KR102345961B1 - Liquid crystal display element, liquid crystal alignment film, and liquid crystal alignment treatment agent - Google Patents

Abstract

(S¹ 및 S² 는, 탄소수 1 ∼ 4 의 알킬기를 나타낸다)
[화학식 2-1]

(Y¹, Y², Y³ 은 단결합 등을 나타내고, Y⁴, Y⁵ 는 벤젠 고리 등을 나타내고, n 은 0 ∼ 4 를 나타내고, Y⁶ 은 탄소수 1 ∼ 18 의 알킬기 등을 나타낸다)
[화학식 2-2]

(Y⁷ 은 단결합 등을 나타내고, Y⁸ 은 탄소수 8 ∼ 22 의 알킬기 등을 나타낸다)It has a liquid crystal layer between a pair of board|substrates provided with an electrode, The liquid-crystal composition containing the polymeric compound which superposes|polymerizes by at least one of an active energy ray and a heat|fever between the pair of board|substrates is arrange|positioned, and at least one of the board|substrates A liquid crystal display element obtained by having a liquid crystal aligning film that vertically aligns the liquid crystal, and curing the liquid crystal composition in a state where part or all of the liquid crystal composition exhibits liquid crystallinity to form a cured product composite of liquid crystal and a polymerizable compound And the said liquid crystal aligning film contains the solvent shown by following formula [1], The polymer which has at least 1 sort(s) selected from the group which consists of a structure shown by following formula [2-1] and Formula [2-2] The liquid crystal display element which consists of a liquid crystal aligning film obtained from the liquid-crystal aligning agent to contain.
[Formula 1]

(S ¹ and S ² is an alkyl group having from 1 to 4 carbon atoms)
[Formula 2-1]

(Y ¹ , Y ² , Y ³ represents a single bond, etc., Y ⁴ , Y ⁵ represents a benzene ring, etc., n represents 0 to 4, Y ⁶ represents an alkyl group having 1 to 18 carbon atoms, etc.)
[Formula 2-2]

(Y ⁷ represents a single bond or the like, Y ⁸ represents an alkyl group, such as the number of carbon atoms from 8 to 22)

Description

A liquid crystal display element, a liquid crystal aligning film, and a liquid-crystal aligning agent {LIQUID CRYSTAL DISPLAY ELEMENT, LIQUID CRYSTAL ALIGNMENT FILM, AND LIQUID CRYSTAL ALIGNMENT TREATMENT AGENT}

This invention becomes a transparent state at the time of no voltage application, and relates to the liquid crystal display element of the transmission scattering type used as a scattering state at the time of voltage application, the liquid crystal aligning film for it, and the liquid-crystal aligning agent for forming this.

As a liquid crystal display element using a liquid crystal material, TN (Twisted Nematic) mode is put to practical use. In this mode, light is switched using the optical rotation characteristic of a liquid crystal, and when using it as a liquid crystal display element, it is necessary to use a polarizing plate. However, the use efficiency of light becomes low by using a polarizing plate.

As a liquid crystal display element with high light utilization efficiency without using a polarizing plate, there is a liquid crystal display element that switches between a transmissive state (also called a transparent state) and a scattering state of liquid crystal, and is generally a polymer dispersed liquid crystal (PDLC (PDLC) Also known as Polymer Dispersed Liquid Crystal) or a polymer network liquid crystal (PNLC (Polymer Network Liquid Crystal)).

A liquid crystal display element using these has a liquid crystal layer between a pair of substrates provided with electrodes, and a liquid crystal composition comprising a polymerizable compound that is polymerized by at least one of an active energy ray and heat between the pair of substrates It is a liquid crystal display device manufactured through a step of disposing a liquid crystal composition, curing the liquid crystal composition in a state where part or all of the liquid crystal composition exhibits liquid crystallinity, and forming a cured product complex of liquid crystal and a polymerizable compound. This liquid crystal display element controls the transmission state and the scattering state of a liquid crystal by application of a voltage.

In conventional liquid crystal display devices using PDLC or PNLC, when no voltage is applied, the liquid crystal molecules are oriented in a random direction, so they become cloudy (scattered). state (also referred to as a normal type element). However, in this normal element, since it is necessary to always apply a voltage in order to obtain a transmissive state, power consumption becomes large when used for applications that are often used in a transparent state, for example, a window glass or the like. .

A liquid crystal display element (also referred to as a reverse-type element) using PDLC that becomes a transmissive state when no voltage is applied and a scattering state when a voltage is applied with respect to a normal element has been reported (for example, Patent Document 1, see 2).

Japanese Patent No. 2885116 Japanese Patent No. 4132424

In a reverse-type element, the liquid crystal aligning film (it is also called a vertical liquid crystal aligning film) which orientates a liquid crystal perpendicularly|vertically is used. In that case, since a vertical liquid crystal aligning film is a film|membrane with high hydrophobicity, the adhesiveness of a liquid crystal layer and a liquid crystal aligning film will become low. Therefore, the polymerizable compound (it is also mentioned a hardening|curing agent) for improving the adhesiveness of a liquid crystal layer and a liquid crystal aligning film must be introduce|transduced into the liquid crystal composition used for a reverse type element abundantly. However, when a polymeric compound is introduced in a large amount, the vertical alignment property of the liquid crystal is inhibited, and the transparency at the time of no voltage application and the scattering characteristic at the time of the voltage application greatly decrease. Therefore, the liquid crystal aligning film used for a reverse type element requires that the vertical alignment property of a liquid crystal is high.

Currently, as for the liquid crystal aligning film mainly used, it is excellent in durability, and the organic film which consists of a polyimide-type polymer suitable for control of the pretilt angle of a liquid crystal is used. This polyimide-type polymer is the polyimide which imidated the polyamic acid and/or polyamic acid which are polyimide precursors, and the liquid-crystal aligning film is produced with the liquid-crystal aligning agent using these polymers. Since the solvent solubility of these polyimide-type polymers is low for the solvent of the liquid-crystal aligning agent using this polyimide-type polymer, highly polar solvents, such as N-methyl- 2-pyrrolidone (it is also mentioned NMP), is used. These highly polar solvents have a high boiling point, for example, the boiling point of NMP is 200 degreeC or more. Therefore, in order to produce a liquid crystal aligning film using the liquid-crystal aligning agent which used NMP for the solvent, in order to eliminate NMP which remain|survives in a liquid crystal aligning film, baking at the high temperature of about 200 degreeC which is the boiling point vicinity of NMP is required.

On the other hand, when using a thin and lightweight plastic substrate with low heat resistance for the board|substrate of a liquid crystal display element, it is necessary to perform baking at the time of producing a liquid crystal aligning film at low temperature. Similarly, reducing the energy cost in manufacture of a liquid crystal display element is also calculated|required by lowering this baking temperature.

Moreover, in a liquid crystal display element, it is calculated|required that the coating-film uniformity of a liquid crystal aligning film is high. That is, it is required that there are no coating-film defects, such as repelling and a pinhole, and coating-film nonuniformity. When the coating-film uniformity of a liquid crystal aligning film is low, a coating-film defect and a coating-film nonuniformity will become a display defect and a display nonuniformity, and will reduce the display characteristic of a liquid crystal display element. Therefore, it is required for a liquid-crystal aligning agent that wet-diffusion property is high with respect to the glass substrate and plastic substrate which are board|substrates of a liquid crystal display element.

According to the present invention, the vertical alignment of the liquid crystal is high, good optical properties are obtained, the adhesion between the liquid crystal layer and the vertical liquid crystal aligning film is high, and the coating film uniformity of the vertical liquid crystal aligning film is high, alignment due to poor coating film such as repelling or pinholes It aims at providing the liquid crystal display element which a defect does not generate|occur|produce easily.

Moreover, it aims at providing the liquid-crystal aligning agent which baking at the time of producing the perpendicular|vertical liquid crystal aligning film used for a liquid crystal display element is possible at low temperature.

As a result of this inventor earnestly researching, the liquid crystal display element using the vertical liquid crystal aligning film obtained from the liquid-crystal aligning agent containing the solvent of a specific structure and the polymer which has a side chain of a specific structure is very effective in order to achieve the said objective found out and came to complete this invention. That is, this invention has the following summary.

(1) having a liquid crystal layer between a pair of substrates provided with electrodes, a liquid crystal composition comprising a polymerizable compound that polymerizes by at least one of active energy rays and heat is disposed between the pair of substrates; a liquid crystal obtained by curing the liquid crystal composition in a state in which at least one of the liquid crystals has a liquid crystal aligning film for vertically aligning the liquid crystal, and 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 It is a display element, and the said liquid crystal aligning film has at least 1 sort(s) selected from the group which contains the solvent shown by following formula [1], and also consists of a structure shown by following formula [2-1] and formula [2-2] The liquid crystal display element which consists of a liquid crystal aligning film obtained from the liquid-crystal aligning agent containing a polymer.

[Formula 1]

(S ¹ and S ² each independently represent an alkyl group having 1 to 4 carbon atoms)

[Formula 2]

(Y ¹ is a single bond, -(CH ₂ ) _a - (a represents an integer of 1 to 15), -O-, -CH ₂ O-, -COO- and -OCO- at least one selected from Y ² represents a single bond or -(CH ₂ ) _b - (b represents an integer of 1 to 15), Y ³ represents a single bond, -(CH ₂ ) _c - (c is an integer of 1 to 15) represents at least one selected from ), -O-, -CH ₂ O-, -COO- and -OCO-, and Y ⁴ is at least one ring selected from a benzene ring, a cyclohexane ring and a heterocyclic ring. Represents a cyclic group or a C17-51 divalent organic group having a steroid skeleton, wherein arbitrary hydrogen atoms on the cyclic group are an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, and fluorine-containing having 1 to 3 carbon atoms. may be substituted with an alkyl group, a fluorine-containing alkoxy group having 1 to 3 carbon atoms, or a fluorine atom, Y ⁵ represents at least one cyclic group selected from a benzene ring, a cyclohexane ring, and a heterocyclic ring, and any of these cyclic groups A hydrogen atom may be substituted with a C1-C3 alkyl group, a C1-C3 alkoxy group, a C1-C3 fluorine-containing alkyl group, a C1-C3 fluorine-containing alkoxy group, or a fluorine atom, and n is 0-4 represents an integer of, and Y ⁶ represents at least one selected from an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, and a fluorine-containing alkoxy group having 1 to 18 carbon atoms. )

[Formula 3]

(Y ⁷ is from a single bond, -O-, -CH ₂ O-, -CONH-, -NHCO-, -CON(CH ₃ )-, -N(CH ₃ )CO-, -COO- and -OCO- represents at least one selected bonding group, and Y ⁸ represents an alkyl group having 8 to 22 carbon atoms or a fluorine-containing alkyl group having 6 to 18 carbon atoms)

(2) at least one solvent selected from the group consisting of 2-butanone, 3-pentanone, 4-methyl-2-pentanone and 2,6-dimethyl-4-heptanone, the solvent represented by the formula [1] The liquid crystal display element as described in said (1) which is.

(3) wherein the polymer is at least one polymer selected from acrylic polymer, methacrylic polymer, novolak resin, polyhydroxystyrene, polyimide precursor, polyimide, polyamide, polyester, cellulose and polysiloxane ( The liquid crystal display element as described in 1) or (2).

(4) Polyimide obtained by using for a part of raw materials the diamine which has the at least 1 sort(s) of side chain chosen from the group which the said polymer consists of the structure shown by the said Formula [2-1] and Formula [2-2], The liquid crystal display element as described in said (3) which is at least 1 sort(s) of polymer chosen from the group which consists of a precursor and a polyimide.

(5) Liquid crystal display element as described in said (4) whose said diamine is diamine represented by following formula [2].

[Formula 4]

(Y represents at least 1 sort(s) of structure chosen from the group which consists of structures shown by said Formula [2-1] and Formula [2-2], n represents the integer of 1-4)

(6) Said (3)-( said polymer which is at least 1 sort(s) of polymer chosen from the group which consists of a polyimide precursor and polyimide obtained by using the 2nd diamine represented by following formula [3] for a part of raw material, 5) The liquid crystal display element in any one of.

[Formula 5]

(X is at least 1 sort(s) chosen from the structure shown by a following formula [3a] - a formula [3d], and m represents the integer of 1-4)

[Formula 6]

(in formula [3a], a represents the integer of 0-4, in formula [3b], b represents the integer of 0-4, and in formula [3c], X ¹ and X ² each independently represent the number of carbon atoms. represents a hydrocarbon group of 1 to 12, and in formula [3d], X ³ represents an alkyl group of 1 to 5 carbon atoms)

(7) Said (3) said polymer is at least 1 sort(s) of polymer chosen from the group which consists of a polyimide precursor and polyimide obtained by using the tetracarboxylic acid component represented by following formula [4] for a part of a raw material. - The liquid crystal display element in any one of (6).

[Formula 7]

(Z is at least 1 sort(s) selected from the structure shown by a following formula [4a] - a formula [4k])

[Formula 8]

(In the formula [4a], Z ¹ to Z ⁴ each independently represent a hydrogen atom, a methyl group, a chlorine atom, or a benzene ring, and in the formula [4g], Z ⁵ and Z ⁶ are each independently a hydrogen atom or a methyl group. represents)

(8) Alkoxy containing any 1 type of polysiloxane obtained by making the said polymer polycondensate the alkoxysilane shown by following formula [A1], Formula [A1], and the alkoxysilane shown by following formula [A2] or Formula [A3] The liquid crystal display as described in said (3) which is at least 1 sort(s) of polysiloxane selected from polysiloxane obtained by polycondensing a silane, and polysiloxane obtained by making polycondensation of the alkoxysilane shown by Formula [A1], Formula [A2], and Formula [A3] device.

[Formula 9]

(A ¹ represents at least one structure selected from the group consisting of structures represented by the formulas [2-1] and [2-2], and A ² represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. represents, A ³ represents an alkyl group having 1 to 5 carbon atoms, m represents an integer of 1 or 2, n represents an integer of 0 to 2, and p represents an integer of 0 to 3. However, m+n +p represents an integer of 4)

[Formula 10]

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

[Formula 11]

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

(9) Said liquid-crystal aligning agent containing at least 1 sort(s) of solvent chosen from the group which consists of N-methyl- 2-pyrrolidone, N-ethyl- 2-pyrrolidone, and (gamma)-butyrolactone ( 1) The liquid crystal display element in any one of - (8).

(10) The liquid crystal aligning agent is 1-hexanol, cyclohexanol, 1,2-ethanediol, 1,2-propanediol, propylene glycol monobutyl ether, ethylene glycol monobutyl ether and dipropylene glycol dimethyl ether. The liquid crystal display element in any one of said (1)-(9) containing the at least 1 solvent chosen from the group which consists of.

(11) Said (1)-(10) in which the said liquid-crystal aligning agent contains at least 1 solvent chosen from the group which consists of a solvent shown by cyclopentanone, cyclohexanone, and a following formula [S1] - a formula [S3] ) The liquid crystal display element in any one of.

[Formula 12]

(Wherein [S1] of, T ¹ represents an alkyl group having a carbon number of 1 to 3, formula [S2] of, T ² represents an alkyl group having a carbon number of 1 to 3, formula [S3] in, T ³ is a group having from 1 to 4 carbon atoms represents an alkyl group of

(12) Liquid crystal in any one of said (1)-(11) in which the said liquid-crystal aligning agent contains at least 1 sort(s) of generator chosen from the group which consists of a photoradical generator, a photo-acid generator, and a photobase generator display element.

(13) The said liquid-crystal aligning agent in any one of said (1)-(12) containing the at least 1 compound chosen from the group which consists of a compound which has a structure shown by the following formula [M1] - a formula [M8] The liquid crystal display element described.

[Formula 13]

(In formula [M4], W ¹ represents a hydrogen atom or a benzene ring, in formula [M7], W ² represents at least one cyclic group selected from a benzene ring, a cyclohexane ring and a heterocyclic ring, and W ³ represents 1 type selected from a C1-C18 alkyl group, a C1-C18 fluorine-containing alkyl group, a C1-C18 alkoxy group, and a C1-C18 fluorine-containing alkoxy group)

(14) The liquid-crystal aligning agent is an epoxy group, an isocyanate group, an oxetane group, a cyclocarbonate group, a hydroxyl group, a hydroxyalkyl group, and a compound which has at least 1 type of substituent selected from the group which consists of a lower alkoxyalkyl group 2 or more The liquid crystal display element in any one of said (1)-(13) containing.

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

(16) The liquid crystal aligning film used for the liquid crystal display element in any one of said (1)-(15).

(17) Liquid-crystal aligning agent for forming the liquid-crystal aligning film as described in said (16).

The liquid crystal display element of this invention uses the vertical alignment film obtained from the liquid-crystal aligning agent containing the solvent of a specific structure, and the polymer which has a side chain of a specific structure, the vertical alignment property of a liquid crystal is high, favorable optical properties are obtained, and liquid crystal The layer and the vertical liquid crystal aligning film have high adhesion, so alignment defects due to poor coating such as repelling or pinholes do not easily occur. In particular, a reverse-type device that becomes a transmissive state when no voltage is applied and a scattering state when voltage is applied. It can be preferably used for a liquid crystal display for display purposes, and furthermore, it can be used as a dimming window or optical shutter element for controlling the transmission and blocking of light.

Moreover, a plastic substrate can be used for a board|substrate by baking at the time of producing a vertical liquid crystal aligning film at low temperature.

The present invention has a liquid crystal layer between a pair of substrates provided with electrodes, and a liquid crystal composition comprising 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 has a liquid crystal aligning film for vertically aligning the liquid crystal, and curing the liquid crystal composition in a state in which part or all of the liquid crystal composition exhibits liquid crystallinity, thereby forming a cured product composite of liquid crystal and polymerizable compound The liquid crystal display element obtained by making it form WHEREIN: The said liquid crystal aligning film contains the solvent (it is also mentioned a specific solvent) shown by said Formula [1], The structure shown by said Formula [2-1] and Formula [2-2] It is a liquid crystal display element which consists of a liquid crystal aligning film obtained from the liquid-crystal aligning agent containing the polymer (it is also mentioned a specific polymer) which has at least 1 sort(s) chosen from the group which consists of (it is also mentioned specific side chain structure in total).

The liquid crystal display element of the present invention can be preferably used for a reverse-type element that mainly enters a transmissive state when no voltage is applied and becomes a scattering state when a voltage is applied.

Since a boiling point is low compared with the solvent used for the conventional liquid-crystal aligning agent, for example, NMP, the specific solvent used for this invention can perform the baking process at the time of producing a liquid crystal aligning film at low temperature.

Moreover, since the viscosity as a solvent is low, when a specific solvent apply|coats the liquid-crystal aligning agent using it to a board|substrate, the wet-diffusion property of a liquid-crystal aligning agent becomes high, and the liquid crystal aligning film excellent in coating-film uniformity can be obtained. In particular, since the liquid crystal aligning film used for a reverse type element needs to make the vertical alignment property of a liquid crystal high, it is necessary to introduce|transduce hydrophobic side chain group abundantly in the polymer used for the liquid-crystal aligning agent which produces it. Therefore, although the wet-diffusion property of a liquid-crystal aligning agent becomes low easily, the liquid-crystal aligning agent used for preparation of this element can improve it by using the specific solvent of this invention.

In specific side chain structure, the structure of Formula [2-1] has a C17-C51 divalent organic group which has a benzene ring, a cyclohexane ring, a heterocyclic ring, or steroid skeleton in a side chain site|part. Since the side chain structure of these rings and an organic group shows a rigid structure, in the reverse element using the vertical liquid crystal aligning film which has the specific side chain structure shown by Formula [2-1], high and stable vertical alignment property of a liquid crystal is obtained lose

By using the vertical alignment film obtained from the liquid-crystal aligning agent containing the solvent of a specific structure, and the polymer which has a specific side chain structure from the above point, the vertical alignment property of a liquid crystal is high, favorable optical properties are obtained, and a liquid crystal layer and vertical liquid crystal A liquid crystal display element with high adhesiveness of an alignment film can be obtained.

Moreover, by using the liquid-crystal aligning agent of this invention, the coating-film uniformity of a vertical liquid crystal aligning film is high, and the liquid crystal display element with which the orientation defect accompanying coating-film defects, such as repelling and a pinhole, does not generate|occur|produce easily can be obtained.

The liquid crystal display element of the present invention can be preferably used for a reverse-type element, which is in a transmissive state especially when no voltage is applied, and is in a scattering state when a voltage is applied. It can be used as a dimming window, an optical shutter element, etc. which control blocking. Moreover, since baking at the time of producing a vertical liquid crystal aligning film can be performed at low temperature, a plastic substrate can be used for a board|substrate.

<Liquid crystal display element>

The liquid crystal display element of the present invention has a liquid crystal layer between a pair of substrates provided with electrodes, and contains a polymerizable compound that polymerizes by at least one of an active energy ray and heat between the pair of substrates A liquid crystal composition is disposed, and at least one of the substrates has a liquid crystal aligning film for vertically aligning the liquid crystal, and the liquid crystal composition is cured in a state where part or all of the liquid crystal composition exhibits liquid crystallinity, It can be suitably used for a reverse-type device manufactured through a process of forming a cured product composite, in a transmission state when no voltage is applied, and in a scattering state when voltage is applied.

<Specific solvent>

A specific solvent is represented by following formula [1].

[Formula 14]

S ¹ and S ² each independently represent an alkyl group having 1 to 4 carbon atoms.

As a formula [1], it is preferable that it is at least 1 sort(s) chosen from 2-butanone, 3-pentanone, 4-methyl-2-pentanone, and 2, 6- dimethyl- 4-heptanone.

Moreover, a specific solvent can be used 1 type or in mixture of 2 or more types according to characteristics, such as the solubility of a specific polymer, the vertical alignment property of a liquid crystal when it is set as a vertical liquid crystal aligning film, and also the optical characteristic of a liquid crystal display element.

<Specific side chain structure>

The liquid crystal display element of this invention is an element which has a perpendicular|vertical liquid crystal aligning film which orientates a liquid crystal perpendicularly|vertically on at least one side of a board|substrate. The said perpendicular|vertical liquid crystal aligning film is obtained from the liquid-crystal aligning agent containing the specific polymer which has a structure of following formula [2-1] or formula [2-2].

[Formula 15]

Y ^{1 represents at least one selected} from a single bond, -(CH ₂ ) _a - (a is an integer of 1 to 15), -O-, -CH ₂ O-, -COO-, and -OCO-. Among them, from the viewpoint of availability of raw materials and ease of synthesis, a single bond, -(CH ₂ ) _a - (a is an integer of 1 to 15), -O-, -CH ₂ O- or -COO- desirable. More preferably, they are a single bond, -(CH ₂ ) _a - (a is an integer of 1 to 10), -O-, -CH ₂ O-, or -COO-.

Y ² represents a single bond or -(CH ₂ ) _b - (b represents an integer of 1 to 15). Among them, a single bond or a - is preferably a (b is an integer of _{1 ~ 10) - (CH 2} ) b.

Y ³ represents at least one selected from a single bond, -(CH ₂ ) _c - (c represents an integer of 1 to 15), -O-, -CH _{2 O-, -COO-, and -OCO-} . Among them, a single bond, -(CH ₂ ) _c - (c represents an integer of 1 to 15), -O-, -CH ₂ O-, or -COO- is preferable from the point of synthesis easiness. Even more preferably, a single _{bond, - (CH 2) c -} (c is an integer of 1 to 10), is -O-, -CH ₂ O- or -COO-.

Y ⁴ represents at least one cyclic group selected from a benzene ring, a cyclohexane ring and a heterocyclic ring, and any hydrogen atom on these cyclic groups is an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, or a carbon number You may be substituted with a 1-3 fluorine-containing alkyl group, a C1-C3 fluorine-containing alkoxy group, or a fluorine atom. Further, Y ⁴ may be a divalent organic group selected from organic groups having a steroid skeleton and having 17 to 51 carbon atoms. Especially, a C17-C51 organic group which has a benzene ring, a cyclohexane ring, or a steroid skeleton from the point of the easiness of a synthesis|combination is preferable.

