TWI771380B - Compound, liquid crystal composition and liquid crystal display element - Google Patents

Abstract

式中之記號之定義係如說明書記載之所述。[Subject] The present invention is to provide a liquid crystal display device, which is characterized by high vertical alignment of the liquid crystal and good optical properties, that is, the transparency when no voltage is applied and the scattering properties when the voltage is applied are good, and the liquid crystal layer and the The liquid crystal alignment film has high adhesion, and can maintain these properties even in an environment of high temperature, high humidity or exposure to light for a long time. [Solution] The object of the present invention is achieved by using the compound of the following formula [1a] as a liquid crystal composition for a liquid crystal display element,

The definitions of the symbols in the formula are as described in the description.

Description

Compound, liquid crystal composition and liquid crystal display element

The present invention relates to a novel compound, a liquid crystal composition comprising the compound, and a transmission-scattering liquid crystal display element obtained by using the liquid crystal composition.

Liquid crystal display elements of TN (Twisted Nematic) mode have been put into practical use. In this mode, light switching is performed by utilizing the optical rotatory properties of the liquid crystal, so it is necessary to use a polarizing plate. When a polarizing plate is used, the utilization efficiency of light becomes low. As a liquid crystal display element that does not use a polarizing plate, it is known to switch between the transparent state (also known as the transparent state) and the scattering state of the liquid crystal, and there is a polymer dispersed liquid crystal (also known as PDLC (Polymer Dispersed Liquid Crystal)). Or polymer network liquid crystal (also known as PNLC (Polymer Network Liquid Crystal).

In these liquid crystal display elements, a liquid crystal composition containing a polymerizable compound polymerized by ultraviolet rays is disposed between a pair of substrates provided with electrodes. By curing the liquid crystal composition by irradiation with ultraviolet rays, a complex with the cured product (eg, polymer network) of the liquid crystal and the polymerizable compound can be formed. In such a liquid crystal display element, the transmission state and the scattering state of the liquid crystal are controlled by applying a voltage.

Conventional liquid crystal display elements using PDLC or PNLC are mostly in a cloudy (scattering) state because the liquid crystal molecules are oriented in random directions when no voltage is applied. It transmits and becomes a transmissive state (such a liquid crystal display element is also called a normal type element). However, in normal type elements, in order to obtain the transparent state, it is necessary to apply a voltage frequently. Therefore, for applications that are often used in the transparent state, such as the use of window glass, the power consumption will change. big. On the other hand, there has been proposed a liquid crystal display element (also referred to as a reverse type element) using PDLC that is in a transmissive state when no voltage is applied and in a scattering state when a voltage is applied (refer to Patent Documents 1 and 2). . [Prior Art Literature] [Patent Literature]

[Patent Document 1] Japanese Patent No. 2885116 [Patent Document 2] Japanese Patent No. 4132424

The polymerizable compound in the liquid crystal composition forms a polymer network to obtain desired optical properties, and has functions to improve the liquid crystal layer (the composite of the aforementioned liquid crystal and the cured product of the polymerizable compound) and the liquid crystal. The function of the adhesion of the alignment film. The liquid crystal alignment film used in the reverse type element is a film with high hydrophobicity in order to align liquid crystal vertically, so there is a problem that the adhesion between the liquid crystal layer and the liquid crystal alignment film is low. In order to improve the adhesion, it is necessary to make the polymer network denser, so it is necessary to introduce many polymerizable compounds into the liquid crystal composition of the reverse element. However, if the polymer network is made dense, the vertical alignment of the liquid crystal will be hindered, and the transparency of the reverse type element when no voltage is applied and the scattering characteristics of the applied voltage will be deteriorated. Therefore, the polymerizable compound used in the liquid crystal composition of the reverse element must be one that improves the vertical alignment of the liquid crystal when forming the liquid crystal layer.

Furthermore, the reverse type element is used by being attached to the window glass of automobiles or buildings, so even in severe environments such as prolonged exposure, high temperature and high humidity, or exposure to light, the liquid crystal will The vertical alignment will not decrease, and the adhesion between the liquid crystal layer and the liquid crystal alignment film must be high. So far, no liquid crystal display element under such conditions has been found.

The present invention aims to provide a liquid crystal with high vertical alignment and good optical properties, that is, good transparency when no voltage is applied and good scattering properties when voltage is applied, and furthermore, the adhesion between the liquid crystal layer and the liquid crystal alignment film Therefore, even in an environment of long time, high temperature and high humidity, or exposure to light, a liquid crystal display element that can maintain these characteristics is intended.

The present inventors have completed the present invention having the following gist as a result of intensive research in order to achieve the aforementioned object. That is, the present invention is applicable to the following 1 to 16 of the liquid crystal composition of the liquid crystal display element.

1. A compound of the following formula [1a] (hereinafter, also referred to as a specific compound), characterized by:

T ¹ represents a structure selected from the following formulas [2-1a] to [2-7a]; T ² represents a straight-chain or branched alkylene group having 2 to 18 carbon atoms, and T 1 and T ¹ and Any -CH ₂ - of the aforementioned alkylene groups that are not adjacent to T ³ may be -O-, -CO-, -COO-, -OCO-, -CONH-, -NHCO-, -NH-, benzene ring or Cyclohexane ring substitution; T ³ represents a structure selected from the following formula [1-1b] ~ formula [1-4b]; T ⁴ represents a single bond or an alkylene group with 1 to 24 carbon atoms, and T ³ Any -CH ₂ - of the aforementioned non-adjacent alkylene groups can be -O-, -CO-, -COO-, -OCO-, -CONH-, -NHCO-, -NH-, -CON(CH ₃ )-, -S- or -SO ₂ - substituted; T ⁵ represents a bivalent cyclic group selected from benzene ring, cyclohexane ring and heterocyclic ring or 2 of carbon number 17-51 with steroid skeleton A valence organic group, and any hydrogen atom on the aforementioned cyclic group can be an alkyl group with 1 to 3 carbon atoms, an alkoxy group with a carbon number of 1 to 3, a fluorine-containing alkyl group with a carbon number of 1 to 3, 1~3 fluorine-containing alkoxy groups or fluorine atoms; T ⁶ represents single bond, -O-, -OCH ₂ -, -CH ₂ O-, -COO- or -OCO-; T ⁷ represents selected from benzene A cyclic group in a ring, a cyclohexane ring and a heterocyclic ring, and any hydrogen atom on these cyclic groups can be an alkyl group with 1 to 3 carbon atoms, an alkoxy group with a carbon number of 1 to 3, or an alkoxy group with a carbon number of 1 to 3. 1~3 fluorine-containing alkyl group, 1~3 carbon number fluorine-containing alkoxy group or fluorine atom substitution; T ⁸ represents the carbon number 1~18 alkyl group, the carbon number 2~18 alkenyl group, the carbon number 1 ~18 fluorine-containing alkyl group, carbon number 1~18 alkoxy group or carbon number 1~18 fluorine-containing alkoxy group; mT represents an integer from 1 to 4; nT represents an integer from 0 to 4.

^WA represents a hydrogen atom or a benzene ring.

T ^B represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.

2. The compound according to 1, wherein the compound of the aforementioned formula [1a] is the following formula [1b] or [1c].

Each of T ⁹ , T ¹¹ , T ¹⁷ and T ¹⁹ represents a structure selected from the aforementioned formulas [2-1a] to [2-7a], and T ¹⁰ and T ¹⁸ represent a straight chain having 2 to 12 carbon atoms. Or branched alkylene, T ¹² and T ²⁰ represent structures selected from the aforementioned formula [1-1b] ~ formula [1-4b], T ¹³ and T ²¹ represent a single bond or carbon number 1～8 The alkyl group, T ¹⁴ and T ¹⁵ represent a benzene ring or a cyclohexane ring, T ¹⁶ represents an alkyl group or an alkoxy group with a carbon number of 1 to 12, and T ²² represents a steroid skeleton with a carbon number of 17 to 51 The divalent organic group, pT represents an integer from 0 to 4.

3. A liquid crystal composition containing at least one compound selected from the group consisting of formula [1a], formula [1b], and formula [1c].

4. A liquid crystal display element comprising a liquid crystal layer, and the liquid crystal layer is cured by irradiating ultraviolet rays to a liquid crystal composition comprising a liquid crystal and a polymerizable compound disposed between a pair of substrates having electrodes, and the substrate is At least one of them is provided with a liquid crystal alignment film that aligns liquid crystals vertically.

The liquid crystal composition contains at least one compound selected from the group consisting of the aforementioned formula [1a], formula [1b], and formula [1c].

5. The liquid crystal display element according to 4, wherein the liquid crystal composition comprises the compound of the following formula [2a].

W ¹ represents a structure selected from the following formula [2-1a] to formula [2-7a], W ² represents a single bond, -O-, -COO- or -OCO-; W ³ represents a single bond Or alkylidene with carbon number 1~12; W ⁴ represents single bond, -O-, -COO- or -OCO-, W ⁵ represents benzene ring, cyclohexane ring or carbon number 17~ with steroid skeleton Divalent organic group of 51, W ⁶ represents a single bond, -CH ₂ -, -CH ₂ O-, -OCH ₂ -, -O-, -COO-, -OCO-, -NHCO- or -CONH- , W ⁷ represents a benzene ring or a cyclohexane ring, W ⁸ represents an alkyl group with a carbon number of 1 to 18, an alkenyl group with a carbon number of 2 to 18, a fluorine-containing alkyl group with a carbon number of 1 to 18, and a carbon number of 1 to 18. For the alkoxy group of 18 or the fluorine-containing alkoxy group having 1 to 18 carbon atoms, mW represents an integer of 0 to 4.

^WA represents a hydrogen atom or a benzene ring.

6. The liquid crystal display element according to 4 or 5, wherein the liquid crystal alignment film is obtained from a liquid crystal alignment treatment agent comprising a polymer having a side chain structure of the following formula [4-1a] or formula [4-2a] Liquid crystal alignment film.

X ¹ and X ³ each represent a single bond, -(CH ₂ ) _a - (a is an integer of 1 to 15), -O-, -CH ₂ O-, -COO- or -OCO-; X ² represents Single bond or -(CH ₂ ) _b - (b is an integer from 1 to 15); X ⁴ represents a divalent cyclic group selected from a benzene ring, a cyclohexane ring and a heterocyclic ring or a carbon with a steroid skeleton A divalent organic group of 17-51, and any hydrogen atom on the aforementioned cyclic group can be an alkyl group with 1-3 carbon atoms, an alkoxy group with 1-3 carbon atoms, or a group containing 1-3 carbon atoms. A fluoroalkyl group, a fluorine-containing alkoxy group having 1 to 3 carbon atoms or a fluorine atom is substituted; X ⁵ represents at least one cyclic group selected from a benzene ring, a cyclohexane ring and a heterocyclic ring, and these Any hydrogen atom on the cyclic group can be an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, or a fluorine-containing alkyl group having 1 to 3 carbon atoms. Oxygen or fluorine atom substitution; X ⁶ represents alkyl with 1-18 carbons, alkenyl with 2-18 carbons, fluorine-containing alkyl with 1-18 carbons, alkoxy with 1-18 carbons or Fluorine-containing alkoxy with 1-18 carbon atoms; n is an integer of 0-4.

