonium salts, triarylsulfonium salts, triarylphosphonium salts, iron arene complexes, and the like can be used, but the present invention is not limited thereto. More specifically, there may be mentioned, for example, diphenyliodonium chloride, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium methanesulfonate, diphenyliodonium toluenesulfonate, diphenyliodine bromide, diphenyliodonium tetrafluoroborate, diphenyliodonium hexafluoroantimonate, diphenyliodonium hexafluoroarsenate, bis (4-tert-butylphenyl) iodonium hexafluorophosphate, bis (p-tert-butylphenyl) iodonium methanesulfonate, bis (p-tert-butylphenyl) iodonium toluenesulfonate, bis (p-tert-butylphenyl) iodonium trifluoromethanesulfonate, bis (p-tert-butylphenyl) iodonium tetrafluoroborate, bis (p-tert-butylphenyl) iodonium chloride, bis (p-chlorophenyl) iodonium tetrafluoroborate, triphenylsulfonium chloride, triphenylsulfonium bromide, tris (p-methoxyphenyl) sulfonium tetrafluoroborate, tris (p-methoxyphenyl) sulfonium hexafluorophosphate, Tris (p-ethoxyphenyl) sulfonium tetrafluoroborate, triphenylphosphonium chloride, triphenylphosphonium bromide, tris (p-methoxyphenyl) phosphonium tetrafluoroborate, tris (p-methoxyphenyl) phosphonium hexafluorophosphate, tris (p-ethoxyphenyl) phosphonium tetrafluoroborate. Examples thereof include bis [ [ (2-nitrobenzyl) oxy ] carbonylhexane-1, 6-diamine ], nitrobenzylcyclohexylcarbamate, bis (methoxybenzyl) hexamethylenedicarbamate, bis [ [ (2-nitrobenzyl) oxy ] carbonylhexane-1, 6-diamine ], nitrobenzylcyclohexylcarbamate, bis (methoxybenzyl) hexamethylenedicarbamate and the like.

In the liquid crystal display element of the present invention, a radical type polymerizable compound is preferably used among the polymerizable compounds described above from the viewpoint of the optical characteristics of the element.

The amount of the polymerizable compound to be introduced into the liquid crystal composition is not particularly limited, and when the amount of the polymerizable compound to be introduced is large, the polymerizable compound does not dissolve in the liquid crystal, the temperature at which the liquid crystal composition exhibits a liquid crystal phase does not exist, or the change between the transparent state and the scattering state of the device is small, and the optical properties are deteriorated. When the amount of the polymerizable compound to be introduced is small, curability of the liquid crystal layer is low, adhesion between the liquid crystal layer and the vertical liquid crystal alignment film is low, and alignment of the liquid crystal is likely to be disturbed by external mechanical pressure. Therefore, the amount of the polymerizable compound to be introduced is preferably 1 to 70 parts by mass, and particularly preferably 5 to 60 parts by mass, based on 100 parts by mass of the liquid crystal. Particularly preferably 11 to 50 parts by mass.

The amount of the radical initiator and the ionic initiator to be introduced for promoting the reaction of the polymerizable compound is not particularly limited, but is preferably 0.01 to 20 parts by mass, particularly preferably 0.05 to 10 parts by mass, based on 100 parts by mass of the liquid crystal. Particularly preferably 0.05 to 5 parts by mass.

< method for producing vertical liquid Crystal alignment film/liquid Crystal display device >

The substrate used in the liquid crystal display element of the present invention is not particularly limited as long as it is a substrate having high transparency, and in addition to a glass substrate, a plastic substrate such as an acrylic substrate, a polycarbonate substrate, or a PET (polyethylene terephthalate) substrate may be used.

The liquid crystal display element of the present invention is preferably a plastic substrate when it is used as a converse type element for a light control window or the like. In addition, from the viewpoint of simplifying the process, a substrate on which an ITO (Indium Tin Oxide) electrode or the like for driving a liquid crystal is formed is preferably used. In the case of a reflection-type reverse type device, a substrate formed with a dielectric multilayer film of silicon wafer, metal such as aluminum, or the like can be used as long as it is a single-sided substrate.

At least one substrate of the liquid crystal display element of the present invention has a vertical liquid crystal alignment film for vertically aligning liquid crystal molecules. The vertical liquid crystal alignment film can be obtained by applying a liquid crystal alignment treatment agent to a substrate, baking the applied liquid crystal alignment treatment agent, and then performing alignment treatment such as brushing treatment or light irradiation. In the case of the vertical liquid crystal alignment film of the present invention, it can be used as a vertical liquid crystal alignment film without performing such alignment treatment.

The method of applying the liquid crystal alignment treatment agent is not particularly limited, and there are industrial screen printing, gravure printing, offset printing, inkjet method, dip coating method, roll coating method, slit coating method, spinner method, spray coating method, and the like, and it can be appropriately selected according to the kind of substrate and the target film thickness of the vertical liquid crystal alignment film.

The vertical liquid crystal alignment film can be obtained by coating a liquid crystal alignment treatment agent on a substrate and then evaporating the solvent at a temperature of 30 to 300 ℃, preferably 30 to 250 ℃ depending on the solvent used in the liquid crystal alignment treatment agent by heating means such as a hot plate, a thermal cycle oven, or an IR (infrared) oven. When the thickness of the vertical liquid crystal alignment film after firing is too large, it is disadvantageous in terms of power consumption of the liquid crystal display element, and when the thickness is too small, the reliability of the element may be lowered, and therefore, it is preferably 5 to 300nm, more preferably 10 to 200 nm.

The liquid crystal composition used in the liquid crystal display element of the present invention is a liquid crystal composition having at least a liquid crystal and a polymerizable compound. Examples of the other substances 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.

The method of injecting the liquid crystal composition is not particularly limited, and examples thereof include the following methods. That is, when a glass substrate is used as the substrate, the following methods can be used: a pair of substrates on which vertical liquid crystal alignment films are formed are prepared, a sealant is applied to all but a part of the four sides of one substrate, and then the substrate is attached to the other substrate so that the surface of the vertical liquid crystal alignment film faces inward, thereby producing an empty cell. Then, the liquid crystal composition was injected under reduced pressure from a portion where the sealant was not applied, to obtain a cell in which the liquid crystal composition was injected.

When a plastic substrate is used as the substrate, the following methods can be used: a pair of substrates on which vertical liquid crystal alignment films are formed are prepared, a liquid crystal composition is dropped on One substrate by an ODF (One Drop Filling) method, an ink jet method, or the like, and then the other substrate is bonded to obtain a cell in which the liquid crystal composition is injected. In this case, in the liquid crystal display element of the present invention, since the liquid crystal layer has high adhesion to the vertical liquid crystal alignment film, the sealant may not be applied to the four sides of the substrate.

The gap of the liquid crystal display element can be controlled by spacers or the like. The method includes: a method of introducing a spacer of a target size into the liquid crystal composition, 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, and more preferably 2 to 50 μm. Particularly preferably 3 to 30 μm. When the gap is too small, the contrast of the liquid crystal display element decreases, and when the gap is too large, the driving voltage of the element increases.

The liquid crystal display element of the present invention is obtained by curing a liquid crystal composition in a state where a part or all of the liquid crystal composition exhibits liquid crystallinity to form a cured product composite of a liquid crystal and a polymerizable compound. The liquid crystal composition is cured by at least one of irradiation with active energy rays and heating of the cell into which the liquid crystal composition has been injected. Here, the active energy ray is suitably ultraviolet ray. The ultraviolet ray has a wavelength of 250 to 400nm, preferably 310 to 370 nm. In addition, the temperature of the heat treatment is 40 to 120 ℃, preferably 60 to 80 ℃. Further, both the ultraviolet treatment and the heat treatment may be performed simultaneously, or the heat treatment may be performed after the ultraviolet treatment. In the present invention, it is preferable that the curing of the liquid crystal composition is carried out by ultraviolet ray treatment only.

As described above, the liquid crystal display element using the vertical liquid crystal alignment film obtained from the liquid crystal alignment treatment agent containing the specific polymer according to the present invention has high liquid crystal vertical alignment properties, can obtain good optical characteristics, and has high adhesion between the liquid crystal layer and the vertical liquid crystal alignment film. Further, by using the liquid crystal aligning agent of the present invention, it is possible to provide a liquid crystal display element in which the uniformity of the coating film of the liquid crystal alignment film is high and alignment defects associated with coating film defects such as shrinkage and pinholes are less likely to occur. Further, firing for forming a vertical liquid crystal alignment film can be performed at a low temperature. Therefore, the liquid crystal display element of the present invention can be suitably used particularly for a reverse type element which exhibits a transmissive state when no voltage is applied and a scattering state when a voltage is applied, a liquid crystal display for the purpose of representation, and a light control window, a shutter element, and the like for controlling the transmission and isolation of light. In this case, a plastic substrate can be used as the substrate of the liquid crystal display element.

The liquid crystal display element of the present invention can be suitably used for liquid crystal display elements used in transportation machines and transportation machines such as automobiles, trains, and airplanes, specifically, light control windows for controlling light transmission and isolation, optical shutter elements used in rearview mirrors, and the like.