Y ⁵ represents at least one cyclic group selected from a benzene ring, a cyclohexane ring and a heterocyclic ring, and an arbitrary hydrogen atom on these cyclic groups is an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms; You may be substituted by a C1-C3 fluorine-containing alkyl group, a C1-C3 fluorine-containing alkoxy group, or a fluorine atom. Among them, a benzene ring or a cyclohexane ring is preferable.

n represents the integer of 0-4. Especially, from the point of the availability of a raw material and the easiness of a synthesis|combination, 0-3 are preferable. More preferably, it is 0-2.

Y ⁶ represents 1 type selected from a C1-C18 alkyl group, a C1-C18 fluorine-containing alkyl group, a C1-C18 alkoxy group, and a C1-C18 fluorine-containing alkoxy group. Especially, a C1-C18 alkyl group, a C1-C10 fluorine-containing alkyl group, a C1-C18 alkoxy group, or a C1-C10 fluorine-containing alkoxy group is preferable. More preferably, they are a C1-C12 alkyl group or a C1-C12 alkoxy group, Especially preferably, they are a C1-C9 alkyl group or a C1-C9 alkoxy group.

Formula ^{[2-1] Y 1, Y 2} , Y 3, Y 4, Y 5, Y 6 , and a preferred combination of n, International Publication page 13 of WO2011 / 132751 (published 2011.10.27) in the - Combinations similar to those in (2-1) to (2-629) shown in Tables 6 to 47 on page 34 are exemplified. Further, by reading the table, each of International Publication, there is Y ¹ ~ Y ⁶ in the present invention, is shown as Y1 ~ Y6, Y1 ~ Y6 is changed to Y ¹ ~ Y ^6. Moreover, in (2-605) - (2-629) published in each table|surface of International Publication, the organic group of 17-C51 which has a steroid skeleton in this invention has a C12-C25 which has a steroid skeleton Although shown as an organic group, a C12-C25 organic group which has a steroid skeleton shall be read as a C17-C51 organic group which has a steroid skeleton.

[Formula 16]

Y ⁷ is a single bond, -O-, -CH ₂ O-, -CONH-, -NHCO-, -CON(CH ₃ )-, -N(CH ₃ )CO-, -COO- and -OCO- selected from at least 1 type of bonding group which becomes Among them, a single bond, -O-, -CH ₂ O-, -CONH-, -CON(CH ₃ )-, or -COO- is preferable. More preferably, it is a single bond, -O-, -CONH-, or -COO-.

Y ⁸ represents a fluorine-containing alkyl group of a carbon number of 8 to 22 carbon atoms or an alkyl group of 6 to 18. Especially, a C8-C18 alkyl group is preferable.

As a specific side chain structure, it is preferable to use the specific side chain structure shown by said Formula [2-1] from the point which can obtain the vertical alignment property of a high and stable liquid crystal.

<Specific Polymer>

Although there is no limitation in particular as a specific polymer which has a specific side chain structure, It consists of an acrylic polymer, a methacryl polymer, a novolak resin, polyhydroxystyrene, a polyimide precursor, a polyimide, polyamide, polyester, a cellulose, and polysiloxane. It is preferably at least one polymer selected from the group. Especially, a polyimide precursor, a polyimide, or polysiloxane is preferable.

When using a polyimide precursor or polyimide (collectively referred to as a polyimide-based polymer) for the specific polymer of the present invention, they are a polyimide precursor or polyimide obtained by reacting a diamine component with a tetracarboxylic acid component. desirable.

A polyimide precursor is a structure shown by a following formula [A].

[Formula 17]

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

As said diamine component, it is a diamine which has two primary or secondary amino groups in a molecule|numerator, As a tetracarboxylic acid component, A tetracarboxylic acid compound, tetracarboxylic dianhydride, a tetracarboxylic acid dihalide compound; A tetracarboxylic-acid dialkyl ester compound or a tetracarboxylic-acid dialkyl ester dihalide compound is mentioned.

The polyimide-type polymer of this invention is represented by a following formula [D] from the reason that it is obtained comparatively simply by using tetracarboxylic dianhydride shown by a following formula [B], and diamine represented by a following formula [C] as raw materials. A polyamic acid having the structural formula of the repeating unit or a polyimide obtained by imidizing the polyamic acid is preferable. Especially, it is preferable for the specific polyimide-type polymer of this invention to use a polyimide from the point of the physical and chemical stability of a vertical liquid crystal aligning film.

[Formula 18]

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

[Formula 19]

(R ¹ and R ² are synonymous with those defined in formula [A])

In addition, the polymers of the usual synthesis techniques, equation [D] obtained in the above-mentioned formula [A] represented by A ¹ and A carbon number of alkyl group of 1-8 of Figure ^2, and the equation [A] represented by A ³ and A ⁴ An alkyl group or acetyl group having 1 to 5 carbon atoms may be introduced.

As a method of introduce|transducing a specific side chain structure into a polyimide-type polymer, it is preferable to use for a part of raw materials the diamine which has a specific side chain structure. In particular, the diamine (it is also mentioned specific side chain type diamine) of following formula [2] is preferable.

[Formula 20]

Y is a structure shown by said Formula [2-1] or Formula [2-2]. Especially, the structure shown by Formula [2-1] is preferable at the point which can obtain the vertical alignment property of a high and stable liquid crystal. n represents the integer of 1-4. Especially, the integer of 1 is preferable.

As specific side chain type diamine, it is preferable to use the diamine of a following formula [2-1a] from the point which can obtain the vertical alignment property of a high and stable liquid crystal.

[Formula 21]

Y ^{1 represents at least one selected} from a single bond, -(CH ₂ ) _a - (a is an integer of 1 to 15), -O-, -CH ₂ O-, -COO-, and -OCO-. Among them, from the viewpoint of availability of raw materials and ease of synthesis, a single bond, -(CH ₂ ) _a - (a is an integer of 1 to 15), -O-, -CH ₂ O- or -COO- desirable. More preferably, they are a single bond, -(CH ₂ ) _a - (a is an integer of 1 to 10), -O-, -CH ₂ O-, or -COO-.

Y ² represents a single bond or -(CH ₂ ) _b - (b represents an integer of 1 to 15). Among them, a single bond or a - is preferably a (b is an integer of _{1 ~ 10) - (CH 2} ) b.

Y ³ represents at least one selected from a single bond, -(CH ₂ ) _c - (c represents an integer of 1 to 15), -O-, -CH _{2 O-, -COO-, and -OCO-} . Among them, a single bond, -(CH ₂ ) _c - (c represents an integer of 1 to 15), -O-, -CH ₂ O-, or -COO- is preferable from the point of synthesis easiness. Even more preferably, a single _{bond, - (CH 2) c -} (c is an integer of 1 to 10), is -O-, -CH ₂ O- or -COO-.

Y ⁴ represents at least one cyclic group selected from a benzene ring, a cyclohexane ring and a heterocyclic ring, and any hydrogen atom on these cyclic groups is an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, or a carbon number You may be substituted with a 1-3 fluorine-containing alkyl group, a C1-C3 fluorine-containing alkoxy group, or a fluorine atom. Further, Y ⁴ may be a divalent organic group selected from organic groups having a steroid skeleton and having 17 to 51 carbon atoms. Especially, a C17-C51 organic group which has a benzene ring, a cyclohexane ring, or a steroid skeleton from the point of the easiness of a synthesis|combination is preferable.

Y ⁵ represents at least one cyclic group selected from a benzene ring, a cyclohexane ring and a heterocyclic ring, and an arbitrary hydrogen atom on these cyclic groups is an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms; You may be substituted by a C1-C3 fluorine-containing alkyl group, a C1-C3 fluorine-containing alkoxy group, or a fluorine atom. Among them, a benzene ring or a cyclohexane ring is preferable. n represents the integer of 0-4. Especially, from the point of the availability of a raw material and the easiness of a synthesis|combination, 0-3 are preferable. More preferably, it is 0-2.

Y ⁶ represents 1 type selected from a C1-C18 alkyl group, a C1-C18 fluorine-containing alkyl group, a C1-C18 alkoxy group, and a C1-C18 fluorine-containing alkoxy group. Especially, a C1-C18 alkyl group, a C1-C10 fluorine-containing alkyl group, a C1-C18 alkoxy group, or a C1-C10 fluorine-containing alkoxy group is preferable. More preferably, they are a C1-C12 alkyl group or a C1-C12 alkoxy group, Especially preferably, they are a C1-C9 alkyl group or a C1-C9 alkoxy group.

^{As a preferable combination of Y 1} , Y ² , Y ³ , Y ⁴ , Y ⁵ , Y ⁶ and n in formula [2-1a], it is page 13 of International Publication WO2011/132751 (published on October 27, 2011) - Combinations similar to those in (2-1) to (2-629) shown in Tables 6 to 47 on page 34 are exemplified. Further, by reading the table, each of International Publication, there is Y ¹ ~ Y ⁶ in the present invention, is shown as Y1 ~ Y6, Y1 ~ Y6 is replaced with Y ¹ ~ Y ^6. Moreover, in (2-605) - (2-629) published in each table|surface of International Publication, the organic group of 17-C51 which has a steroid skeleton in this invention has a C12-C25 which has a steroid skeleton Although represented as an organic group, the C12-C25 organic group which has a steroid skeleton shall be read as a C17-C51 organic group which has a steroid skeleton.

Among them, (2-25) to (2-96), (2-145) to (2-168), (2-217) to (2-240), (2-268) to (2-315) , (2-364) to (2-387), (2-436) to (2-483) or a combination of (2-603) to (2-615) is preferable. Particularly preferable combinations are (2-49) to (2-96), (2-145) to (2-168), (2-217) to (2-240), and (2-603) to (2- 606), (2-607) to (2-609), (2-611), (2-612) or (2-624).

m is an integer of 1-4. Preferably, it is an integer of 1.

More specifically, the diamine shown by a following formula [2a-1] - a formula [2a-31] is mentioned.

[Formula 22]

(R ¹ each independently represents at least one bonding group selected from -O-, -OCH ₂ -, -CH _{2 O-, -COOCH 2} - and -CH ₂ ^{OCO-, R 2} is each independently 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 fluorine-containing alkyl group having 1 to 22 carbon atoms, or a straight chain or branched alkyl group having 1 to 22 carbon atoms. represents a chain or branched fluorine-containing alkoxy group)

[Formula 23]

(R ³ is, each independently, -COO-, -OCO-, -CONH-, -NHCO-, -COOCH ₂ -, -CH ₂ OCO-, -CH ₂ O-, -OCH ₂ - and -CH ₂ - represents at least one bonding group selected from, and R ⁴ is each independently a linear or branched alkyl group having 1 to 22 carbon atoms, a linear or branched alkoxy group having 1 to 22 carbon atoms, and 1 to 22 carbon atoms. represents a linear or branched fluorine-containing alkyl group of, or a linear or branched fluorine-containing alkoxy group having 1 to 22 carbon atoms)

[Formula 24]

(R ⁵ is each independently -COO-, -OCO-, -CONH-, -NHCO-, -COOCH ₂ -, -CH ₂ OCO-, -CH ₂ O-, -OCH ₂ -, -CH ₂ - , -O- and -NH- represent at least one bonding group selected from, and R ⁶ is each independently a fluorine group, a cyano group, a trifluoromethane group, a nitro group, an azo group, a formyl group, an acetyl group, an acetonitrile group At least 1 type selected from a oxy group and a hydroxyl group is represented)

[Formula 25]

(R ⁷ each independently represents a linear or branched alkyl group having 3 to 12 carbon atoms, and the cis-trans isomers of 1,4-cyclohexylene each represent a trans isomer)

[Formula 26]

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

[Formula 27]

(A ₄ represents a linear or branched alkyl group having 3 to 20 carbon atoms which may be substituted with a fluorine atom, A ₃ represents a 1,4-cyclohexylene group or a 1,4-phenylene group, A ₂ represents represents an oxygen atom or -COO-* (however, the bond attached to "*" bonds to A ₃ ), A ₁ is an oxygen atom or -COO-* (however, the bond attached to "*" is (CH ₂ ) a ₂ ) is combined with). In addition, a ₁ represents an integer of 0 or 1, a ₂ represents an integer of 2 ~ 10, a ₃ represents an integer of 0 or 1.)

[Formula 28]

[Formula 29]

[Formula 30]

[Formula 31]

[Formula 32]

Diamine of a particularly preferable structure is a formula [2a-1] - a formula [2a-6], a formula [2a-9] - a formula [2a-13], a formula [2a-22] - a formula [2a-31], such as is diamine.

Moreover, as specific side chain type diamine which has the specific side chain structure of the said Formula [2-2], it is preferable to use the diamine of a following formula [2a-32] - a formula [2a-35].

[Formula 33]

(A ¹ each independently represents a C1-C22 alkyl group or a C1-C22 fluorine-containing alkyl group).

As for specific side chain type diamine, 10 mol% or more and 80 mol% or less of the whole diamine component are preferable from the point of the vertical alignment property of the liquid crystal in a liquid crystal display element, and the adhesive point of a liquid crystal layer and a vertical liquid crystal aligning film. More preferably, it is 10 mol% or more and 70 mol% or less.

Specific side chain type diamine is one type or two or more types depending on characteristics such as solubility in a solvent of a polyimide-based polymer, vertical alignment property of a liquid crystal when it is set as a vertical liquid crystal aligning film, and further, optical characteristics of a liquid crystal display element It can be mixed and used.

In this invention, when using a polyimide-type polymer for a specific polymer, as a diamine component, it is preferable to use for a part of raw materials the 2nd diamine shown by following formula [3] with the said specific side chain type diamine. do.

[Formula 34]

X represents at least 1 sort(s) chosen from the structure shown by a following formula [3a] - a formula [3d].

[Formula 35]

a represents the integer of 0-4. Among these, the integer of 0 or 1 is preferable from the point of the availability of a raw material and the easiness of a synthesis|combination. b represents the integer of 0-4. Among these, the integer of 0 or 1 is preferable from the point of the availability of a raw material and the easiness of a synthesis|combination. X ¹ and X ² each independently represent a hydrocarbon group having 1 to 12 carbon atoms. X ³ represents an alkyl group having 1 to 5 carbon atoms.

m represents the integer of 1-4. Especially, the integer of 1 is preferable.

As 2nd diamine, the following diamine is specifically mentioned.

2,4-Dimethyl-m-phenylenediamine, 2,6-diaminotoluene, 2,4-diaminophenol, 3,5-diaminophenol, 3,5-diaminobenzyl alcohol, 2,4-dia Minobenzyl alcohol, 4,6-diaminoresorcinol, 2,4-diaminobenzoic acid, 2,5-diaminobenzoic acid, 3,5-diaminobenzoic acid, etc. are mentioned.

Moreover, the diamine of the structure shown by a following formula [3-1] - a formula [3-6] is mentioned.

[Formula 36]

[Formula 37]

Among the second diamines, 2,4-diaminophenol, 3,5-diaminophenol, 3,5-diaminobenzyl alcohol, 2,4-diaminobenzyl alcohol, 4,6-diaminoresorcinol, 2 Using diamine represented by 4-diaminobenzoic acid, 2,5-diaminobenzoic acid, 3,5-diaminobenzoic acid, formula [3-1], formula [3-2] or formula [3-3] is desirable. Particularly preferably, 2,4-diaminophenol, 3,5-diaminophenol, 3,5-diaminobenzyl alcohol, 3,5-diaminobenzoic acid, formula [3-1] or formula [3-2] It is a diamine represented by ].

The second diamine is, depending on characteristics such as the solubility of the polyimide-based polymer of the present invention in a solvent, the vertical alignment property of the liquid crystal when a vertical liquid crystal aligning film is used, and further the optical characteristics of the liquid crystal display element of the present invention, one type or Two or more types can be mixed and used.

As a diamine component in the case of using a polyimide-type polymer for a specific polymer, diamines other than the specific side chain type diamine shown by the said Formula [2], and the 2nd diamine shown by the said Formula [3] (it is also mentioned another diamine) It can also be used as a diamine component. Although the specific example of other diamine is given below, it is not limited to these examples.

That is, m-phenylenediamine, p-phenylenediamine, 4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4 , 4'-diaminobiphenyl, 3,3'-dihydroxy-4,4'-diaminobiphenyl, 3,3'-dicarboxy-4,4'-diaminobiphenyl, 3,3' -difluoro-4,4'-diaminobiphenyl, 3,3'-trifluoromethyl-4,4'-diaminobiphenyl, 3,4'-diaminobiphenyl, 3,3'- Diaminobiphenyl, 2,2'-diaminobiphenyl, 2,3'-diaminobiphenyl, 4,4'-diaminodiphenylmethane, 3,3'-diaminodiethylmethane, 3,4 '-diaminodiphenylmethane, 2,2'-diaminodiphenylmethane, 2,3'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl Ether, 3,4'-diaminodiphenyl ether, 2,2'-diaminodiphenyl ether, 2, 3'-diaminodiphenyl ether, 4,4'-sulfonyldianiline, 3,3'-sulfo Nyldianiline, bis(4-aminophenyl)silane, bis(3-aminophenyl)silane, dimethyl-bis(4-aminophenyl)silane, dimethyl-bis(3-aminophenyl)silane, 4,4'-thiodi Aniline, 3,3'-thiodianiline, 4,4'-diaminodiphenylamine, 3,3'-diaminodiphenylamine, 3,4'-diaminodiphenylamine, 2,2'-dia minodiphenylamine, 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, 4,4' -diaminobenzophenone, 3,3'-diaminobenzophenone, 3,4'-diaminobenzophenone, 1,4-diaminonaphthalene, 2,2'-diaminobenzophenone, 2,3'-dia Minobenzophenone, 1,5-diaminonaphthalene, 1,6-diaminonaphthalene, 1,7-diaminonaphthalene, 1,8-diaminonaphthalene, 2,5-diaminonaphthalene, 2,6-diaminonaphthalene , 2,7-diaminonaphthalene, 2,8-diaminonaphthalene, 1,2-bis(4-aminophenyl)ethane, 1,2-bis(3-aminophenyl)ethane, 1,3-bis(4) -aminophenyl)propane, 1,3-bis(3-aminophenyl)propane, 1,4-bis(4aminophenyl)butane, 1,4-bis(3-aminophenyl)butane, bis(3,5-diethyl-4-aminophenyl)methane, 1,4-bis(4-amino Phenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenyl)benzene, 1,3-bis(4-aminophenyl)benzene, 1,4-bis (4-aminobenzyl)benzene, 1,3-bis(4-aminophenoxy)benzene, 4,4'-[1,4-phenylenebis(methylene)]dianiline, 4,4'-[1, 3-phenylenebis(methylene)]dianiline, 3,4'-[1,4-phenylenebis(methylene)]dianiline, 3,4'-[1,3-phenylenebis(methylene)]di Aniline, 3,3'-[1,4-phenylenebis(methylene)]dianiline, 3,3'-[1,3-phenylenebis(methylene)]dianiline, 1,4-phenylenebis[ (4-aminophenyl)methanone], 1,4-phenylenebis[(3-aminophenyl)methanone], 1,3-phenylenebis[(4-aminophenyl)methanone], 1,3- Phenylenebis[(3-aminophenyl)methanone], 1,4-phenylenebis(4-aminobenzoate), 1,4-phenylenebis(3-aminobenzoate), 1,3-phenylene Bis(4-aminobenzoate), 1,3-phenylenebis(3-aminobenzoate), bis(4-aminophenyl)terephthalate, bis(3-aminophenyl)terephthalate, bis(4-aminophenyl) )isophthalate, bis(3-aminophenyl)isophthalate, N,N'-(1,4-phenylene)bis(4-aminobenzamide), N,N'-(1,3-phenylene)bis (4-aminobenzamide), N,N'-(1,4-phenylene)bis(3-aminobenzamide), N,N'-(1,3-phenylene)bis(3-aminobenzamide ), N,N'-bis(4-aminophenyl)terephthalamide, N,N'-bis(3-aminophenyl)terephthalamide, N,N'-bis(4-aminophenyl)isophthalamide, N, N'-bis(3-aminophenyl)isophthalamide, 9,10-bis(4-aminophenyl)anthracene, 4,4'-bis(4-aminophenoxy)diphenylsulfone, 2,2'-bis [4-(4-aminophenoxy)phenyl]propane, 2,2'-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2,2'-bis(4-aminophenyl)hexa Fluoropropane, 2,2'-bis(3-aminophenyl)hexafluoropropane, 2,2'-bis (3-amino-4-methylphenyl) hexafluoropropane, 2,2'-bis (4-aminophenyl) propane, 2,2'-bis (3-aminophenyl) propane, 2,2'-bis (3 -Amino-4-methylphenyl)propane, 1,3-bis(4-aminophenoxy)propane, 1,3-bis(3-aminophenoxy)propane, 1,4-bis(4-aminophenoxy)butane , 1,4-bis(3-aminophenoxy)butane, 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) Cy) nonane, 1,10-bis (4-aminophenoxy) decane, 1,10-bis (3-aminophenoxy) decane, 1,11-bis (4-aminophenoxy) undecane, 1,11 -bis(3-aminophenoxy)undecane, 1,12-bis(4-aminophenoxy)dodecane, 1,12-bis(3-aminophenoxy)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, etc. can be heard

Moreover, as other diamine, the diamine shown by a following formula [DA1] - a formula [DA11] can be used.

[Formula 38]

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

[Formula 39]

[Formula 40]

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

[Formula 41]

(in formula [DA8], A ¹ is a single bond, -CH ₂ -, -C ₂ H ₄ -, -C(CH ₃ ) ₂ -, -CF ₂ -, -C(CF ₃ ) ₂ -, -O -, -CO-, -NH-, -N(CH ₃ )-, -CONH-, -NHCO-, -CH ₂ O-, -OCH ₂ -, -COO-, -OCO-, -CON(CH ₃ )- and -N(CH ₃ )CO- represent at least one bonding group, m ¹ and m ² each independently represent an integer of 0 to 4, and m ¹ + m ² are 1 to 4 represents an integer of, in formula [DA9], m ³ and m ⁴ each independently represents an integer of 1 to 5, in formula [DA10], A ² represents a linear or branched alkyl group having 1 to 5 carbon atoms; , m ⁵ represents an integer of 1 to 5, in formula [DA11], A ³ is a single bond, -CH ₂ -, -C ₂ H ₄ -, -C(CH ₃ ) ₂ -, -CF ₂ -, -C(CF ₃ ) ₂ -, -O-, -CO-, -NH-, -N(CH ₃ )-, -CONH-, -NHCO-, -CH ₂ O-, -OCH ₂ -, -COO -, -OCO-, -CON(CH ₃ )-, and -N(CH ₃ )CO- represent at least 1 type of bonding group selected from, and m ⁶ represents the integer of 1-4)

Moreover, as other diamine, unless the effect of this invention is impaired, the diamine shown by a following formula [DA12] can also be used.

[Formula 42]

(A ¹ is -O-, -NH-, -N(CH ₃ )-, -CONH-, -NHCO-, -CH ₂ O-, -OCO-, -CON(CH ₃ )- and -N(CH ₃ ) represents at least one type of bonding group selected from CO-, A ² represents at least one type selected from a single bond, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, a non-aromatic cyclic hydrocarbon group and an aromatic hydrocarbon group, A ³ is a single bond, -O-, -NH-, -N(CH ₃ )-, -CONH-, -NHCO-, -COO-, -OCO-, -CON(CH ₃ )-, -N(CH ₃ )CO- and -O(CH ₂ ) _m - (m is an integer of 1 to 5) represents at least one bonding group, A ⁴ represents a nitrogen-containing aromatic heterocycle, and n represents 1 to 4 represents an integer)

Moreover, as other diamine, the diamine shown by a following formula [DA13] and a formula [DA14] can be used.

[Formula 43]

Other diamines are one type or two depending on characteristics such as the solubility of the polyimide-based polymer of the present invention in a solvent, the vertical alignment property of the liquid crystal when a vertical liquid crystal aligning film is used, and further, the optical characteristics of the liquid crystal display element of the present invention. More than one species can be mixed and used.

As a tetracarboxylic-acid component in the case of using a polyimide-type polymer for a specific polymer, the tetracarboxylic acid and tetracarboxylic-acid di which are tetracarboxylic dianhydride shown by following formula [4], and its tetracarboxylic-acid derivative. It is preferable to use a halide compound, a tetracarboxylic-acid dialkyl ester compound, or a tetracarboxylic-acid dialkyl ester dihalide compound (all are generically called a specific tetracarboxylic-acid component) for a part of a raw material.

[Formula 44]

Z represents the at least 1 sort(s) of structure chosen from a following formula [4a] - a formula [4k].