X ⁷ represents a single bond, -O-, -CH ₂ O-, -CONH-, -NHCO-, -CON(CH ₃ )-, -N(CH ₃ )CO-, -COO- or -OCO-; X ⁸ represents an alkyl group having 8 to 18 carbon atoms or a fluorine-containing alkyl group having 6 to 18 carbon atoms.

7. The liquid crystal display element according to 6, wherein the liquid crystal alignment treatment agent is selected from the group consisting of acrylic polymers, methacrylic polymers, phenolic resins, polyhydroxystyrene, polyimide precursors, polyimide, polyimide At least one of amide, polyester, cellulose and polysiloxane.

8. The liquid crystal display element according to 7, wherein the liquid crystal alignment treatment agent comprises a polyimide precursor obtained by the reaction of a diamine component and a tetracarboxylic acid component or the polyimide precursor is imidized The said diamine component contains the diamine which has the side chain structure of the said formula [4-1a] or formula [4-2a].

9. The liquid crystal display element according to 8, wherein the diamine having the side chain structure of the aforementioned formula [4-1a] or formula [4-2a] is represented by the following formula [4a].

X represents the structure of the aforementioned formula [4-1a] or formula [4-2a], and m represents an integer of 1 to 4.

10. The liquid crystal display element according to 8 or 9, wherein the tetracarboxylic acid component is a tetracarboxylic dianhydride of the following formula [5].

Z represents a structure selected from the following formulas [5a] to [51].

Each of Z ¹ to Z ⁴ represents a hydrogen atom, a methyl group, a chlorine atom or a benzene ring, and each of Z ⁵ and Z ⁶ represents a hydrogen atom or a methyl group.

11. The liquid crystal display element according to 7, wherein the liquid crystal alignment treatment agent comprises a polysiloxane obtained by polycondensation of an alkoxysilane of the following formula [A1], or a polysiloxane obtained by polycondensing an alkoxysilane of the formula [A1] Polysiloxane obtained by polycondensation of silane and alkoxysilane of the following formula [A2] and/or formula [A3].

A ¹ represents the structure of the aforementioned formula [4-1a] or formula [4-2a], 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, p represents an integer of 0 to 3, but m+n+p is 4.

B ¹ represents at least one organic group with 2 to 12 carbon atoms selected from vinyl, epoxy, amine, mercapto, isocyanate, methacrylic, acrylic, urea and cinnamyl groups , B ² represents a hydrogen atom or an alkyl group with 1 to 5 carbon atoms, B ³ represents an alkyl group with 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 2. Indicates an integer from 0 to 3, but m+n+p is 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.

12. The liquid crystal display element according to any one of claims 6 to 11, wherein the liquid crystal alignment agent contains a liquid crystal aligning agent having at least one structure selected from the following formulas [b-1] to [b-11] compound.

B ^A represents a hydrogen atom or a benzene ring, and B ^B to B ^D each represent an alkyl group having 1 to 5 carbon atoms.

13. The liquid crystal display element according to any one of 6 to 12, wherein the liquid crystal alignment agent contains at least one selected from the group consisting of an epoxy group, an isocyanate group, an oxetanyl group, a cyclic carbonate group, a hydroxyl group , hydroxyalkyl and lower alkoxyalkyl compounds.

14. The liquid crystal display element according to any one of 6 to 13, wherein the liquid crystal alignment treatment agent contains a monoethyl alcohol selected from the group consisting of 1-hexanol, cyclohexanol, 1,2-ethylene glycol, 1,2-propanediol, and propylene glycol At least one of butyl ether, ethylene glycol monobutyl ether, dipropylene glycol dimethyl ether, cyclohexanone, cyclopentanone, and the solvents of the following formulas [D1] to [D3].

D ¹ and D ² represent an alkyl group having 1 to 3 carbon atoms, and D ³ represents an alkyl group having 1 to 4 carbon atoms.

15. The liquid crystal display element according to 6 to 14, wherein the liquid crystal alignment treatment agent contains a compound selected from the group consisting of N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone and γ-butyrolactone At least 1 species.

16. The liquid crystal display element according to any one of 4 to 15, wherein the substrate is a plastic substrate.

According to the present invention, a good optical characteristic can be obtained, that is, the transparency when no voltage is applied and the scattering characteristic when voltage is applied are good, and the adhesion between the liquid crystal layer and the liquid crystal alignment film is high, so even for a long time. , High temperature and high humidity, or exposed to light in the environment, can still maintain these characteristics of the liquid crystal display element. Therefore, the liquid crystal display element of the present invention can be used as a reverse type element in a liquid crystal display for display purposes, a dimming window or a light shutter element for controlling the transmission and blocking of light.

[The best form of implementing the invention]

<Specific compound and liquid crystal composition> The specific compound is the compound of the aforementioned formula [1a]. In the formula, T ¹ to T ⁸ , mT and nT are as defined above, but among them, the following are preferred.

T1 system From the point of the adhesiveness of the liquid crystal layer of ^a liquid crystal display element, and a liquid crystal alignment film, Formula [2-1a] - Formula [2-4a] are preferable. Preferably it is the formula [2-1a] or the formula [2-2a]. T ² is preferably a straight-chain or branched alkylene with carbon number of 2 to 12, and any -CH ₂ - of the aforementioned alkylene where T ¹ and T ³ are not adjacent can be -O-, -CO -, -COO-, -OCO-, -CONH-, -NHCO- or -NH- substituted. It is preferably a linear or branched alkylene having 2 to 8 carbon atoms. The T ³ system is preferably the formula [1-1b], the formula [1-2b], or the formula [1-4b] from the viewpoint of the optical properties of the liquid crystal display element. Preferably it is the formula [1-1b] or the formula [1-2b].

T ⁴ is preferably a single bond or an alkylene group having 1 to 12 carbon atoms, and any -CH ₂ - of the aforementioned alkylene group that is not adjacent to T ³ can be -O-, -CO-, -COO-, -OCO-, -CONH-, -NHCO-, -NH-, -CON( _CH3 )-, -S- or _-SO2- substituted. Preferably it is a single bond or an alkylene group having 1 to 8 carbon atoms. ^The T5 series is preferably a divalent organic group having a carbon number of 17 to 51 having a benzene ring, a cyclohexane ring, or a steroid skeleton from the viewpoint of the optical properties of the liquid crystal display element. Preferably, T ⁶ is a single bond, -O-, -COO- or -OCO-. A single bond is preferred. T ⁷ series is preferably a benzene ring or a cyclohexane ring from the viewpoint of the optical properties of the liquid crystal display element.

T ⁸ is preferably an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, or an alkoxy group having 1 to 18 carbon atoms in terms of optical properties of the liquid crystal display element. Preferably, it is an alkyl group having 1 to 12 carbon atoms or an alkoxy group having 1 to 12 carbon atoms. In terms of the adhesion between the liquid crystal layer of the liquid crystal display element and the liquid crystal alignment film, mT is preferably 2 to 4. Preferably it is 2. nT is preferably 0~3. Preferably it is 0~2.

The synthesis method of the specific compound is not particularly limited, but for example, the isocyanate compound of the following formula [TA] and the compound of the following formula [TA-1] to [TA-5] can be prepared under an alkaline catalyst. Heat to synthesize.

T ¹ and T ² are the same as those defined by the formula [1a].

T ⁴ to T ⁸ and nT are the same as those defined by the formula [1a], and T ^a represents an alkyl group having 1 to 3 carbon atoms.

The specific compound is preferably a compound of the following formula [1b] or [1c].

T ⁹ , T ¹¹ , T ¹⁷ and T ¹⁹ each represent the structures of the aforementioned formulas [2-1a] to [2-7a], in which the adhesion between the liquid crystal layer of the liquid crystal display element and the liquid crystal alignment film is In terms of formula [2-1a]~formula [2-4a], preferably formula [2-1a] or formula [2-2a], T ¹⁰ and T ¹⁸ represent a straight line with 2 to 12 carbon atoms. Chain or branched alkylene, among them, straight-chain or branched alkylene having 2 to 8 carbon atoms is preferred.

T ¹² and T ²⁰ represent the structures of the aforementioned formulas [1-1b] to [1-4b]. Among them, the formula [1-1b], the formula [1-2b], or the formula [1-4b] is preferable in terms of the optical properties of the liquid crystal display element. Preferably it is the formula [1-1b] or the formula [1-2b]. T ¹³ and T ²¹ represent a single bond or an alkylene group having 1 to 8 carbon atoms. T ¹⁴ and T ¹⁵ each represent a benzene ring or a cyclohexane ring.

T ¹⁶ represents an alkyl group or an alkoxy group having 1 to 12 carbon atoms. Among them, in terms of the optical properties of the liquid crystal display element, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, or an alkoxy group having 1 to 18 carbon atoms is preferable. Preferably, it is an alkyl group having 1 to 12 carbon atoms or an alkoxy group having 1 to 12 carbon atoms. ^T22 represents a divalent organic group having a carbon number of 17 to 51 having a steroid skeleton. pT represents an integer from 0 to 4. Among them, 0 to 3 are preferred. Preferably it is 0~2.

Specific examples of the specific compounds of the formula [1b] and the formula [1c] include the following formulae [1a-1] to [1a-16], but these are preferably used.

T ^A represents a structure selected from formula [1-1b]~formula [1-4b], T ^B represents a single bond, -O-, -COO- or -OCO-, and T ^C represents carbon number 1~ Alkyl of 12 or alkoxy of carbon number 1-12, p1 and p2 represent integers from 0 to 7, p1+p2 represent integers from 1 to 7, p3 represents integers from 0 to 8, and p4 represents 0 An integer of ~2, p5, p6, and p7 each represent an integer of 0 to 6, and p5+p6+p7 is an integer of 1 to 6.

TD represents a structure selected from the formula [ ^1-1b ]~formula [ ^1-4b ], TE represents a single bond, -O-, -COO- or -OCO-, and ^TF represents a single bond, -CH ₂ -, -O-, -COO- or -OCO-, ^TG represents an alkyl group with a carbon number of 1~12 or an alkoxy group with a carbon number of 1~12, p8 and p9 represent an integer of 0~7, p8 +p9 represents an integer from 1 to 7, p10 represents an integer from 0 to 8, p11, p12 and p13 each represent an integer from 0 to 6, and p11+p12+p13 represents an integer from 1 to 6.

^TH represents a structure selected from formula [1-1b]~formula [ ^1-4b ], TI represents a single bond, -O-, -COO- or -OCO-, p14 and p15 represent 0~ An integer of 7, p14+p15 represents an integer from 1 to 7, p16 represents an integer from 0 to 8, p17, p18 and p19 each represent an integer from 0 to 6, and p17+p18+ p19 represents an integer from 1 to 6.