In particular, as described above, since the liquid crystal display element of the present invention has excellent transparency when no voltage is applied and excellent scattering properties when a voltage is applied, when the element is used for a window glass of a vehicle, the light extraction efficiency at night is higher than that in the case of using a conventional inversion type element, and further, the effect of preventing glare from external light is also higher. Therefore, safety when driving the vehicle and comfort when riding can be further improved. Further, when the liquid crystal display element of the present invention is produced using a film substrate and used by being attached to a glass window of a vehicle, the reliability of the element of the present invention is higher than that of a conventional reverse type element. That is, defects and deterioration due to low adhesion between the liquid crystal layer and the vertical alignment film are less likely to occur.

The Liquid Crystal Display element of the present invention can also 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, and a back plate of a transparent Display using the Display. Specifically, when the liquid crystal display device is used as a back plate of a transparent display, the liquid crystal display device of the present invention can be used to suppress light from entering from the back surface thereof when a transparent display and the liquid crystal display device of the present invention are combined to display a screen on the transparent display. Thus, the liquid crystal display element of the present invention can be made clear by exhibiting a scattering state by applying a voltage when displaying a screen on a transparent display, and can be made transparent by not applying a voltage after the completion of the screen display.

Examples

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto. The compounds used in the synthesis examples, examples and comparative examples are abbreviated as follows.

< liquid Crystal composition >

(liquid Crystal)

L1: MLC-6608 (manufactured by Merck Corporation)

(polymerizable compound): the following formula [ R1]

(photoinitiator): the following formula [ P1]

(specific side chain type diamine)

A1: 1, 3-diamino-4- [4- (trans-4-n-heptylcyclohexyl) phenoxy ] benzene

A2: 1, 3-diamino-4- [4- (trans-4-n-heptylcyclohexyl) phenoxymethyl ] benzene

A3: 1, 3-diamino-4- {4- [ trans-4- (trans-4-n-pentylcyclohexyl) cyclohexyl ] phenoxy } benzene

A4: a compound represented by the following formula [ A4]

A5: 1, 3-diamino-4-octadecyloxybenzene

(second diamine)

(other diamines)

(tetracarboxylic acid component)

< alkoxysilane >

E1: an alkoxysilane represented by the formula [ E1]

E2: octadecyltriethoxysilane

E3: 3-methacryloxypropyltrimethoxysilane

E4: 3-Urea propyl triethoxy silane

E5: tetraethoxysilane

< specific solvent >

MEK: 2-butanone

MIBK: 4-methyl-2-pentanone

And (3) DIBK: 2, 6-dimethyl-4-heptanone

< other solvents >

NMP: n-methyl-2-pyrrolidone

NEP: n-ethyl-2-pyrrolidone

gamma-BL: gamma-butyrolactone

PGME: propylene glycol monomethyl ether

And (3) ECS: ethylene glycol monoethyl ether

BCS: ethylene glycol monobutyl ether

PB: propylene glycol monobutyl ether

EC: diethylene glycol monoethyl ether

< specific Generation agent >

< specific adhesion Compound >

< specific crosslinkable Compound >

"determination of molecular weight"

The measurement was carried out by the following procedure using a Gel Permeation Chromatography (GPC) apparatus (GPC-101) (manufactured by Showa Denko K.K.) and columns (KD-803, KD-805) (manufactured by Shodex).

Column temperature: 50 deg.C

Eluent: n, N' -dimethylformamide (as additive, lithium bromide monohydrate (LiBr. H)₂O) 30mmol/L (liter), phosphoric acid anhydrous crystal (orthophosphoric acid) 30mmol/L, Tetrahydrofuran (THF) 10ml/L)

Flow rate: 1.0 ml/min

Standard sample for standard curve preparation: TSK standard polyethylene oxides (molecular weight: about 900000, 150000, 100000 and 30000) (manufactured by Tosoh Corp.) and polyethylene glycols (molecular weight: about 12000, 4000 and 1000) (manufactured by Polymer Laboratories Ltd.).

"measurement of imidization Rate"

20mg of the sample powder was put into an NMR (nuclear magnetic resonance) sample tube (NMR sample tube specification,

(grass-field science)Manufactured by kokai corporation)), deuterated dimethyl sulfoxide (DMSO-d6, 0.05 mass% TMS (tetramethylsilane) mixture) (0.53ml) was added thereto, and the mixture was dissolved completely with ultrasonic waves. The proton NMR of the solution at 500MHz was measured by an NMR spectrometer (JNW-ECA500) (manufactured by JEOL DATUM). The imidization ratio is determined using a proton derived from a structure that does not change before and after imidization as a reference proton, and is obtained by the following equation using the peak integral value of the proton and the peak integral value of a proton derived from an NH group of amic acid present in the vicinity of 9.5 to 10.0 ppm.

Imidization ratio (%) - (1-. alpha.x/y). times.100

In the above formula, x represents a peak integral value of a proton derived from an NH group of amic acid, y represents a peak integral value of a reference proton, and α represents a ratio of the number of the reference protons to 1 proton of the NH group of amic acid (imidization ratio of 0%).

Synthesis of polyimide-based Polymer "

< Synthesis example 1>

D1(2.96g, 15.1mmol), A1(2.91g, 7.65mmol), B1(0.93g, 6.11mmol) and C2(0.17g, 1.57mmol) were mixed with NEP (21.0g) and reacted at 40 ℃ for 8 hours to obtain a polyamic acid solution (1) having a resin solid concentration (Rs) of 25 mass%. The polyamic acid had a number-average molecular weight (Mn) of 23600 and a weight-average molecular weight (Mw) of 71800.

< Synthesis example 2>

D2(3.83g, 15.3mmol), A2(6.04g, 15.3mmol) and B1(2.33g, 15.3mmol) were mixed with NMP (26.4g) and reacted at 50 ℃ for 2 hours, then D1(2.94g, 15.0mmol) and NMP (23.8g) were added and reacted at 40 ℃ for 6 hours to obtain a polyamic acid solution (2) with Rs of 25 mass%. The polyamic acid had Mn of 22500 and Mw of 67100.

< Synthesis example 3>

To a polyamic acid solution (2) (30.0g) obtained in Synthesis example 2, NMP was added and the solution was diluted to 6% by mass, and then acetic anhydride (3.90g) and pyridine (2.40g) as imidization catalysts were added and the mixture was reacted at 70 ℃ for 2 hours. The reaction solution was poured into methanol (460ml), and the resulting precipitate was collected by filtration. The precipitate was washed with methanol and dried under reduced pressure at 100 ℃ to obtain polyimide powder (3). The polyimide had an imidization ratio of 60%, an Mn of 20100 and an Mw of 57100.

< Synthesis example 4>

D2(2.64g, 10.6mmol), A3(4.56g, 10.5mmol), B1(1.60g, 10.5mmol) and B2(1.07g, 5.26mmol) were mixed with NMP (21.9g), and reacted at 80 ℃ for 5 hours, then D1(3.02g, 15.8mmol) and NMP (17.2g) were added, and reacted at 40 ℃ for 8 hours to obtain a polyamic acid solution with Rs of 25 mass%.

NMP was added to the obtained polyamic acid solution (30.0g) to dilute the solution to 6 mass%, and acetic anhydride (3.85g) and pyridine (2.42g) as imidization catalysts were added thereto to conduct a reaction at 50 ℃ for 2 hours. The reaction solution was poured into methanol (460ml), and the resulting precipitate was collected by filtration. The precipitate was washed with methanol and dried under reduced pressure at 100 ℃ to obtain polyimide powder (4). The polyimide had an imidization ratio of 56%, Mn of 18500 and Mw of 54000.

< Synthesis example 5>

D2(2.50g, 10.0mmol), A4(2.96g, 6.00mmol), B1(1.52g, 10.0mmol), B2(0.41g, 2.00mmol) and C1(0.22g, 2.00mmol) were mixed with NMP (19.0g), reacted at 80 ℃ for 5 hours, then D1(1.92g, 9.80mmol) and NMP (9.50g) were added, and reacted at 40 ℃ for 6 hours to obtain a polyamic acid solution with Rs of 25 mass%.

NMP was added to the obtained polyamic acid solution (30.0g) to dilute the solution to 6 mass%, and acetic anhydride (4.00g) and pyridine (2.50g) as imidization catalysts were added thereto to conduct a reaction at 50 ℃ for 2 hours. The reaction solution was poured into methanol (460ml), and the resulting precipitate was collected by filtration. The precipitate was washed with methanol and dried under reduced pressure at 100 ℃ to obtain polyimide powder (5). The polyimide had an imidization ratio of 49%, Mn of 16100 and Mw of 49800.

< Synthesis example 6>

D3(5.45g, 24.3mmol), A2(5.81g, 14.7mmol), B1(1.12g, 7.36mmol) and B2(0.50g, 2.46mmol) were mixed with NMP (38.6g) and reacted at 40 ℃ for 10 hours to obtain a polyamic acid solution with Rs of 25 mass%.

NMP was added to the obtained polyamic acid solution (30.0g) to dilute the solution to 6 mass%, and acetic anhydride (4.00g) and pyridine (2.48g) as imidization catalysts were added thereto to conduct a reaction at 70 ℃ for 2 hours. The reaction solution was poured into methanol (460ml), and the resulting precipitate was collected by filtration. The precipitate was washed with methanol and dried under reduced pressure at 100 ℃ to obtain polyimide powder (6). The polyimide had an imidization ratio of 63%, Mn of 17200, and Mw of 49100.