[Formula 45]

Z ¹ to Z ⁴ are each independently a hydrogen atom, a methyl group, a chlorine atom, or a benzene ring. Z ⁵ and Z ⁶ each independently represent a hydrogen atom or a methyl group.

As a specific tetracarboxylic-acid component, from the point of the ease of synthesis|combination and the easiness of polymerization reactivity at the time of manufacturing a polymer, Z of said Formula [4] is Formula [4a], Formula [4c], Formula [4d] It is preferable that it is a structure shown by a formula [4e], a formula [4f], or a formula [4g]. A more preferable thing is a formula [4a], a formula [4e], a formula [4f], or a formula [4g], A formula [4e], a formula [4f], or a formula [4g] is especially preferable.

1 mol% or more in all the tetracarboxylic-acid components is preferable, as for a specific tetracarboxylic-acid component, 5 mol% or more is more preferable, and 10 mol% or more is especially preferable.

Moreover, when using the specific tetracarboxylic-acid component whose Z of Formula [4] is a structure of Formula [4e], Formula [4f], or Formula [4g], the usage-amount is 20 of the whole tetracarboxylic-acid component It is preferable to set it as mol% or more. More preferably, it is 30 mol% or more. Moreover, the tetracarboxylic-acid component of the structure of a formula [4e], a formula [4f], or a formula [4g] may be sufficient as all of a tetracarboxylic-acid component.

As long as the effect of this invention is not impaired for the tetracarboxylic-acid component in the case of using a polyimide-type polymer for a specific polymer, other tetracarboxylic-acid components other than a specific tetracarboxylic-acid component can be used.

As another tetracarboxylic-acid component, the tetracarboxylic-acid compound shown below, tetracarboxylic dianhydride, a dicarboxylic acid dihalide compound, a dicarboxylic acid dialkyl ester compound, or a dialkyl ester dihalide compound is mentioned. .

Examples of the other tetracarboxylic acid component include pyromellitic acid, 2,3,6,7-naphthalenetetracarboxylic acid, 1,2,5,6-naphthalenetetracarboxylic acid, and 1,4,5,8-naphthalene. tetracarboxylic acid, 2,3,6,7-anthracenetetracarboxylic acid, 1,2,5,6-anthracenetetracarboxylic acid, 3,3',4,4'-biphenyltetracarboxylic acid, 2,3,3',4'-biphenyltetracarboxylic acid, bis(3,4-dicarboxyphenyl)ether, 3,3',4,4'-benzophenonetetracarboxylic acid, bis(3, 4-dicarboxyphenyl)sulfone, bis(3,4-dicarboxyphenyl)methane, 2,2-bis(3,4-dicarboxyphenyl)propane, 1,1,1,3,3,3-hexafluoro Rho-2,2-bis(3,4-dicarboxyphenyl)propane, bis(3,4-dicarboxyphenyl)dimethylsilane, bis(3,4-dicarboxyphenyl)diphenylsilane, 2,3,4 ,5-pyridinetetracarboxylic acid, 2,6-bis(3,4-dicarboxyphenyl)pyridine, 3,3',4,4'-diphenylsulfonetetracarboxylic acid, 3,4,9,10 -perylenetetracarboxylic acid or 1,3-diphenyl-1,2,3,4-cyclobutanetetracarboxylic acid is mentioned.

The specific tetracarboxylic acid component and other tetracarboxylic acid components depend on characteristics such as the solubility of the polyimide-based polymer in the solvent, the vertical alignment property of the liquid crystal when a vertical liquid crystal aligning film is used, and further, the optical characteristics of the liquid crystal display element. , 1 type or a mixture of 2 or more types can be used.

Although the method of producing this polyimide-type polymer is not specifically limited when using a polyimide-type polymer for a specific polymer, Usually, the method of making a diamine component and a tetracarboxylic-acid component react, and producing is known. That is, it is a method of obtaining a polyamic acid by making at least 1 type of tetracarboxylic acid component selected from the group which consists of tetracarboxylic acid and its derivative(s), and the diamine component which consists of 1 type or multiple types of diamine react. More specifically, a method of polycondensing tetracarboxylic dianhydride and primary or secondary diamine to obtain polyamic acid, tetracarboxylic acid and primary or secondary diamine are subjected to dehydration polycondensation reaction to polyamic acid is a method for obtaining polyamic acid, or by polycondensing dicarboxylic acid dihalide and primary or secondary diamine.

In order to obtain a polyamic acid alkylester, a method of polycondensing a tetracarboxylic acid obtained by dialkyl esterification of a carboxylic acid group and a primary or secondary diamine, a dicarboxylic acid dihalide obtained by dialkyl esterification of a carboxylic acid group, A method of polycondensing primary or secondary diamine, or a method of converting a carboxyl group of a polyamic acid into an ester is used.

In order to obtain a polyimide, the method of ring-closing the said polyamic acid or polyamic-acid alkylester, and setting it as a polyimide is used.

Reaction of a diamine component and a tetracarboxylic-acid component is normally performed in a solvent. As a solvent used in that case, if the specific solvent of this invention and the produced|generated polyimide precursor melt|dissolve, it will not specifically limit. Although the specific example of the solvent used for reaction is given below, it is not limited to these examples.

For example, certain solvents of the present invention, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone or γ-butyrolactone, N,N-dimethylformamide, N,N-dimethylacet and amide, dimethyl sulfoxide, 1,3-dimethyl-imidazolidinone, cyclohexanone, cyclopentanone, and 4-hydroxy-4-methyl-2-pentanone.

These may be used independently and may be mixed and used for them. Moreover, even if it is a solvent in which a polyimide precursor is not dissolved, you may use it in the range in which the produced|generated polyimide precursor does not precipitate, mixing with the said solvent. Moreover, since moisture in a solvent inhibits a polymerization reaction and becomes a cause of hydrolyzing the produced|generated polyimide precursor by extension, it is preferable to use the solvent which carried out dehydration and drying.

When the diamine component and the tetracarboxylic acid component are reacted in a solvent, a solution in which the diamine component is dispersed or dissolved in the solvent is stirred, and the tetracarboxylic acid component is added as it is or by dispersing or dissolving it in the solvent, conversely, tetracarboxylic acid component is added. A method of adding a diamine component to a solution in which a carboxylic acid component is dispersed or dissolved in a solvent, a method of alternately adding a diamine component and a tetracarboxylic acid component, etc. are mentioned, and any of these methods may be used. Moreover, when making a diamine component or a tetracarboxylic-acid component use two or more types, respectively, and making it react, you may make it react in the state previously mixed, you may make it react individually, you may make it react individually, and the low-molecular-weight body made to react individually is mixed and reacted, and a polymer can be done with

Although the polymerization temperature in that case can select the arbitrary temperature of -20-150 degreeC, Preferably it is the range of -5-100 degreeC. In addition, although the reaction can be carried out at any concentration, if the concentration is too low, it becomes difficult to obtain a high molecular weight polymer, and if the concentration is too high, the viscosity of the reaction solution becomes too high and uniform stirring becomes difficult. Therefore, Preferably it is 1-50 mass %, More preferably, it is 5-30 mass %. The initial reaction may be carried out at a high concentration, and then a solvent may be added.

In the polymerization reaction of a polyimide precursor, it is preferable that ratio of the total number of moles of a diamine component and the total number of moles of a tetracarboxylic-acid component is 0.8-1.2. The molecular weight of the polyimide precursor produced|generated, so that this molar ratio is close to 1.0 becomes large.

When the polyimide precursor is ring-closed, a polyimide is obtained. The imidation ratio of the polyimide (the ring-closing ratio of the amic acid group) is not necessarily 100%, and can be arbitrarily adjusted according to the use or purpose.

As a method of imidating a polyimide precursor, the thermal imidation which heats the solution of a polyimide precursor as it is, or catalyst imidation which adds a catalyst to the solution of a polyimide precursor is mentioned.

The temperature in the case of thermal imidation of a polyimide precursor in a solution is 100-400 degreeC, Preferably it is 120-250 degreeC, It is more preferable to carry out, removing the water produced|generated by imidation reaction to the outside of a system.

Catalyst imidation of a polyimide precursor is -20-250 degreeC, adding a basic catalyst and an acid anhydride to the solution of a polyimide precursor, Preferably it can perform by stirring at 0-180 degreeC. The amount of the basic catalyst is 0.5 to 30 mole times of the amic acid group, preferably 2 to 20 mole times, and the amount of the acid anhydride is 1 to 50 mole times, preferably 3 to 30 mole times of the amic acid group. Examples of the basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine, and trioctylamine, and among them, pyridine is preferable because it has suitable basicity to advance the reaction. Examples of the acid anhydride include acetic anhydride, trimellitic anhydride, and pyromellitic anhydride, and among these, acetic anhydride is preferably used because purification after completion of the reaction becomes easy. The imidation rate by catalytic imidation can be controlled by adjusting the catalyst amount, reaction temperature, and reaction time.

When collect|recovering the produced|generated polyimide precursor or polyimide from the reaction solution of a polyimide precursor or a polyimide, what is necessary is just to inject|throw-in a reaction solution to a solvent and just to precipitate. Examples of the solvent used for precipitation include methanol, ethanol, isopropyl alcohol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, toluene, benzene, and water. The polymer charged and precipitated in the solvent can be collected by filtration, then dried under normal pressure or reduced pressure at room temperature or by heating. Moreover, when the polymer which carried out precipitation collection|recovery is made to melt|dissolve again in a solvent, and operation which carries out reprecipitation collection|recovery is repeated 2 to 10 times, the impurity in a polymer can be decreased. Examples of the solvent at this time include alcohols, ketones, hydrocarbons, and the like, and the use of three or more solvents selected from these is preferable because the efficiency of purification further increases.

The molecular weight of the polyimide-based polymer is 5,000 to 1,000,000 as the weight average molecular weight measured by the GPC (Gel Permeation Chromatography) method when the strength of the vertical liquid crystal aligning film obtained therefrom, workability at the time of forming the vertical film, and coating film properties are taken into consideration. It is preferable, More preferably, it is 10,000-150,000.

When using polysiloxane for a specific polymer, polysiloxane obtained by making polycondensation of the alkoxysilane shown by following formula [A1], Formula [A1], Any 1 type of the alkoxysilane shown by following formula [A2], or Formula [A3] is included It is preferable that it is any 1 type of polysiloxane obtained by polycondensing the alkoxysilane to be made, or polysiloxane obtained by polycondensing the alkoxysilane shown by Formula [A1], Formula [A2], and Formula [A3] (it is also generically called a polysiloxane polymer). do.

[Formula 46]

In formula [A1], A<^1> shows the at least 1 sort(s) of structure chosen from the group which consists of said formula [2-1] and formula [2-2]. Especially, the structure shown by Formula [2-1] is preferable from the point which can obtain the vertical alignment of a high and stable liquid crystal.

Formula ^{[2-1] Y 1, Y 2} , Y 3, Y 4, Y 5, Y 6 , and a preferred combination of n, International Publication page 13 of WO2011 / 132751 (published 2011.10.27) in the - Combinations similar to those in (2-1) to (2-629) shown in Tables 6 to 47 on page 34 are exemplified. Further, by reading the table, each of International Publication, there is Y ¹ ~ Y ⁶ in the present invention, is shown as Y1 ~ Y6, Y1 ~ Y6 is replaced with Y ¹ ~ Y ^6. Moreover, in (2-605)-(2-629) published in each table|surface of international publication, the C17-C51 organic group which has a steroid skeleton in this invention has a C12-C25 organic group which has a steroid skeleton Although represented as an organic group, the C12-C25 organic group which has a steroid skeleton shall be read as a C17-C51 organic group which has a steroid skeleton.

A ² represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. Especially, a hydrogen atom or a C1-C3 alkyl group is preferable. A ³ represents a C1-C5 alkyl group. Especially, a C1-C3 alkyl group is preferable from the point of the reactivity of polycondensation. m represents the integer of 1 or 2. Among them, 1 is preferable from the viewpoint of synthesis. n represents the integer of 0-2. p represents the integer of 0-3. Especially, the integer of 1-3 is preferable from the point of the reactivity of polycondensation. More preferably, it is 2 or 3. m+n+p represents the integer of 4.

As a specific example of the alkoxysilane of Formula [A1] which has the specific side chain structure of the said Formula [2-1], the alkoxysilane of a following formula [A1-1] - a formula [A1-32] is mentioned.

[Formula 47]

(In formulas [A1-1] to [A1-4], R ¹ , R ³ , R ⁵ and R ⁷ each independently represent an alkyl group having 1 to 3 carbon atoms, R ² , R ⁴ , R ⁶ and R ⁸ each independently represents an alkyl group having 1 to 3 carbon atoms, m each independently represents 2 or 3, n each independently represents 0 or 1)

[Formula 48]

(In formulas [A1-5] to [A1-8], R ¹ , R ³ , R ⁵ and R ⁷ each independently represent an alkyl group having 1 to 3 carbon atoms, R ² , R ⁴ , R ⁶ and R ⁸ each independently represents an alkyl group having 1 to 3 carbon atoms, m each independently represents 2 or 3, n each independently represents 0 or 1.)

[Formula 49]

(In formulas [A1-9] to [A1-12], R ¹ , R ³ , R ⁵ and R ⁷ each independently represent an alkyl group having 1 to 3 carbon atoms, R ² , R ⁴ , R ⁶ and R ⁸ each independently represents an alkyl group having 1 to 3 carbon atoms, m each independently represents 2 or 3, n each independently represents 0 or 1)

[Formula 50]

(In formulas [A1-13] to [A1-16], R ¹ , R ³ , R ⁵ and R ⁷ each independently represent an alkyl group having 1 to 3 carbon atoms, R ² , R ⁴ , R ⁶ and R ⁸ each independently represents an alkyl group having 1 to 3 carbon atoms, m each independently represents 2 or 3, n each independently represents 0 or 1)

[Formula 51]

(In formulas [A1-17] and [A1-18], R ¹ and R ³ each independently represent an alkyl group having 1 to 3 carbon atoms, and R ² and R ⁴ each independently represent an alkyl group having 1 to 3 carbon atoms represents an alkyl group, m each independently represents 2 or 3, n each independently represents 0 or 1)

[Formula 52]

(In formulas [A1-19] to [A1-22], R ¹ , R ⁵ , R ⁹ and R ¹³ each independently represents an alkyl group having 1 to 3 carbon atoms, R ² , R ⁶ , R ¹⁰ and R ¹⁴ each independently represents an alkyl group having 1 to 3 carbon atoms, R ³ , R ⁷ , R ¹¹ and R ¹⁵ are each independently -O-, -COO-, -OCO-, -CONH-, -NHCO-, -CON(CH ₃ )-, -N(CH ₃ )CO-, -OCH ₂ -, represents at least one bonding group selected from -CH ₂ O-, -COOCH ₂ - and -CH ₂ ^{OCO-, R 4} , R ⁸ , R ¹² and R ¹⁶ are each independently an alkyl group having 1 to 12 carbon atoms; represents an alkoxy group having 1 to 12 carbon atoms, a fluorine-containing alkyl group having 1 to 12 carbon atoms or a fluorine-containing alkoxy group having 1 to 12 carbon atoms, m each independently represents 2 or 3, n represents each independently 0 or 1; Each of the cis-trans isomers of 1,4-cyclohexylene in formulas [A1-20] to [A1-22] represents a trans isomer)

[Formula 53]

(In formulas [A1-23] and [A1-24], R ¹ and R ⁵ each independently represent an alkyl group having 1 to 3 carbon atoms, and R ² and R ⁶ are each independently a C 1 to C 3 alkyl group. represents an alkyl group, and R ³ and R ⁷ are each independently -O-, -COO-, -OCO-, -CONH-, -NHCO-, -CON(CH ₃ )-, -N(CH ₃ )CO- , -OCH ₂ -, -CH ₂ O-, -COOCH ₂ - and -CH ₂ OCO- represents at least one bonding group, R ⁴ and R ⁸ are each independently an alkyl group having 1 to 12 carbon atoms; A C1-C12 alkoxy group, a C1-C12 fluorine-containing alkyl group, a C1-C12 fluorine-containing alkoxy group, a fluorine group, a cyano group, a trifluoromethane group, a nitro group, an azo group, a formyl group, an acetyl group; represents at least one organic group selected from the group consisting of an acetoxy group and a hydroxyl group, m each independently represents 2 or 3, n each independently represents 0 or 1)

[Formula 54]

(In formulas [A1-25] to [A1-28], R ¹ , R ⁵ , R ⁹ and R ¹³ each independently represent an alkyl group having 1 to 3 carbon atoms, R ² , R ⁶ , R ¹⁰ and R ¹⁴ each independently represents an alkyl group having 1 to 3 carbon atoms, R ³ , R ⁷ , R ¹¹ and R ¹⁵ are each independently -O-, -COO-, -OCO-, -CONH-, -NHCO represents at least one bonding group selected from -, -CON(CH ₃ )-, -N(CH ₃ )CO-, -OCH ₂ -, -CH ₂ O-, -COOCH ₂ -, and -CH _{2 OCO-;} , R ⁴ , R ⁸ , R ¹² and R ¹⁶ are each independently an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a fluorine-containing alkyl group having 1 to 12 carbon atoms or a fluorine-containing alkoxy group having 1 to 12 carbon atoms. , m each independently represents 2 or 3, n each independently represents 0 or 1, and the cis-trans isomerism of 1,4-cyclohexylene in formulas [A1-26] to [A1-28] is , represent trans isomers, respectively)

[Formula 55]

(In formulas [A1-29] to [A1-31], R ¹ , R ⁵ and R ⁹ each independently represent an alkyl group having 1 to 3 carbon atoms, and R ² , R ⁶ and R ¹⁰ are each independently represents an alkyl group having 1 to 3 carbon atoms, and R ³ , R ⁷ and R ¹¹ are each independently -O-, -COO-, -OCO-, -CONH-, -NHCO-, -CON(CH ₃ )- , -N(CH ₃ )CO-, -OCH ₂ -, -CH ₂ O-, -COOCH ₂ - and -CH ₂ OCO- represent at least one bonding group selected from, R ⁴ , R ⁸ and R ¹² each independently represents an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a fluorine-containing alkyl group having 1 to 12 carbon atoms or a fluorine-containing alkoxy group having 1 to 12 carbon atoms, and m is each independently 2 or 3; , n each independently represent 0 or 1, and the cis-trans isomers of 1,4-cyclohexylene in formulas [A1-29] to [A1-31] each represent a trans isomer)

[Formula 56]

(In formula [A1-32], R ¹ represents an alkyl group having 1 to 3 carbon atoms, R ² represents an alkyl group having 1 to 3 carbon atoms, m represents 2 or 3, n represents 0 or 1 , B ⁴ represents an optionally substituted C3-C20 alkyl group, B ³ represents a 1,4-cyclohexylene group or 1,4-phenylene group, B ² represents an oxygen atom or -COO-* (However, the bond attached with "*" bonds with B ³ ), B ¹ is an oxygen atom or -COO-* (however, the bond attached with "*" bonds with (CH ₂ )a ² ) do) is In addition, a ¹ represents an integer of 0 or 1, a ² represents an integer of 2 ~ 10, a ³ represents an integer of 0 or 1)

Among the alkoxysilanes shown by the said formula [A1-1] - a formula [A1-32], the alkoxysilane of a especially preferable structure is a formula [A1-9] - a formula [A1-18], a formula [A1-19] - a formula It is an alkoxysilane shown by [A1-21], a formula [A1-23] - a formula [A1-28], or a formula [A1-32].

Moreover, the following alkoxysilane is mentioned as a specific example of the alkoxysilane shown by Formula [A1] which has the specific side chain structure shown by said Formula [2-2].

That is, octyltrimethoxysilane, octyltriethoxysilane, decyltrimethoxysilane, dodecyltrimethoxysilane, dodecyltriethoxysilane, hexadecyltrimethoxysilane, hexadecyltriethoxysilane, pentilt Rethoxysilane, heptadecyltrimethoxysilane, heptadecyltriethoxysilane, octadecyltrimethoxysilane, octadecyltriethoxysilane, nonadecyltrimethoxysilane, nonadecyltriethoxysilane, isooctyltriethoxy Silane, phenethyltriethoxysilane, pentafluorophenylpropyltrimethoxysilane, m-styrylethyltrimethoxysilane, p-styrylethyltrimethoxysilane, 1-naphthyltriethoxysilane, 1-naphthylt Remethoxysilane, triethoxy-1H,1H,2H,2H-tridecafluoro-n-octylsilane, dimethoxydiphenylsilane, dimethoxymethylphenylsilane, triethoxyphenylsilane, etc. are mentioned.

The alkoxysilane represented by the said Formula [A1] is solubility with respect to the solvent of a polysiloxane-type polymer, the vertical alignment property of a liquid crystal when it is set as a vertical liquid crystal aligning film, Furthermore, according to characteristics, such as the optical characteristic of a liquid crystal display element, 2 or more types It can be mixed and used.

[Formula 57]

Formula [A2] in, B ¹ is a vinyl group, an epoxy group, an amino group, a mercapto group, an isocyanate group, a methacrylic group, an acrylic group, a ureido group and cinnamoyl having a carbon number of 2 to 12 with at least one member selected from the group of organic represents the flag. Especially, the C2-C12 organic group which has a vinyl group, an epoxy group, an amino group, a methacryl group, an acryl group, or a ureido group from the point of availability is preferable. More preferably, it is a C2-C12 organic group which has a methacryl group, an acryl group, or a ureido group.

B ² represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. Especially, a hydrogen atom or a C1-C3 alkyl group is preferable.

B ³ represents an alkyl group having 1 to 5 carbon atoms. Especially, a C1-C3 alkyl group is preferable from the point of the reactivity of polycondensation.

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

n represents the integer of 0-2.

p represents the integer of 0-3. Especially, the integer of 1-3 is preferable from the point of the reactivity of polycondensation. More preferably, it is 2 or 3.

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

The following alkoxysilane is mentioned as a specific example of the alkoxysilane shown by Formula [A2] of this invention.

That is, allyltriethoxysilane, allyltrimethoxysilane, diethoxymethylvinylsilane, dimethoxymethylvinylsilane, triethoxyvinylsilane, vinyltrimethoxysilane, vinyltris(2-methoxyethoxy)silane, m-styrylethyltriethoxysilane, p-styrylethyltriethoxysilane, m-styrylmethyltriethoxysilane, p-styrylmethyltriethoxysilane, 3-(N-styrylmethyl-2 -Aminoethylamino)propyltrimethoxysilane, diethoxy(3-glycidyloxypropyl)methylsilane, 3-glycidyloxypropyl(dimethoxy)methylsilane, 3-glycidyloxypropyltrimethoxysilane , 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-(2-aminoethylamino)propyldimethoxymethyl silane, 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- (trimethoxysilyl) propyl methacrylate, 3- (triethoxysilyl) propyl acrylate, 3- (trimethoxysilyl) propyl acrylate , 3-(triethoxysilyl)ethyl methacrylate, 3-(trimethoxysilyl)ethyl methacrylate, 3-(triethoxysilyl)ethyl acrylate, 3-(trimethoxysilyl)ethyl acrylate , 3- (triethoxysilyl) methyl methacrylate, 3- (trimethoxysilyl) methyl methacrylate, 3- (triethoxysilyl) methyl acrylate, 3- (trimethoxysilyl) methyl acrylate , γ-ureidopropyltriethoxysilane, γ-ureidopropyltrimethoxysilane, γ-ureidopropyltripropoxysilane, (R)-N-1-phenylethyl-N′-triethoxysilylpropyl Urea, (R)-N-1-phenylethyl-N'-trimethoxysilylpropylurea, bis[3-(trimethoxysilyl)propyl]urea, bis[3-(tripropoxysilyl)propyl]urea , 1-[3-(trimethoxysilyl)propyl]urea, and the like.

Especially, as an alkoxysilane shown by said formula [A2], Allyltriethoxysilane, allyltrimethoxysilane, diethoxymethylvinylsilane, dimethoxymethylvinylsilane, triethoxyvinylsilane, vinyltrimethoxysilane , Vinyltris (2-methoxyethoxy) silane, 3- (triethoxysilyl) propyl methacrylate, 3- (trimethoxysilyl) propyl acrylate, 3- (trimethoxysilyl) propyl methacrylate , 3-glycidyloxypropyl(dimethoxy)methylsilane, 3-glycidyloxypropyl(diethoxy)methylsilane, 3-glycidyloxypropyltrimethoxysilane or 2-(3,4-epoxycyclo Preference is given to using hexyl)ethyltrimethoxysilane.