Specific examples of the specific compounds of the formula [1b] and the formula [1c] are preferably the formula [1a-5], the formula [1a-7], the formula [1a-11], and the formula [1a-15], in terms of liquid crystal display From the viewpoint of the optical properties of the element, the formula [1a-5], the formula [1a-7], or the formula [1a-15] is particularly preferable.

Regarding the optical properties of the liquid crystal display element, the use ratio of the specific compound is preferably 1 to 40 parts by mass relative to 100 parts by mass of the liquid crystal in the liquid crystal composition. Preferably it is 1-30 mass parts. It is especially preferable that it is 1-15 mass parts. In addition, a specific compound can be used by mixing 1 type or 2 or more types according to each characteristic. The specific compound of the present invention can be used not only as a component of the liquid crystal composition of the liquid crystal display element of the present invention, but also as a component of the liquid crystal composition of other liquid crystal display elements.

The liquid crystal composition used for the liquid crystal display element of the present invention contains a liquid crystal, a polymerizable compound, and the specific compound of the aforementioned formula [1a]. Among the liquid crystals, a nematic liquid crystal, a smectic liquid crystal, or a cholesteric liquid crystal can be used. Among them, those having negative dielectric anisotropy are preferred. In addition, in terms of low-voltage driving and scattering characteristics, it is preferable that the anisotropy of the dielectric constant is large and the anisotropy of the refractive index is large. In addition, in the liquid crystal, two or more kinds of liquid crystals may be mixed and used according to the above-mentioned physical property values of the inversion temperature, dielectric anisotropy, and refractive index anisotropy.

In order to drive a liquid crystal display element as an active element such as a TFT (Thin Film Transistor), it is required that the liquid crystal has a high resistance and a high voltage holding ratio (also referred to as VHR). Therefore, as a liquid crystal, it is preferable to use a fluorine-based or chlorine-based liquid crystal which has a high resistance and does not lower the VHR by active energy rays such as ultraviolet rays.

The liquid crystal display element can also be used as a guest-host type element by dissolving a dichroic dye in a liquid crystal composition. In this case, an element that is transparent when no voltage is applied and absorbs (scatters) when a voltage is applied can be obtained. In addition, in this liquid crystal display element, the direction of the director of the liquid crystal (the direction of alignment) is changed by 90 degrees depending on the presence or absence of an applied voltage. Therefore, by utilizing the difference in the light absorption characteristics of the dichroic dyes, this device can obtain a higher contrast ratio than the conventional guest-host type device in which random alignment and vertical alignment are switched. In addition, in the guest-host type element in which the dichroic dye is dissolved, when the liquid crystal is aligned 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 switches from colorless and transparent when no voltage is applied to a state of colored opaque, colored and transparent according to an applied voltage.

In the formation of the polymer network, the polymerizable compound can be introduced into the liquid crystal composition and subjected to a polymerization reaction by irradiation with ultraviolet rays during the production of the liquid crystal display element, or the polymerizable compound can be subjected to a polymerization reaction in advance and made to undergo a polymerization reaction. The obtained polymer was introduced into the liquid crystal composition. However, even in the case of a polymer, it is necessary to have a site where the polymerization reaction proceeds by irradiation with ultraviolet rays. It is preferable to introduce a polymerizable compound into the liquid crystal composition in terms of the handling of the liquid crystal composition (ie, suppression of high viscosity of the liquid crystal composition or solubility in liquid crystal), and to display the liquid crystal composition. It is preferable to irradiate the ultraviolet rays during the fabrication of the device to make it polymerize to form a polymer network.

The polymerizable compound in the liquid crystal composition is not particularly limited as long as it can be dissolved in the liquid crystal. When the polymerizable compound is dissolved in the liquid crystal, the temperature at which the liquid crystal phase is displayed is a part or the whole of the liquid crystal composition. as necessary. Even when a part of the liquid crystal composition exhibits a liquid crystal phase, the liquid crystal display element may be confirmed with the naked eye, and the transparency and scattering properties in the entire element can be obtained substantially the same.

The polymerizable compound may be any compound as long as it is polymerized by ultraviolet rays, and in this case, the polymer network may be formed by polymerizing in any reaction form. Specific reaction forms include radical polymerization, cationic polymerization, anionic polymerization, or polyaddition reaction. Among them, the reaction form of the polymerizable compound is preferably radical polymerization from the viewpoint of the optical properties of the liquid crystal display element. In this case, as the polymerizable compound, the following radical-type polymerizable compound or the oligomer can be used. Moreover, as mentioned above, the polymer obtained by carrying out a polymerization reaction of these polymerizable compounds can also be used.

Specific examples of these radical-type polymerizable compounds or the oligomers include the radical-type polymerizable compounds described on pages 69 to 71 of International Publication No. 2015/146987 (published on October 1, 2015). . The use ratio of the radical type polymerizable compound or the oligomer is based on the adhesiveness of the liquid crystal layer of the liquid crystal display element and the liquid crystal alignment film, relative to 100 parts by mass of the liquid crystal in the liquid crystal composition, 70~ 120 parts by mass is preferred. Preferably it is 80-110 mass parts. Moreover, these radical type polymerizable compounds can be used 1 type or 2 or more types according to each characteristic.

In order to promote the formation of the aforementioned polymer network and to promote the radical polymerization of the polymerizable compound, it is preferable to introduce a radical initiator (also called a polymerization initiator) that generates radicals by ultraviolet rays into the liquid crystal composition. agent). Specifically, the radical initiators described in pages 71 to 72 of International Publication No. 2015/146987 (published on October 1, 2015) can be mentioned. The use ratio of the radical initiator is preferably 0.01 to 10 parts by mass relative to 100 parts by mass of the liquid crystal in the liquid crystal composition in terms of the adhesion between the liquid crystal layer of the liquid crystal display element and the liquid crystal alignment film. , and preferably 0.05 to 5 parts by mass. In addition, as for the radical initiator, one type or two or more types can be used according to each characteristic.

In the liquid crystal composition used in the liquid crystal display element of the present invention, in order to improve the optical properties of the liquid crystal display element, especially the transparency, it is preferable to introduce a compound of the following formula [2a] (also called an additive compound), especially , preferably used together with specific compounds.

W ¹ represents a structure selected from the following formulas [2-1a] to [2-7a], W ² represents a single bond, -O-, -COO- or -OCO-, and W ³ represents a single bond Or alkylidene with carbon number 1~12, W ⁴ represents single bond, -O-, -COO- or -OCO-, W ⁵ represents benzene ring, cyclohexane ring or carbon number 17~ with steroid skeleton Divalent organic group of 51, W ⁶ represents a single bond, -CH ₂ -, -CH ₂ O-, -OCH ₂ -, -O-, -COO-, -OCO-, -NHCO- or -CONH- , W ⁷ represents a benzene ring or a cyclohexane ring, W ⁸ represents an alkyl group with a carbon number of 1 to 18, an alkenyl group with a carbon number of 2 to 18, a fluorine-containing alkyl group with a carbon number of 1 to 18, and a carbon number of 1 to 18. For the alkoxy group of 18 or the fluorine-containing alkoxy group having 1 to 18 carbon atoms, mW represents an integer of 0 to 4.

^WA represents a hydrogen atom or a benzene ring.

More specifically, as the compound of the above-mentioned formula [2a], the compounds of the following formulae [2a-1] to [2a-6] are exemplified, and from the viewpoint of the optical properties of the liquid crystal display element, these compounds are used. It is better to wait.

W ^A represents a single bond, -O-, -COO- or -OCO-, W ^B represents an alkyl group with 1 to 12 carbon atoms or an alkoxy group with 1 to 12 carbon atoms, and p1 represents an integer from 1 to 8 , p2 represents an integer from 0 to 2.

W ^C means single bond, -O-, -COO- or -OCO-, W ^D means single bond, -CH ₂ -, -O-, -COO- or -OCO-, W ^E means carbon number 1 The alkyl group of ~12 or the alkoxy group of carbon number 1~12, p3 is an integer of 1~8.

^WF represents a single bond, -O-, -COO- or -OCO-, and p4 represents an integer from 0 to 8.

As the compound of the formula [2a], the formula [2a-1], the formula [2a-2], the formula [2a-7], or the formula [2a-8] in terms of the optical properties of the liquid crystal display element is good. Preferably it is the formula [2a-1] or the formula [2a-2].

From the viewpoint of the optical properties of the liquid crystal display element, the use ratio of the additive compound is preferably 1 to 30 parts by mass relative to 100 parts by mass of the liquid crystal in the liquid crystal composition. Preferably it is 1-20 mass parts, Most preferably, it is 1-15 mass parts. In addition, the additive compound system can be used by mixing 1 type or 2 or more types according to each characteristic.

<Polymer> In the liquid crystal alignment film in the liquid crystal display element of the present invention, a liquid crystal alignment treatment agent comprising a polymer having a specific side chain structure of the following formula [4-1a] or formula [4-2a] is used The obtained liquid crystal alignment film is preferred.

X ¹ represents a single bond, -(CH ₂ ) _a - (a is an integer of 1 to 15), -O-, -CH ₂ O-, -COO- or -OCO-. Among them, in terms of the availability of raw materials or the ease of synthesis. A single bond, -(CH ₂ ) _a - (a is an integer of 1 to 15), -O-, -CH ₂ O- or -COO- is preferable. Preferably it is a single bond, -(CH ₂ ) _a - (a is an integer of 1 to 10), -O-, -CH ₂ O- or -COO-. X ² represents a single bond or -(CH ₂ ) _b - (b is an integer of 1 to 15). Among them, a single bond or -(CH ₂ ) _b - (b is an integer of 1 to 10) is preferred.

X ³ represents a single bond, -(CH ₂ ) _a - (a is an integer of 1 to 15), -O-, -CH ₂ O-, -COO- or -OCO-. Among them, a single bond, -(CH ₂ ) _a - (a is an integer of 1 to 15), -O-, -CH ₂ O- or -COO- is preferable in terms of ease of synthesis. Preferably it is a single bond, -(CH ₂ ) _a - (a is an integer of 1 to 10), -O-, -CH ₂ O- or -COO-. X ⁴ represents a bivalent cyclic group selected from a benzene ring, a cyclohexane ring and a heterocyclic ring or a bivalent organic group with a carbon number of 17 to 51 having a steroid skeleton, any hydrogen on the aforementioned cyclic group The atomic system may be substituted with an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxy group having 1 to 3 carbon atoms, or a fluorine atom. Among them, in terms of ease of synthesis, a benzene ring, a cyclohexane ring, or an organic group having a carbon number of 17 to 51 having a steroid skeleton is preferable.

X ⁵ represents a cyclic group selected from a benzene ring, a cyclohexane ring and a heterocyclic ring, and any hydrogen atom on these cyclic groups can be an alkyl group with 1 to 3 carbon atoms, or an alkyl group with 1 to 3 carbon atoms. The alkoxy group, the fluorine-containing alkyl group with 1 to 3 carbon atoms, the fluorine-containing alkoxy group with 1 to 3 carbon atoms, or the fluorine atom is substituted. Among them, a benzene ring or a cyclohexane ring is preferable.