< Synthesis example 7>

D3(5.45g, 24.3mmol), A4(3.63g, 7.37mmol) and B1(2.61g, 17.2mmol) were mixed with NMP (35.1g) and reacted at 40 ℃ for 5 hours to obtain a polyamic acid solution with Rs of 25 mass%.

NMP was added to the obtained polyamic acid solution (30.0g) to dilute the solution to 6 mass%, and acetic anhydride (8.00g) and pyridine (2.50g) as imidization catalysts were added thereto to conduct a reaction at 50 ℃ for 3 hours. The reaction solution was poured into methanol (460ml), and the resulting precipitate was collected by filtration. The precipitate was washed with methanol and dried under reduced pressure at 100 ℃ to obtain polyimide powder (7). The polyimide had an imidization ratio of 54%, Mn of 17400 and Mw of 47800.

< Synthesis example 8>

D4(4.59g, 15.3mmol), A3(6.62g, 15.3mmol), B1(1.86g, 12.2mmol) and B2(0.62g, 3.05mmol) were mixed with NMP (27.6g), and reacted at 40 ℃ for 8 hours, then D1(2.94g, 15.0mmol) and NMP (22.3g) were added, and reacted at 25 ℃ for 10 hours to obtain a polyamic acid solution with Rs of 25 mass%.

NMP was added to the obtained polyamic acid solution (30.0g) to dilute the solution to 6 mass%, and acetic anhydride (7.25g) and pyridine (2.22g) as imidization catalysts were added thereto to conduct a reaction at 40 ℃ for 1.5 hours. The reaction solution was poured into methanol (460ml), and the resulting precipitate was collected by filtration. The precipitate was washed with methanol and dried under reduced pressure at 100 ℃ to obtain polyimide powder (8). The polyimide had an imidization ratio of 71%, Mn of 17100 and Mw of 38800.

< Synthesis example 9>

D2(3.83g, 15.3mmol), A5(5.76g, 15.3mmol) and B1(2.33g, 15.3mmol) were mixed with NMP (26.4g) and reacted at 50 ℃ for 2 hours, then D1(2.94g, 15.0mmol) and NMP (23.8g) were added and reacted at 40 ℃ for 6 hours to obtain a polyamic acid solution with Rs of 25 mass%.

To the obtained polyamic acid solution (30.0g) was added NMP and diluted to 6 mass%, and then acetic anhydride (3.90g) and pyridine (2.40g) as imidization catalysts were added and reacted at 70 ℃ for 2 hours. The reaction solution was poured into methanol (460ml), and the resulting precipitate was collected by filtration. The precipitate was washed with methanol and dried under reduced pressure at 100 ℃ to obtain polyimide powder (9). The polyimide had an imidization ratio of 61%, Mn of 19000 and Mw of 58100.

< Synthesis example 10>

D2(3.83g, 15.3mmol) and B1(4.66g, 30.6mmol) were mixed with NMP (37.5g) and reacted at 50 ℃ for 2 hours, then D1(2.94g, 15.0mmol) and NMP (12.8g) were added and reacted at 40 ℃ for 6 hours to obtain a polyamic acid solution (10) with Rs of 25 mass%. The polyamic acid had Mn of 25900 and Mw of 79100.

< Synthesis example 11>

To a polyamic acid solution (10) (30.0g) obtained in Synthesis example 10 was added NMP and diluted to 6 mass%, and then acetic anhydride (3.85g) and pyridine (2.40g) as imidization catalysts were added and reacted at 70 ℃ for 2 hours. The reaction solution was poured into methanol (460ml), and the resulting precipitate was collected by filtration. The precipitate was washed with methanol and dried under reduced pressure at 100 ℃ to obtain polyimide powder (11). The polyimide had an imidization ratio of 59%, Mn of 21200 and Mw of 60100.

The polyimide-based polymers obtained are summarized in table 1. In table 1, ". x 1" represents polyamic acid.

[ Table 1]

Synthesis of polysiloxane Polymer "

< Synthesis example 12>

Comprising a thermometer and a thermometerA200 mL four-necked reaction flask with flow tube was mixed with ECS (28.3g), E1(4.10g), E3(7.45g) and E5(32.5g) to prepare a solution of alkoxysilane monomer. To this solution, a solution prepared by mixing ECS (14.2g), water (10.8g) and oxalic acid (0.70g) as a catalyst in advance was added dropwise at 25 ℃ over 30 minutes, and further stirred at 25 ℃ for 30 minutes. Thereafter, the mixture was heated and refluxed for 30 minutes using an oil bath, and then a mixed solution of a methanol solution (1.20g) having an E4 content of 92 mass% and ECS (0.90g) prepared in advance was added. Further refluxed for 30 minutes, and then cooled to obtain SiO₂Polysiloxane solution (1) having a concentration of 12% by mass as converted.

< Synthesis example 13>

A solution of an alkoxysilane monomer was prepared by mixing EC (25.4g), E1(8.20g), E3(19.9g), and E5(20.0g) in a 200ml four-necked reaction flask equipped with a thermometer and a reflux tube. To this solution was added dropwise a solution prepared by mixing EC (12.7g), water (10.8g) and oxalic acid (1.10g) as a catalyst in advance at 25 ℃ over 30 minutes. Thereafter, after heating and refluxing for 30 minutes using an oil bath, a mixed solution of a methanol solution (1.20g) having an E4 content of 92 mass% and EC (0.90g) prepared in advance was added. Further refluxed for 30 minutes, and then cooled to obtain SiO₂A polysiloxane solution (2) having a concentration of 12% by mass as converted.

< Synthesis example 14>

A solution of an alkoxysilane monomer was prepared by mixing EC (29.2g), E1(4.10g) and E5(38.8g) in a 200ml four-necked reaction flask equipped with a thermometer and a reflux tube. To this solution, a solution prepared by mixing EC (14.6g), water (10.8g), and oxalic acid (0.50g) as a catalyst in advance was added dropwise at 25 ℃ over 30 minutes, and further stirred at 25 ℃ for 30 minutes. Thereafter, after heating and refluxing for 30 minutes using an oil bath, a mixed solution of a methanol solution (1.20g) having an E4 content of 92 mass% and EC (0.90g) prepared in advance was added. Further refluxed for 30 minutes, and then cooled to obtain SiO₂A polysiloxane solution (3) having a concentration of 12% by mass as converted.

< Synthesis example 15>

In a 200ml four-necked reaction flask equipped with a thermometer and a reflux tube, ECS (28.3g) and E2(4.0 g) were mixed7g) E3(7.45g) and E5(32.5g), solutions of alkoxysilane monomer were prepared. To this solution, a solution prepared by mixing ECS (14.2g), water (10.8g) and oxalic acid (0.70g) as a catalyst in advance was added dropwise at 25 ℃ over 30 minutes, and further stirred at 25 ℃ for 30 minutes. Thereafter, the mixture was heated and refluxed for 30 minutes using an oil bath, and then a mixed solution of a methanol solution (1.20g) having an E4 content of 92 mass% and ECS (0.90g) prepared in advance was added. Further refluxed for 30 minutes, and then cooled to obtain SiO₂A polysiloxane solution (4) having a concentration of 12% by mass as converted.

The polysiloxane polymers (polysiloxane solutions) thus obtained are summarized in table 2.

[ Table 2]

(preparation of liquid Crystal composition (1))

L1(11.5g), R1(1.73g) and P1(0.12g) were mixed to obtain a liquid crystal composition (1).

(preparation of liquid Crystal composition (2))

L1(12.0g), R1(2.40g) and P1(0.12g) were mixed to obtain a liquid crystal composition (2).

"production and evaluation of liquid Crystal alignment treating agent, vertical liquid Crystal alignment film, and liquid Crystal display element"

Examples of the production of the liquid crystal aligning agent are described in examples and comparative examples below. The obtained liquid crystal aligning agent was used for the production of a vertical liquid crystal alignment film and a liquid crystal display element (a reverse type element) and the evaluation thereof.

The obtained liquid crystal aligning agents are summarized in tables 3 to 7. In tables 3 to 7, ". x 1" represents the content (parts by mass) of the specific solvent and the other solvents with respect to 100 parts by mass of the total solvents. "x2" indicates the content (parts by mass) of the specific propellant per 100 parts by mass of the specific polymer. "x3" represents the content (parts by mass) of the specific adhesion compound with respect to 100 parts by mass of the specific polymer. ". 4" represents the content (parts by mass) of the specific crosslinkable compound with respect to 100 parts by mass of the specific polymer.

Further, using the liquid crystal alignment treatment agents obtained in examples and comparative examples, evaluation of coating uniformity of a vertical liquid crystal alignment film (glass substrate, plastic substrate), production of a liquid crystal display element (glass substrate, plastic substrate), evaluation of liquid crystal alignment properties (glass substrate, plastic substrate), and evaluation of adhesion between a liquid crystal layer and a vertical liquid crystal alignment film (glass substrate, plastic substrate) were carried out.

"evaluation of coating film uniformity of vertical liquid Crystal alignment film (glass substrate)"

The liquid crystal alignment treatment agents of examples and comparative examples were pressure-filtered through a membrane filter having a pore size of 1 μm, and then spin-coated on the ITO surface of an unwashed glass substrate (100 mm in length: 100mm in width: 100mm in thickness: 0.7mm) with an ITO electrode of 100X 100mm, followed by heat treatment at 80 ℃ for 3 minutes on a hot plate, thereby producing a substrate with a vertical liquid crystal alignment film.