The alkoxysilane represented by the said formula [A2] is solubility with respect to the solvent of a polysiloxane type polymer, the vertical alignment property of a liquid crystal when it is set as a vertical liquid crystal aligning film, Furthermore, according to characteristics, such as the optical characteristic of a liquid crystal display element, 2 or more types It can be mixed and used.

[Formula 58]

In formula [A3], although D<^1> represents a hydrogen atom or a C1-C5 alkyl group, these may be substituted by the halogen atom, a nitrogen atom, an oxygen atom, and a sulfur atom. Especially, a hydrogen atom or a C1-C3 alkyl group is preferable.

D ² represents an alkyl group of 1 to 5 carbon atoms. Especially, a C1-C3 alkyl group is preferable from the point of the reactivity of polycondensation.

n represents the integer of 0-3.

The following alkoxysilane is mentioned as a specific example of the alkoxysilane shown by a formula [A3].

That is, tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltrimethoxy Silane, propyltriethoxysilane, methyltripropoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diethoxydiethylsilane, dibutoxydimethylsilane, (chloromethyl)triethoxysilane, 3-chloropropyldimethoxy Methylsilane, 3-chloropropyltriethoxysilane, 2-cyanoethyltriethoxysilane, trimethoxy(3,3,3-trifluoropropyl)silane, hexyltrimethoxysilane, 3-trimethoxy Silylpropyl chloride, etc. are mentioned.

Moreover, as an alkoxysilane whose n is 0 in formula [A3], tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, or tetrabutoxysilane is mentioned, In the alkoxysilane shown by Formula [A3] It is preferable to use these alkoxysilanes.

The alkoxysilane represented by the above formula [A3] is the solubility of the polysiloxane-based polymer of the present invention in a solvent, the vertical alignment property of the liquid crystal when a vertical liquid crystal aligning film is used, and further, depending on characteristics such as the optical characteristics of the liquid crystal display element, 2 More than one species can be mixed and used.

When using a polysiloxane-type polymer for the specific polymer of this invention, polysiloxane obtained by making polycondensation of the alkoxysilane shown by the said Formula [A1], Formula [A1], and the alkoxysilane shown by the said Formula [A2] or Formula [A3] It is preferable that it is any 1 type of polysiloxane obtained by polycondensing the polysiloxane obtained by polycondensing the alkoxysilane containing any 1 type, or the alkoxysilane shown by a formula [A1], a formula [A2], and a formula [A3].

That is, in polysiloxane obtained by polycondensing only with the alkoxysilane shown by formula [A1], polysiloxane obtained by polycondensing two types of alkoxysilanes shown by formula [A1] and formula [A2], formula [A1] and formula [A3] It is any 1 type of polysiloxane obtained by polycondensing the polysiloxane obtained by polycondensing 2 types of alkoxysilanes shown, or the polysiloxane obtained by making polycondensation of 3 types of alkoxysilanes shown by a formula [A1], a formula [A2], and a formula [A3].

Among these, polysiloxane obtained by polycondensing a plurality of types of alkoxysilanes is preferable from the viewpoint of the reactivity of polycondensation or the solubility of the polysiloxane-based polymer to a solvent. That is, the polysiloxane obtained by polycondensing the polysiloxane obtained by making polycondensation of 2 types of alkoxysilanes shown by a formula [A1] and a formula [A2], a polysiloxane obtained by making polycondensation of 2 types of alkoxysilanes shown by a formula [A1] and a formula [A3], or a formula Polysiloxane obtained by polycondensing 3 types of alkoxysilanes shown by [A1], a formula [A2], and a formula [A3] is preferable.

When manufacturing a polysiloxane-type polymer and using multiple types of alkoxysilanes, it is preferable that the alkoxysilane shown by Formula [A1] is 1-40 mol% in all the alkoxysilanes, More preferably, it is 1-30 mol % to be. Moreover, it is preferable that the alkoxysilane shown by a formula [A2] is 1-70 mol% in all the alkoxysilanes, More preferably, it is 1-60 mol%. Moreover, it is preferable that the alkoxysilane shown by a formula [A3] is 1-99 mol% in all the alkoxysilanes, More preferably, it is 1-80 mol%.

The method for producing the polysiloxane-based polymer used in the present invention is not particularly limited. A method obtained by polycondensing the alkoxysilane represented by the formula [A1] in a solvent, a method obtained by polycondensing the alkoxysilane represented by the formula [A1] and the formula [A2] in a solvent, a formula [A1] and the formula [A3] The method obtained by polycondensing the alkoxysilane shown by ] in a solvent, and the method of making polycondensation of the alkoxysilane shown by a formula [A1], a formula [A2], and a formula [A3] in a solvent, and obtaining it is mentioned. Moreover, the polysiloxane-type polymer of this invention polycondensates these alkoxysilanes, and it is obtained as a solution which melt|dissolved uniformly in the solvent.

The method for polycondensing the polysiloxane-based polymer is not particularly limited. For example, the method of hydrolysis and polycondensation reaction of an alkoxysilane in the specific solvent of this invention, an alcohol solvent, or a glycol solvent is mentioned. In that case, the hydrolysis/polycondensation reaction may be partially hydrolyzed, or may be completely hydrolyzed. In the case of complete hydrolysis, in theory, 0.5 times molar amount of water of all the alkoxy groups in the alkoxysilane may be added, but it is preferable to add water in an excess of 0.5 times molar amount. In order to obtain the polysiloxane-based polymer of the present invention, the amount of water used in the hydrolysis/polycondensation reaction can be appropriately selected depending on the purpose, but is preferably 0.5 to 2.5 times the molar amount of all the alkoxy groups in the alkoxysilane.

In addition, for the purpose of accelerating the hydrolysis/polycondensation reaction, acidic compounds such as hydrochloric acid, sulfuric acid, nitric acid, acetic acid, formic acid, oxalic acid, maleic acid, and fumaric acid, ammonia, methylamine, ethylamine, ethanolamine, triethylamine, etc. Catalysts, such as alkaline compounds, or metal salts, such as hydrochloric acid, nitric acid, and oxalic acid, can be used. Moreover, the hydrolysis and polycondensation reaction can also be accelerated|stimulated also by heating the solution in which the alkoxysilane melt|dissolved. The heating temperature and heating time in that case can be suitably selected according to the objective. For example, conditions, such as heating and stirring at 50 degreeC for 24 hours, and stirring under reflux conditions after that for 1 hour, are mentioned.

Moreover, as another method of polycondensation, the method of heating the mixture of an alkoxysilane, a solvent, and oxalic acid, and carrying out a polycondensation reaction is mentioned. Specifically, after adding oxalic acid to a solvent beforehand and setting it as a solution of oxalic acid, it is a method of mixing the alkoxysilane in the state which heated the solution. In that case, it is preferable that the quantity of the oxalic acid used for the said reaction shall be 0.2-2.0 mol with respect to 1 mol of all the alkoxy groups in an alkoxysilane. Moreover, although this reaction can be performed at the temperature of a solution 50-180 degreeC, it is preferable to carry out for several tens of minutes to several tens of hours under reflux so that evaporation or volatilization of a solvent does not occur.

In the polycondensation reaction for producing a polysiloxane-based polymer, in the case of using multiple types of the alkoxysilanes represented by the formulas [A1], [A2] and [A3] You may make it react using it, and you may make it react, adding several types of alkoxysilanes one by one.

As a solvent used for the polycondensation reaction of an alkoxysilane, if the specific solvent and alkoxysilane of this invention melt|dissolve, it will not specifically limit. Moreover, even if it is a solvent in which an alkoxysilane does not melt|dissolve, what is necessary is just to melt|dissolve with advancing of the polycondensation reaction of an alkoxysilane. As a solvent used for the polycondensation reaction, since alcohol is generally generated by the polycondensation reaction of an alkoxysilane, an alcohol solvent, a glycol solvent, a glycol ether solvent, or a solvent having good compatibility with alcohol is used.

As a specific example of the solvent used for such a polycondensation reaction, The specific solvent of this invention; Alcohol solvents, such as methanol, ethanol, a propanol, a butanol, and diacetone alcohol; Ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, hexylene glycol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1 Glue such as ,2-pentanediol, 1,3-pentanediol, 1,4-pentanediol, 1,5-pentanediol, 2,4-pentanediol, 2,3-pentanediol, 1,6-hexanediol Cole solvent; 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, propylene glycol dibutyl ether, etc. glycol ether solvent; N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, γ-butyrolactone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, tetramethylurea, solvents having good compatibility with alcohols such as hexamethylphosphotriamide and m-cresol; can be heard

Moreover, in this invention, at the time of a polycondensation reaction, these solvents can also be used in mixture of 2 or more types.

The solution of the polysiloxane polymer obtained by the above method preferably has a concentration (also referred to as a concentration in terms of SiO ₂ ) of 20 mass% or less _{in terms of SiO 2 of silicon atoms contained in all the alkoxysilanes injected as a raw material.} Especially, it is preferable that it is 5-15 mass %. By selecting an arbitrary concentration in this concentration range, the generation of a gel in the solution can be suppressed, and a uniform polysiloxane-based polymer solution can be obtained.

In the present invention, the polysiloxane-based polymer solution obtained by the above method may be used as it is as a specific polymer, and if necessary, the polysiloxane-based polymer solution obtained by the above method is concentrated, diluted by adding a solvent, or used with another solvent. It can also be substituted and can also be used as a specific polymer.

The solvent (also referred to as an added solvent) used when adding and diluting the solvent may be a solvent or other solvent used for the polycondensation reaction. This addition solvent is not specifically limited as long as the polysiloxane-type polymer is melt|dissolving uniformly, 1 type(s) or 2 or more types can be selected arbitrarily and can be used. As such an addition solvent, in addition to the solvent used for the said polycondensation reaction, ester solvents, such as methyl acetate, ethyl acetate, and ethyl lactate, etc. are mentioned.

In addition, in the present invention, when using a polysiloxane-based polymer and a polymer other than that for a specific polymer, before mixing the polysiloxane-based polymer with a polymer other than that, alcohol generated during the polycondensation reaction of the polysiloxane-based polymer is removed under normal pressure. Or it is preferable to carry out distillation under reduced pressure.

<Liquid crystal aligning agent>

The liquid-crystal aligning agent of this invention is a coating solution for forming a perpendicular|vertical liquid crystal aligning film, The group which consists of a structure shown by the specific solvent shown by said Formula [1], and said Formula [2-1] and Formula [2-2] It is a coating solution containing the specific polymer which has at least 1 sort(s) of specific side chain structure selected from.

Although there is no limitation in particular as a specific polymer which has a specific side chain structure as mentioned above, An acrylic polymer, a methacryl polymer, a novolak resin, polyhydroxystyrene, a polyimide precursor, a polyimide, a polyamide, polyester, a cellulose and at least one polymer selected from the group consisting of polysiloxane. Especially, a polyimide precursor, a polyimide, or polysiloxane is preferable, and a polyimide or polysiloxane is especially preferable. Moreover, 1 type(s) or 2 or more types in these polymers can be used for the specific polymer of this invention.

As for all the polymer components in the liquid-crystal aligning agent of this invention, the specific polymer of this invention may be sufficient as all, and other polymers other than that may be mixed. In that case, content of other polymers other than that is 0.5-15 mass parts with respect to 100 mass parts of specific polymers of this invention, Preferably it is 1-10 mass parts. As another polymer other than that, the said polymer which does not have the specific side chain structure shown by said Formula [2-1] or Formula [2-2] is mentioned.

Content of the solvent in the liquid-crystal aligning agent of this invention can be suitably selected from the viewpoint of obtaining the coating method of a liquid-crystal aligning agent, and the objective film thickness. Especially, it is preferable that content of the solvent in a liquid-crystal aligning agent from a viewpoint of forming a uniform vertical liquid crystal aligning film by application|coating is 50-99.9 mass %. Especially, 60-99 mass % is preferable, Especially preferably, it is 65-99 mass %.

Although the specific solvent of this invention may be sufficient as all as for the solvent used for the liquid-crystal aligning agent of this invention, it is preferable to use together and use the solvent in which a specific polymer is dissolved with the specific solvent of this invention. In that case, when the specific polymer of the present invention is a polyimide precursor, polyimide, polyamide or polyester, or when the acrylic polymer, methacrylic polymer, novolac resin, polyhydroxystyrene, cellulose or polysiloxane has low solubility in a solvent In this case, it is preferable to use a solvent (also referred to as solvent A) as shown below.

That is, N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, dimethylsulfoxide, γ-butyrolactone, 1, 3-dimethyl-imidazolidinone, cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone, and the like. Among them, it is preferable to use N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone or γ-butyrolactone.

Moreover, these may be used independently and may be mixed and used.

When the specific polymer is an acrylic polymer, methacrylic polymer, novolac resin, polyhydroxystyrene, cellulose or polysiloxane, further, the specific polymer of the present invention is a polyimide precursor, polyimide, polyamide or polyester, and these specific When the solubility of the polymer in the solvent is high, it is preferable to use a solvent (also referred to as solvent B) as shown below.

That is, ethanol, isopropyl alcohol, 1-butanol, 2-butanol, isobutyl alcohol, tert-butyl alcohol, 1-pentanol, 2-pentanol, 3-pentanol, 2-methyl-1-butanol, isopentyl Alcohol, tert-pentyl alcohol, 3-methyl-2-butanol, neopentyl alcohol, 1-hexanol, 2-methyl-1-pentanol, 2-methyl-2-pentanol, 2-ethyl-1-butanol, 1-heptanol, 2-heptanol, 3-heptanol, 1-octanol, 2-octanol, 2-ethyl-1-hexanol, cyclohexanol, 1-methylcyclohexanol, 2-methylcyclohexane ol, 3-methylcyclohexanol, 1,2-ethanediol, 1,2-propanediol, 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, ethylene glycol monobutyl ether, ethylene glycol monoisoamyl ether, ethylene glycol monohexyl ether, 2-(hexyloxy) ethanol, furfuryl alcohol, diethylene glycol, propylene glycol, propylene glycol monobutyl ether, 1-( Butoxyethoxy)propanol, propylene glycol monomethyl ether acetate, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, tripropylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl Ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monoacetate, ethylene glycol diacetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, 2-(2-ethoxyethoxy) ethyl acetate, di Ethylene Glycol Ace Tate, triethylene glycol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether, methyl pyruvate, ethyl pyruvate, 3-Methoxy methyl propionate, 3-ethoxy methyl ethyl propionate, 3-methoxy ethyl propionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, 3-methoxypropionic acid propyl, 3-methoxybutyl propionate, methyl lactate It is ester, lactic acid ethyl ester, lactic acid n-propyl ester, lactic acid n-butyl ester, lactic acid isoamyl ester, cyclopentanone, cyclohexanone, or a solvent represented by a following formula [S1] - a formula [S3].

[Formula 59]

(T ¹ , T ² and T ³ have the same meaning as defined above)

Among them, it is preferable to use 1-hexanol, cyclohexanol, 1,2-ethanediol, 1,2-propanediol, propylene glycol monobutyl ether, ethylene glycol monobutyl ether or dipropylene glycol dimethyl ether. .

Moreover, it is also preferable to use the solvent shown by cyclopentanone, cyclohexanone, or said Formula [S1] - Formula [S3].

Since these solvent B can improve the coating-film property and surface smoothness of the vertical liquid crystal aligning film at the time of apply|coating a liquid-crystal aligning agent, when a polyimide precursor, a polyimide, a polyamide, or polyester is used for a specific polymer, the said It is preferable to use it in mixture with solvent A.

Although all may be the specific solvent of this invention as for the solvent in the liquid-crystal aligning agent of this invention, it is 1-80 mass % of the whole solvent preferably contained in a liquid-crystal aligning agent. More preferably, it is 1-70 mass %, Especially preferably, it is 5-60 mass %. Most preferably, it is 5-50 mass %.

It is preferable to introduce|transduce into the liquid-crystal aligning agent of this invention at least 1 generator (it is also mentioned a specific generator) chosen from the group which consists of a photo-radical generator, a photo-acid generator, and a photobase generator.

There is no restriction|limiting in particular as a photo-radical generator as long as it generate|occur|produces a radical by an ultraviolet-ray, For example, the photo-radical generator shown below is mentioned.

That is, tert-butylperoxy-iso-phthalate, 2,5-dimethyl-2,5-bis(benzoyldioxy)hexane, 1,4-bis[α-(tert-butyldioxy)-iso-propoxy ] Benzene, di-tert-butyl peroxide, 2,5-dimethyl-2,5-bis (tert-butyldioxy) hexene hydroperoxide, α-(iso-propylphenyl)-iso-propyl hydroperoxide, 2,5-Dimethylhexane, tert-butylhydroperoxide, 1,1-bis(tert-butyldioxy)-3,3,5-trimethylcyclohexane, butyl-4,4-bis(tert-butyldioxy) ) Valerate, cyclohexanone peroxide, 2,2',5,5'-tetra(tert-butylperoxycarbonyl)benzophenone, 3,3',4,4'-tetra(tert-butylperoxycarbonyl) Bornyl)benzophenone, 3,3',4,4'-tetra(tert-amylperoxycarbonyl)benzophenone, 3,3',4,4'-tetra(tert-hexylperoxycarbonyl)benzophenone organic peroxides such as , 3,3'-bis(tert-butylperoxycarbonyl)-4,4'-dicarboxybenzophenone, tert-butylperoxybenzoate, and di-tert-butyldiperoxyisophthalate; quinones such as 9,10-anthraquinone, 1-chloroanthraquinone, 2-chloroanthraquinone, octamethylanthraquinone, and 1,2-benzanthraquinone; benzoin derivatives such as benzoinmethyl, benzoinethyl ether, α-methylbenzoin, and α-phenylbenzoin; etc.

Moreover, there is no restriction|limiting in particular as a photo-acid generator and a photobase generator, if it generate|occur|produces an acid or a base by ultraviolet-ray, For example, a triazine-type compound, an acetophenone derivative compound, a disulfone-type compound, a diazomethane-type compound, a sulfonic acid A derivative compound, a diaryliodonium salt, a triarylsulfonium salt, a triarylphosphonium salt, iron arene complex, etc. are mentioned. More specifically, the following photoacid generators and photobase generators are mentioned.

That is, diphenyl iodonium chloride, diphenyl iodonium trifluoromethane sulfonate, diphenyl iodonium mesylate, diphenyl iodonium tosylate, diphenyl iodonium bromide, diphenyl iodonium tetrafluoroborate, diphenyl iodonium hexafluoroantimonate, diphenyliodonium hexafluoroarsenate, bis(p-tert-butylphenyl)iodonium hexafluorophosphate, bis(p-tert-butylphenyl)iodonium mesylate, Bis(p-tert-butylphenyl)iodonium tosylate, bis(p-tert-butylphenyl)iodonium trifluoromethanesulfonate, bis(p-tert-butylphenyl)iodoniumtetrafluoroborate, bis( p-tert-butylphenyl)iodonium chloride, bis(p-chlorophenyl)iodonium chloride, bis(p-chlorophenyl)iodoniumtetrafluoroborate, triphenylsulfonium chloride, triphenylsulfonium bromide, tri( p-methoxyphenyl)sulfoniumtetrafluoroborate, tri(p-methoxyphenyl)sulfonium hexafluorophosphonate, tri(p-ethoxyphenyl)sulfoniumtetrafluoroborate, triphenylphosphonium chloride , triphenylphosphonium bromide, tri (p-methoxyphenyl) phosphonium tetrafluoroborate, tri (p-methoxyphenyl) phosphonium hexafluorophosphonate, tri (p-ethoxyphenyl) phosphonium tetra Fluoroborate, bis[[(2-nitrobenzyl)oxy]carbonylhexane-1,6-diamine], nitrobenzylcyclohexylcarbamate, di(methoxybenzyl)hexamethylenedicarbamate, bis[[( 2-nitrobenzyl)oxy]carbonylhexane-1,6-diamine], nitrobenzylcyclohexylcarbamate, di(methoxybenzyl)hexamethylenedicarbamate, and the like.

Especially, it is preferable to use a photoradical generator for the specific generator of this invention from the point which can improve the adhesiveness of a liquid crystal layer and a perpendicular|vertical liquid crystal aligning film.

It is preferable that content of the specific generator in the liquid-crystal aligning agent of this invention is 0.01-50 mass parts with respect to 100 mass parts of all the polymer components. More preferably, it is 0.01-30 mass parts, Especially preferably, it is 0.1-20 mass parts.

Moreover, the specific generator can be used in mixture of 2 or more types according to characteristics, such as the solubility with respect to the solvent of a specific generator, the vertical alignment property of a liquid crystal when it is set as a vertical liquid crystal aligning film, and also the optical characteristic of a liquid crystal display element. have.

To the liquid-crystal aligning agent of this invention, for the purpose of improving the adhesiveness of a liquid-crystal layer and a perpendicular|vertical liquid crystal aligning film, at least 1 compound selected from the group which consists of a compound which has a structure shown by a following formula [M1] - a formula [M8] (specific adhesiveness) compound) is preferably introduced. In that case, it is preferable to have two or more structures shown by these formula [M1] - a formula [M8] in a compound.

[Formula 60]

In formula [M4], W<^1> represents a hydrogen atom or a benzene ring.

In the formula [M7], W ² represents at least one cyclic group selected from a benzene ring, a cyclohexane ring, and a heterocyclic ring, and W ³ is an alkyl group having 1 to 18 carbon atoms or a fluorine-containing alkyl group having 1 to 18 carbon atoms. , 1 type selected from a C1-C18 alkoxy group and a C1-C18 fluorine-containing alkoxy group is shown.

More specifically, those shown below are mentioned.

That is, trimethylol propane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, tri (meth) acryloyloxyethoxy trimethylol propane, glycerin polyglycerol Compound which has 3 polymerizable unsaturated groups, such as a cydyl ether poly (meth)acrylate, in a molecule|numerator; Ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, polypropylene glycol Di(meth)acrylate, butylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, ethylene oxide bisphenol A type di(meth)acrylate, propylene oxide bisphenol type di(meth)acrylate, 1,6-Hexanediol di(meth)acrylate, glycerin di(meth)acrylate, pentaerythritol di(meth)acrylate, ethylene glycol diglycidyl ether di(meth)acrylate, diethylene glycol digly compounds having two polymerizable unsaturated groups in the molecule, such as cidyl ether di(meth)acrylate, phthalic acid diglycidyl ester di(meth)acrylate, and hydroxypivalate neopentyl glycol di(meth)acrylate; 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, glycerin mono (meth) acrylate, 2- (meth) acryloyloxyethyl phosphoric acid compounds having one polymerizable unsaturated group in the molecule, such as ester and N-methylol (meth)acrylamide; etc.

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

[Formula 61]

(in formula [7A], E ¹ is at least selected from the group consisting of a cyclohexane ring, a bicyclohexane ring, a benzene ring, a biphenyl ring, a terphenyl ring, a naphthalene ring, a fluorene ring, an anthracene ring, and a phenanthrene ring It represents one or, E ² represents the following formula [7a] or formula [7b], n is an integer of 1-4.)

[Formula 62]

It is preferable that content of the specific adhesive compound in the liquid-crystal aligning agent of this invention is 0.1-150 mass parts with respect to 100 mass parts of all the polymer components. In order for a crosslinking reaction to advance and to express the objective effect, 0.1-100 mass parts is more preferable with respect to 100 mass parts of all polymer components, and 1-50 mass parts is the most preferable especially.

In addition, a specific adhesive compound can be used in mixture of 2 or more types according to characteristics, such as the solubility with respect to the solvent of a specific adhesive compound, the vertical alignment property of a liquid crystal when it is set as a vertical liquid crystal aligning film, and also the optical characteristic of a liquid crystal display element. have.

In the liquid-crystal aligning agent of this invention, unless the effect of this invention is impaired, the compound which has an epoxy group, an isocyanate group, an oxetane group, or a cyclocarbonate group, a hydroxyl group, a hydroxyalkyl group, and a lower alkoxyalkyl group are selected from the group consisting of at least It is preferable to introduce a compound having one type of substituent (collectively referred to as a specific crosslinkable compound). In that case, it is necessary to have two or more of these substituents in a crosslinkable compound.