X ⁶ represents an alkyl group with 1 to 18 carbon atoms, an alkenyl group with a carbon number of 2 to 18, a fluorine-containing alkyl group with a carbon number of 1 to 18, an alkoxy group with a carbon number of 1 to 18, or an alkoxy group with a carbon number of 1 to 18. Fluoroalkoxy. Among them, an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having a carbon number of 1 to 10, an alkoxy group having a carbon number of 1 to 18, or a fluorine-containing alkoxy group having a carbon number of 1 to 10 are preferred. Preferably, it is an alkyl group having 1 to 12 carbon atoms or an alkoxy group having 1 to 12 carbon atoms. Particularly preferred is an alkyl group having 1 to 9 carbon atoms or an alkoxy group having 1 to 9 carbon atoms. n represents an integer from 0 to 4. Among them, 0 to 3 are preferred in terms of availability of raw materials or ease of synthesis. Preferably it is 0~2.

Preferred combinations of X ¹ to X ⁶ and n include (2-1) to Tables 6 to 47 on pages 13 to 34 of International Publication WO2011/132751 (published on October 27, 2011). (2-629). Furthermore, in each table of the International Publication, X ¹ to X ⁶ in the present invention are represented as Y1 to Y6, but Y1 to Y6 can be interpreted as X ¹ to X ⁶ . In addition, in (2-605) to (2-629) published in the respective tables of the International Publication, the organic group having 17 to 51 carbon atoms of a steroid skeleton in the present invention is represented as having 12 carbon atoms of a steroid skeleton. The organic group of ~25, but the organic group having the carbon number of 12 to 25 of the steroid skeleton can be interpreted as the organic group of the carbon number of 17 to 51 of the steroid skeleton.

Among them, (2-25)~(2-96), (2-145)~(2-168), (2-217)~(2-240), (2-268)~(2-315), A combination of (2-364)~(2-387), (2-436)~(2-483) or (2-603)~(2-615) is preferred. Preferably (2-49)~(2-96), (2-145)~(2-168), (2-217)~(2-240), (2-603)~(2-606) , (2-607)~(2-609), (2-611), (2-612) or (2-624) are the best combinations.

X ⁷ represents a single bond, -O-, -CH ₂ O-, -CONH-, -NHCO-, -CON(CH ₃ )-, -N(CH ₃ )CO-, -COO- or -OCO-, Among them, single bond, -O-, -CH ₂ O-, -CONH-, -CON(CH ₃ )- or -COO- is preferred, preferably single bond, -O-, -CONH- or -COO- , X ⁸ represents an alkyl group with a carbon number of 8-18 or a fluorine-containing alkyl group with a carbon number of 6-18, among which, an alkyl group with a carbon number of 8-18 is preferred.

The specific side chain structure in the present invention is as described above, and the formula [4-1a] is preferable in that a high and stable vertical alignment of the liquid crystal can be obtained.

The specific polymer with specific side chain structure is not limited, but can be selected from acrylic polymer, methacrylic polymer, novolac resin, polyhydroxystyrene, polyimide precursor, polyimide A polymer of at least one of amine, polyamide, polyester, cellulose and polysiloxane is preferred. Also preferred is a polyimide precursor, polyimide or polysiloxane. When a polyimide precursor or polyimide (also collectively referred to as a polyimide-based polymer) is used in a specific polymer, these are polyimide obtained by reacting a diamine component with a tetracarboxylic acid component An imine precursor or polyimide is preferred.

The so-called polyimide precursor has a structure of the following formula [A].

R ¹ represents a tetravalent organic group, R ² represents a divalent organic group, A ¹ and A ² each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and A ³ and A ⁴ represent each independently A hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or an acetyl group, and n represents a positive integer.

As a diamine component, the diamine which has two primary or secondary amine groups in a molecule|numerator is mentioned. As the tetracarboxylic acid component, a tetracarboxylic acid compound, a tetracarboxylic dianhydride, a tetracarboxylic acid dihalide compound, a tetracarboxylic acid dialkyl ester compound, or a tetracarboxylic acid dialkyl ester dihalide compound can be mentioned.

The polyimide-based polymer is obtained by using the tetracarboxylic dianhydride of the following formula [B] and the diamine of the following formula [C] as raw materials, and for the reason that it can be obtained relatively easily, the following Preferably, the polyamic acid composed of the structural formula of the repeating unit of the formula [D] or the polyimide obtained by imidizing the polyamic acid is preferred.

R ¹ and R ² are the same as those defined by the formula [A].

R ¹ and R ² are the same as those defined by the formula [A].

In addition, according to a general synthesis method, into the polymer of the formula [D] obtained above, the alkyl group having 1 to 8 carbon atoms of A ¹ and A ² of the formula [A] and the alkyl group of the formula [A] can also be introduced The carbon number of A ³ and A ⁴ is an alkyl group or an acetyl group with 1 to 5 carbon atoms.

<Specific side chain type diamine> As a method of introducing a specific side chain structure into a polyimide-based polymer, it is preferable to use a diamine having a specific side chain structure in a part of the raw material, especially The diamine of the following formula [4a] (also referred to as a specific side chain type diamine) is preferable.

X represents the structure of the aforementioned formula [4-1a] or formula [4-2a]. In addition, in the formula [4-1a], the detailed and preferred combination of X ¹ , X ² , X ³ , X ⁴ , X ⁵ , X ⁶ and n is the same as the aforementioned formula [4-1a], the formula [ The detailed and preferred combination of X ⁷ and X ⁸ in 4-2a] is the same as the aforementioned formula [4-2a]. m is an integer of 1 to 4, and among them, 1 is preferred. In the present invention, as described above, it is preferable to use a specific side chain type diamine having a specific side chain structure of the formula [4-1a] from the viewpoint of the vertical alignment of the liquid crystal.

Specific examples of the specific side chain type diamine having the specific side chain structure of the formula [4-1a] include the formula [2] described on pages 15 to 19 of International Publication WO2013/125595 (published on August 29, 2013). The diamine compound of -1] to formula [2-6] and formula [2-9] to formula [2-36]. In addition, in the records of International Publication WO2013/125595, R 2 in formula [2-1] ~ formula [2-3] and R ₄ in formula [ _2-4 ] ~ formula [2-6] represent carbon 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. In addition, A ₄ in the formula [2-13] represents a linear or branched alkyl group having 3 to 18 carbon atoms. In addition, R ₃ in formula [2-4] to formula [2-6] represents -O-, -CH ₂ O-, -COO-, and -OCO-.

Among them, the preferred diamines are the formulas [2-1] to [2-6], the formulas [2-9] to [2-13] or the formulas [2-22] described in International Publication WO2013/125595. ] ~ formula [2-31]. From the viewpoint of the optical properties of the liquid crystal display element, diamines of the following formulae [4a-32] to [4a-41] are also preferred.

R ¹ and R ² represent an alkyl group having 3 to 12 carbon atoms.

R ³ and R ⁴ represent an alkyl group having 3 to 12 carbon atoms, and the cis-trans isomerism of the 1,4-cyclohexylene group is a trans isomer.

Particularly preferred are diamines of formula [4a-35] to formula [4a-37], formula [4a-40], or formula [4a-41] from the viewpoint of the optical properties of the liquid crystal display element.

Specific examples of the specific side chain type diamine having the specific side chain structure of the aforementioned formula [4-2a] include the formula [DA1]～described on page 23 of International Publication WO2013/125595 (published on August 29, 2013). The compound of the diamine of formula [DA11]. In addition, in the description of this International Publication WO2013/125595, A ₁ in the formulae [DA1] to [DA5] represents an alkyl group having 8 to 22 carbon atoms or a fluorine-containing alkyl group having 6 to 18 carbon atoms.

The use ratio of the specific side chain diamine is preferably 10-80 mol% relative to the entire diamine component in terms of the optical properties of the liquid crystal display element and the adhesion between the liquid crystal layer and the liquid crystal alignment film. Preferably it is 20-70 mol%. Moreover, the specific side chain type diamine system can be used by mixing 1 type or 2 or more types according to each characteristic.

<Second diamine> It is preferable that the diamine (also referred to as the second diamine) of the following formula [4b] is contained as a diamine component for producing the polyimide polymer.

Y ¹ represents a single bond, -O-, -NH-, -N(CH ₃ )-, -CH ₂ O-, -CONH-, -NHCO-, -CON(CH ₃ )-, -N(CH ₃ )CO-, -COO- or -OCO-, wherein single bond, -O-, -CH ₂ O-, -CONH-, -COO- or -OCO- is preferred, in terms of the availability of raw materials or the ease of synthesis In terms of degree, it is preferably a single bond, -O-, -CH ₂ O- or -COO-.

Y ² represents an organic group with a carbon number of 6 to 24 selected from a single bond, an alkylene group having 1 to 18 carbon atoms or a cyclic group in a benzene ring, a cyclohexane ring and a heterocyclic ring. Any of the above hydrogen atoms can be an alkyl group with 1-3 carbon atoms, an alkoxy group with a carbon number of 1-3, a fluorine-containing alkyl group with a carbon number of 1-3, a fluorine-containing alkoxy group with a carbon number of 1-3, or Substituted with fluorine atom, among them, single bond, alkylene with 1-12 carbon atoms, benzene ring or cyclohexane ring are preferred, and in terms of the adhesion between the liquid crystal layer and the liquid crystal alignment film, single bond or carbon The number 1 to 12 of the extended alkyl group.

Y ³ represents a single bond, -O-, -NH-, -N(CH ₃ )-, -CH ₂ O-, -CONH-, -NHCO-, -CON(CH ₃ )-, -N(CH ₃ )CO-, -COO- or -OCO-, wherein, a single bond, -O-, -COO- or -OCO- is preferred, preferably a single bond or -OCO-, Y ⁴ is represented by the following formula The structure in [4b-a]~formula [4b-i], formula [4b-a]~formula [4b-f] is better, wherein, formula [4b-a]~formula [4b-e] is better, In terms of the adhesion between the liquid crystal layer and the liquid crystal alignment film, formula [4b-a], formula [4b-b], formula [4b-d] or formula [4b-e] is preferable.

Y ^A is a hydrogen atom or a benzene ring, and m is an integer of 1 to 4, wherein 1 or 2 is preferred. n represents an integer from 1 to 4, wherein 1 is preferred.

Specific examples of the second diamine include the following formulae [4b-1] to [4b-12], and these are preferably used.

n1 represents an integer from 2 to 12.

n2 represents an integer from 0 to 12, and n3 represents an integer from 2 to 12.

Specific examples of the second diamine, wherein the formula [4b-1], the formula [4b-2], the formula [4b-5] to the formula [4b-7], the formula [4b-11], or the formula [4b- 12] is better. Preferably it is the formula [4b-5] to the formula [4b-7], the formula [4b-11], or the formula [4b-12].