The substrate with the obtained homeotropic liquid crystal alignment film was used to evaluate pinholes. Specifically, the number of pinholes in the vertical liquid crystal alignment film was visually observed under a sodium lamp. In this evaluation, the smaller the number of pinholes, the more excellent the evaluation was (the number of pinholes in tables 8 to 12).

"evaluation of coating film uniformity of vertical liquid Crystal alignment film (Plastic substrate)"

The liquid crystal alignment treatment agent was pressure-filtered through a film filter having a pore diameter of 1 μm, and then applied to an uncleaned ITO surface of a PET (polyethylene terephthalate) substrate (length: 150mm, width: 150mm, thickness: 0.2mm) having an ITO electrode of 150X 150mm by a bar coater, followed by heat treatment at 80 ℃ for 3 minutes on a hot plate to prepare a substrate having a vertical liquid crystal alignment film.

The substrate with the obtained vertical liquid crystal alignment film was used to evaluate pinholes under the same conditions as in the above-described "evaluation of coating uniformity of vertical liquid crystal alignment film (glass substrate)". In this evaluation, the smaller the number of pinholes, the more excellent the evaluation was (the number of pinholes in tables 8 to 12).

Production of liquid Crystal display element (glass substrate) "

The liquid crystal alignment treatment agent was pressure-filtered through a membrane filter having a pore diameter of 1 μm, and then spin-coated on the ITO surface of a glass substrate (longitudinal: 100mm, lateral: 100mm, thickness: 0.7mm) with an ITO electrode of 100X 100mm cleaned with pure water and IPA (isopropyl alcohol), and the ITO surface was heat-treated at 80 ℃ for 3 minutes on a hot plate and at 150 ℃ for 10 minutes in a thermal cycle type cleaning oven, thereby obtaining an ITO substrate with a vertical liquid crystal alignment film having a film thickness of 100 nm. 2 pieces of the obtained ITO substrates with the vertical liquid crystal alignment films were prepared, and a spacer of 6 μm was applied to the vertical liquid crystal alignment film surface of one of the substrates. Then, the liquid crystal composition was dropped on the vertical liquid crystal alignment film surface coated with the spacer of the substrate by an odf (one Drop filling) method, and then the liquid crystal composition was attached so as to face the vertical liquid crystal alignment film interface of the other substrate, thereby obtaining a liquid crystal display element before treatment.

The obtained liquid crystal display element before treatment was converted to 7J/cm at 365nm by cutting off the wavelength of 350nm or less with a metal halide lamp having an illuminance of 60mW²The liquid crystal display element (glass substrate) was obtained by the ultraviolet irradiation of (1). The temperature in the irradiation device when the liquid crystal cell was irradiated with ultraviolet rays was controlled to 25 ℃.

Production of liquid Crystal display element (Plastic substrate) "

The liquid crystal alignment treatment agent was pressure-filtered through a membrane filter having a pore diameter of 1 μm, and then applied to an ITO surface of a PET (polyethylene terephthalate) substrate (longitudinal: 150mm, lateral: 150mm, thickness: 0.2mm) with an ITO electrode of 150X 150mm cleaned with pure water by a bar coater, and heat-treated at 80 ℃ for 3 minutes on a hot plate and at 120 ℃ for 10 minutes in a thermal cycle type cleaning oven, to obtain an ITO substrate with a vertical liquid crystal alignment film having a film thickness of 100 nm. 2 pieces of the obtained ITO substrates with the vertical liquid crystal alignment films were prepared, and a spacer of 6 μm was coated on the vertical liquid crystal alignment film surface of one of the substrates. Then, the liquid crystal composition was dropped on the vertical liquid crystal alignment film surface of the substrate coated with the spacer by the ODF method, and then the liquid crystal composition was attached to the vertical liquid crystal alignment film surface of the other substrate so as to face the vertical liquid crystal alignment film interface, thereby obtaining a liquid crystal display element before treatment.

The liquid crystal display element before treatment was irradiated with ultraviolet rays under the same conditions as in the above-described "production of a liquid crystal display element (glass substrate)", thereby obtaining a liquid crystal display element (plastic substrate).

"evaluation of liquid Crystal alignment Properties (glass substrate, Plastic substrate)"

The liquid crystal display elements (glass substrates, plastic substrates) obtained by the same method as described above were used to evaluate the liquid crystal alignment properties. Regarding the liquid crystal alignment, whether the liquid crystal was vertically aligned or not was confirmed by observing the device with a polarized light microscope (ECLIPSE E600WPOL) (manufactured by nikon). Specifically, the liquid crystal was considered excellent in the vertical alignment (as shown in tables 8 to 12).

Further, the liquid crystal display element (glass substrate, plastic substrate) whose evaluation of the liquid crystal alignment property was completed was stored in a high temperature tank at a temperature of 80 ℃ for 240 hours. After cooling, the liquid crystal alignment was evaluated under the same conditions as described above. Specifically, it was considered that the liquid crystal alignment was not disturbed and the liquid crystal was uniformly aligned (as shown in tables 8 to 12).

Evaluation of adhesion between liquid Crystal layer and vertical liquid Crystal alignment film (glass substrate, Plastic substrate) "

The adhesion between the liquid crystal layer and the vertical liquid crystal alignment film was evaluated by using the liquid crystal display element (glass substrate, plastic substrate) subjected to the evaluation of the liquid crystal alignment property. Specifically, the liquid crystal display element (glass substrate, plastic substrate) was stored in a high-temperature and high-humidity chamber at a temperature of 80 ℃ and a humidity of 90% RH for 48 hours, and it was confirmed whether or not air bubbles were present in the element and the element was peeled off. In this evaluation, it was considered that the state was excellent when no bubble was observed in the device and the device was not peeled (the state where the liquid crystal layer was peeled from the vertical liquid crystal alignment film) (good indications in tables 8 to 12).

In the following examples and comparative examples, the liquid crystal display element was produced, and the evaluation results of "the coating film uniformity of the vertical liquid crystal alignment film, the liquid crystal alignment property, and the adhesion between the liquid crystal layer and the vertical liquid crystal alignment film" described above were performed, and summarized in tables 8 to 12.

In tables 8 to 12, "× 1" indicates the number of pinholes in the vertical liquid crystal alignment films of the glass substrate/plastic substrate. "x2" indicates the liquid crystal alignment of the glass substrate/plastic substrate. "x3" indicates adhesion between the liquid crystal layer of the glass substrate/plastic substrate and the vertical liquid crystal alignment film. "-" indicates not implemented.

In table 12, "x4" - "12" indicates the following meanings, respectively.

*4: the liquid crystals are not vertically aligned.

*5: the liquid crystal was not vertically aligned and thus could not be measured.

*6: no orientation defects associated with pinholes were observed.

*7: alignment defects accompanied by pinholes were observed, and the liquid crystal alignment was visually disturbed.

*8: air bubbles are observed within the cell.

*9: a small amount of air bubbles can be observed within the cell.

*10: a large number of orientation defects associated with pinholes can be observed.

*11: peeling occurs between the liquid crystal layer and the vertical liquid crystal alignment film in the element.

*12: a small amount of orientation defects associated with pinholes can be observed.

< example 1>

To the polyamic acid solution (1) (10.0g) obtained in Synthesis example 1 were added NMP (15.9g), NEP (3.11g), PB (10.6g), MIBK (15.9g), S2(0.25g), M2(0.125g), and K1(0.25g), and the mixture was stirred at 25 ℃ for 5 hours to obtain a liquid crystal aligning agent (1). The liquid crystal aligning agent was not observed to be abnormal such as clouding and precipitation, and was confirmed to be a uniform solution.

Using the obtained liquid crystal aligning agent (1) and the liquid crystal composition (1), a liquid crystal display element having a glass substrate was produced, and the above-described evaluations were performed.

< example 2>

To polyamic acid solution (2) (10.0g) obtained in Synthesis example 2 were added NMP (19.0g), BCS (10.6g) and MIBK (15.9g), and the mixture was stirred at 25 ℃ for 5 hours to obtain liquid crystal alignment treatment agent (2). The liquid crystal aligning agent was not observed to be abnormal such as clouding and precipitation, and was confirmed to be a uniform solution.

Using the obtained liquid crystal aligning agent (2) and the liquid crystal composition (1), a liquid crystal display element having glass as a substrate was produced, and the above-described evaluations were performed.

< example 3>

Using the liquid crystal aligning agent (2) and the liquid crystal composition (2) obtained in example 2, a liquid crystal display element having glass as a substrate was produced, and the above-described evaluations were performed.

< example 4>

To the polyimide powder (3) (2.20g) obtained in Synthesis example 3 were added NMP (18.7g) and NEP (4.67g), and the mixture was stirred at 70 ℃ for 24 hours to dissolve the NMP. BCS (9.34g) and MIBK (14.0g) were added to the solution, and stirred at 25 ℃ for 2 hours to obtain a liquid crystal alignment treatment agent (3). The liquid crystal aligning agent was not observed to be abnormal such as clouding and precipitation, and was confirmed to be a uniform solution.

Using the obtained liquid crystal aligning agent (3) and the liquid crystal composition (1), a liquid crystal display element having glass as a substrate was produced, and the above-described evaluations were performed.