As a crosslinkable compound which has an epoxy group or an isocyanate group, the following is mentioned, for example.

That is, bisphenol acetone glycidyl ether, phenol novolac epoxy resin, cresol novolac epoxy resin, triglycidyl isocyanurate, tetraglycidylaminodiphenylene, tetraglycidyl-m-xylenediamine, tetra Glycidyl-1,3-bis(aminoethyl)cyclohexane, tetraphenylglycidyletherethane, triphenylglycidyletherethane, bisphenolhexafluoroacetdiglycidylether, 1,3-bis(1 -(2,3-epoxypropoxy)-1-trifluoromethyl-2,2,2-trifluoromethyl)benzene, 4,4-bis(2,3-epoxypropoxy)octafluorobiphenyl; Triglycidyl-p-aminophenol, tetraglycidyl metaxylenediamine, 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-epoxypropoxy)phenyl)-1-methylethyl)phenyl)ethyl)phenoxy)-2-propanol and the like.

The crosslinkable compound which has an oxetane group is a crosslinkable compound which has at least two oxetane groups shown by a following formula [4A].

[Formula 63]

The crosslinking|crosslinked compound specifically, shown by the formula [4a] published on page 58 - page 59 of international publication WO2011/132751 (published on October 27, 2011) - a formula [4k] is mentioned.

As a crosslinkable compound which has a cyclocarbonate group, it is a crosslinkable compound which has at least two cyclocarbonate groups shown by following formula [5A].

[Formula 64]

The crosslinking|crosslinked compound specifically, shown by Formula [5-1] - Formula [5-42] published on page 76 - page 82 of international publication WO2012/014898 (published on February 2, 2012) is mentioned.

Examples of the crosslinkable compound having at least one substituent selected from the group consisting of a hydroxyl group and an alkoxy group include an amino resin having a hydroxyl group or an alkoxy group, such as a melamine resin, a urea resin, a guanamine resin, glycoluril-formaldehyde resin, succinylamide-formaldehyde resin, or 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 methylol group and/or an alkoxymethyl group can be used. This melamine derivative or benzoguanamine derivative may exist as a dimer or a trimer. It is preferable that these have an average of 3 or more and 6 or less of a methylol group or an alkoxymethyl group per triazine ring.

Examples of such a melamine derivative or benzoguanamine derivative include MX-750, in which an average of 3.7 methoxymethyl groups are substituted per triazine ring, and MW in which an average of 5.8 methoxymethyl groups are substituted per triazine ring. -30 (above, manufactured by Sanwa Chemical) Ina, Cymel 300, 301, 303, 350, 370, 771, 325, 327, 703, 712 Methoxymethylated melamine, Cymel 235, 236, 238, 212, Methoxymethylated butoxymethylated melamine such as 253 and 254, butoxymethylated melamine such as Cymel 506 and 508, carboxyl group-containing methoxymethylated isobutoxymethylated melamine such as Cymel 1141, methoxymethylated ethoxy such as Cymel 1123 Methylated benzoguanamine, methoxymethylated butoxymethylated benzoguanamine such as Cymel 1123-10, butoxymethylated benzoguanamine such as Cymel 1128, carboxyl group-containing methoxymethylated ethoxymethylated benzo such as Cymel 1125-80 Guanamine (above, the Mitsui cyanamide company make) is mentioned. Moreover, as an example of glycoluril, a butoxymethylation glycoluril like Cymel 1170, a methylolation glycoluril like Cymel 1172, methoxymethylolation glycoluril like Powder Link 1174, etc. are mentioned.

Examples of the benzene or phenolic 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, etc. are mentioned.

More specifically, the crosslinking|crosslinked compound shown by Formula [6-1] - Formula [6-48] published on page 62 - page 66 of international publication WO2011/132751 (published on October 27, 2011) is mentioned. .

It is preferable that content of the specific crosslinkable compound in the liquid-crystal aligning agent of this invention is 0.1-100 mass parts with respect to 100 mass parts of all polymer components. In order for a crosslinking reaction to advance and to express the objective effect, 0.1-50 mass parts is more preferable with respect to 100 mass parts of all the polymer components, and 1-40 mass parts is the most preferable especially.

Moreover, the said specific crosslinking|crosslinked compound is mixed with 2 or more types according to characteristics, such as the solubility with respect to the solvent of a specific crosslinkable compound, the vertical alignment property of a liquid crystal when it is set as a vertical liquid crystal aligning film, and by extension, the optical characteristic of a liquid crystal display element. year can be used

In the liquid crystal display element of this invention, it is a compound which accelerates|stimulates the charge transfer in a liquid crystal aligning film, and accelerates|stimulates the charge release of an element, Comprising: It is published on page 69 - 73 of international publication WO2011/132751 (published on October 27, 2011), You can also add the nitrogen-containing heterocyclic amine compound shown by a formula [M1] - a formula [M156]. Although you may add this amine compound directly to a liquid-crystal aligning agent, it is 0.1-10 mass % of density|concentrations with an appropriate solvent, It is preferable to add, after setting it as the preferably 1-7 mass % solution. As a solvent, if it is an organic solvent in which the specific polymer mentioned above is dissolved, it will not specifically limit.

Unless the effect of this invention is impaired, the compound which improves the uniformity and surface smoothness of the film thickness of the perpendicular|vertical liquid crystal aligning film when the liquid-crystal aligning agent is apply|coated can be used for the liquid-crystal aligning agent of this invention. Moreover, the compound etc. which improve the adhesiveness of a vertical liquid crystal aligning film and a board|substrate can also be used.

As a compound which improves the uniformity of the film thickness of a vertical liquid crystal aligning film, and surface smoothness, a fluorine-type surfactant, a silicone type surfactant, a nonionic surfactant, etc. are mentioned. More specifically, for example, EFTOP EF301, EF303, EF352 (above, manufactured by Tochem Products), Megapac F171, F173, R-30 (above, manufactured by Dainippon Ink), Fluorad FC430, FC431 (above, manufactured by Tochem Products) , Sumitomo 3M Co., Ltd.), Asahigard AG710, Sufflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (above, manufactured by Asahi Glass Co., Ltd.), etc. are mentioned. Preferably the usage ratio of these surfactant is 0.01-2 mass parts with respect to 100 mass parts of all the polymer components contained in a liquid-crystal aligning agent, More preferably, it is 0.01-1 mass part.

As a specific example of the compound which improves the adhesiveness of a vertical liquid crystal aligning film and a board|substrate, the functional silane containing compound and epoxy group containing compound shown below are mentioned.

For example, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N-(2-aminoethyl)-3 -Aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, N-ethoxy Carbonyl-3-aminopropyltrimethoxysilane, N-ethoxycarbonyl-3-aminopropyltriethoxysilane, N-triethoxysilylpropyltriethylenetriamine, N-trimethoxysilylpropyltriethylenetri Amine, 10-trimethoxysilyl-1,4,7-triazadecane, 10-triethoxysilyl-1,4,7-triazadecane, 9-trimethoxysilyl-3,6-diazanonyl Acetate, 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-aminopropyltri Ethoxysilane, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol di Glycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5,6-tetraglycidyl ether Cydyl-2,4-hexanediol, N,N,N',N',-tetraglycidyl-m-xylenediamine, 1,3-bis(N,N-diglycidylaminomethyl)cyclo hexane, N,N,N',N',-tetraglycidyl-4,4'-diaminodiphenylmethane, etc. are mentioned.

When using the compound made to adhere with a board|substrate, 0.1-30 mass parts is preferable with respect to 100 mass parts of all the polymer components contained in a liquid-crystal aligning agent, More preferably, it is 1-20 mass parts. The effect of an adhesive improvement cannot be anticipated as it is less than 0.1 mass part, and when it increases more than 30 mass parts, the storage stability of a liquid-crystal aligning agent may worsen. To the liquid-crystal aligning agent of this invention, if it is a range in which the effect of this invention is not impaired other than the compound other than the above, you may add the dielectric material and electrically-conductive substance for the purpose of changing electrical characteristics, such as the dielectric constant and electroconductivity of a vertical liquid crystal aligning film.

<Liquid crystal composition>

A nematic liquid crystal or a smectic liquid crystal can be used for the liquid crystal in the liquid crystal composition used for the liquid crystal display element of this invention. Especially, in the liquid crystal display element of this invention, what has negative dielectric anisotropy is preferable. Moreover, from the point of the low voltage drive and scattering characteristic of the liquid crystal display element of this invention, it is preferable that the anisotropy of a dielectric constant is large and the anisotropy of a refractive index is large. Moreover, in order to drive the liquid crystal display element of this invention as an active element, such as a TFT (Thin Film Transistor), it is calculated|required that the electrical resistance of a liquid crystal is high and voltage retention (it is also mentioned VHR) high. Therefore, it is preferable to use the liquid crystal of a fluorine type or chlorine type for a liquid crystal which has high electrical resistance and VHR does not fall by active energy rays, such as an ultraviolet-ray. Moreover, it is preferable to use the thing with a large birefringence ((DELTA)n) for the liquid crystal used for the liquid crystal display element of this invention.

In the liquid crystal display element of this invention, a dichroic dye can be melt|dissolved in a liquid crystal composition, and it can also be set as the element of a guest host type. In this case, an element that is transparent when no voltage is applied and that absorbs (scatters) when voltage is applied is obtained. Moreover, in the liquid crystal display element of this invention, the orientation direction of a liquid crystal changes 90 degrees with the presence or absence of voltage application. Therefore, in the liquid crystal display element of this invention, high contrast is acquired compared with the conventional guest host type element which switches by random orientation and vertical orientation by using the difference in the light absorption characteristic of this dichroic dye. Moreover, in the guest host type element in which the dichroic dye was dissolved, when a liquid crystal orientates in the horizontal direction, it becomes colored and becomes opaque only in a scattering state. Therefore, it is also possible to obtain an element that changes from colorless and transparent at the time of no voltage application to colored opaque and colored transparent as voltage is applied.

In the liquid crystal composition in the liquid crystal display element of this invention, the polymeric compound which superposes|polymerizes by at least one of active energy rays, such as an ultraviolet-ray, and a heat|fever is contained. In that case, polymerization may proceed in any reaction mode to form a cured product composite of a liquid crystal and a polymerizable compound. As a specific reaction format of polymerization, radical polymerization, cationic polymerization, anionic polymerization, or polyaddition reaction is mentioned.

Any compound may be sufficient as the polymeric compound of this invention as long as it melt|dissolves in a liquid crystal. However, when a polymeric compound is melt|dissolved in a liquid crystal, it is required that the temperature at which a part or all of the liquid-crystal composition of this invention shows a liquid-crystal phase exists. Even when a part of liquid-crystal composition shows a liquid-crystal phase, the liquid crystal display element of this invention is confirmed visually, and the transparency and the scattering characteristic that the whole inside of an element is substantially uniform should just be acquired.

When the reaction format of the polymerizable compound is radical polymerization, the following radical-type polymerizable compound can be used.

That is, 2-ethylhexyl acrylate, butyl ethyl acrylate, butoxyethyl acrylate, 2-cyanoethyl acrylate, benzyl acrylate, cyclohexyl acrylate, 2-hydroxypropyl acrylate, 2-ethoxyethyl acrylate, N,N-diethylaminoethyl acrylate, N,N-dimethylaminoethyl acrylate, dicyclopentanyl acrylate, dicyclopentenyl acrylate, glycidyl acrylate, tetrahydrofurfuryl acrylate, Isobornyl acrylate, isodecyl acrylate, lauryl acrylate, morpholine acrylate, phenoxyethyl acrylate, phenoxydiethylene glycol acrylate, 2,2,2-trifluoroethyl acrylate, 2,2 ,3,3,3-pentafluoropropyl acrylate, 2,2,3,3-tetrafluoropropyl acrylate, 2,2,3,4,4,4-hexafluorobutyl acrylate, 2- Ethylhexyl methacrylate, butyl ethyl methacrylate, butoxyethyl methacrylate, 2-cyanoethyl methacrylate, benzyl methacrylate, cyclohexyl methacrylate, 2-hydroxypropyl methacrylate, 2- Ethoxyethyl acrylate, N,N-diethylaminoethyl methacrylate, N,N-dimethylaminoethyl methacrylate, dicyclopentanyl methacrylate, dicyclopentenyl methacrylate, glycidyl methacrylate , tetrahydrofurfuryl methacrylate, isobornyl methacrylate, isodecyl methacrylate, lauryl methacrylate, morpholine methacrylate, phenoxyethyl methacrylate, phenoxydiethylene glycol methacrylate, 2 ,2,2-trifluoroethyl methacrylate, 2,2,3,3-tetrafluoropropyl methacrylate, 2,2,3,4,4,4-hexafluorobutyl methacrylate, 4 , 4'-biphenyl diacrylate, diethyl stilbestrol diacrylate, 1,4-bisacryloyloxybenzene, 4,4'-bisacryloyloxydiphenyl ether, 4,4'-bisacrylo Iloxydiphenylmethane, 3,9-[1,1-dimethyl-2-acryloyloxyethyl]-2,4,8,10-tetraspiro[5,5]undecane, α,α'-bis[ 4-acryloyloxyphenyl]-1,4-diisopropylbenzene, 1,4-bisacryloyloxytetrafluorobenzene, 4,4'-bisacrylo Iloxyoctafluorobiphenyl, diethylene glycol acrylate, 1,4-butanediol diacrylate, 1,3-butylene glycol diacrylate, dicyclopentanyl diacrylate, glycerol diacrylate, 1,6-hexane Diol diacrylate, neopentyl glycol diacrylate, tetraethylene glycol diacrylate, trimethylolpropane triacrylate, pentaerythritol tetraacrylate, pentaerythritol triacrylate, ditrimethylolpropane tetraacrylate, dipenta Erythritol hexaacrylate, dipentaerythritol monohydroxypentaacrylate, 4,4'-diacryloyloxystilbene, 4,4'-diacryloyloxydimethylstilbene, 4,4'-di Acryloyloxydiethylstilbene, 4,4'-Diacryloyloxydipropylstilbene, 4,4'-Diacryloyloxydibutylstilbene, 4,4'-Diacryloyloxydipentylstilbene , 4,4'-Diacryloyloxydihexylstilbene, 4,4'-Diacryloyloxydifluorostilbene, 2,2,3,3,4,4-hexafluoropentanediol-1, 5-diacrylate, 1,1,2,2,3,3-hexafluoropropyl-1,3-diacrylate, diethylene glycol dimethacrylate, 1,4-butanediol dimethacrylate, 1 ,3-Butylene glycol dimethacrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol dimethacrylate, tetraethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, pentaerythritol tetra Methacrylate, pentaerythritol trimethacrylate, ditrimethylolpropane tetramethacrylate, dipentaerythritol hexamethacrylate, dipentaerythritol monohydroxypentamethacrylate or 2,2,3,3; monomers and oligomers such as 4,4-hexafluoropentanediol-1,5-dimethacrylate.

Especially, in the liquid crystal display element of this invention, it is preferable to use the polymeric compound of the polyfunctional radical type which has 3 or more functional groups for the purpose of making the scattering characteristic at the time of voltage application high.

Specifically, trimethylolpropane triacrylate, pentaerythritol tetraacrylate, pentaerythritol triacrylate, ditrimethylolpropane tetraacrylate, dipentaerythritol hexaacrylate, dipentaerythritol monohydroxypentaacrylic Late, trimethylolpropane trimethacrylate, pentaerythritol tetramethacrylate, pentaerythritol trimethacrylate, ditrimethylolpropane tetramethacrylate, dipentaerythritol hexamethacrylate or dipentaerythritol monohydrate Monomers and oligomers, such as hydroxypentamethacrylate, are mentioned.

According to the optical characteristic of a liquid crystal display element, and the adhesive characteristic of a liquid crystal layer and a vertical liquid crystal aligning film, the said radical type polymeric compound can also mix and use 2 or more types.

Moreover, when the reaction format of a polymeric compound is radical polymerization, the radical initiator which generate|occur|produces a radical by an ultraviolet-ray can also be introduce|transduced in a liquid crystal composition.

Specifically, tert-butylperoxy-iso-phthalate, 2,5-dimethyl-2,5-bis(benzoyldioxy)hexane, 1,4-bis[α-(tert-butyldioxy)-iso- Propoxy] benzene, di-tert-butyl peroxide, 2,5-dimethyl-2,5-bis (tert-butyldioxy) hexene hydroperoxide, α- (iso-propylphenyl) -iso-propyl hydroper Oxide, 2,5-dimethylhexane, tert-butylhydroperoxide, 1,1-bis(tert-butyldioxy)-3,3,5-trimethylcyclohexane, butyl-4,4-bis(tert-butyl Deoxy) valerate, cyclohexanone peroxide, 2,2',5,5'-tetra(tert-butylperoxycarbonyl)benzophenone, 3,3',4,4'-tetra(tert-butylperoxide) Oxycarbonyl)benzophenone, 3,3′,4,4′-tetra(tert-amylperoxycarbonyl)benzophenone, 3,3′,4,4′-tetra(tert-hexylperoxycarbonyl) Organic peroxides such as benzophenone, 3,3'-bis(tert-butylperoxycarbonyl)-4,4'-dicarboxybenzophenone, tert-butylperoxybenzoate, and di-tert-butyldiperoxyisophthalate ; quinones such as 9,10-anthraquinone, 1-chloroanthraquinone, 2-chloroanthraquinone, octamethylanthraquinone, and 1,2-benzanthraquinone; benzoin derivatives such as benzoinmethyl, benzoinethyl ether, α-methylbenzoin, and α-phenylbenzoin; and the like.

When the reaction format of the polymerizable compound is cationic polymerization or anionic polymerization, the following ionic polymerizable compound can be used.

That is, it is a compound which has at least 1 sort(s) of crosslinking-forming group selected from the group which consists of a hydroxyl group, a hydroxyalkyl group, and a lower alkoxyalkyl group. Specifically, it is a melamine derivative, a benzoguanamine derivative, or glycoluril in which the hydrogen atom of the amino group is substituted with a methylol group and/or an alkoxymethyl group. An oligomer may be sufficient as a melamine derivative and a benzoguanamine derivative. It is preferable that these have an average of 3 or more and less than 6 methyl groups or alkoxymethyl groups per triazine ring.

Examples of such a melamine derivative or benzoguanamine derivative include MX-750, in which an average of 3.7 methoxymethyl groups are substituted per triazine ring, and MW in which an average of 5.8 methoxymethyl groups are substituted per triazine ring. -30 (above, manufactured by Sanwa Chemical) Ina, Cymel 300, 301, 303, 350, 370, 771, 325, 327, 703, 712 Methoxymethylated melamine, Cymel 235, 236, 238, 212, Methoxymethylated butoxymethylated melamine such as 253 and 254, butoxymethylated melamine such as Cymel 506 and 508, carboxyl group-containing methoxymethylated isobutoxymethylated melamine such as Cymel 1141, methoxymethylated ethoxy such as Cymel 1123 Methylated benzoguanamine, methoxymethylated butoxymethylated benzoguanamine such as Cymel 1123-10, butoxymethylated benzoguanamine such as Cymel 1128, carboxyl group-containing methoxymethylated ethoxymethylated benzo such as Cymel 1125-80 Guanamine (above, the Mitsui Cytec company make) is mentioned.

Moreover, as an example of glycoluril, a butoxymethylation glycoluril like Cymel 1170, a methylolation glycoluril like Cymel 1172, etc. are mentioned.

As benzene having a hydroxyl group or an alkoxy group, or a phenolic compound, for example, 1,3,5-tris(methoxymethoxy)benzene, 1,2,4-tris(isopropoxymethoxy)benzene, 1,4-bis(sec-butoxymethoxy)benzene, 2,6-dihydroxymethyl-p-tert-butylphenol, etc. are mentioned.

As an ionic polymeric compound of this invention, the compound which contains an epoxy group or an isocyanate group and has a crosslinking-forming group can also be used. Specifically, bisphenol acetone glycidyl ether, phenol novolac epoxy resin, cresol novolac epoxy resin, triglycidyl isocyanurate, tetraglycidylaminodiphenylene, tetraglycidyl-m-xylenediamine , Tetraglycidyl-1,3-bis(aminoethyl)cyclohexane, tetraphenylglycidyletherethane, triphenylglycidyletherethane, bisphenolhexafluoroacetdiglycidylether, 1,3-bis (1-(2,3-epoxypropoxy)-1-trifluoromethyl-2,2,2-trifluoromethyl)benzene, 4,4-bis(2,3-epoxypropoxy)octafluorobi Phenyl, triglycidyl-p-aminophenol, tetraglycidyl metaxylenediamine, 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 etc. are mentioned.

According to the optical characteristic of a liquid crystal display element, or the adhesive characteristic of a liquid crystal layer and a vertical liquid crystal aligning film, the said ionic polymeric compound can also mix and use 2 or more types.

Moreover, when the reaction format of a polymeric compound is cationic polymerization or anionic polymerization, the ionic initiator which generate|occur|produces an acid or a base by ultraviolet-ray can also be introduce|transduced into a liquid crystal composition.

Specifically, a triazine-based compound, an acetophenone derivative compound, a disulfone-based compound, a diazomethane-based compound, a sulfonic acid derivative compound, a diaryliodonium salt, a triarylsulfonium salt, a triarylphosphonium salt, an iron arene complex, etc. can be used. However, it is not limited to these. More specifically, for example, diphenyl iodonium chloride, diphenyl iodonium trifluoromethane sulfonate, diphenyl iodonium mesylate, diphenyl iodonium tosylate, diphenyl iodonium bromide, diphenyl iodonium tetra Fluoroborate, diphenyliodonium hexafluoroantimonate, diphenyliodonium hexafluoroarsenate, bis(p-tert-butylphenyl)iodonium hexafluorophosphate, bis(p-tert-butylphenyl) ) iodonium mesylate, bis (p-tert-butylphenyl) iodonium tosylate, bis (p-tert-butylphenyl) iodonium trifluoromethanesulfonate, bis (p-tert-butylphenyl) iodonium tetra Fluoroborate, bis(p-tert-butylphenyl)iodonium chloride, bis(p-chlorophenyl)iodonium chloride, bis(p-chlorophenyl)iodoniumtetrafluoroborate, triphenylsulfonium chloride, triphenyl Sulfonium bromide, tri (p-methoxyphenyl) sulfonium tetrafluoroborate, tri (p-methoxyphenyl) sulfonium hexafluorophosphonate, tri (p-ethoxyphenyl) sulfonium tetrafluoroborate , triphenylphosphonium chloride, triphenylphosphonium bromide, tri (p-methoxyphenyl) phosphonium tetrafluoroborate, tri (p-methoxyphenyl) phosphonium hexafluorophosphonate, tri (p- toxyphenyl) phosphonium tetrafluoroborate. Bis[[(2-nitrobenzyl)oxy]carbonylhexane-1,6-diamine], nitrobenzylcyclohexylcarbamate, di(methoxybenzyl)hexamethylenedicarbamate, bis[[(2-nitrobenzyl) )oxy]carbonylhexane-1,6-diamine], nitrobenzylcyclohexylcarbamate, di(methoxybenzyl)hexamethylenedicarbamate, and the like.

In the liquid crystal display element of this invention, it is preferable to use the polymeric compound of a radical type among the said polymeric compound from the point of the optical characteristic of this element.

Although there is no restriction|limiting in particular in the introduction amount of the polymeric compound in a liquid crystal composition, When the introduction amount of a polymeric compound is large, a polymeric compound does not melt|dissolve in a liquid crystal, there is no temperature at which the liquid crystal composition exhibits a liquid crystal phase, or the transparent state of an element and the change of the scattering state becomes small, and the optical characteristic deteriorates. Moreover, when there is little introduction amount of a polymeric compound, sclerosis|hardenability of a liquid crystal layer becomes low, by extension, the adhesiveness of a liquid crystal layer and a perpendicular|vertical liquid crystal aligning film falls, and it becomes easy to disturb the orientation of a liquid crystal with respect to a mechanical external pressure. Therefore, it is preferable that it is 1-70 mass parts with respect to 100 mass parts of liquid crystals, and, as for the introduction amount of a polymeric compound, 5-60 mass parts is especially preferable. Especially preferably, it is 11-50 mass parts.

Moreover, although there is no restriction|limiting in particular in the introduction amount of the radical initiator and ionic initiator which accelerate|stimulate reaction of a polymeric compound, Preferably it is 0.01-20 mass parts with respect to 100 mass parts of liquid crystals, Especially, 0.05-10 mass parts is preferable. Especially preferably, it is 0.05-5 mass parts.