In terms of the optical properties of the liquid crystal display element and the adhesion between the liquid crystal layer and the liquid crystal alignment film, the use ratio of the second diamine is preferably 10 to 70 mol % relative to the entire diamine component. 20-60 mol% is better. Moreover, the 2nd diamine can be used by mixing 1 type or 2 or more types according to each characteristic.

<Third diamine> It is also preferable that the diamine (also referred to as the third diamine) of the following formula [4c] is contained as a diamine component for producing the polyimide polymer.

W represents a structure selected from the following formulas [4c-a] to [4c-d], and m represents an integer of 1 to 4, wherein 1 is preferable.

a represents an integer from 0 to 4, where 0 or 1 is preferred in terms of availability of raw materials or ease of synthesis, and b represents an integer from 0 to 4, where availability of raw materials or ease of synthesis In terms of degree, 0 or 1 is preferred, ^WA and WB each represent an alkyl group having ¹ to 12 carbon atoms, and ^WC represents an alkyl group having 1 to 5 carbon atoms.

Specific examples of the third diamine include the following. For example, 2,4-dimethyl-m-phenylenediamine, 2,6-diaminotoluene, 2,4-diaminophenol, 3,5-diaminophenol, 3,5-diaminobenzyl Alcohol, 2,4-diaminobenzyl alcohol, 4,6-diaminoresorcinol, 2,4-diaminobenzoic acid, 2,5-diaminobenzoic acid, 3,5-diamine benzoic acid. In addition, the diamine of following formula [4c-1] and [4c-2] is mentioned.

Specific examples of the third diamine include 2,4-diaminophenol, 3,5-diaminophenol, 3,5-diaminobenzyl alcohol, 2,4-diaminobenzyl alcohol, 4 ,6-diaminoresorcinol, 2,4-diaminobenzoic acid, 2,5-diaminobenzoic acid, 3,5-diaminobenzoic acid, formula [4c-1] or formula [ The diamine of 4c-2] is preferred. 2,4-diaminophenol, 3,5-diaminophenol, 3,4-diaminophenol, 3,5-diaminophenol, 3, 5-diaminobenzyl alcohol, 3,5-diaminobenzoic acid or formula [2a-1].

Diamines other than the above-mentioned diamines (also referred to as other diamines) may be used as the diamine component system for producing the polyimide-based polymer. Specifically, other diamine compounds described on pages 27 to 30 of International Publication WO2015/012368 (published on January 29, 2015) and the formula [DA1] described on pages 30 to 32 of the same publication can be mentioned. ~ The diamine compound of formula [DA14]. Moreover, according to each characteristic, other diamine type can be used by mixing 1 type or 2 or more types.

<Tetracarboxylic acid component> As the tetracarboxylic acid component for preparing the polyimide polymer, tetracarboxylic dianhydride of the following formula [5], or tetracarboxylic acid, tetracarboxylic acid, and tetracarboxylic acid derivative thereof are used. A carboxylic acid dihalide compound, a tetracarboxylic acid dialkyl ester compound, or a tetracarboxylic acid dialkyl ester dihalide compound (also collectively referred to as a specific tetracarboxylic acid component) is preferable.

Z represents a structure selected from the following formulas [5a] to [51].

Each of Z ¹ to Z ⁴ represents a hydrogen atom, a methyl group, a chlorine atom or a benzene ring, and each of Z ⁵ and Z ⁶ represents a hydrogen atom or a methyl group.

Among them, in the formula [5], Z is represented by the formula [5a], the formula [5c], the formula [5d], the formula [ 5e], formula [5f], formula [5g], formula [5k] or formula [5l] are preferred. The formula [5a], the formula [5e], the formula [5f], the formula [5g], the formula [5k], or the formula [5l] is preferred, and the formula is particularly preferred in terms of optical properties in the liquid crystal display element. [5a], formula [5e], formula [5f], formula [5g], or formula [5l].

The use ratio of the specific tetracarboxylic acid component is preferably 1 mol % or more, preferably 5 mol % or more, and particularly preferably 10 mol % or more with respect to the total tetracarboxylic acid component. From the viewpoint of the optical properties of the liquid crystal display element, 10 to 90 mol % is optimal.

In the polyimide-based polymer, other tetracarboxylic acid components other than the specific tetracarboxylic acid component can be used as long as the effects of the present invention are not impaired. Examples of other tetracarboxylic acid components include tetracarboxylic acid compounds, tetracarboxylic dianhydrides, tetracarboxylic acid dihalide compounds, tetracarboxylic acid dialkyl ester compounds, and dialkyl ester dihalide compounds shown below. compound.

Specifically, other tetracarboxylic acid components described in pages 34 to 35 of International Publication WO2015/012368 (published on January 29, 2015) can be mentioned. A specific tetracarboxylic-acid component and other tetracarboxylic-acid components can be used by mixing 1 type or 2 or more types according to each characteristic. The method of synthesizing the polyimide-based polymer is not particularly limited. Usually, it can be obtained by making a diamine component and a tetracarboxylic-acid component react. Specifically, the method described in pages 35 to 36 of International Publication WO2015/012368 (published on January 29, 2015) can be mentioned.

<Polyimide-based polymer and its production> The reaction system of the diamine component and the tetracarboxylic acid component is usually carried out in a solvent containing the diamine component and the tetracarboxylic acid component. What is necessary is to dissolve the produced polyimide precursor, which is not particularly limited. Specific examples include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, γ- Butyrolactone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethylsulfoxide or 1,3-dimethyl-imidazolidinone, etc., and if polyamide When the solvent solubility of the imine precursor is high, methyl ethyl ketone, cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone or the following formulas [D1]~ can be used [D3] solvent.

D ¹ and D ² represent an alkyl group having 1 to 3 carbon atoms, and D ³ represents an alkyl group having 1 to 4 carbon atoms. These can be used alone or in combination, and even if they are insoluble The solvent of the polyimide precursor can be mixed with the above-mentioned solvent as long as the polyimide precursor is not precipitated. Moreover, the moisture in the organic solvent hinders the polymerization reaction, and further Since it becomes the cause of hydrolyzing the produced polyimide precursor, it is preferable to use the organic solvent which has been dehydrated and dried.

Polyimide is a polyimide obtained by ring-closing the polyimide precursor, and the ring-closure rate of the amide group in the polyimide (also known as the rate of imidization) does not have to be 100. %, according to the application or purpose, can be adjusted arbitrarily. Among them, 30 to 80% of the polyimide-based polymer is preferably 30 to 80% in terms of solubility in a solvent and the like. Preferably it is 40~70%.

The molecular weight of the polyimide-based polymer, when considering the strength of the liquid crystal alignment film obtained here, the workability during the formation of the liquid crystal alignment film, and the film coating properties, is determined by GPC (Gel Permeation Chromatography) method Mw ( The weight average molecular weight) is preferably 5,000 to 1,000,000, more preferably 10,000 to 150,000.

<Production of polysiloxane-based polymer> When polysiloxane is used in a specific polymer, a polysiloxane obtained by polycondensation of an alkoxysilane of the following formula [A1], or a polysiloxane of the formula The alkoxysilane of [A1] is compared with the polysiloxane (also collectively referred to as polysiloxane-based polymer) obtained by polycondensation of the alkoxysilane of the following formula [A2] and/or formula [A3] good.

The alkoxysilane of formula [A1]:

A ¹ represents the structure of the aforementioned formula [4-1a] or formula [4-2a], and X ¹ , X ² , X ³ , X ⁴ , X ⁵ , X ⁶ and n in the formula [4-1a] The detailed and preferred combination is as described in the aforementioned formula [4-1a], and the detailed and preferred combination of X ⁷ and X ⁸ in the formula [4-2a] is as described in the aforementioned formula [4-2a] Among them, the structure of formula [4-1a] is preferable in terms of obtaining high and stable vertical alignment of liquid crystals, and A ² represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, wherein , a hydrogen atom or an alkyl group with a carbon number of 1 to 3 is preferred, A ³ represents an alkyl group with a carbon number of 1 to 5, wherein, in terms of the reactivity of condensation polymerization, the alkyl group with a carbon number of 1 to 3 is good.

m is an integer representing 1 or 2. Among them, 1 is preferable in terms of ease of synthesis. n represents an integer from 0 to 2. p represents an integer from 0 to 3. Among them, p is preferably 1 to 3, and more preferably 2 or 3, in terms of the reactivity of the polycondensation polymerization. m+n+p is 4.

Specific examples of the alkoxysilanes of the formula [A1] include the formulas [2a-1] to [2a-32] described on pages 17 to 21 of International Publication WO2015/008846 (published on January 22, 2015). The alkoxysilane, wherein the alkoxylate of formula [2a-9] ~ formula [2a-21], formula [2a-25] ~ formula [2a-28] or formula [2a-32] in the same publication The alkoxysilane is preferable, and the alkoxysilane of the formula [A1] can be used in combination of one or two or more types according to each characteristic.

Alkoxysilane of formula [A2]:

B ¹ represents an organic group with 2 to 12 carbon atoms having at least one selected from the group consisting of vinyl, epoxy, amine, mercapto, isocyanate, methacrylic, acrylic, ureido, and cinnamyl groups, Among them, the organic group having a vinyl group, an epoxy group, an amino group, a methacrylic group, an acrylic group, or a urea group is preferable in terms of easy availability. It is preferably an organic group with methacrylic acid group, acrylic acid group or urea group, B ² represents a hydrogen atom or an alkyl group with 1 to 5 carbon atoms, wherein, a hydrogen atom or an alkyl group with 1 to 3 carbon atoms is preferred, B ³ represents an alkyl group having 1 to 5 carbon atoms, and among them, an alkyl group having 1 to 3 carbon atoms is preferable from the viewpoint of the reactivity of polycondensation polymerization.

m is an integer representing 1 or 2. Among them, an integer of 1 is preferable from the viewpoint of the easiness of synthesis. n represents an integer from 0 to 2. p represents an integer from 0 to 3. Among them, p is preferably an integer of 1 to 3, and preferably 2 or 3, from the viewpoint of the reactivity of the polycondensation polymerization. m+n+p is 4.

Specific examples of the alkoxysilanes of the formula [A2] include specific examples of the alkoxysilanes of the formula [2b] described on pages 21 to 24 of International Publication WO2015/008846 (published on January 22, 2015). Among them, allyltriethoxysilane, allyltrimethoxysilane, diethoxymethylvinylsilane, dimethoxymethylvinylsilane, triethoxyvinylsilane, vinyl Trimethoxysilane, Vinyl(2-methoxyethoxy)silane, 3-(triethoxysilyl)propyl methacrylate, 3-(trimethoxysilyl)propyl acrylate , 3-(trimethoxysilyl)propyl methacrylate, 3-glycidyloxypropyl(dimethoxy)methylsilane, 3-glycidyloxypropyl(diethoxy) ) methylsilane, 3-glycidyloxypropyltrimethoxysilane or 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane are preferred. The alkoxysilanes of the formula [A2] can be used in combination of one or two or more kinds according to each characteristic.