< example 5>

Using the liquid crystal aligning agent (3) and the liquid crystal composition (2) obtained in example 4, a liquid crystal display element having glass as a substrate was produced, and the above-described evaluations were performed.

< example 6>

To the polyimide powder (3) (2.15g) obtained in Synthesis example 3 were added γ -BL (9.13g) and PGME (13.7g), and the mixture was stirred at 70 ℃ for 24 hours to dissolve the same. To the solution were added PB (9.13g) and MEK (13.7g), and the mixture was stirred at 25 ℃ for 2 hours to obtain a liquid crystal alignment treatment agent (4). The liquid crystal aligning agent was not observed to be abnormal such as clouding and precipitation, and was confirmed to be a uniform solution.

Using the obtained liquid crystal aligning agent (4) and the liquid crystal composition (1), 2 liquid crystal display elements each having a glass or plastic substrate were produced, and the above-described evaluations were performed.

The adhesion between the liquid crystal layer and the vertical liquid crystal alignment film (plastic substrate) was evaluated as an accelerated test together with the standard test, when the substrate was stored in a high-temperature and high-humidity chamber at a temperature of 80 ℃ and a humidity of 90% RH for 96 hours (other conditions were the same as the above conditions). As a result, no bubble was observed in the element.

< example 7>

To the polyimide powder (3) (2.20g) obtained in Synthesis example 3 were added γ -BL (4.67g) and PGME (28.0g), and the mixture was stirred at 70 ℃ for 24 hours to dissolve the particles. To the solution were added MEK (9.34g), MIBK (4.67g), S1(0.154g), M1(0.22g) and K1(0.33g), and the mixture was stirred at 25 ℃ for 2 hours to give a liquid crystal alignment treating agent (5). The liquid crystal aligning agent was not observed to be abnormal such as clouding and precipitation, and was confirmed to be a uniform solution.

Using the obtained liquid crystal aligning agent (5) and the liquid crystal composition (1), 2 liquid crystal display elements each having a glass or plastic substrate were produced, and the above-described evaluations were performed.

< example 8>

To the polyimide powder (4) (2.20g) obtained in Synthesis example 4 were added γ -BL (9.34g) and PGME (18.7g), and the mixture was stirred at 70 ℃ for 24 hours to dissolve the same. To the solution were added EC (14.0g), DIBK (4.67g), S2(0.22g), M2(0.11g) and K1(0.22g), and the mixture was stirred at 25 ℃ for 2 hours to obtain a liquid crystal aligning agent (6). The liquid crystal aligning agent was not observed to be abnormal such as clouding and precipitation, and was confirmed to be a uniform solution.

Using the obtained liquid crystal aligning agent (6) and the liquid crystal composition (1), 2 liquid crystal display elements each having a glass or plastic substrate were produced, and the above-described evaluations were performed.

< example 9>

Using the liquid crystal aligning agent (6) and the liquid crystal composition (2) obtained in example 8, 2 liquid crystal display elements each having a substrate of glass or plastic were produced, and the above-described evaluations were performed.

< example 10>

To the polyimide powder (4) (2.25g) obtained in Synthesis example 4 were added γ -BL (2.39g) and PGME (28.7g), and the mixture was stirred at 70 ℃ for 24 hours to dissolve the same. To the solution were added PB (4.78g), MEK (7.96g), MIBK (3.98g), S2(0.225g), M1(0.113g) and K1(0.45g), and the mixture was stirred at 25 ℃ for 2 hours to obtain a liquid crystal alignment treatment agent (7). The liquid crystal aligning agent was not observed to be abnormal such as clouding and precipitation, and was confirmed to be a uniform solution.

Using the obtained liquid crystal aligning agent (7) and the liquid crystal composition (1), 2 liquid crystal display elements each having a glass or plastic substrate were produced, and the above-described evaluations were performed.

< example 11>

To the polyimide powder (4) (2.25g) obtained in Synthesis example 4 were added γ -BL (4.78g) and PGME (19.1g), and the mixture was stirred at 70 ℃ for 24 hours to dissolve the same. To the solution were added MIBK (23.9g), S1(0.068g), M2(0.068g) and K1(0.158g), and the mixture was stirred at 25 ℃ for 2 hours to obtain a liquid crystal alignment treatment agent (8). The liquid crystal aligning agent was not observed to be abnormal such as clouding and precipitation, and was confirmed to be a uniform solution.

Using the obtained liquid crystal aligning agent (8) and the liquid crystal composition (1), 2 liquid crystal display elements each having a glass or plastic substrate were produced, and the above-described evaluations were performed.

< example 12>

NEP (18.7g) was added to the polyimide powder (5) (2.20g) obtained in Synthesis example 5, and the mixture was stirred at 70 ℃ for 24 hours to dissolve the NEP. To the solution were added PB (9.34g), MIBK (14.0g) and DIBK (4.67g), and the mixture was stirred at 25 ℃ for 2 hours to give a liquid crystal alignment treatment agent (9). The liquid crystal aligning agent was not observed to be abnormal such as clouding and precipitation, and was confirmed to be a uniform solution.

Using the obtained liquid crystal aligning agent (9) and the liquid crystal composition (2), a liquid crystal display element having glass as a substrate was produced, and the above-described evaluations were performed.

< example 13>

To the polyimide powder (5) (2.20g) obtained in Synthesis example 5 were added γ -BL (4.67g) and PGME (28.0g), and the mixture was stirred at 70 ℃ for 24 hours to dissolve the particles. To the solution were added MEK (4.67g), MIBK (9.34g) and K1(0.22g), and the mixture was stirred at 25 ℃ for 2 hours to give a liquid crystal alignment treatment agent (10). The liquid crystal aligning agent was not observed to be abnormal such as clouding and precipitation, and was confirmed to be a uniform solution.

Using the obtained liquid crystal aligning agent (10) and the liquid crystal composition (1), 2 liquid crystal display elements each having a substrate of glass or plastic were produced, and the above-described evaluations were performed.

In addition, an accelerated test was performed under the same conditions as in example 6 (in which the inside of the high-temperature and high-humidity chamber was kept for 144 hours) with respect to the evaluation of the adhesion between the liquid crystal layer and the vertical liquid crystal alignment film (plastic substrate) together with the above-described standard test. As a result, a small amount of air bubbles were observed in the cell.

< example 14>

To the polyimide powder (5) (2.20g) obtained in Synthesis example 5 were added γ -BL (4.67g) and PGME (28.0g), and the mixture was stirred at 70 ℃ for 24 hours to dissolve the particles. To the solution were added MEK (4.67g), MIBK (9.34g), S1(0.22g) and K1(0.22g), and the mixture was stirred at 25 ℃ for 2 hours to give a liquid crystal alignment treatment agent (11). The liquid crystal aligning agent was not observed to be abnormal such as clouding and precipitation, and was confirmed to be a uniform solution.

Using the obtained liquid crystal aligning agent (11) and liquid crystal composition (1), 2 liquid crystal display elements having glass and plastic as substrates were produced, and the above-described evaluations were performed.

< example 15>

To the polyimide powder (5) (2.20g) obtained in Synthesis example 5 were added γ -BL (4.67g) and PGME (28.0g), and the mixture was stirred at 70 ℃ for 24 hours to dissolve the particles. To the solution were added MEK (4.67g), MIBK (9.34g), S1(0.22g), M2(0.154g) and K1(0.22g), and the mixture was stirred at 25 ℃ for 2 hours to give a liquid crystal alignment treating agent (12). The liquid crystal aligning agent was not observed to be abnormal such as clouding and precipitation, and was confirmed to be a uniform solution.

Using the obtained liquid crystal aligning agent (12) and the liquid crystal composition (1), 2 liquid crystal display elements each having a substrate of glass or plastic were produced, and the above-described evaluations were performed.

In addition, an accelerated test was performed under the same conditions as in example 6 (in which the inside of the high-temperature and high-humidity chamber was kept for 144 hours) with respect to the evaluation of the adhesion between the liquid crystal layer and the vertical liquid crystal alignment film (plastic substrate) together with the above-described standard test. As a result, no bubble was observed in the element.

< example 16>

To the polyimide powder (6) (2.10g) obtained in Synthesis example 6 were added γ -BL (11.1g) and PGME (20.0g), and the mixture was stirred at 70 ℃ for 24 hours to dissolve the same. To the solution were added BCS (2.28g), MIBK (11.1g) and K1(0.42g), and the mixture was stirred at 25 ℃ for 2 hours to obtain a liquid crystal alignment treatment agent (13). The liquid crystal aligning agent was not observed to be abnormal such as clouding and precipitation, and was confirmed to be a uniform solution.

Using the obtained liquid crystal aligning agent (13) and liquid crystal composition (2), 2 liquid crystal display elements having glass and plastic as substrates were produced, and the above-described evaluations were performed.

< example 17>

To the polyimide powder (6) (2.20g) obtained in Synthesis example 6 were added γ -BL (11.7g) and PGME (28.0g), and the mixture was stirred at 70 ℃ for 24 hours to dissolve the same. To the solution were added PB (4.67g), MIBK (2.33g), S2(0.066g), M1(0.11g) and K1(0.066g), and the mixture was stirred at 25 ℃ for 2 hours to obtain a liquid crystal aligning agent (14). The liquid crystal aligning agent was not observed to be abnormal such as clouding and precipitation, and was confirmed to be a uniform solution.