<The manufacturing method of a vertical liquid crystal aligning film, a liquid crystal display element>

It will not specifically limit as a board|substrate used for the liquid crystal display element of this invention, if it is a board|substrate with high transparency, In addition to a glass substrate, plastic substrates, such as an acrylic board|substrate, a polycarbonate board|substrate, a PET (polyethylene terephthalate) board|substrate, etc. can be used.

When using the liquid crystal display element of this invention as a reverse-type element, for a dimming window etc., it is preferable that it is a plastic substrate. Moreover, it is preferable to use the board|substrate with which the ITO (Indium Tin Oxide) electrode etc. for a liquid crystal drive were formed from a viewpoint of process simplification. In the case of a reflective reverse device, a silicon wafer or a substrate on which a metal such as aluminum or a dielectric multilayer film is formed can be used as long as it is only a one-side substrate.

The liquid crystal display element of this invention has the perpendicular|vertical liquid crystal aligning film in which at least one of a board|substrate orientates a liquid crystal molecule perpendicularly|vertically. After apply|coating a liquid-crystal aligning agent on a board|substrate and baking this perpendicular|vertical liquid crystal aligning film, it orientation-processes by a rubbing process, light irradiation, etc., and can be obtained. Moreover, in the case of the vertical liquid crystal aligning film of this invention, even without these orientation processing, it can be used as a vertical liquid crystal aligning film.

Although the application method of a liquid-crystal aligning agent is not specifically limited, Industrially, there exist screen printing, offset printing, flexographic printing, the inkjet method, the dip method, the roll coater method, the slit coater method, the spinner method, the spray method, etc., and board|substrate It can select suitably according to the film thickness of the vertical liquid crystal aligning film made into the kind and the objective.

After apply|coating a liquid-crystal aligning agent on a board|substrate, it is 30-300 degreeC according to the solvent used for a liquid-crystal aligning agent by heating means, such as a hot plate, heat circulation type oven, IR (infrared) type|mold oven, Preferably can obtain a vertical liquid crystal aligning film by evaporating the solvent at a temperature of 30 to 250 °C. When the thickness of the vertical liquid crystal aligning film after baking is too thick, it becomes disadvantageous in terms of power consumption of a liquid crystal display element, and since the reliability of this element may fall when it is too thin, Preferably it is 5-300 nm, More preferably 10 to 200 nm.

The liquid crystal composition used for the liquid crystal display element of this invention is a liquid crystal composition which has a liquid crystal and a polymeric compound at least. As things other than a liquid crystal and a polymeric compound, the spacer for controlling the said initiator and the electrode gap (it is also mentioned a gap) of a liquid crystal display element is mentioned.

Although the injection method of a liquid crystal composition is not specifically limited, For example, the following method is mentioned. That is, when using a glass substrate for a board|substrate, a pair of board|substrates with a vertical liquid crystal aligning film are prepared, and a sealing compound is apply|coated except a part to 4 pieces of one side board|substrate, After that, a vertical liquid crystal aligning film An empty cell is produced by bonding the other side board|substrate together so that the surface of is made to be inside. And the liquid-crystal composition is pressure-reduced from the place to which the sealing compound is not apply|coated, and the method of obtaining a liquid-crystal composition injection|pouring cell is mentioned.

In addition, when using a plastic substrate as a substrate, a pair of substrates on which a vertical liquid crystal aligning film is formed is prepared, and a liquid crystal composition is dripped on the substrate on one side by an ODF (One Drop Filling) method or an inkjet method, and then The method of bonding together the board|substrate of the other side and obtaining a liquid-crystal composition injection|pouring cell is mentioned. In this case, in the liquid crystal display element of this invention, since the adhesiveness of a liquid crystal layer and a perpendicular|vertical liquid crystal aligning film is high, it is not necessary to apply|coat a sealing compound to 4 pieces of a board|substrate.

The gap of the liquid crystal display element of this invention is controllable with a spacer etc. Examples of the method include a method of introducing a spacer of a target size into the liquid crystal composition described above, and a method of using a substrate having a column spacer of a target size. Moreover, as for the magnitude|size of a gap, 1-100 micrometers is preferable, More preferably, it is 2-50 micrometers. Especially preferably, it is 3-30 micrometers. When a gap is too small, the contrast of a liquid crystal display element will fall, and when too large, the drive voltage of this element will become high.

The liquid crystal display element of this invention hardens a liquid crystal composition in the state in which a part or all of a liquid crystal composition shows liquid crystal, and forms the hardened|cured material composite_body|complex of a liquid crystal and a polymeric compound, and is obtained. Hardening of this liquid crystal composition is performed to the liquid-crystal composition injection|pouring cell obtained above by the process of at least one of irradiation of an active energy ray, and a heating. Here, as for an active energy ray, an ultraviolet-ray is preferable. As an ultraviolet-ray, a wavelength is 250-400 nm, Preferably, it is 310-370 nm. Moreover, in the case of heat processing, the temperature is 40-120 degreeC, Preferably it is 60-80 degreeC. Moreover, both an ultraviolet treatment and a heat treatment may be performed simultaneously, and after performing an ultraviolet treatment, you may heat-process. In this invention, only ultraviolet treatment is preferable for hardening of a liquid crystal composition.

As mentioned above, the liquid crystal display element using the vertical liquid crystal aligning film obtained from the liquid-crystal aligning agent containing the specific polymer of this invention has high vertical alignment property of a liquid crystal, favorable optical properties are obtained, and the adhesiveness of a liquid crystal layer and a vertical liquid crystal aligning film It becomes this high liquid crystal display element. Moreover, by using the liquid-crystal aligning agent of this invention, the coating-film uniformity of a liquid crystal aligning film is high, and the liquid crystal display element by which the orientation defect accompanying coating-film defects, such as repelling and a pinhole, does not easily generate|occur|produce can be provided. Moreover, baking to produce a vertical liquid crystal aligning film can be performed at low temperature. Therefore, the liquid crystal display element of the present invention can be suitably used for a reverse-type element that is in a transmissive state especially when no voltage is applied, and is in a scattering state when a voltage is applied, and can be used in liquid crystal displays for display purposes, furthermore It can be used as a dimming window or optical shutter element for controlling light transmission and blocking. In that case, a plastic substrate can be used for the board|substrate of this liquid crystal display element.

In addition, the liquid crystal display element of the present invention is a liquid crystal display element used in transportation equipment such as automobiles, railroads and aircraft, and transport machinery, specifically, an optical shutter element used in a dimming window or a rearview mirror for controlling light transmission and blocking, etc. It can be used preferably.

In particular, as described above, the liquid crystal display device of the present invention has good transparency when no voltage is applied and good scattering properties when voltage is applied. Compared with the case, the light introduction efficiency in night time is high, and the effect of preventing glare from external light also becomes high. Therefore, it becomes possible to further improve the safety at the time of driving a passenger vehicle and the comfort at the time of boarding. Moreover, when the liquid crystal display element of this invention is produced with a film substrate, and it is pasted on the glass window of a passenger car and used, compared with the conventional reverse-type element, the reliability of the element of this invention becomes high. That is, the low adhesiveness of a liquid-crystal layer and a perpendicular|vertical alignment film becomes difficult to produce the defect and deterioration of the factor.

Further, the liquid crystal display device of the present invention can be used for a light guide plate of a display device such as a liquid crystal display (LCD) or an organic light-emitting diode (OLED) display, or a back plate of a transparent display using these displays. Specifically, when using for the back plate of a transparent display, when matching a transparent display and the liquid crystal display element of this invention, and performing screen display on a transparent display, the incident of the light from the back surface of the liquid crystal display of this invention It can be used in order to suppress by element. Thereby, the liquid crystal display element of this invention becomes a voltage-applied scattering state when performing screen display on a transparent display, screen display can be made clear, and after screen display is finished, a voltage is applied and it becomes a transparent state. .

Example

Hereinafter, the present invention will be described in more detail by way of Examples, but the present invention is not limited thereto. The abbreviations of the compounds used in Synthesis Examples, Examples and Comparative Examples are 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]

[Formula 65]

(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

[Formula 66]

[Formula 67]

[Formula 68]

(second diamine)

[Formula 69]

(Other diamines)

[Formula 70]

(Tetracarboxylic acid component)

[Formula 71]

<Alkoxysilane>

E1: Alkoxysilane represented by the following formula [E1]

E2: octadecyltriethoxysilane

E3: 3-methacryloxypropyltrimethoxysilane

E4: 3-Ureidopropyltriethoxysilane

E5: tetraethoxysilane

[Formula 72]

<Specific solvent>

MEK: 2-butanone

MIBK: 4-methyl-2-pentanone

DIBK: 2,6-dimethyl-4-heptanone

<Other solvents>

NMP: N-methyl-2-pyrrolidone

NEP: N-ethyl-2-pyrrolidone

γ-BL: γ-butyrolactone

PGME: propylene glycol monomethyl ether

ECS: Ethylene glycol monoethyl ether

BCS: Ethylene glycol monobutyl ether

PB: propylene glycol monobutyl ether

EC: Diethylene glycol monoethyl ether

<Specific generator>

[Formula 73]

<Specific adhesive compound>

[Formula 74]

<Specific crosslinkable compound>

[Formula 75]

「Molecular weight measurement」

It measured as follows using the normal temperature gel permeation chromatography (GPC) apparatus (GPC-101) (made by Showa Denko), and a column (KD-803, KD-805) (made by Shodex) as follows.

Column temperature: 50℃

Eluent: N,N'-dimethylformamide (as an additive, lithium bromide-hydrate (LiBr·H ₂ O) is 30 mmol/L (liter), phosphoric acid and anhydrous crystals (o-phosphoric acid) are 30 mmol/L, Tetrahydrofuran (THF) is 10 ml/L)

Flow rate: 1.0 ml/min

Standard samples for calibration curve preparation: TSK standard polyethylene oxide (molecular weight; about 900,000, 150,000, 100,000 and 30,000) (manufactured by Tosoh Corporation) and polyethylene glycol (molecular weight; about 12,000, 4,000 and 1,000) (manufactured by Polymer Laboratories).

"Measurement of imidization rate"

20 mg of sample powder was placed in an NMR (nuclear magnetic resonance) sample tube (NMR sampling tube standard, φ5 (manufactured by Kusano Scientific)), and deuterated dimethyl sulfoxide (DMSO-d6, 0.05 mass% TMS (tetramethylsilane) mixture) ) (0.53 ml) was added, and ultrasonic wave was applied to dissolve it completely. Proton NMR of 500 MHz was measured for this solution with the NMR measuring instrument (JNW-ECA500) (made by Nippon Electronics Datum). The imidation rate is determined by determining a proton derived from a structure that does not change before and after imidization as a reference proton, and integrating the peak value of this proton and the proton peak derived from the NH group of the amic acid appearing around 9.5 to 10.0 ppm. It calculated|required by the following formula using the value.

Imidization rate (%) = (1 - α·x/y) × 100

In the above formula, x is the integrated value of the proton peak derived from the NH group of the amic acid, y is the integrated peak value of the reference proton, and α is the NH of the amic acid in the case of polyamic acid (imidization rate is 0%) It is the ratio of the number of reference protons to one original proton.

“Synthesis of Polyimide Polymer”

<Synthesis Example 1>

D1 (2.96 g, 15.1 mmol), A1 (2.91 g, 7.65 mmol), B1 (0.93 g, 6.11 mmol) and C2 (0.17 g, 1.57 mmol) are mixed in NEP (21.0 g), 40 It was made to react at degreeC for 8 hours, and the polyamic-acid solution (1) of 25 mass % of resin solid content concentration (Rs) was obtained. The number average molecular weight (Mn) of this polyamic acid was 23,600, and the weight average molecular weight (Mw) was 71,800.

<Synthesis Example 2>

D2 (3.83 g, 15.3 mmol), A2 (6.04 g, 15.3 mmol) and B1 (2.33 g, 15.3 mmol) were mixed in NMP (26.4 g), and after reacting at 50° C. for 2 hours, D1 ( 2.94 g, 15.0 mmol) and NMP (23.8 g) were added, and it was made to react at 40 degreeC for 6 hours, and Rs obtained the polyamic-acid solution (2) whose 25 mass %. Mn of this polyamic acid was 22,500, and Mw was 67,100.

<Synthesis Example 3>

After adding NMP to the polyamic acid solution (2) (30.0 g) obtained in Synthesis Example 2 and diluting it to 6 mass %, acetic anhydride (3.90 g) and pyridine (2.40 g) are added as an imidation catalyst, It was made to react at 70 degreeC for 2 hours. This reaction solution was poured into methanol (460 ml), and the obtained precipitate was separated by filtration. Methanol wash|cleaned this deposit, and it dried under reduced pressure at 100 degreeC, and obtained polyimide powder (3). The imidation ratio of this polyimide was 60 %, Mn was 20,100, and Mw was 57,100.

<Synthesis Example 4>

D2 (2.64 g, 10.6 mmol), A3 (4.56 g, 10.5 mmol), B1 (1.60 g, 10.5 mmol) and B2 (1.07 g, 5.26 mmol) were mixed in NMP (21.9 g), 80 After making it react at degreeC for 5 hours, D1 (3.02g, 15.8 mmol) and NMP (17.2g) were added, it was made to react at 40 degreeC for 8 hours, and Rs obtained the polyamic-acid solution whose 25 mass %.

After adding NMP to the obtained polyamic-acid solution (30.0g) and diluting to 6 mass %, acetic anhydride (3.85g) and pyridine (2.42g) were added as an imidation catalyst, and it was made to react at 50 degreeC for 2 hours. . This reaction solution was poured into methanol (460 ml), and the obtained precipitate was separated by filtration. Methanol wash|cleaned this deposit, and it dried under reduced pressure at 100 degreeC, and obtained polyimide powder (4). The imidation ratio of this polyimide was 56 %, Mn was 18,500, and Mw was 54,000.

<Synthesis Example 5>

D2 (2.50 g, 10.0 mmol), A4 (2.96 g, 6.00 mmol), B1 (1.52 g, 10.0 mmol), B2 (0.41 g, 2.00 mmol) and C1 (0.22 g, 2.00 mmol) After mixing in NMP (19.0 g) and making it react at 80 degreeC for 5 hours, D1 (1.92 g, 9.80 mmol) and NMP (9.50 g) are added, it is made to react at 40 degreeC for 6 hours, Rs is 25 mass % A phosphorus polyamic acid solution was obtained.

After adding NMP to the obtained polyamic-acid solution (30.0g) and diluting to 6 mass %, acetic anhydride (4.00g) and pyridine (2.50g) were added as an imidation catalyst, and it was made to react at 50 degreeC for 2 hours. . This reaction solution was poured into methanol (460 ml), and the obtained precipitate was separated by filtration. Methanol wash|cleaned this deposit, it dried under reduced pressure at 100 degreeC, and the polyimide powder (5) was obtained. The imidation ratio of this polyimide was 49 %, Mn was 16,100, and Mw was 49,800.

<Synthesis Example 6>

D3 (5.45 g, 24.3 mmol), A2 (5.81 g, 14.7 mmol), B1 (1.12 g, 7.36 mmol) and B2 (0.50 g, 2.46 mmol) were mixed in NMP (38.6 g), 40 It was made to react at degreeC for 10 hours, and Rs obtained the polyamic-acid solution whose Rs is 25 mass %.

After adding NMP to the obtained polyamic-acid solution (30.0g) and diluting to 6 mass %, acetic anhydride (4.00g) and pyridine (2.48g) were added as an imidation catalyst, and it was made to react at 70 degreeC for 2 hours. . This reaction solution was poured into methanol (460 ml), and the obtained precipitate was separated by filtration. Methanol wash|cleaned this deposit, and it dried under reduced pressure at 100 degreeC, and obtained polyimide powder (6). The imidation ratio of this polyimide was 63 %, Mn was 17,200, and Mw was 49,100.

<Synthesis Example 7>

D3 (5.45 g, 24.3 mmol), A4 (3.63 g, 7.37 mmol) and B1 (2.61 g, 17.2 mmol) were mixed in NMP (35.1 g), and reacted at 40°C for 5 hours, so that Rs was 25 A polyamic acid solution of mass % was obtained.

After adding NMP to the obtained polyamic-acid solution (30.0g) and diluting to 6 mass %, acetic anhydride (8.00g) and pyridine (2.50g) were added as an imidation catalyst, and it was made to react at 50 degreeC for 3 hours. This reaction solution was poured into methanol (460 ml), and the obtained precipitate was separated by filtration. Methanol wash|cleaned this deposit, and it dried under reduced pressure at 100 degreeC, and obtained polyimide powder (7). The imidation ratio of this polyimide was 54 %, Mn was 17,400, and Mw was 47,800.

<Synthesis Example 8>

D4 (4.59 g, 15.3 mmol), A3 (6.62 g, 15.3 mmol), B1 (1.86 g, 12.2 mmol) and B2 (0.62 g, 3.05 mmol) were mixed in NMP (27.6 g), 40 After making it react at degreeC for 8 hours, D1 (2.94 g, 15.0 mmol) and NMP (22.3 g) were added, it was made to react at 25 degreeC for 10 hours, and Rs obtained the polyamic-acid solution whose Rs is 25 mass %.

After adding NMP and diluting to 6 mass % to the obtained polyamic-acid solution (30.0g), acetic anhydride (7.25g) and pyridine (2.22g) were added as an imidation catalyst, and it was made to react at 40 degreeC for 1.5 hours. . This reaction solution was poured into methanol (460 ml), and the obtained precipitate was separated by filtration. Methanol wash|cleaned this deposit, and it dried under reduced pressure at 100 degreeC, and obtained polyimide powder (8). The imidation ratio of this polyimide was 71 %, Mn was 17,100, and Mw was 38,800.

<Synthesis Example 9>

D2 (3.83 g, 15.3 mmol), A5 (5.76 g, 15.3 mmol) and B1 (2.33 g, 15.3 mmol) were mixed in NMP (26.4 g), and after reacting at 50° C. for 2 hours, D1 ( 2.94 g, 15.0 mmol) and NMP (23.8 g) were added, it was made to react at 40 degreeC for 6 hours, and Rs obtained the polyamic-acid solution whose 25 mass %.

After adding NMP to the obtained polyamic-acid solution (30.0g) and diluting to 6 mass %, acetic anhydride (3.90g) and pyridine (2.40g) were added as an imidation catalyst, and it was made to react at 70 degreeC for 2 hours. . This reaction solution was poured into methanol (460 ml), and the obtained precipitate was separated by filtration. Methanol wash|cleaned this deposit, and it dried under reduced pressure at 100 degreeC, and obtained polyimide powder (9). The imidation ratio of this polyimide was 61 %, Mn was 19,000, and Mw was 58,100.

<Synthesis Example 10>

D2 (3.83 g, 15.3 mmol) and B1 (4.66 g, 30.6 mmol) were mixed in NMP (37.5 g), and after reacting at 50° C. for 2 hours, D1 (2.94 g, 15.0 mmol) and NMP ( 12.8 g) was added, and it was made to react at 40 degreeC for 6 hours, and Rs obtained the polyamic-acid solution (10) whose 25 mass %. Mn of this polyamic acid was 25,900, and Mw was 79,100.

<Synthesis Example 11>

After adding NMP to the polyamic acid solution (10) (30.0 g) obtained in Synthesis Example 10 and diluting to 6 mass %, acetic anhydride (3.85 g) and pyridine (2.40 g) are added as an imidation catalyst, It was made to react at 70 degreeC for 2 hours. This reaction solution was poured into methanol (460 ml), and the obtained precipitate was separated by filtration. The deposit was wash|cleaned by methanol, it dried under reduced pressure at 100 degreeC, and the polyimide powder (11) was obtained. The imidation ratio of this polyimide was 59 %, Mn was 21,200, and Mw was 60,100.

The obtained polyimide-type polymer is put together in Table 1, and is shown. In Table 1, "*1" represents a polyamic acid.

“Synthesis of Polysiloxane-Based Polymer”

<Synthesis Example 12>

ECS (28.3 g), E1 (4.10 g), E3 (7.45 g) and E5 (32.5 g) are mixed in a 200 ml four-necked reaction flask equipped with a thermometer and a reflux tube to prepare a solution of an alkoxysilane monomer did To this solution, ECS (14.2 g), water (10.8 g), and a solution prepared by mixing oxalic acid (0.70 g) as a catalyst in advance was added dropwise at 25°C over 30 minutes, and further at 25°C for 30 minutes stirred. Then, after heating using an oil bath and making it reflux for 30 minutes, the methanol solution (1.20g) and ECS (0.90g) whose content of E4 prepared previously is 92 mass % and ECS (0.90g) were added. Also After refluxing for 30 minutes, bangraeng to SiO ₂ in terms of a concentration of 12 mass% to obtain a polysiloxane solution (1).

<Synthesis Example 13>

EC (25.4 g), E1 (8.20 g), E3 (19.9 g) and E5 (20.0 g) are mixed in a 200 ml four-necked reaction flask equipped with a thermometer and a reflux tube to prepare a solution of an alkoxysilane monomer did To this solution, EC (12.7 g), water (10.8 g), and a solution prepared by mixing oxalic acid (1.10 g) as a catalyst in advance was added dropwise at 25°C over 30 minutes, and further at 25°C for 30 minutes. stirred. Then, after heating using an oil bath and making it reflux for 30 minutes, the methanol solution (1.20g) and EC (0.90g) prepared previously with a content of 92 mass % of E4 were added. Also After refluxing for 30 minutes, bangraeng to SiO ₂ in terms of the concentration to obtain a polysiloxane solution (2) 12% by mass.

<Synthesis Example 14>

In a 200 mL four-necked reaction flask equipped with a thermometer and a reflux tube, EC (29.2 g), E1 (4.10 g) and E5 (38.8 g) were mixed to prepare a solution of an alkoxysilane monomer. To this solution, EC (14.6 g), water (10.8 g), and a solution prepared by mixing oxalic acid (0.50 g) as a catalyst in advance was added dropwise at 25°C over 30 minutes, and further at 25°C for 30 minutes. stirred. Then, after heating using an oil bath and making it reflux for 30 minutes, the methanol solution (1.20g) and EC (0.90g) prepared previously with a content of 92 mass % of E4 were added. Also After refluxing for 30 minutes, bangraeng to SiO ₂ in terms of a concentration of 12 mass% to obtain a polysiloxane solution (3).

<Synthesis Example 15>

ECS (28.3 g), E2 (4.07 g), E3 (7.45 g) and E5 (32.5 g) were mixed in a 200 ml four-necked reaction flask equipped with a thermometer and a reflux tube to prepare a solution of an alkoxysilane monomer did. To this solution, ECS (14.2 g), water (10.8 g), and a solution prepared by mixing oxalic acid (0.70 g) as a catalyst in advance was added dropwise at 25°C over 30 minutes, and further at 25°C for 30 minutes stirred. Then, after heating using an oil bath and making it recirculate|reflux for 30 minutes, the methanol solution (1.20g) and ECS (0.90g) whose content of E4 prepared previously is 92 mass % and ECS (0.90g) was added. Also After refluxing for 30 minutes, bangraeng to SiO ₂ in terms of the concentration to obtain a polysiloxane solution (4) 12% by mass.

The obtained polysiloxane-type polymer (polysiloxane solution) is collectively shown in Table 2.

(Preparation of liquid crystal composition (1))

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

(Preparation of liquid crystal composition (2))

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

"Production of a liquid crystal aligning agent, a vertical liquid crystal aligning film, and a liquid crystal display element and its evaluation"

In the below-mentioned Example and comparative example, the manufacture example of a liquid-crystal aligning agent was described. The obtained liquid-crystal aligning agent was used for preparation of a vertical liquid crystal aligning film and a liquid crystal display element (reverse type element), and its evaluation.

The obtained liquid-crystal aligning agent is put together in Tables 3-7, and is shown. In addition, in Tables 3-7, "*1" shows content (mass part) of the specific solvent with respect to 100 mass parts of all solvents, and other solvent. "*2" shows content (mass part) of a specific generator with respect to 100 mass parts of specific polymers. "*3" shows content (mass part) of a specific adhesive compound with respect to 100 mass parts of specific polymers. "*4" shows content (mass part) of a specific crosslinkable compound with respect to 100 mass parts of specific polymers.