The alkoxysilane of formula [A3]:

D ¹ represents a hydrogen atom or an alkyl group with a carbon number of 1-5, wherein, a hydrogen atom or an alkyl group with a carbon number of 1-3 is preferred, and D ² represents an alkyl group with a carbon number of 1-5, wherein the abbreviation In terms of the reactivity of the polymerization, an alkyl group having 1 to 3 carbon atoms is preferable, and n represents an integer of 0 to 3.

Specific examples of the alkoxysilanes of the formula [A3] include specific examples of the alkoxysilanes of the formula [2c] described on pages 24 to 25 of International Publication WO2015/008846 (published on January 22, 2015).

Moreover, in formula [A3], as the alkoxysilane in which n is 0, tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, or tetrabutoxysilane can be mentioned as formula [A3] It is preferable to use these alkoxysilanes as the alkoxysilanes. The alkoxysilanes of the formula [A3] can be used in combination of one or two or more types according to each characteristic.

The polysiloxane-based polymer is a polysiloxane obtained by polycondensing the alkoxysilane of the formula [A1], or the alkoxysilane of the formula [A1] and the alkoxysilane of the formula [A2] and/or the formula [A3] The polysiloxane obtained by polycondensation of the alkoxysilane. That is, the polysiloxane-based polymer is a polysiloxane obtained by polycondensation of only the alkoxysilane of the formula [A1], and the alkoxysilane of the formula [A1] and the two types of the formula [A2]. Polysiloxane obtained by polycondensation, polysiloxane obtained by polycondensation of two alkoxysilanes of formula [A1] and formula [A3], and polysiloxane of formula [A1], formula [A2] and formula [A3] Any one of the polysiloxanes obtained by polycondensation of the three kinds of alkoxysilanes in [A3] is preferred.

Among them, polysiloxanes obtained by polycondensation of various alkoxysilanes are preferred in terms of the reactivity of polycondensation polymerization and the solubility of polysiloxane-based polymers to solvents. That is, polysiloxane obtained by polycondensation of two kinds of alkoxysilanes of formula [A1] and formula [A2], and two kinds of alkoxysilanes of formula [A1] and formula [A3] are polycondensed Any one of polysiloxane obtained by polymerization and polysiloxane obtained by polycondensation of three kinds of alkoxysilanes of formula [A1], formula [A2] and formula [A3] is preferred.

When multiple alkoxysilanes are used in the production of polysiloxane-based polymers, the proportion of the alkoxysilanes of the formula [A1] used is 1 to 40 moles in all the alkoxysilanes. % is better, preferably 1-30 mol%. In addition, the use ratio of the alkoxysilane of the formula [A2] is preferably 1-70 mol %, more preferably 1-60 mol % in the total alkoxysilane. Furthermore, the usage ratio of the alkoxysilane of the formula [A3] is preferably 1 to 99 mol %, and more preferably 1 to 80 mol % in the total alkoxysilane.

The method of polycondensing the polysiloxane-based polymer is not particularly limited. Specifically, the method described in pages 26 to 29 of International Publication WO2015/008846 (published on January 22, 2015) can be mentioned.

In the polycondensation reaction for the production of polysiloxane-based polymers, if multiple alkoxysilanes of formula [A1], formula [A2] or formula [A3] are used, even if multiple alkoxysilanes that have been mixed in advance are used A mixture of silanes may be used for the reaction, or a plurality of alkoxysilanes may be sequentially added to perform the reaction.

In the present invention, the solution of the polysiloxane-based polymer obtained by the aforementioned method can be used as it is as a specific polymer, or the solution of the polysiloxane-based polymer obtained by the aforementioned method can be concentrated as required. It can be used as a specific polymer by substituting a solution or adding a solvent and diluting it with another solvent.

The solvent used for the dilution (also referred to as the addition solvent) may be the solvent used for the polycondensation reaction or other solvents. The addition solvent is not particularly limited as long as the polysiloxane-based polymer can be dissolved uniformly, and one or two or more of them can be arbitrarily selected. Examples of the additive solvent include ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and the like, methyl acetate, ethyl acetate, ethyl lactate, and the like, in addition to the solvent used in the aforementioned polycondensation reaction. Ester solvent.

Furthermore, when a polysiloxane-based polymer and other polymers are used in the specific polymer, it is preferable to carry out the treatment under normal pressure or before mixing the other polymers into the polysiloxane-based polymer. The alcohol produced when the polysiloxane-based polymer was subjected to the polycondensation reaction was distilled off under reduced pressure.

<Liquid crystal alignment treatment agent> The liquid crystal alignment treatment agent in the present invention is a solution for forming a liquid crystal alignment film, and contains a specific polymer having the specific side chain structure of the aforementioned [4-1a] or formula [4-2a] and Solvent solutions are preferred. All of the polymer components in the liquid crystal aligning agent may be a specific polymer, or a polymer other than that may be mixed. In this case, the content of the polymer other than that is 0.5 to 15 parts by mass, preferably 1 to 10 parts by mass, with respect to 100 parts by mass of the specific polymer. As a polymer other than this, the said polymer which does not have the specific side chain structure of Formula [4-1a] or Formula [4-2a] is mentioned.

The content of the solvent in the liquid crystal aligning agent can be appropriately selected from the viewpoint of the coating method of the liquid crystal aligning agent or the obtainment of the intended film thickness. Among them, from the viewpoint of forming a uniform vertical liquid crystal alignment film by coating, the content of the solvent in the liquid crystal alignment treatment agent is preferably 50-99.9 mass %, preferably 60-99 mass %, It is especially preferable that it is 65-99 mass %.

<Solvent> The solvent used in the liquid crystal aligning agent is not particularly limited as long as it can dissolve the specific polymer. Among them, if the specific polymer is polyimide precursor, polyimide, polyimide or polyester, or, acrylic polymer, methacrylic polymer, phenolic resin, polyhydroxystyrene, cellulose Or when the solubility to a solvent of polysiloxane is low, it is preferable to use the solvent (it is also called solvent A type) as shown below.

For example N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, dimethylsulfoxide , γ-butyrolactone, 1,3-dimethyl-imidazolidinone, methyl ethyl ketone, cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone, etc. Among them, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone or γ-butyrolactone is preferably used. In addition, these systems may be used individually or in mixture.

If the specific polymer is acrylic polymer, methacrylic polymer, phenolic resin, polyhydroxystyrene, cellulose or polysiloxane, further, if the specific polymer is polyimide precursor, polyimide , polyamide, or polyester, and when the solubility of these specific polymers to solvents is high, the following solvents (also referred to as solvent B) can be used.

Specific examples of the solvent type B include the type of solvent described on pages 58 to 60 of International Publication WO2014/171493 (published on October 23, 2014). Among them, 1-hexanol, cyclohexanol, 1,2-ethylene glycol, 1,2-propanediol, propylene glycol monobutyl ether, ethylene glycol monobutyl ether, dipropylene glycol dimethyl ether, cyclohexane are used. Ketone, cyclopentanone or the solvent of the aforementioned formula [D1] to [D3] are preferred.

In addition, when these solvents B are used, for the purpose of improving the coating properties of the liquid crystal alignment agent, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone or N-ethyl-2-pyrrolidone of solvent A is used together with Gamma-butyrolactone is preferred. Preferably, it is used together with γ-butyrolactone.

These type B solvents can improve the coating properties and surface smoothness of the liquid crystal alignment film when the liquid crystal alignment treatment agent is applied. Therefore, if a polyimide precursor, polyimide, In the case of polyamide or polyester, it is preferable to use it together with the aforementioned solvent A. In this case, the solvent B type is preferably 1 to 99 mass % of the entire solvent contained in the liquid crystal aligning agent, and among them, 10 to 99 mass %, and 20 to 95 mass %.

<Specific compound A> The liquid crystal aligning agent has at least one selected from the following formulas [b-1] to [b-11] from the viewpoint of the optical properties of the liquid crystal display element. Compounds (also referred to as specific compounds (A)) are preferred.

B ^A represents a hydrogen atom or a benzene ring. ^BB ~ ^BD represents an alkyl group having 1 to 5 carbon atoms.

Specific examples of the specific compound A include compounds of the following formula [b-1a] to [b-24a], and these are preferred.

k1 represents an integer from 1 to 12, wherein, in terms of the optical characteristics of the liquid crystal display element, 1 to 8 is preferred, and k2 represents an integer from 0 to 4, in which, in terms of the optical characteristics of the liquid crystal display element In terms of, preferably 1 or 2, Ka represents ^a single bond, -O-, -CH ₂ O-, -CONH-, -NHCO-, -CON(CH ₃ )-, -N(CH ₃ )CO -, -COO- or -OCO-, among them, -O- or -COO- is preferred in terms of availability of raw materials and ease of synthesis.

K ^b represents an alkyl group with 1 to 18 carbon atoms, a fluorine-containing alkyl group with a carbon number of 1 to 18, an alkoxy group with a carbon number of 1 to 18 or a fluorine-containing alkoxy group with a carbon number of 1 to 18. An alkyl group having 1 to 12 carbon atoms or an alkoxy group having 1 to 8 carbon atoms is preferable, and an alkyl group having 1 to 8 carbon atoms or an alkoxy group is preferable.

k3 represents an integer from 1 to 12, among which, 1 to 8 is preferable in terms of the optical characteristics of the liquid crystal display element, and K ^c represents a single bond, -(CH ₂ ) _c - (c is 1 to 15 Integer), -O-, -CH ₂ O-, -COO- or -OCO-, among which, -COO- or -OCO- is preferred in terms of availability of raw materials or ease of synthesis; K ^d represents a single bond, -O-, -CH ₂ O-, -CONH-, -NHCO-, -CON(CH ₃ )-, -N(CH ₃ )CO-, -COO- or -OCO-, Among them, -O- or -COO- is preferable in terms of availability of raw materials and ease of synthesis.

K ^e represents an alkyl group with 1-18 carbon atoms, a fluorine-containing alkyl group with a carbon number of 1-18, an alkoxy group with a carbon number of 1-18 or a fluorine-containing alkoxy group with a carbon number of 1-18, wherein the carbon Preferably, an alkyl group having 1 to 12 carbons or an alkoxy group having 1 to 12 carbons is preferred, and preferably an alkyl group having 1 to 8 carbons or an alkoxy group having 1 to 8 carbons.

k4 represents an integer from 0 to 4, among which, in terms of the optical properties of the liquid crystal display element, 1 or 2 is preferred; K ^f represents an alkyl group with 1 to 18 carbon atoms, and a group containing 1 to 18 carbon atoms. Fluoroalkyl, alkoxy with 1-18 carbons or fluorine-containing alkoxy with 1-18 carbons, among them, alkyl with 1-12 carbons or alkoxy with 1-12 carbons is preferred, Preferably, it is an alkyl group having 1 to 8 carbon atoms or an alkoxy group having 1 to 8 carbon atoms.

k5 represents an integer from 1 to 12, among which, in terms of the optical characteristics of the liquid crystal display element, 1 to 8 is preferred, and k6 represents an integer from 0 to 4, in which, in terms of the optical characteristics of the liquid crystal display element In terms of 1 or 2, K ^g represents an alkyl group with 1 to 18 carbon atoms, a fluorine-containing alkyl group with a carbon number of 1 to 18, an alkoxy group with a carbon number of 1 to 18, or an alkyl group with 1 to 18 carbon atoms. Fluorine-containing alkoxy group, wherein, an alkyl group with 1-12 carbon atoms or an alkoxy group with a carbon number of 1-12 is preferred, preferably an alkyl group with 1-8 carbon atoms or an alkoxy group with 1-8 carbon atoms base.