Using the obtained liquid crystal aligning agent (14) and the liquid crystal composition (1), 2 liquid crystal display elements each having a substrate of glass or plastic were produced, and the above-described evaluations were performed.

< example 18>

To the polyimide powder (6) (1.65g) obtained in Synthesis example 6 were added NMP (4.67g) and NEP (14.0g), and the mixture was stirred at 70 ℃ for 24 hours to dissolve the NMP. To the solution were added BCS (9.34g), PB (4.67g), DIBK (14.0g) and K1(0.44g), and the mixture was stirred at 25 ℃ for 2 hours to obtain a liquid crystal alignment treatment agent (15). The liquid crystal aligning agent was not observed to be abnormal such as clouding and precipitation, and was confirmed to be a uniform solution.

Using the obtained liquid crystal aligning agent (15) and the liquid crystal composition (1), a liquid crystal display element having a glass substrate was produced, and the above-described evaluations were performed.

< example 19>

To the polyimide powder (7) (2.15g) obtained in Synthesis example 7 were added γ -BL (2.28g) and PGME (29.7g), and the mixture was stirred at 70 ℃ for 24 hours to dissolve the same. To the solution were added MEK (13.7g), S2(0.323g), M2(0.108g) and K1(0.323g), and the mixture was stirred at 25 ℃ for 2 hours to obtain a liquid crystal aligning agent (16). The liquid crystal aligning agent was not observed to be abnormal such as clouding and precipitation, and was confirmed to be a uniform solution.

Using the obtained liquid crystal aligning agent (16) and the liquid crystal composition (1), 2 liquid crystal display elements each having a substrate of glass or plastic were produced, and the above-described evaluations were performed.

< example 20>

NEP (14.0g) was added to the polyimide powder (7) (2.20g) obtained in Synthesis example 7, and the mixture was stirred at 70 ℃ for 24 hours to dissolve the NEP. To the solution were added BCS (4.67g), PB (18.7g), DIBK (9.34g), S1(0.066g), M1(0.154g) and K1(0.22g), and the mixture was stirred at 25 ℃ for 2 hours to obtain a liquid crystal aligning agent (17). The liquid crystal aligning agent was not observed to be abnormal such as clouding and precipitation, and was confirmed to be a uniform solution.

Using the obtained liquid crystal aligning agent (17) and the liquid crystal composition (2), a liquid crystal display element having glass as a substrate was produced, and the above-described evaluations were performed.

< example 21>

NMP (16.3g) was added to the polyimide powder (8) (2.20g) obtained in synthesis example 8, and the mixture was stirred at 70 ℃ for 24 hours to dissolve the NMP. To the solution were added BCS (7.00g), PB (14.0g), DIBK (9.34g), S2(0.11g), M2(0.22g) and K1(0.22g), and the mixture was stirred at 25 ℃ for 2 hours to obtain a liquid crystal aligning agent (18). The liquid crystal aligning agent was not observed to be abnormal such as clouding and precipitation, and was confirmed to be a uniform solution.

Using the obtained liquid crystal aligning agent (18) and the liquid crystal composition (1), a liquid crystal display element having glass as a substrate was produced, and the above-described evaluations were performed.

< example 22>

To the polyimide powder (8) (2.20g) obtained in Synthesis example 8 were added γ -BL (4.67g) and PGME (30.4g), and the mixture was stirred at 70 ℃ for 24 hours to dissolve the particles. To the solution were added MIBK (11.7g), S1(0.22g), M1(0.11g) and K1(0.44g), and the mixture was stirred at 25 ℃ for 2 hours to obtain a liquid crystal alignment treatment agent (19). The liquid crystal aligning agent was not observed to be abnormal such as clouding and precipitation, and was confirmed to be a uniform solution.

Using the obtained liquid crystal aligning agent (19) and the liquid crystal composition (1), 2 liquid crystal display elements each having a glass or plastic substrate were produced, and the above-described evaluations were performed.

< example 23>

NEP (18.7g) was added to the polyimide powder (8) (2.20g) obtained in Synthesis example 8, and the mixture was stirred at 70 ℃ for 24 hours to dissolve the NEP. To the solution were added PB (18.7g) and DIBK (9.34g), and the mixture was stirred at 25 ℃ for 2 hours to obtain a liquid crystal aligning agent (20). The liquid crystal aligning agent was not observed to be abnormal such as clouding and precipitation, and was confirmed to be a uniform solution.

Using the obtained liquid crystal aligning agent (20) and the liquid crystal composition (1), a liquid crystal display element having a glass substrate was produced, and the above-described evaluations were performed.

< example 24>

To the polyimide powder (9) (2.20g) obtained in Synthesis example 9, NMP (4.67g) and NEP (18.7g) were added and the mixture was stirred at 70 ℃ for 24 hours to dissolve the NMP. BCS (9.34g) and MIBK (14.0g) were added to the solution, and stirred at 25 ℃ for 2 hours to obtain a liquid crystal alignment treatment agent (21). The liquid crystal aligning agent was not observed to be abnormal such as clouding and precipitation, and was confirmed to be a uniform solution.

Using the obtained liquid crystal aligning agent (21) and the liquid crystal composition (1), a liquid crystal display element having a glass substrate was produced, and the above-described evaluations were performed.

< example 25>

To the polyimide powder (9) (2.10g) obtained in Synthesis example 9 were added γ -BL (8.91g) and PGME (13.4g), and the mixture was stirred at 70 ℃ for 24 hours to dissolve the same. To the solution were added PB (8.91g) and MEK (13.4g), and the mixture was stirred at 25 ℃ for 2 hours to obtain a liquid crystal alignment treatment agent (22). The liquid crystal aligning agent was not observed to be abnormal such as clouding and precipitation, and was confirmed to be a uniform solution.

Using the obtained liquid crystal aligning agent (22) and the liquid crystal composition (1), 2 liquid crystal display elements each having a substrate of glass or plastic were produced, and the above-described evaluations were performed.

In addition, the "evaluation of the adhesion between the liquid crystal layer and the vertical liquid crystal alignment film (plastic substrate)", an acceleration test was performed under the same conditions as in example 6, together with the standard test. As a result, a small amount of air bubbles were observed in the cell.

< example 26>

To the polysiloxane solution (1) (20.0g) obtained in Synthesis example 12 were added ECS (7.87g), BCS (10.2g), MIBK (15.3g), S2(0.12g) and M2(0.12g), and the mixture was stirred at 25 ℃ for 5 hours to obtain a liquid crystal alignment treatment agent (23). The liquid crystal aligning agent was not observed to be abnormal such as clouding and precipitation, and was confirmed to be a uniform solution.

Using the obtained liquid crystal aligning agent (23) and the liquid crystal composition (1), 2 liquid crystal display elements each having a glass or plastic substrate were produced, and the above-described evaluations were performed.

In addition, an acceleration test was performed under the same conditions as in example 6 with respect to the evaluation of the adhesion between the liquid crystal layer and the vertical liquid crystal alignment film (plastic substrate) together with the standard test described above. As a result, no bubble was observed in the element.

< example 27>

Using the liquid crystal aligning agent (23) and the liquid crystal composition (2) obtained in example 26, 2 liquid crystal display elements each having a substrate of glass or plastic were produced, and the above-described evaluations were performed.

< example 28>

To the polysiloxane solution (2) (20.0g) obtained in Synthesis example 13 were added EC (7.87g), PB (5.09g), MEK (5.09g) and MIBK (15.3g), and the mixture was stirred at 25 ℃ for 5 hours to obtain a liquid crystal alignment treatment agent (24). The liquid crystal aligning agent was not observed to be abnormal such as clouding and precipitation, and was confirmed to be a uniform solution.

Using the obtained liquid crystal aligning agent (24) and the liquid crystal composition (1), 2 liquid crystal display elements each having a substrate of glass or plastic were produced, and the above-described evaluations were performed.

< example 29>

Using the liquid crystal aligning agent (24) and the liquid crystal composition (2) obtained in example 28, 2 liquid crystal display elements each having a substrate of glass or plastic were produced, and the above-described evaluations were performed.

< example 30>

To the polysiloxane solution (3) (21.0g) obtained in Synthesis example 14 were added EC (8.26g), BCS (16.0g), MIBK (2.68g), DIBK (8.03g), and K1(0.076g), and the mixture was stirred at 25 ℃ for 5 hours to obtain a liquid crystal alignment treatment agent (25). The liquid crystal aligning agent was not observed to be abnormal such as clouding and precipitation, and was confirmed to be a uniform solution.

Using the obtained liquid crystal aligning agent (25) and liquid crystal composition (2), 2 liquid crystal display elements having glass and plastic as substrates were produced, and the above-described evaluations were performed.

< example 31>

To the polysiloxane solution (3) (21.0g) obtained in Synthesis example 14 were added EC (8.26g), BCS (16.0g), MIBK (2.68g), DIBK (8.03g), S1(0.126g), M2(0.252g), and K1(0.076g), and the mixture was stirred at 25 ℃ for 5 hours to obtain a liquid crystal alignment treatment agent (26). The liquid crystal aligning agent was not observed to be abnormal such as clouding and precipitation, and was confirmed to be a uniform solution.