Moreover, using the liquid-crystal aligning agent obtained by the Example and the comparative example, evaluation of the coating-film uniformity of a vertical liquid crystal aligning film (glass substrate, a plastic substrate), preparation of a liquid crystal display element (a glass substrate, a plastic substrate), evaluation of liquid-crystal orientation (glass) Evaluation of the adhesiveness of a board|substrate and a plastic substrate) and a liquid crystal layer and a perpendicular|vertical liquid crystal aligning film (a glass substrate, a plastic substrate) was performed.

"Evaluation of the coating film uniformity of a vertical liquid crystal aligning film (glass substrate)"

After pressure-filtering the liquid-crystal aligning agent of an Example or a comparative example with a membrane filter with a pore diameter of 1 micrometer, the glass substrate (length: 100 mm, width: 100 mm, thickness: 0.7) with an undefined 100x100 mm ITO electrode mm), it spin-coated on the ITO surface, it heat-processed at 80 degreeC for 3 minute(s) on a hotplate, and produced the board|substrate with a vertical liquid crystal aligning film.

The pinhole was evaluated using the obtained board|substrate with a vertical liquid crystal aligning film. Specifically, the number of pinholes on the vertical liquid crystal aligning film was confirmed by visual observation under a sodium lamp. In this evaluation, it was said that the thing with few number of pinholes was excellent (the number of pinholes in Tables 8-12).

"Evaluation of the coating film uniformity of a vertical liquid crystal aligning film (plastic substrate)"

After pressure-filtering a liquid-crystal aligning agent with the membrane filter of 1 micrometer of pore diameters, PET (polyethylene terephthalate) board|substrate (length: 150 mm, width: 150 mm, thickness: 0.2) with an undefined 150x150 mm ITO electrode mm), it apply|coated with the bar coater on the ITO surface, it heat-processed at 80 degreeC for 3 minute(s) on a hotplate, and the board|substrate with a vertical liquid crystal aligning film was produced.

Using the obtained board|substrate with a vertical liquid crystal aligning film, pinhole was evaluated on the conditions similar to the said "evaluation of the coating-film uniformity of a vertical liquid crystal aligning film (glass substrate)". In this evaluation, it was said that the thing with few number of pinholes was excellent (the number of pinholes in Tables 8-12).

"Production of liquid crystal display element (glass substrate)"

After pressure-filtering a liquid-crystal aligning agent with the membrane filter of 1 micrometer of pore diameters, the glass substrate with a 100 x 100 mm ITO electrode wash|cleaned by pure water and IPA (isopropyl alcohol) (length: 100 mm, width: 100 mm) , thickness: 0.7 mm), spin-coated on the ITO surface, heated at 80 ° C. for 3 minutes on a hot plate, and 150 ° C. for 10 minutes in a heat-circulating clean oven, a vertical liquid crystal aligning film with a film thickness of 100 nm The formed ITO substrate was obtained. Two ITO board|substrates with the obtained vertical liquid crystal aligning film were prepared, and the 6 micrometers spacer was apply|coated to the vertical liquid crystal aligning film surface of the one board|substrate. Thereafter, the liquid crystal composition is dripped onto the surface of the vertical liquid crystal aligning film on which the spacer is applied on the substrate by an ODF (One Drop Filling) method, and then the liquid crystal before processing is performed so that the vertical liquid crystal aligning film interface of the other substrate faces. A display element was obtained.

Using a metal halide lamp with an illuminance of 60 mW, the wavelength of 350 nm or less was cut to the liquid crystal display element before the obtained process, 7 J/cm<2> ultraviolet irradiation was performed in conversion of 365 nm, a liquid crystal display element (glass substrate) got it The temperature in the irradiation apparatus at the time of irradiating an ultraviolet-ray to a liquid crystal cell was controlled at 25 degreeC.

"Production of liquid crystal display element (plastic substrate)"

After pressure-filtering a liquid-crystal aligning agent with the membrane filter with a pore diameter of 1 micrometer, PET (polyethylene terephthalate) board|substrate (length: 150 mm, width: 150 mm, thickness with a 150 x 150 mm ITO electrode wash|cleaned with pure water) : 0.2 mm) applied with a bar coater on the ITO side, and heat-treated on a hot plate at 80 ° C. for 3 minutes and at 120 ° C. for 10 minutes in a heat circulation type clean oven, a vertical liquid crystal aligning film with a film thickness of 100 nm The formed ITO substrate was obtained. Two ITO board|substrates with the obtained vertical liquid crystal aligning film were prepared, and the 6 micrometers spacer was apply|coated to the vertical liquid crystal aligning film surface of the one board|substrate. Then, the said liquid crystal composition was dripped by the ODF method to the vertical liquid crystal aligning film surface to which the spacer of the board|substrate was apply|coated, Then, it bonded so that the vertical liquid crystal aligning film interface of the other board|substrate faced, and the liquid crystal display element before a process was obtained.

The liquid crystal display element before the obtained process was irradiated with an ultraviolet-ray on the conditions similar to the said "preparation of a liquid crystal display element (glass substrate)", and the liquid crystal display element (plastic substrate) was obtained.

"Evaluation of liquid crystal orientation (glass substrate, plastic substrate)"

Liquid-crystal orientation was evaluated using the liquid crystal display element (a glass substrate, a plastic substrate) obtained by the method similar to the above. The liquid-crystal orientation observed this element with the polarization microscope (ECLIPSE E600WPOL) (made by Nikon Corporation), and confirmed whether the liquid crystal was orientating vertically. Specifically, it was said that the liquid crystal was vertically oriented (good display in Tables 8 - 12).

Moreover, the liquid crystal display element (a glass substrate, a plastic substrate) in which evaluation of the said liquid-crystal orientation was complete|finished was stored in the high temperature tank with a temperature of 80 degreeC for 240 hours. After standing to cool, evaluation of the liquid-crystal orientation was performed on the conditions similar to the above. Disorder was not seen in liquid-crystal orientation specifically, and it was said that it was excellent that the liquid crystal is orientating uniformly (good display in Tables 8-12).

“Evaluation of adhesion between liquid crystal layer and vertical liquid crystal alignment film (glass substrate, plastic substrate)”

Adhesive evaluation of a liquid crystal layer and a perpendicular|vertical liquid crystal aligning film was performed using the liquid crystal display element (a glass substrate, a plastic substrate) which evaluated the said liquid-crystal orientation. Specifically, the liquid crystal display element (a glass substrate, a plastic substrate) was stored in the high-temperature, high-humidity tank with a temperature of 80 degreeC and a humidity of 90 %RH for 48 hours, and the presence or absence of the bubble in this element and peeling of an element were confirmed. In this evaluation, it was said that it was excellent that a bubble was not seen in this element, and peeling (a liquid-crystal layer and the state in which the perpendicular|vertical liquid crystal aligning film is peeling) of the element did not occur (good display in Tables 8-12).

In the following Examples and Comparative Examples, the above-described liquid crystal display element was produced, and the above-described "coating film uniformity evaluation of a vertical liquid crystal aligning film, liquid crystal orientation evaluation, and "adhesive evaluation of a liquid crystal layer and a vertical liquid crystal aligning film" were performed. Tables 8 to 12 are collectively shown.

In addition, in Tables 8-12, "*1" shows the number of pinholes on the vertical liquid crystal aligning film in a glass substrate / plastic substrate. "*2" shows the liquid-crystal orientation in a glass substrate / plastic substrate. "*3" shows the adhesiveness of the liquid crystal layer of a glass substrate/plastic substrate, and a perpendicular|vertical liquid crystal aligning film. "-" indicates that it is not implemented.

In addition, in Table 12, "*4" - "*12" mean the following, respectively.

*4: The liquid crystal was not vertically aligned.

*5: Since the liquid crystal was not vertically aligned, it could not be measured.

*6: Orientation defects were observed due to pinholes.

*7: Disorder in liquid-crystal orientation was seen with the orientation defect accompanying a pinhole.

*8: Bubbles were seen in the element.

*9: A small amount of air bubbles were observed in the device.

*10: Many orientation defects were observed due to pinholes.

*11: The element peeled between a liquid crystal layer and a vertical liquid crystal aligning film.

*12: A small amount of orientation defects due to pinholes were observed.

<Example 1>

To the polyamic acid solution (1) (10.0 g) obtained in Synthesis Example 1, NMP (15.9 g), NEP (3.11 g), PB (10.6 g), MIBK (15.9 g), S2 (0.25 g), M2 ( 0.125 g) and K1 (0.25 g) were added, and it stirred at 25 degreeC for 5 hours, and obtained the liquid-crystal aligning agent (1). Abnormalities, such as turbidity and precipitation, were not looked at by this liquid-crystal aligning agent, but it was confirmed that it is a uniform solution.

Using the obtained liquid-crystal aligning agent (1) and liquid-crystal composition (1), the liquid crystal display element which uses glass as a board|substrate was produced, and each said evaluation was performed.

<Example 2>

NMP (19.0g), BCS (10.6g), and MIBK (15.9g) are added to the polyamic-acid solution (2) (10.0g) obtained by the synthesis example 2, and it stirs at 25 degreeC for 5 hours, and liquid-crystal aligning agent (2) was obtained. Abnormalities, such as turbidity and precipitation, were not looked at by this liquid-crystal aligning agent, but it was confirmed that it is a uniform solution.

Using the obtained liquid-crystal aligning agent (2) and liquid-crystal composition (1), the liquid crystal display element which uses glass as a board|substrate was produced, and each said evaluation was performed.

<Example 3>

Using the liquid-crystal aligning agent (2) and liquid-crystal composition (2) obtained in Example 2, the liquid crystal display element which uses glass as a board|substrate was produced, and each said evaluation was performed.

<Example 4>

NMP (18.7g) and NEP (4.67g) were added to the polyimide powder (3) (2.20g) obtained by the synthesis example 3, and it stirred at 70 degreeC for 24 hours, and was made to melt|dissolve. BCS (9.34 g) and MIBK (14.0 g) were added to this solution, and it stirred at 25 degreeC for 2 hours, and obtained the liquid-crystal aligning agent (3). Abnormalities, such as turbidity and precipitation, were not seen by this liquid-crystal aligning agent, but it was confirmed that it is a uniform solution.

Using the obtained liquid-crystal aligning agent (3) and liquid-crystal composition (1), the liquid crystal display element which uses glass as a board|substrate was produced, and each said evaluation was performed.

<Example 5>

Using the liquid-crystal aligning agent (3) and liquid-crystal composition (2) obtained in Example 4, the liquid crystal display element which uses glass as a board|substrate was produced, and each said evaluation was performed.

<Example 6>

γ-BL (9.13 g) and PGME (13.7 g) were added to the polyimide powder (3) (2.15 g) obtained in Synthesis Example 3, and stirred at 70° C. for 24 hours to dissolve. PB (9.13g) and MEK (13.7g) were added to this solution, and it stirred at 25 degreeC for 2 hours, and obtained the liquid-crystal aligning agent (4). Abnormalities, such as turbidity and precipitation, were not seen by this liquid-crystal aligning agent, but it was confirmed that it is a uniform solution.

Using the obtained liquid-crystal aligning agent (4) and liquid-crystal composition (1), 2 types of liquid crystal display elements which make glass and plastic a board|substrate were produced, and each said evaluation was performed.

In addition, regarding evaluation of the adhesiveness of a liquid crystal layer and a vertical liquid crystal aligning film (plastic substrate), it is an emphasis test together with the said standard test, Comprising: Evaluation at the time of storing in the high-temperature, high-humidity tank of a temperature of 80 degreeC and 90%RH of humidity for 96 hours (Other conditions are the same as the above conditions). As a result, bubbles were not seen in the element.

<Example 7>

γ-BL (4.67 g) and PGME (28.0 g) were added to the polyimide powder (3) (2.20 g) obtained in the synthesis example 3, and it stirred at 70 degreeC for 24 hours, and was made to melt|dissolve. MEK (9.34 g), MIBK (4.67 g), S1 (0.154 g), M1 (0.22 g), and K1 (0.33 g) are added to this solution, and it stirs at 25 degreeC for 2 hours, and liquid-crystal aligning agent (5 ) was obtained. Abnormalities, such as turbidity and precipitation, were not seen by this liquid-crystal aligning agent, but it was confirmed that it is a uniform solution.

Using the obtained liquid-crystal aligning agent (5) and liquid-crystal composition (1), 2 types of liquid crystal display elements which make glass and plastic a board|substrate were produced, and each said evaluation was performed.

<Example 8>

γ-BL (9.34 g) and PGME (18.7 g) were added to the polyimide powder (4) (2.20 g) obtained in the synthesis example 4, and it stirred at 70 degreeC for 24 hours, and was made to melt|dissolve. EC (14.0 g), DIBK (4.67 g), S2 (0.22 g), M2 (0.11 g), and K1 (0.22 g) are added to this solution, and it stirs at 25 degreeC for 2 hours, and liquid-crystal aligning agent (6 ) was obtained. Abnormalities, such as turbidity and precipitation, were not seen by this liquid-crystal aligning agent, but it was confirmed that it is a uniform solution.

Using the obtained liquid-crystal aligning agent (6) and liquid-crystal composition (1), 2 types of liquid crystal display elements which make glass and plastic a board|substrate were produced, and each said evaluation was performed.

<Example 9>

Using the liquid-crystal aligning agent (6) and liquid-crystal composition (2) obtained in Example 8, 2 types of liquid crystal display elements which make glass and plastic a board|substrate were produced, and each said evaluation was performed.

<Example 10>

γ-BL (2.39 g) and PGME (28.7 g) were added to the polyimide powder (4) (2.25 g) obtained in the synthesis example 4, and it stirred at 70 degreeC for 24 hours, and was made to melt|dissolve. To this solution, PB (4.78 g), MEK (7.96 g), MIBK (3.98 g), S2 (0.225 g), M1 (0.113 g) and K1 (0.45 g) were added, and stirred at 25°C for 2 hours. , the liquid-crystal aligning agent (7) was obtained. Abnormalities, such as turbidity and precipitation, were not seen by this liquid-crystal aligning agent, but it was confirmed that it is a uniform solution.

Using the obtained liquid-crystal aligning agent (7) and liquid-crystal composition (1), 2 types of liquid crystal display elements which make glass and plastic a board|substrate were produced, and each said evaluation was performed.

<Example 11>

γ-BL (4.78 g) and PGME (19.1 g) were added to the polyimide powder (4) (2.25 g) obtained in Synthesis Example 4, and stirred at 70°C for 24 hours to dissolve. MIBK (23.9 g), S1 (0.068 g), M2 (0.068 g), and K1 (0.158 g) were added to this solution, and it stirred at 25 degreeC for 2 hours, and obtained the liquid-crystal aligning agent (8). Abnormalities, such as turbidity and precipitation, were not seen by this liquid-crystal aligning agent, but it was confirmed that it is a uniform solution.

Using the obtained liquid-crystal aligning agent (8) and liquid-crystal composition (1), 2 types of liquid crystal display elements which use glass and plastics as a board|substrate were produced, and each said evaluation was performed.

<Example 12>

NEP (18.7g) was added to the polyimide powder (5) (2.20g) obtained by the synthesis example 5, and it stirred at 70 degreeC for 24 hours, and was made to melt|dissolve. PB (9.34 g), MIBK (14.0 g), and DIBK (4.67 g) were added to this solution, and it stirred at 25 degreeC for 2 hours, and obtained the liquid-crystal aligning agent (9). Abnormalities, such as turbidity and precipitation, were not seen by this liquid-crystal aligning agent, but it was confirmed that it is a uniform solution.

Using the obtained liquid-crystal aligning agent (9) and liquid-crystal composition (2), the liquid crystal display element which uses glass as a board|substrate was produced, and each said evaluation was performed.

<Example 13>

γ-BL (4.67 g) and PGME (28.0 g) were added to the polyimide powder (5) (2.20 g) obtained in the synthesis example 5, and it stirred at 70 degreeC for 24 hours, and was made to melt|dissolve. MEK (4.67 g), MIBK (9.34 g), and K1 (0.22 g) were added to this solution, and it stirred at 25 degreeC for 2 hours, and obtained the liquid-crystal aligning agent (10). Abnormalities, such as turbidity and precipitation, were not seen by this liquid-crystal aligning agent, but it was confirmed that it is a uniform solution.

Using the obtained liquid-crystal aligning agent (10) and liquid-crystal composition (1), 2 types of liquid crystal display elements which make glass and plastic a board|substrate were produced, and each said evaluation was performed.

In addition, with respect to the evaluation of the adhesion between the liquid crystal layer and the vertical liquid crystal aligning film (plastic substrate), an emphasis test was performed under the same conditions as in Example 6 (however, storage in a high-temperature, high-humidity tank for 144 hours) together with the above standard test. . As a result, a small amount of air bubbles was observed in the device.

<Example 14>

γ-BL (4.67 g) and PGME (28.0 g) were added to the polyimide powder (5) (2.20 g) obtained in the synthesis example 5, and it stirred at 70 degreeC for 24 hours, and was made to melt|dissolve. MEK (4.67 g), MIBK (9.34 g), S1 (0.22 g), and K1 (0.22 g) were added to this solution, and it stirred at 25 degreeC for 2 hours, and obtained the liquid-crystal aligning agent (11). Abnormalities, such as turbidity and precipitation, were not seen by this liquid-crystal aligning agent, but it was confirmed that it is a uniform solution.

Using the obtained liquid-crystal aligning agent (11) and liquid-crystal composition (1), 2 types of liquid crystal display elements which make glass and plastic a board|substrate were produced, and each said evaluation was performed.

In addition, with respect to the evaluation of the adhesion between the liquid crystal layer and the vertical liquid crystal aligning film (plastic substrate), an emphasis test was performed under the same conditions as in Example 6 (however, storage in a high-temperature, high-humidity tank for 144 hours) together with the above standard test. . As a result, a small amount of air bubbles was observed in the device.

<Example 15>

γ-BL (4.67 g) and PGME (28.0 g) were added to the polyimide powder (5) (2.20 g) obtained in the synthesis example 5, and it stirred at 70 degreeC for 24 hours, and was made to melt|dissolve. MEK (4.67 g), MIBK (9.34 g), S1 (0.22 g), M2 (0.154 g) and K1 (0.22 g) are added to this solution, and it stirs at 25 degreeC for 2 hours, and liquid-crystal aligning agent (12) ) was obtained. Abnormalities, such as turbidity and precipitation, were not seen by this liquid-crystal aligning agent, but it was confirmed that it is a uniform solution.

Using the obtained liquid-crystal aligning agent (12) and liquid-crystal composition (1), 2 types of liquid crystal display elements which make glass and plastic a board|substrate were produced, and each said evaluation was performed.

In addition, with respect to the evaluation of the adhesion between the liquid crystal layer and the vertical liquid crystal aligning film (plastic substrate), an emphasis test was performed under the same conditions as in Example 6 (however, storage in a high-temperature, high-humidity tank for 144 hours) together with the above standard test. . As a result, bubbles were not seen in the element.

<Example 16>

γ-BL (11.1 g) and PGME (20.0 g) were added to the polyimide powder (6) (2.10 g) obtained in the synthesis example 6, and it stirred at 70 degreeC for 24 hours, and was made to melt|dissolve. BCS (2.28g), MIBK (11.1g), and K1 (0.42g) were added to this solution, it stirred at 25 degreeC for 2 hours, and the liquid-crystal aligning agent (13) was obtained. Abnormalities, such as turbidity and precipitation, were not seen by this liquid-crystal aligning agent, but it was confirmed that it is a uniform solution.

Using the obtained liquid-crystal aligning agent (13) and liquid-crystal composition (2), 2 types of liquid crystal display elements which use glass and plastics as a board|substrate were produced, and each said evaluation was performed.

<Example 17>

γ-BL (11.7 g) and PGME (28.0 g) were added to the polyimide powder (6) (2.20 g) obtained in the synthesis example 6, and it stirred at 70 degreeC for 24 hours, and was made to melt|dissolve. PB (4.67 g), MIBK (2.33 g), S2 (0.066 g), M1 (0.11 g) and K1 (0.066 g) are added to this solution, and it stirs at 25 degreeC for 2 hours, and liquid-crystal aligning agent (14) ) was obtained. Abnormalities, such as turbidity and precipitation, were not seen by this liquid-crystal aligning agent, but it was confirmed that it is a uniform solution.

Using the obtained liquid-crystal aligning agent (14) and liquid-crystal composition (1), 2 types of liquid crystal display elements which make glass and plastic a board|substrate were produced, and each said evaluation was performed.

<Example 18>

NMP (4.67g) and NEP (14.0g) were added to the polyimide powder (6) (1.65g) obtained by the synthesis example 6, and it stirred at 70 degreeC for 24 hours, and was made to melt|dissolve. BCS (9.34 g), PB (4.67 g), DIBK (14.0 g), and K1 (0.44 g) were added to this solution, and it stirred at 25 degreeC for 2 hours, and obtained the liquid-crystal aligning agent (15). Abnormalities, such as turbidity and precipitation, were not seen by this liquid-crystal aligning agent, but it was confirmed that it is a uniform solution.

Using the obtained liquid-crystal aligning agent (15) and liquid-crystal composition (1), the liquid crystal display element which uses glass as a board|substrate was produced, and each said evaluation was performed.

<Example 19>

γ-BL (2.28 g) and PGME (29.7 g) were added to the polyimide powder (7) (2.15 g) obtained in the synthesis example 7, and it stirred at 70 degreeC for 24 hours, and was made to melt|dissolve. MEK (13.7 g), S2 (0.323 g), M2 (0.108 g), and K1 (0.323 g) were added to this solution, and it stirred at 25 degreeC for 2 hours, and obtained the liquid-crystal aligning agent (16). Abnormalities, such as turbidity and precipitation, were not seen by this liquid-crystal aligning agent, but it was confirmed that it is a uniform solution.

Using the obtained liquid-crystal aligning agent (16) and liquid-crystal composition (1), 2 types of liquid crystal display elements which use glass and plastics as a board|substrate were produced, and each said evaluation was performed.

<Example 20>

NEP (14.0 g) was added to the polyimide powder (7) (2.20 g) obtained by the synthesis example 7, and it stirred at 70 degreeC for 24 hours, and was made to melt|dissolve. To this solution, BCS (4.67 g), PB (18.7 g), DIBK (9.34 g), S1 (0.066 g), M1 (0.154 g) and K1 (0.22 g) were added and stirred at 25°C for 2 hours. , the liquid-crystal aligning agent (17) was obtained. Abnormalities, such as turbidity and precipitation, were not seen by this liquid-crystal aligning agent, but it was confirmed that it is a uniform solution.

Using the obtained liquid-crystal aligning agent (17) and liquid-crystal composition (2), the liquid crystal display element which uses glass as a board|substrate was produced, and each said evaluation was performed.

<Example 21>

NMP (16.3g) was added to the polyimide powder (8) (2.20g) obtained by the synthesis example 8, and it stirred at 70 degreeC for 24 hours, and was made to melt|dissolve. To this solution, BCS (7.00 g), PB (14.0 g), DIBK (9.34 g), S2 (0.11 g), M2 (0.22 g) and K1 (0.22 g) were added, followed by stirring at 25°C for 2 hours. , the liquid-crystal aligning agent (18) was obtained. Abnormalities, such as turbidity and precipitation, were not seen by this liquid-crystal aligning agent, but it was confirmed that it is a uniform solution.

Using the obtained liquid-crystal aligning agent (18) and liquid-crystal composition (1), the liquid crystal display element which uses glass as a board|substrate was produced, and each said evaluation was performed.

<Example 22>

γ-BL (4.67 g) and PGME (30.4 g) were added to the polyimide powder (8) (2.20 g) obtained in Synthesis Example 8, and stirred at 70°C for 24 hours to dissolve. MIBK (11.7 g), S1 (0.22 g), M1 (0.11 g), and K1 (0.44 g) were added to this solution, and it stirred at 25 degreeC for 2 hours, and obtained the liquid-crystal aligning agent (19). Abnormalities, such as turbidity and precipitation, were not seen by this liquid-crystal aligning agent, but it was confirmed that it is a uniform solution.

Using the obtained liquid-crystal aligning agent (19) and liquid-crystal composition (1), 2 types of liquid crystal display elements which make glass and plastic a board|substrate were produced, and each said evaluation was performed.