K ^h represents a single bond, -(CH ₂ ) _c - (c is an integer from 1 to 15), -O-, -CH ₂ O-, -COO- or -OCO-, wherein the availability of raw materials or In terms of the ease of synthesis, -COO- or -OCO- is preferred, and K ⁱ represents an alkyl group with 1 to 18 carbon atoms, a fluorine-containing alkyl group with 1 to 18 carbon atoms, and an alkyl group with 1 to 18 carbon atoms. Alkoxy or fluorine-containing alkoxy with carbon number 1-18, wherein, alkyl group with carbon number 1-12 or alkoxy group with carbon number 1-12 is preferred, preferably alkyl group with carbon number 1-8 or an alkoxy group with 1 to 8 carbon atoms.

k7 represents an integer from 1 to 12, among which, in terms of the optical characteristics of the liquid crystal display element, 1 to 8 is preferred, K ^j represents a single bond, -(CH ₂ ) _c - (c is 1 to 15 Integer), -O-, -CH ₂ O-, -COO- or -OCO-, among them, -COO- or -OCO- is preferred in terms of availability of raw materials or ease of synthesis.

K ^k represents an alkyl group with 1 to 18 carbon atoms, a fluorine-containing alkyl group with a carbon number of 1 to 18, an alkoxy group with a carbon number of 1 to 18, or a fluorine-containing alkoxy group with a carbon number of 1 to 18. Preferably, an alkyl group having 1 to 12 carbons or an alkoxy group having 1 to 12 carbons is preferred, and preferably an alkyl group having 1 to 8 carbons or an alkoxy group having 1 to 8 carbons.

Among them, specific examples of the specific compound A are formula [b-1a], formula [b-2a], formula [b-7a], formula [b-8a], formula [b-10a], formula [b-11a] , formula [b-13a], formula [b-14a], formula [b-16a] or formula [b-17a] is preferable.

The usage ratio of the specific compound (A) in the liquid crystal alignment agent is preferably 0.1-30 parts by mass, preferably 0.5-30 parts by mass relative to 100 parts by mass of the specific polymer in terms of the optical properties of the liquid crystal display element 20 parts by mass, particularly preferably 1 to 10 parts by mass. Moreover, you may mix and use 1 type or 2 or more types according to each characteristic of a specific compound A type|system|group.

<Specific cross-linking compound> In order to improve the film strength of the resin film in the liquid crystal alignment treatment agent, a compound having a compound selected from the group consisting of epoxy group, isocyanate group, oxetanyl group, cyclic carbonate group, hydroxyl group, and hydroxyalkyl group is introduced. and a compound having at least one group of lower alkoxyalkyl groups (also collectively referred to as a specific crosslinkable compound) is preferable. In this case, it is necessary to have two or more of these groups in the compound.

Specific examples of the crosslinkable compound having an epoxy group or an isocyanate group include the crosslinking compound having an epoxy group or an isocyanate group described in pages 63 to 64 of International Publication WO2014/171493 (published on October 23, 2014). Linking compounds.

Specific examples of the crosslinkable compound having an oxetanyl group include formulas [4a] to [4k] disclosed on pages 58 to 59 of International Publication WO2011/132751 (published on October 27, 2011). cross-linking compound.

Specific examples of the crosslinkable compound having a cyclic carbonate group include formula [5-1] to formula [5- 42] the cross-linking compound.

Specific examples of the crosslinkable compound having a hydroxyl group, a hydroxyalkyl group and a lower alkoxyalkyl group include the melamine derivatives described in International Publication No. 2014/171493 (published on October 23, 2014) on pages 65 to 66 or A benzoguanamine derivative, and the crosslinkable compound of the formula [6-1] to the formula [6-48] disclosed on pages 62 to 66 of International Publication WO2011/132751 (published on October 27, 2011).

The content of the specific crosslinkable compound in the liquid crystal aligning agent is preferably 0.1 to 100 parts by mass relative to 100 parts by mass of the total polymer component. In order to advance the crosslinking reaction and exhibit the intended effect, the amount is preferably 0.1 to 50 parts by mass, particularly 1 to 30 parts by mass, relative to 100 parts by mass of the total polymer component.

<Specific generator> It is preferable to introduce at least one type of generator (also referred to as specific generator) selected from the group consisting of photoradical generators, photoacid generators and photobase generators in the liquid crystal alignment treatment agent. Specific examples of the specific generating agent include the specific generating agents described on pages 54 to 56 of International Publication No. 2014/171493 (published on October 23, 2014). Among the specific generators, photoradical generators are preferred in terms of the adhesion between the liquid crystal layer of the liquid crystal display element and the liquid crystal alignment film.

<Specific adhesion compound> In the liquid crystal alignment treatment agent, for the purpose of improving the adhesion between the liquid crystal layer of the liquid crystal display element and the vertical liquid crystal alignment film, a compound having a compound selected from the following formula [e-1] to formula [e- A compound having at least one structure in 8] (also referred to as a specific adhesive compound) is preferable.

EA represents a hydrogen atom or a benzene ring, ^EB represents a cyclic group selected from at least one selected from a benzene ring, a cyclohexane ring or a heterocyclic ring, and ^{E C represents} an alkyl group with 1 to 18 carbon atoms, a carbon number 1 to 18 fluorine-containing alkyl groups, 1 to 18 carbon atoms of alkoxy groups, or 1 to 18 of carbon atoms of fluorine-containing alkoxy groups.

Specific examples of the specific adhesive compound include compounds of formula [6] described in International Publication WO2015/012368 (published on January 29, 2015) on pages 43 to 46. Furthermore, the adhesive compounds described in pages 61 to 63 of International Publication WO2014/171493 (published on October 23, 2014) can also be used.

The content of the specific adhesive compound in the liquid crystal aligning agent is preferably 0.1 to 150 parts by mass relative to 100 parts by mass of the total polymer components. For the progress of the cross-linking reaction and the performance of the intended effect, it is relatively With respect to 100 parts by mass of the total polymer component, it is preferably 0.1 to 100 parts by mass, and particularly preferably 1 to 50 parts by mass.

In the liquid crystal alignment treatment agent, in order to promote the charge transfer in the liquid crystal alignment film and promote the charge release of the element, the formula [M1 ]~ The nitrogen-containing heterocyclic amine compound of formula [M156]. The amine compound can be directly added to the liquid crystal aligning agent, but it is preferably added later as a solution adjusted to a concentration of 0.1 to 10 mass %, preferably 1 to 7 mass % with an appropriate solvent. The solvent is not particularly limited as long as it is an organic solvent capable of dissolving the specific polymer.

<The compound that improves the uniformity of the film thickness or the surface smoothness of the liquid crystal alignment film> As the liquid crystal alignment treatment agent, as long as the effect of the present invention is not impaired, a film of the liquid crystal alignment film when the liquid crystal alignment treatment agent is coated can be used Thickness uniformity or surface smoothness enhancing compound. Furthermore, the compound etc. which improve the adhesiveness of a liquid crystal aligning film and a board|substrate can also be used.

As a compound which improves the uniformity and surface smoothness of the film thickness of a liquid crystal alignment film, a fluorine type surfactant, a polysiloxane type surfactant, a nonionic type surfactant, etc. are mentioned. Specifically, the surfactant described on page 67 of International Publication WO2014/171493 (published on October 23, 2014) can be mentioned. Moreover, the usage ratio is preferably 0.01 to 2 parts by mass, more preferably 0.01 to 1 part by mass, with respect to 100 parts by mass of all the polymer components contained in the liquid crystal aligning agent.

As a specific example of the compound which improves the adhesiveness of a liquid crystal alignment film and a board|substrate, the compound described in the international publication WO2014/171493 (2014.10.23 publication) 67-69 pages is mentioned. Moreover, the usage ratio is preferably 0.1-30 mass parts, preferably 1-20 mass parts with respect to 100 mass parts of all polymer components contained in a liquid crystal aligning agent. In addition to the compounds other than the above-mentioned compounds, the liquid crystal aligning agent may be added with a dielectric or conductive substance for the purpose of changing electrical properties such as permittivity and conductivity of the liquid crystal aligning film.

<Method for producing a liquid crystal alignment film and a liquid crystal display element> As a substrate used for a liquid crystal display element, there is no particular limitation as long as it is a substrate with high transparency. In addition to glass substrates, acrylic substrates, polycarbonate substrates, Plastic substrates such as PET (polyethylene terephthalate) substrates, and further such films can be used. When the device is used as a reverse-type device for a dimming window, etc., a plastic substrate or a film is preferred. In addition, from the viewpoint of simplification of the process, it is possible to use an electrode formed with an ITO (Indium Tin Oxide) electrode, an IZO (Indium Zinc Oxide) electrode, an IGZO (Indium Gallium Zinc Oxide) electrode, an organic conductive film, etc. for liquid crystal driving. Substrates are preferred. In addition, when making a reflective type inversion type element, if only one side of the substrate is required, a metal such as silicon wafer or aluminum, or a substrate formed with a dielectric multilayer film can be used.

In the liquid crystal display element, at least one of the substrates preferably has a liquid crystal alignment film such that liquid crystal molecules are vertically aligned. This liquid crystal alignment film can be obtained by applying a liquid crystal alignment treatment agent on a substrate and firing, and then performing alignment treatment by rubbing treatment, light irradiation, or the like. However, in the case of the liquid crystal alignment film in the present invention, it can be used as a liquid crystal alignment film even if the alignment treatment is not performed. The coating method of the liquid crystal alignment agent is not particularly limited, but in the industry, there are screen printing, offset printing, flexographic printing, inkjet method, dipping method, roll coating method, slit coating, The spinner method, the spray method, or the like can be appropriately selected according to the type of substrate and the thickness of the intended liquid crystal alignment film.

After the liquid crystal alignment treatment agent is coated on the substrate, it can be heated by a heating method such as a hot plate, a thermal cycle oven, an IR (infrared) oven, etc., depending on the type of the substrate or the solvent used in the liquid crystal alignment treatment agent. The solvent is evaporated at a temperature of ~300°C (preferably at 30 to 250°C) and then used as a liquid crystal alignment film. In particular, when a plastic substrate is used as the substrate, it is preferable to process at a temperature of 30-150°C.