Using the obtained liquid crystal aligning agent (26) and the liquid crystal composition (2), 2 liquid crystal display elements having glass and plastic as substrates were produced, and the above-described evaluations were performed.

In addition, the evaluation of the adhesion between the liquid crystal layer and the vertical liquid crystal alignment film (plastic substrate) was carried out under the same conditions as in example 6 (in which the storage time in the high-temperature and high-humidity chamber was 144 hours) together with the standard test. As a result, no bubble was observed in the element.

< example 32>

To the polysiloxane solution (4) (20.0g) obtained in Synthesis example 15 were added ECS (7.87g), BCS (10.2g), MIBK (15.3g), S2(0.12g) and M2(0.12g), and the mixture was stirred at 25 ℃ for 5 hours to obtain a liquid crystal alignment treatment agent (27). The liquid crystal aligning agent was not observed to be abnormal such as clouding and precipitation, and was confirmed to be a uniform solution.

Using the obtained liquid crystal aligning agent (27) and the liquid crystal composition (1), 2 liquid crystal display elements each having a substrate of glass or plastic were produced, and the above-described evaluations were performed.

In addition, an acceleration test was performed under the same conditions as in example 6, along with the standard test described above, on the evaluation of the adhesion between the liquid crystal layer and the vertical liquid crystal alignment film (plastic substrate). As a result, a small amount of air bubbles were observed in the cell.

< comparative example 1>

To the polyamic acid solution (10) (10.0g) obtained in Synthesis example 10 were added NMP (19.0g), BCS (10.6g) and MIBK (15.9g), and the mixture was stirred at 25 ℃ for 5 hours to obtain a liquid crystal alignment treatment agent (28). The liquid crystal aligning agent was not observed to be abnormal such as clouding and precipitation, and was confirmed to be a uniform solution.

Using the obtained liquid crystal aligning agent (28) and the liquid crystal composition (1), a liquid crystal display element having glass as a substrate was produced, and the above-described evaluations were performed.

< comparative example 2>

To the polyimide powder (11) (2.20g) obtained in Synthesis example 11 were added NMP (18.7g) and NEP (4.67g), and the mixture was stirred at 70 ℃ for 24 hours to dissolve the NMP. BCS (9.34g) and MIBK (14.0g) were added to the solution, and stirred at 25 ℃ for 2 hours to obtain a liquid crystal alignment treatment agent (29). The liquid crystal aligning agent was not observed to be abnormal such as clouding and precipitation, and was confirmed to be a uniform solution.

Using the obtained liquid crystal aligning agent (29) and the liquid crystal composition (1), a liquid crystal display element having glass as a substrate was produced, and the above-described evaluations were performed.

< comparative example 3>

To polyamic acid solution (2) (10.0g) obtained in Synthesis example 2 were added NMP (29.6g) and BCS (15.9g), and the mixture was stirred at 25 ℃ for 5 hours to obtain a liquid crystal alignment treatment agent (30). The liquid crystal aligning agent was not observed to be abnormal such as clouding and precipitation, and was confirmed to be a uniform solution.

Using the obtained liquid crystal aligning agent (30) and the liquid crystal composition (1), a liquid crystal display element having glass as a substrate was produced, and the above-described evaluations were performed.

< comparative example 4>

Using the liquid crystal aligning agent (30) and the liquid crystal composition (2) obtained in comparative example 3, a liquid crystal display element having glass as a substrate was produced, and the above-described evaluations were performed.

< comparative example 5>

To the polyimide powder (3) (2.15g) obtained in Synthesis example 3 were added NMP (31.9g) and NEP (4.56g), and the mixture was stirred at 70 ℃ for 24 hours to dissolve the NMP. BCS (9.12g) was added to the solution, and the mixture was stirred at 25 ℃ for 2 hours to obtain a liquid crystal aligning agent (31). The liquid crystal aligning agent was not observed to be abnormal such as clouding and precipitation, and was confirmed to be a uniform solution.

Using the obtained liquid crystal aligning agent (31) and the liquid crystal composition (1), a liquid crystal display element having a glass substrate was produced, and the above-described evaluations were performed.

< comparative example 6>

Using the liquid crystal aligning agent (31) and the liquid crystal composition (2) obtained in comparative example 5, a liquid crystal display element having glass as a substrate was produced, and the above-described evaluations were performed.

< comparative example 7>

To the polyimide powder (3) (2.20g) obtained in Synthesis example 3 were added γ -BL (23.3g) and PGME (14.0g), and the mixture was stirred at 70 ℃ for 24 hours to dissolve the same. PB (9.34g) was added to the solution, and the mixture was stirred at 25 ℃ for 2 hours to obtain a liquid crystal alignment treatment agent (32). The liquid crystal aligning agent was not observed to be abnormal such as clouding and precipitation, and was confirmed to be a uniform solution.

Using the obtained liquid crystal aligning agent (32) and the liquid crystal composition (1), 2 liquid crystal display elements each having a substrate of glass or plastic were produced, and the above-described evaluations were performed.

< comparative example 8>

To the polysiloxane solution (2) (20.0g) obtained in Synthesis example 13, EC (23.2g) and PB (10.2g) were added, and the mixture was stirred at 25 ℃ for 5 hours to obtain a liquid crystal alignment treatment agent (33). The liquid crystal aligning agent was not observed to be abnormal such as clouding and precipitation, and was confirmed to be a uniform solution.

Using the obtained liquid crystal aligning agent (33) and the liquid crystal composition (1), 2 liquid crystal display elements each having a glass or plastic substrate were produced, and the above-described evaluations were performed.

< comparative example 9>

Using the liquid crystal aligning agent (33) and the liquid crystal composition (2) obtained in comparative example 8, 2 liquid crystal display elements each having a substrate of glass or plastic were produced, and the above-described evaluations were performed.

[ Table 3]

[ Table 4]

[ Table 5]

[ Table 6]

[ Table 7]

[ Table 8]

[ Table 9]

[ Table 10]

[ Table 11]

[ Table 12]

From the above results, it can be seen that: the vertical liquid crystal alignment films obtained from the liquid crystal alignment treatment agents of examples had higher coating film uniformity, i.e., fewer pinholes than those of comparative examples. Specifically, the examples in which the specific polymer is the same and the specific solvent is used are compared with the comparative examples in which the specific solvent is not used, that is, the examples 2 and 3, the examples 4 and 5, the examples 6 and 7, and the examples 28 and 9.

In addition, the liquid crystal display element using the vertical liquid crystal alignment film obtained from the liquid crystal alignment treatment agent of the example had higher liquid crystal vertical alignment properties and exhibited better liquid crystal alignment properties than the comparative examples. In particular, in the examples of the present invention, no disturbance of the liquid crystal alignment was observed even after long-term storage in the high-temperature tank. Specifically, the examples in which the specific polymer is the same and the specific solvent is used are compared with the comparative examples in which the specific solvent is not used, that is, the examples 2 and 3, the examples 3 and 4, the examples 4 and 5, the examples 5 and 6, the examples 6 and 7, the examples 28 and 8, and the examples 29 and 9. In particular, in the comparative example, an alignment defect accompanied by a pinhole was observed at the initial stage.

Further, the liquid crystal layer of the liquid crystal display element using the vertical liquid crystal alignment film obtained from the liquid crystal alignment treatment agent of the example had higher adhesion to the vertical liquid crystal alignment film than the comparative example. Specifically, the examples in which the specific polymer is the same and the specific solvent is used are compared with the comparative examples in which the specific solvent is not used, that is, the examples 2 and 3, the examples 3 and 4, the examples 4 and 5, the examples 5 and 6, the examples 6 and 7, the examples 28 and 8, and the examples 29 and 9.

When the structure represented by the formula [2-1] is used, the result that the adhesiveness between the liquid crystal layer and the vertical liquid crystal alignment film becomes higher can be obtained as compared with the case where the structure represented by the formula [2-2] is used as the specific side chain structure. Specifically, the results of the accelerated test for the evaluation of the adhesion between the liquid crystal layer and the vertical liquid crystal alignment film (plastic substrate), i.e., the comparison between example 6 and example 25 and between example 26 and comparative example 32.

In addition, when the specific generator and the specific adhesion compound are introduced, the result that the adhesion between the liquid crystal layer and the vertical liquid crystal alignment film is higher can be obtained, as compared with the case where the specific generator and the specific adhesion compound are not introduced into the liquid crystal alignment agent of the present invention. Specifically, the results of the accelerated test for the evaluation of the adhesion between the liquid crystal layer and the vertical liquid crystal alignment film (plastic substrate) are the results of comparison between example 13 and example 14 or example 15, and between example 30 and comparative example 31.

Further, when a polymer not having a specific side chain structure is used, the liquid crystal is not vertically aligned. Specifically, comparative example 1 and comparative example 2.

Industrial applicability

The liquid crystal display element of the present invention can be suitably used for a reverse type element, and further, a vertical liquid crystal alignment film has high coating film uniformity and is less likely to cause alignment defects associated with coating film defects such as shrinkage and pinholes, and therefore, the liquid crystal display element of the present invention can be used for a liquid crystal display for display purposes, a light control window for controlling light transmission and isolation, a shutter element, and the like.

The entire contents of the specification, claims and abstract of japanese patent application No. 2014-065759, which was filed on 27/3/2014, are hereby incorporated by reference as the disclosure of the present invention specification.