<Example 23>

NEP (18.7g) was added to the polyimide powder (8) (2.20g) obtained by the synthesis example 8, and it stirred at 70 degreeC for 24 hours, and was made to melt|dissolve. PB (18.7 g) and DIBK (9.34 g) were added to this solution, and it stirred at 25 degreeC for 2 hours, and obtained the liquid-crystal aligning agent (20). Abnormalities, such as turbidity and precipitation, were not seen by this liquid-crystal aligning agent, but it was confirmed that it is a uniform solution.

Using the obtained liquid-crystal aligning agent (20) and liquid-crystal composition (1), the liquid crystal display element which uses glass as a board|substrate was produced, and each said evaluation was performed.

<Example 24>

NMP (4.67g) and NEP (18.7g) were added to the polyimide powder (9) (2.20g) obtained by the synthesis example 9, and it stirred at 70 degreeC for 24 hours, and was made to melt|dissolve. BCS (9.34 g) and MIBK (14.0 g) were added to this solution, and it stirred at 25 degreeC for 2 hours, and obtained the liquid-crystal aligning agent (21). Abnormalities, such as turbidity and precipitation, were not seen by this liquid-crystal aligning agent, but it was confirmed that it is a uniform solution.

Using the obtained liquid-crystal aligning agent (21) and liquid-crystal composition (1), the liquid crystal display element which uses glass as a board|substrate was produced, and each said evaluation was performed.

<Example 25>

γ-BL (8.91 g) and PGME (13.4 g) were added to the polyimide powder (9) (2.10 g) obtained in Synthesis Example 9, and stirred at 70° C. for 24 hours to dissolve. PB (8.91 g) and MEK (13.4 g) were added to this solution, and it stirred at 25 degreeC for 2 hours, and obtained the liquid-crystal aligning agent (22). Abnormalities, such as turbidity and precipitation, were not seen by this liquid-crystal aligning agent, but it was confirmed that it is a uniform solution.

Using the obtained liquid-crystal aligning agent (22) and liquid-crystal composition (1), 2 types of liquid crystal display elements which make glass and plastic a board|substrate were produced, and each said evaluation was performed.

In addition, about the adhesive evaluation (plastic substrate) of a liquid crystal layer and a perpendicular|vertical liquid crystal aligning film, the emphasis test was implemented on the conditions similar to Example 6 with a standard test. As a result, a small amount of air bubbles was observed in the device.

<Example 26>

To the polysiloxane solution (1) (20.0 g) obtained in Synthesis Example 12, ECS (7.87 g), BCS (10.2 g), MIBK (15.3 g), S2 (0.12 g) and M2 (0.12 g) were added, 25 It stirred at °C for 5 hours, and obtained the liquid-crystal aligning agent (23). Abnormalities, such as turbidity and precipitation, were not seen by this liquid-crystal aligning agent, but it was confirmed that it is a uniform solution.

Using the obtained liquid-crystal aligning agent (23) and liquid-crystal composition (1), 2 types of liquid crystal display elements which make glass and plastic a board|substrate were produced, and each said evaluation was performed.

In addition, about adhesive evaluation (plastic substrate) of a liquid crystal layer and a perpendicular|vertical liquid crystal aligning film, the emphasis test was implemented on the conditions similar to Example 6 with the said standard test. As a result, bubbles were not seen in the element.

<Example 27>

Using the liquid-crystal aligning agent (23) and liquid-crystal composition (2) obtained in Example 26, 2 types of liquid crystal display elements which make glass and plastic a board|substrate were produced, and each said evaluation was performed.

<Example 28>

EC (7.87 g), PB (5.09 g), MEK (5.09 g) and MIBK (15.3 g) were added to the polysiloxane solution (2) (20.0 g) obtained in Synthesis Example 13, and stirred at 25°C for 5 hours , the liquid-crystal aligning agent (24) was obtained. Abnormalities, such as turbidity and precipitation, were not seen by this liquid-crystal aligning agent, but it was confirmed that it is a uniform solution.

Using the obtained liquid-crystal aligning agent (24) and liquid-crystal composition (1), 2 types of liquid crystal display elements which make glass and plastic a board|substrate were produced, and each said evaluation was performed.

<Example 29>

Using the liquid-crystal aligning agent (24) and liquid-crystal composition (2) obtained in Example 28, 2 types of liquid crystal display elements which make glass and plastic a board|substrate were produced, and each said evaluation was performed.

<Example 30>

To the polysiloxane solution (3) (21.0 g) obtained in Synthesis Example 14, EC (8.26 g), BCS (16.0 g), MIBK (2.68 g), DIBK (8.03 g) and K1 (0.076 g) were added, 25 It stirred at °C for 5 hours, and obtained the liquid-crystal aligning agent (25). Abnormalities, such as turbidity and precipitation, were not seen by this liquid-crystal aligning agent, but it was confirmed that it is a uniform solution.

Using the obtained liquid-crystal aligning agent (25) and liquid-crystal composition (2), 2 types of liquid crystal display elements which make glass and plastic a board|substrate were produced, and each said evaluation was performed.

In addition, about the adhesive evaluation (plastic substrate) of a liquid crystal layer and a vertical liquid crystal aligning film, with the said standard test, the stress test was implemented on the conditions similar to Example 6 (however, storage in a high-temperature, high-humidity tank is 144 hours). As a result, a small amount of air bubbles was observed in the device.

<Example 31>

To the polysiloxane solution (3) (21.0 g) obtained in Synthesis Example 14, EC (8.26 g), BCS (16.0 g), MIBK (2.68 g), DIBK (8.03 g), S1 (0.126 g), M2 (0.252 g) ) and K1 (0.076 g) were added, and it stirred at 25 degreeC for 5 hours, and obtained the liquid-crystal aligning agent (26). Abnormalities, such as turbidity and precipitation, were not seen by this liquid-crystal aligning agent, but it was confirmed that it is a uniform solution.

Using the obtained liquid-crystal aligning agent (26) and liquid-crystal composition (2), 2 types of liquid crystal display elements which make glass and plastic a board|substrate were produced, and each said evaluation was performed.

In addition, about the adhesive evaluation (plastic substrate) of a liquid crystal layer and a vertical liquid crystal aligning film, with the said standard test, the stress test was implemented on the conditions similar to Example 6 (however, storage in a high-temperature, high-humidity tank is 144 hours). As a result, bubbles were not seen in the element.

<Example 32>

To the polysiloxane solution (4) (20.0 g) obtained in Synthesis Example 15, ECS (7.87 g), BCS (10.2 g), MIBK (15.3 g), S2 (0.12 g) and M2 (0.12 g) were added, 25 It stirred at °C for 5 hours, and obtained the liquid-crystal aligning agent (27). Abnormalities, such as turbidity and precipitation, were not seen by this liquid-crystal aligning agent, but it was confirmed that it is a uniform solution.

Using the obtained liquid-crystal aligning agent (27), and the liquid-crystal composition (1), 2 types of liquid crystal display elements which make glass and plastic a board|substrate were produced, and each said evaluation was performed.

In addition, about adhesive evaluation (plastic substrate) of a liquid crystal layer and a perpendicular|vertical liquid crystal aligning film, the emphasis test was implemented on the conditions similar to Example 6 with the said standard test. As a result, a small amount of air bubbles was observed in the device.

<Comparative Example 1>

NMP (19.0 g), BCS (10.6 g), and MIBK (15.9 g) are added to the polyamic acid solution (10) (10.0 g) obtained by the synthesis example 10, and it stirs at 25 degreeC for 5 hours, and liquid-crystal aligning agent (28) was obtained. Abnormalities, such as turbidity and precipitation, were not seen by this liquid-crystal aligning agent, but it was confirmed that it is a uniform solution.

Using the obtained liquid-crystal aligning agent (28) and liquid-crystal composition (1), the liquid crystal display element which uses glass as a board|substrate was produced, and each said evaluation was performed.

<Comparative Example 2>

NMP (18.7 g) and NEP (4.67 g) were added to the polyimide powder (11) (2.20 g) obtained by the synthesis example 11, and it stirred at 70 degreeC for 24 hours, and was made to melt|dissolve. BCS (9.34 g) and MIBK (14.0 g) were added to this solution, and it stirred at 25 degreeC for 2 hours, and obtained the liquid-crystal aligning agent (29). Abnormalities, such as turbidity and precipitation, were not seen by this liquid-crystal aligning agent, but it was confirmed that it is a uniform solution.

Using the obtained liquid-crystal aligning agent (29) and liquid-crystal composition (1), the liquid crystal display element which uses glass as a board|substrate was produced, and each said evaluation was performed.

<Comparative example 3>

NMP (29.6g) and BCS (15.9g) were added to the polyamic-acid solution (2) (10.0g) obtained by the synthesis example 2, it stirred at 25 degreeC for 5 hours, and the liquid-crystal aligning agent (30) was obtained. Abnormalities, such as turbidity and precipitation, were not seen by this liquid-crystal aligning agent, but it was confirmed that it is a uniform solution.

Using the obtained liquid-crystal aligning agent (30) and liquid-crystal composition (1), the liquid crystal display element which uses glass as a board|substrate was produced, and each said evaluation was performed.

<Comparative example 4>

Using the liquid-crystal aligning agent (30) and liquid-crystal composition (2) obtained by the comparative example 3, the liquid crystal display element which uses glass as a board|substrate was produced, and each said evaluation was performed.

<Comparative example 5>

NMP (31.9g) and NEP (4.56g) were added to the polyimide powder (3) (2.15g) obtained by the synthesis example 3, and it stirred at 70 degreeC for 24 hours, and was made to melt|dissolve. BCS (9.12g) was added to this solution, and it stirred at 25 degreeC for 2 hours, and obtained the liquid-crystal aligning agent (31). Abnormalities, such as turbidity and precipitation, were not seen by this liquid-crystal aligning agent, but it was confirmed that it is a uniform solution.

Using the obtained liquid-crystal aligning agent (31) and liquid-crystal composition (1), 2 types of liquid crystal display elements which make glass a board|substrate were produced, and each said evaluation was performed.

<Comparative Example 6>

Using the liquid-crystal aligning agent (31) and liquid-crystal composition (2) obtained by the comparative example 5, the liquid crystal display element which uses glass as a board|substrate was produced, and each said evaluation was performed.

<Comparative Example 7>

γ-BL (23.3 g) and PGME (14.0 g) were added to the polyimide powder (3) (2.20 g) obtained in the synthesis example 3, and it stirred at 70 degreeC for 24 hours, and was made to melt|dissolve. PB (9.34 g) was added to this solution, and it stirred at 25 degreeC for 2 hours, and obtained the liquid-crystal aligning agent (32). Abnormalities, such as turbidity and precipitation, were not seen by this liquid-crystal aligning agent, but it was confirmed that it is a uniform solution.

Using the obtained liquid-crystal aligning agent (32) and liquid-crystal composition (1), 2 types of liquid crystal display elements which make glass and plastic a board|substrate were produced, and each said evaluation was performed.

<Comparative Example 8>

EC (23.2 g) and PB (10.2 g) were added to the polysiloxane solution (2) (20.0 g) obtained by the synthesis example 13, it stirred at 25 degreeC for 5 hours, and the liquid-crystal aligning agent (33) was obtained. Abnormalities, such as turbidity and precipitation, were not seen by this liquid-crystal aligning agent, but it was confirmed that it is a uniform solution.

Using the obtained liquid-crystal aligning agent (33) and liquid-crystal composition (1), 2 types of liquid crystal display elements which make glass and plastic a board|substrate were produced, and each said evaluation was performed.

<Comparative example 9>

Using the liquid-crystal aligning agent (33) and liquid-crystal composition (2) obtained by the comparative example 8, 2 types of liquid crystal display elements which make glass and plastic a board|substrate were produced, and each said evaluation was performed.

As for the perpendicular|vertical liquid crystal aligning film obtained from the liquid-crystal aligning agent of an Example so that said result might show, the coating-film uniformity was high compared with the comparative example, ie, there were few number of pinholes. Specifically, it is the same specific polymer, and comparison of Examples and Comparative Examples in which a specific solvent is not used, that is, Example 2 and Comparative Example 3, Example 4 and Comparative Example 5, Example 6 and Comparative Example 7, and Example It is a comparison of Example 28 and Comparative Example 9.

Moreover, the vertical alignment property of a liquid crystal was high compared with the comparative example, and the liquid crystal display element using the vertical liquid crystal aligning film obtained from the liquid-crystal aligning agent of an Example showed favorable liquid-crystal orientation. In particular, in the Example of this invention, even after storing in a high temperature tank for a long time, disorder of the liquid-crystal orientation was not seen. Specifically, it is the same specific polymer, and comparison of Examples and Comparative Examples without using a specific solvent, Example 2 and Comparative Example 3, Example 3 and Comparative Example 4, Example 4 and Comparative Example 5, Example 5 and Comparative Example 6, Example 6 and Comparative Example 7, Example 28 and Comparative Example 8, and Example 29 and Comparative Example 9. In particular, in the comparative example, the orientation defect accompanying a pinhole was initially seen.

Moreover, as for the liquid crystal display element using the perpendicular|vertical liquid crystal aligning film obtained from the liquid-crystal aligning agent of an Example, the adhesiveness of a liquid crystal layer and a perpendicular|vertical liquid crystal aligning film became high compared with the comparative example. Specifically, it is the same specific polymer, and comparison of Examples and Comparative Examples without using a specific solvent, Example 2 and Comparative Example 3, Example 3 and Comparative Example 4, Example 4 and Comparative Example 5, Example 5 and Comparative Example 6, Example 6 and Comparative Example 7, Example 28 and Comparative Example 8, and Example 29 and Comparative Example 9.

When the structure shown by Formula [2-1] was used for specific side chain structure, compared with the case where the structure shown by Formula [2-2] was used, the result that the adhesiveness of a liquid crystal layer and a perpendicular|vertical liquid crystal aligning film becomes higher was obtained . Specifically, it is the result of the emphasis test of adhesive evaluation (plastic substrate) of a liquid crystal layer and a vertical liquid crystal aligning film, ie, Example 6 and Example 25, and a comparison of Example 26 and Comparative Example 32.

Moreover, when a specific generator and a specific adhesive compound were introduce|transduced in the liquid-crystal aligning agent of this invention, compared with the case where they are not introduced, the result that the adhesiveness of a liquid crystal layer and a perpendicular|vertical liquid crystal aligning film becomes higher was obtained. Specifically, it is the result of the emphasis test of adhesive evaluation (plastic substrate) of a liquid crystal layer and a perpendicular|vertical liquid crystal aligning film, ie, Example 13 and Example 14 or Example 15, and Example 30 and comparison of Comparative Example 31.

In addition, when the polymer which does not contain a specific side chain structure was used, a liquid crystal did not vertically align. Specifically, they are Comparative Example 1 and Comparative Example 2.

Industrial Applicability

The liquid crystal display device of the present invention can be preferably used for a reverse device, and the film uniformity of the vertical liquid crystal aligning film is high, and alignment defects due to poor coating such as repelling and pinholes are difficult to occur. It can be used for liquid crystal displays, dimming windows, and optical shutter elements for controlling light transmission and blocking.

In addition, all the content of the specification of JP Patent application 2014-065759 for which it applied on March 27, 2014, a claim, and an abstract is referred here, and it takes in as an indication of this specification.

Claims (17)

It has a liquid crystal layer between a pair of board|substrates provided with an electrode, The liquid-crystal composition containing the polymeric compound which superposes|polymerizes by at least one of an active energy ray and a heat|fever between the pair of board|substrates is arrange|positioned, and at least one of the board|substrates It has a liquid crystal aligning film that vertically aligns the liquid crystal, and is obtained by curing the liquid crystal composition in a state where part or all of the liquid crystal composition exhibits liquid crystallinity to form a cured product composite of liquid crystal and a polymerizable compound, It is a transparent state at the time of no application, and it is a transmission scattering type liquid crystal display element which becomes a scattering state at the time of voltage application, The said liquid crystal aligning film contains the solvent shown by following formula [1], and also following formula [2-1] And it consists of a liquid crystal aligning film obtained from the liquid-crystal aligning agent containing the polymer which has at least 1 sort(s) chosen from the group which consists of a structure shown by Formula [2-2] The liquid crystal display element characterized by the above-mentioned.

(S ¹ and S ² each independently represent an alkyl group having 1 to 4 carbon atoms)

(Y ¹ is a single bond, -(CH ₂ ) _a - (a represents an integer of 1 to 15), -O-, -CH ₂ O-, -COO- and -OCO- at least one selected from Y ² represents a single bond or -(CH ₂ ) _b - (b represents an integer of 1 to 15), Y ³ represents a single bond, -(CH ₂ ) _c - (c is an integer of 1 to 15) represents at least one type selected from ), -O-, -CH ₂ O-, -COO- and -OCO-, and Y ⁴ is at least one ring selected from a benzene ring, a cyclohexane ring and a heterocyclic ring. Represents a cyclic group or a C17-51 divalent organic group having a steroid skeleton, wherein arbitrary hydrogen atoms on the cyclic group are an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, and fluorine-containing having 1 to 3 carbon atoms. may be substituted with an alkyl group, a fluorine-containing alkoxy group having 1 to 3 carbon atoms, or a fluorine atom, Y ⁵ represents at least one cyclic group selected from a benzene ring, a cyclohexane ring, and a heterocyclic ring, and any of these cyclic groups A hydrogen atom may be substituted with a C1-C3 alkyl group, a C1-C3 alkoxy group, a C1-C3 fluorine-containing alkyl group, a C1-C3 fluorine-containing alkoxy group, or a fluorine atom, and n is 0-4 represents an integer of, and Y ⁶ represents at least one selected from an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, and a fluorine-containing alkoxy group having 1 to 18 carbon atoms)

(Y ⁷ is from a single bond, -O-, -CH ₂ O-, -CONH-, -NHCO-, -CON(CH ₃ )-, -N(CH ₃ )CO-, -COO- and -OCO- represents at least one selected bonding group, and Y ⁸ represents an alkyl group having 8 to 22 carbon atoms or a fluorine-containing alkyl group having 6 to 18 carbon atoms) The method of claim 1,
Liquid crystal display in which the solvent shown by said Formula [1] is at least 1 sort(s) of solvent chosen from 2-butanone, 3-pentanone, 4-methyl-2-pentanone, and 2,6-dimethyl-4-heptanone device. The method of claim 1,
The liquid crystal display device in which the said polymer is at least 1 sort(s) of polymer chosen from an acrylic polymer, a methacryl polymer, a novolak resin, polyhydroxystyrene, a polyimide precursor, a polyimide, polyamide, polyester, a cellulose, and polysiloxane. 4. The method of claim 3,
The polyimide precursor and polyimide obtained by using for a part of raw materials the diamine which has the said polymer which has at least 1 sort(s) of side chain chosen from the group which consists of a structure shown by said Formula [2-1] and Formula [2-2], The liquid crystal display element which is at least 1 sort(s) of polymer chosen from the group which consists of mid. 5. The method of claim 4,
The liquid crystal display element whose said diamine is a diamine represented by following formula [2].

(Y represents at least 1 sort(s) chosen from the group which consists of a structure shown by said Formula [2-1] and Formula [2-2], n represents the integer of 1-4) 4. The method of claim 3,
The liquid crystal display element whose said polymer is at least 1 sort(s) of polymer chosen from the group which consists of a polyimide precursor and polyimide obtained by using for a part of raw material 2nd diamine shown by following formula [3].

(X is at least 1 sort(s) chosen from the structure shown by a following formula [3a] - a formula [3d], and m represents the integer of 1-4)

(in formula [3a], a represents an integer of 0 to 4, in formula [3b], b represents an integer of 0 to 4, in formula [3c], X ¹ and X ² each independently represent 1 to 12 hydrocarbon group, and in formula [3d], X ³ represents an alkyl group having 1 to 5 carbon atoms) 4. The method of claim 3,
The liquid crystal display element whose said polymer is the at least 1 sort(s) of polymer chosen from the group which consists of a polyimide precursor and polyimide obtained by using for a part of raw material the tetracarboxylic-acid component shown by following formula [4].

(Z is at least 1 sort(s) selected from the structure shown by a following formula [4a] - a formula [4k])

(In formula [4a], Z ¹ to Z ⁴ each independently represent a hydrogen atom, a methyl group, a chlorine atom or a benzene ring, and in the formula [4g], Z ⁵ and Z ⁶ each independently represent a hydrogen atom or a methyl group. ) 4. The method of claim 3,
Polysiloxane obtained by making the said polymer polycondensate the alkoxysilane shown by following formula [A1], Formula [A1], and the alkoxysilane containing any 1 type of the alkoxysilane shown by following formula [A2] or formula [A3] polycondensation The liquid crystal display element which is at least 1 sort(s) of polysiloxane chosen from polysiloxane obtained by making it combine, and the polysiloxane obtained by making polycondensation of the alkoxysilane shown by Formula [A1], Formula [A2], and Formula [A3].

(A ¹ represents at least one selected from the group consisting of structures represented by the formulas [2-1] and [2-2], A ² represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and A ³ represents an alkyl group having 1 to 5 carbon atoms, m represents an integer of 1 or 2, n represents an integer of 0 to 2, and p represents an integer of 0 to 3. However, m+n+p represents an integer of 4 represents an integer.)

(B ¹ represents an organic group having 2 to 12 carbon atoms having at least one selected from a vinyl group, an epoxy group, an amino group, a mercapto group, an isocyanate group, a methacryl group, an acryl group, a ureido group and a cinnamoyl group, B ² represents a hydrogen atom or an alkyl group ^{having 1 to 5 carbon atoms, B 3} represents an alkyl group having 1 to 5 carbon atoms, m represents an integer of 1 or 2, n represents an integer of 0 to 2, p is 0 to 3 represents an integer of , where m + n + p represents an integer of 4.)

(D ¹ represents a hydrogen atom or an alkyl group ^{having 1 to 5 carbon atoms, D 2} represents an alkyl group having 1 to 5 carbon atoms, and n represents an integer of 0 to 3) The method of claim 1,
The liquid crystal display element in which the said liquid-crystal aligning agent contains the at least 1 solvent chosen from the group which consists of N-methyl- 2-pyrrolidone, N-ethyl- 2-pyrrolidone, and (gamma)-butyrolactone. The method of claim 1,
The said liquid-crystal aligning agent from the group which consists of 1-hexanol, cyclohexanol, 1,2-ethanediol, 1,2-propanediol, propylene glycol monobutyl ether, ethylene glycol monobutyl ether, and dipropylene glycol dimethyl ether A liquid crystal display element containing at least one solvent selected. The method of claim 1,
The liquid crystal display element in which the said liquid-crystal aligning agent contains the at least 1 solvent chosen from the group which consists of a solvent shown by cyclopentanone, cyclohexanone, and a following formula [S1] - a formula [S3].

(Wherein [S1] of, T ¹ represents an alkyl group having a carbon number of 1 to 3, formula [S2] of, T ² represents an alkyl group having a carbon number of 1 to 3, formula [S3] in, T ³ is a group having from 1 to 4 carbon atoms represents an alkyl group of The method of claim 1,
The liquid crystal display element in which the said liquid-crystal aligning agent contains the at least 1 sort(s) of generator chosen from the group which consists of a photo-radical generator, a photo-acid generator, and a photobase generator. The method of claim 1,
The liquid crystal display element in which the said liquid-crystal aligning agent contains the at least 1 compound chosen from the group which consists of a compound which has a structure shown by following formula [M1] - a formula [M8].

(In formula [M4], W ¹ represents a hydrogen atom or a benzene ring, in formula [M7], W ² represents at least one cyclic group selected from a benzene ring, a cyclohexane ring and a heterocyclic ring, and W ³ represents 1 type selected from a C1-C18 alkyl group, a C1-C18 fluorine-containing alkyl group, a C1-C18 alkoxy group, and a C1-C18 fluorine-containing alkoxy group) The method of claim 1,
The liquid-crystal aligning agent is an epoxy group, an isocyanate group, an oxetane group, a cyclocarbonate group, a hydroxyl group, a hydroxyalkyl group, and a compound having at least one substituent selected from the group consisting of a lower alkoxyalkyl group containing two or more liquid crystal display device. The method of claim 1,
The liquid crystal display element in which the said board|substrate is a plastic board|substrate. The liquid crystal aligning film used for the liquid crystal display element in any one of Claims 1-15. The liquid-crystal aligning agent for forming the liquid crystal aligning film of Claim 16.