Claims

1. A transmission/scattering type liquid crystal display element which exhibits a transparent state when no voltage is applied and exhibits a scattering state when a voltage is applied, characterized in that the liquid crystal display element is obtained by providing a liquid crystal layer between a pair of substrates having electrodes, disposing a liquid crystal composition containing a polymerizable compound which is polymerized by at least one of an active energy ray and heat between the pair of substrates, further providing at least one of the substrates with a liquid crystal alignment film which vertically aligns the liquid crystal, and curing the liquid crystal composition in a state where a part or all of the liquid crystal composition exhibits liquid crystallinity to form a cured product composite of the liquid crystal and the polymerizable compound, wherein the liquid crystal alignment film contains a liquid crystal alignment film obtained from a liquid crystal alignment treatment agent containing a solvent represented by the following formula [1], and comprises a polymer having at least 1 structure selected from the group consisting of structures represented by the following formulae [2-1] and [2-2],

S¹and S²Each independently represents an alkyl group having 1 to 4 carbon atoms,

Y¹represents a group selected from a single bond, - (CH)₂)_a-、-O-、-CH₂At least 1 of O-, -COO-and-OCO-, wherein a represents an integer of 1 to 15; y is²Represents a single bond or- (CH)₂)_b-, wherein b represents an integer of 1 to 15; y is³Represents a group selected from a single bond, - (CH)₂)_c-、-O-、-CH₂At least 1 of O-, -COO-and-OCO-, wherein c represents an integer of 1-15; y is⁴Represents at least 1 cyclic group selected from a benzene ring, a cyclohexane ring and a heterocycle or a C17-51 organic group having a steroid skeleton, any hydrogen atom on the cyclic group being optionally substituted by a C1-3 alkyl group, a C1-3 alkoxy group, a C1-3 fluoroalkyl group, a C1-3 fluoroalkoxy group or a fluorine atom; y is⁵Represents at least 1 cyclic group selected from a benzene ring, a cyclohexane ring and a heterocycle, any hydrogen atom on the cyclic groups is optionally substituted by alkyl with 1 to 3 carbon atoms, alkoxy with 1 to 3 carbon atoms, fluorine-containing alkyl with 1 to 3 carbon atoms, fluorine-containing alkoxy with 1 to 3 carbon atoms or fluorine atom; n represents an integer of 0 to 4; y is⁶Represents at least 1 kind selected from alkyl with 1-18 carbon atoms, fluorine-containing alkyl with 1-18 carbon atoms, alkoxy with 1-18 carbon atoms and fluorine-containing alkoxy with 1-18 carbon atoms,

-Y⁷-Y⁸ [2-2]

Y⁷is selected fromSingle bond, -O-, -CH₂O-、-CONH-、-NHCO-、-CON(CH₃)-、-N(CH₃) At least 1 bonding group selected from CO-, -COO-and-OCO-; y is⁸Represents an alkyl group having 8 to 22 carbon atoms or a fluoroalkyl group having 6 to 18 carbon atoms,

wherein the polymer is at least 1 polysiloxane selected from the following polysiloxanes: a polysiloxane obtained by condensation polymerization of an alkoxysilane represented by the following formula [ A1 ]; a polysiloxane obtained by polycondensing an alkoxysilane represented by the following formula [ A1] with an alkoxysilane containing any of the alkoxysilanes represented by the following formula [ A2] or formula [ A3 ]; and a polysiloxane obtained by polycondensing an alkoxysilane represented by the formula [ A1] or the formula [ A2] or the formula [ A3],

(A¹)_mSi(A²)_n(OA³)_p [A1]

A¹represents a group selected from the group consisting of the formula [2-1]And formula [2-2]At least 1 of the group consisting of the structures shown; a. the²Represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms; a. the³Represents 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; p represents an integer of 0 to 3, wherein m + n + p represents an integer of 4,

(B¹)_mSi(B²)_n(OB³)_p [A2]

B¹an organic group having 2 to 12 carbon atoms and containing at least 1 selected from a vinyl group, an epoxy group, an amino group, a mercapto group, an isocyanate group, a methacryloyl group, an acryloyl group, a ureido group and a cinnamoyl group; b is²Represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms; b is³Represents 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; p represents an integer of 0 to 3, wherein m + n + p represents an integer of 4,

(D¹)_nSi(OD²)_4-n [A3]

D¹represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms; d²Represents an alkyl group having 1 to 5 carbon atoms; n represents an integer of 0 to 3.

2. The liquid crystal display element according to claim 1, wherein the solvent represented by formula [1] is at least 1 solvent selected from the group consisting of 2-butanone, 3-pentanone, 4-methyl-2-pentanone, and 2, 6-dimethyl-4-heptanone.

3. The liquid crystal display element according to claim 1 or 2, wherein the liquid crystal alignment treatment agent further comprises at least 1 polymer selected from the group consisting of an acrylic polymer, a methacrylic polymer, a novolac resin, polyhydroxystyrene, a polyimide precursor, polyimide, polyamide, polyester, and cellulose.

4. The liquid crystal display element according to claim 3, wherein the polymer is at least 1 polymer selected from the group consisting of a polyimide precursor and a polyimide obtained by using a diamine having at least 1 side chain selected from the group consisting of structures represented by the formulae [2-1] and [2-2] as a part of raw materials.

5. The liquid crystal display element according to claim 4, wherein the diamine is a diamine represented by the following formula [2],

y represents at least 1 selected from the group consisting of the structures represented by the formulas [2-1] and [2-2 ]; n represents an integer of 1 to 4.

6. The liquid crystal display element according to claim 3, wherein the polymer is at least 1 polymer selected from the group consisting of a polyimide precursor obtained by using a second diamine represented by the following formula [3] as a part of a raw material and a polyimide,

x is at least 1 selected from the group consisting of the structures represented by the following formulae [3a ] to [3d ]; m represents an integer of 1 to 4,

formula [3a ]]Wherein a represents an integer of 0 to 4; formula [3b]Wherein b represents an integer of 0 to 4; formula [3c]In, X¹And X²Each independently represents a C1-12 hydrocarbon group; formula [3d]In, X³Represents an alkyl group having 1 to 5 carbon atoms.

7. The liquid crystal display element according to claim 3, wherein the polymer is at least 1 polymer selected from the group consisting of a polyimide precursor obtained by using a tetracarboxylic acid component represented by the following formula [4] as a part of a raw material and a polyimide,

z is at least 1 selected from the group consisting of the structures represented by the following formulae [4a ] to [4k ],

formula [4a ]]In, Z¹～Z⁴Each independently represents a hydrogen atom, a methyl group, a chlorine atom or a benzene ring; formula [4g ]]In, Z⁵And Z⁶Each independently represents a hydrogen atom or a methyl group.

8. The liquid crystal display element according to claim 1 or 2, wherein the liquid crystal alignment treatment agent contains at least 1 solvent selected from the group consisting of N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, and γ -butyrolactone.

9. The liquid crystal display element according to claim 1 or 2, wherein the liquid crystal alignment treatment agent contains at least 1 solvent selected from the group consisting of 1-hexanol, cyclohexanol, 1, 2-ethylene glycol, 1, 2-propylene glycol, propylene glycol monobutyl ether, ethylene glycol monobutyl ether, and dipropylene glycol dimethyl ether.

10. The liquid crystal display element according to claim 1 or 2, wherein the liquid crystal alignment treatment agent contains at least 1 kind of solvent selected from the group consisting of cyclopentanone, cyclohexanone, and solvents represented by the following formulae [ S1] to [ S3],

formula [ S1]In, T¹Represents an alkyl group having 1 to 3 carbon atoms; formula [ S2]In, T²Represents an alkyl group having 1 to 3 carbon atoms; formula [ S3]In, T³Represents an alkyl group having 1 to 4 carbon atoms.

11. The liquid crystal display element according to claim 1 or 2, wherein the liquid crystal alignment treatment agent contains at least 1 kind of generating agent selected from the group consisting of a photoradical generating agent, a photoacid generating agent, and a photobase generating agent.

12. The liquid crystal display element according to claim 1 or 2, wherein the liquid crystal alignment treatment agent contains at least 1 compound selected from the group consisting of compounds having structures represented by the following formulae [ M1] to [ M8],

formula [ M4]In, W¹Represents a hydrogen atom or a benzene ring; formula [ M7]In, W²Represents at least 1 cyclic group selected from a benzene ring, a cyclohexane ring and a heterocycle; w³Represents 1 kind selected from alkyl with 1-18 carbon atoms, fluorine-containing alkyl with 1-18 carbon atoms, alkoxy with 1-18 carbon atoms and fluorine-containing alkoxy with 1-18 carbon atoms.

13. The liquid crystal display element according to claim 1 or 2, wherein the liquid crystal alignment treatment agent comprises a compound having 2 or more substituents selected from the group consisting of an epoxy group, an isocyanate group, an oxetanyl group, a cyclocarbonate group, a hydroxyl group, a hydroxyalkyl group, and a lower alkoxyalkyl group.

14. The liquid crystal display element according to claim 1 or 2, wherein the substrate is a plastic substrate.

15. A liquid crystal alignment film for use in the liquid crystal display element according to any one of claims 1 to 14.

16. A liquid crystal alignment treatment agent for forming the liquid crystal alignment film according to claim 15.