If the thickness of the liquid crystal alignment film after firing is too thick, it will be disadvantageous in terms of power consumption of the liquid crystal display element, and if it is too thin, the reliability of the element may be reduced, so it is preferably 5 to 500 nm. It is preferably 10 to 300 nm, and particularly preferably 10 to 250 nm. The liquid crystal composition used in the liquid crystal display element is the same as the above-mentioned liquid crystal composition, but a spacer for controlling the electrode gap (also called the spacing) of the liquid crystal display element can also be introduced therein.

Although the injection method of a liquid crystal composition is not specifically limited, For example, the following method is mentioned. That is, when a glass substrate is used as the substrate, a pair of substrates on which a liquid crystal alignment film is formed is prepared, and a part of the four sides of the one-side substrate is removed, and then a sealant is applied, and thereafter, the surface of the liquid crystal alignment film is inwardly bonded to The other single-sided substrate is used to make an empty unit cell. Then, a method of obtaining a "liquid crystal composition-injected unit cell" by injecting a liquid crystal composition under reduced pressure from a place where the sealant is not applied can be exemplified. Furthermore, when a plastic substrate or a film is used as the substrate, a pair of substrates with a liquid crystal alignment film formed thereon is prepared, and a liquid crystal composition is dropped on one side of the substrate by the ODF (One Drop Filling) method or the inkjet method. After that, the method of laminating the other side of the substrate to obtain a "liquid crystal composition-injected unit cell". In the liquid crystal display element of the present invention, since the adhesion between the liquid crystal layer and the liquid crystal alignment film is high, it is unnecessary to apply a sealant on the four sides of the substrate.

The distance between the liquid crystal display elements can be controlled by the aforementioned spacers or the like. As the method described above, a method of introducing a spacer of the intended size into the liquid crystal composition, a method of using a substrate having a columnar spacer of the intended size, etc. are mentioned. In addition, if the substrates are made of plastic or film substrates and the substrates are laminated by lamination, the spacing can be controlled without introducing spacers.

The distance between the liquid crystal display elements is preferably 1 to 100 μm, more preferably 1 to 50 μm. Particularly preferred is 2 to 30 μm. If the pitch is too small, the contrast ratio of the element will be reduced, and if the pitch is too large, the driving voltage of the element will be increased.

The liquid crystal display element of the present invention is obtained by curing the liquid crystal composition in a state in which a part or the whole of the liquid crystal composition exhibits liquid crystallinity, and forming a cured product complex (liquid crystal layer) of the liquid crystal and the polymerizable compound. . The curing of the liquid crystal composition is performed by irradiating the above-mentioned "cell into which the liquid crystal composition is injected" with ultraviolet rays. As a light source of the ultraviolet irradiation apparatus used at this time, a metal halide lamp or a high-pressure mercury-vapor lamp is mentioned, for example. In addition, the wavelength of the ultraviolet rays is preferably 250 to 400 nm. Among them, 310-370 nm is preferable. Moreover, you may heat-process after irradiating an ultraviolet-ray. The temperature at this time is 40-120 degreeC, Preferably it is 40-80 degreeC. [Example]

Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited to these. The abbreviations used hereinafter are as follows.

"Compounds used in liquid crystal compositions" <Specific compounds>

<Additional compound>

<Liquid crystal> L1: MLC-6608 (manufactured by Merck)

<Polymerizable compound>

R3: BlemmerTA-604AU (manufactured by NOF Corporation)

<Radical Initiator>

"Compounds Used in Liquid Crystal Alignment Agents"

<Specific side chain type diamine>

<2nd Diamine>

<3rd Diamine>

<Other diamines>

<Specific tetracarboxylic acid component>

＜Monomers for producing polysiloxane-based polymers＞

E2: Octadecyltriethoxysilane E3: 3-Methacryloyloxypropyltrimethoxysilane E4: 3-Ureidopropyltriethoxysilane E5: Tetraethoxysilane

<Specific Compound A>

<Specific crosslinkable compound>

<Specific generator>

<Solvent> NMP: N-methyl-2-pyrrolidone γ-BL: γ-butyrolactone BCS: Ethylene glycol monobutyl ether PB: Propylene glycol monobutyl ether PGME: Propylene glycol monomethyl ether ECS: Ethylene glycol Glycol Monoethyl Ether

EC: Diethylene glycol monoethyl ether

"Molecular weight measurement of polyimide polymers"

The measurement was performed as follows using a room temperature gel permeation chromatography (GPC) apparatus (GPC-101) (manufactured by Showa Denko) and columns (KD-803, KD-805) (manufactured by Shodex).

Column temperature: 50℃

Elution solution: N,N'-dimethylformamide (additive: lithium bromide-hydrate (LiBr. H ₂ O): 30 mmol/L (liter), phosphoric acid. anhydrous crystal (o-phosphoric acid): 30 mmol/L , tetrahydrofuran (THF): 10ml/L)

Flow rate: 1.0ml/min

Standard samples for calibration line 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) ).

"Determination of imidization rate of polyimide polymers"

5(草野科學公司製))中，並添加氘化二甲基亞碸(DMSO-d6，0.05質量%TMS(四甲基矽烷)混合品)(0.53ml)，利用超音波使其完全地溶解。藉由NMR測定機(JNW-ECA500)(日本電子datum公司製)測定該溶液的500MHz的質子NMR。醯亞胺化率係將來自於醯亞胺化前後未變化之構造的質子作為基準質子，使用該質 子之波峰累積值、與在9.5ppm~10.0ppm附近所出現來自於醯胺酸的NH基之質子波峰累積值，藉由下述式而可求得。 Put 20 mg of polyimide powder into an NMR (nuclear magnetic resonance) sample tube (NMR sampling tube stand,

5 (manufactured by Kusano Science Co., Ltd.), deuterated dimethyl sulfite (DMSO-d6, 0.05 mass % TMS (tetramethylsilane) mixture) (0.53 ml) was added, and it was completely dissolved by ultrasonic . The 500 MHz proton NMR of this solution was measured by the NMR measuring machine (JNW-ECA500) (made by JEOL datum). The imidization rate is based on the proton derived from the unchanged structure before and after imidization as the reference proton, and the peak accumulation value of the proton and the NH group derived from the imidic acid appearing in the vicinity of 9.5 ppm to 10.0 ppm are used as the reference proton. The cumulative value of the proton peaks can be obtained by the following formula.

Imidization rate (%)=(1-α.x/y)×100

(x is the cumulative peak value of protons derived from the NH group of aramidic acid, y represents the peak cumulative value of the reference proton, and relative to aramidic acid when α is polyamide acid (imidation rate 0%) The ratio of the number of reference protons to 1 NH proton).

"Synthesis of Polyimide-Based Polymers"

<Synthesis example 1>

Mix D2 (2.13 g, 8.50 mmol), A1 (4.91 g, 12.9 mmol), C1 (0.98 g, 6.46 mmol) and F1 (0.23 g, 2.15 mmol) in NMP (28.7 g) and react at 80°C for 4 hours Then, D1 (2.50 g, 12.8 mmol) and NMP (14.3 g) were added, and it was made to react at 40 degreeC for 6 hours, and the polyamic acid solution (1) whose resin solid content concentration was 20 mass % was obtained. The number average molecular weight (also referred to as Mn) of the polyamic acid was 17,300, and the weight average molecular weight (also referred to as Mw) was 56,200.

<Synthesis example 2>

To the polyamic acid solution (1) (30.0 g) obtained by the method of Synthesis Example 1, NMP was added and diluted to 6 mass %, and then acetic anhydride (3.70 g) and pyridine were added as imidization catalysts. (2.30 g), and it was made to react at 60 degreeC for 2.5 hours. The reaction solution was poured into methanol (450 ml), and the resulting precipitate was collected by filtration. The precipitate was washed with methanol and dried under reduced pressure at 100°C to obtain a polyimide powder (2). The imidization rate of this polyimide was 52%, Mn was 15,400, and Mw was 41,500.

<Synthesis Example 3> D4 (1.52 g, 7.65 mmol), A2 (2.55 g, 6.46 mmol) and C1 (0.98 g, 6.46 mmol) were mixed with γ-BL (16.1 g), and reacted at 60°C for 4 hours Then, D1 (1.00 g, 5.10 mmol) and γ-BL (8.06 g) were added and reacted at 40° C. for 6 hours to obtain a polyamic acid solution (3) having a resin solid content concentration of 20 mass %. The Mn of the polyamide resin is 12,500 and the Mw is 41,300.

<Synthesis Example 4> D4 (1.52 g, 7.65 mmol), A2 (2.55 g, 6.46 mmol) and B1 (1.71 g, 6.46 mmol) were mixed with γ-BL (18.1 g), and reacted at 60°C for 4 hours Then, D1 (1.00 g, 5.10 mmol) and γ-BL (9.03 g) were added and reacted at 40° C. for 6 hours to obtain a polyamic acid solution (4) having a resin solid content concentration of 20 mass %. The Mn of the polyamide acid was 11,100 and the Mw was 37,600.

<Synthesis Example 5> Mix D4 (1.31 g, 6.63 mmol), A3 (2.03 g, 4.70 mmol), B2 (1.09 g, 5.37 mmol) and C1 (0.51 g, 3.36 mmol) in γ-BL (16.7 g) , after reacting at 60°C for 4 hours, D1 (1.30 g, 6.63 mmol) and γ-BL (8.33 g) were added and reacted at 40°C for 6 hours to obtain a polymer with a resin solid content concentration of 20% by mass. Amino acid solution (5). The Mn of the polyamide is 11,300 and the Mw is 39,100.

<Synthesis Example 6> D4 (1.01 g, 5.10 mmol), A4 (1.91 g, 3.87 mmol), B1 (0.68 g, 2.58 mmol), B2 (0.53 g, 2.58 mmol) and C1 (0.59 g, 3.87 mmol) were mixed After γ-BL (16.6 g) was reacted at 60°C for 4 hours, D1 (1.50 g, 7.65 mmol) and γ-BL (8.29 g) were added and reacted at 40°C for 6 hours to obtain a resin A polyamide solution (6) having a solid content concentration of 20% by mass. The Mn of the polyamide acid was 10,900, and the Mw was 36,900.

<Synthesis Example 7> D3 (1.71 g, 7.65 mmol), A4 (2.23 g, 4.52 mmol), B1 (1.54 g, 5.81 mmol) and C1 (0.39 g, 2.58 mmol) were mixed in γ-BL (18.3 g) , after reacting at 60°C for 4 hours, D1 (1.00 g, 5.10 mmol) and γ-BL (9.16 g) were added and reacted at 40°C for 6 hours to obtain a polymer with a resin solid content concentration of 20% by mass. Amino acid solution (7). The Mn of the polyamide acid was 10,500 and the Mw was 36,200.

<Synthesis Example 8> D3 (4.00 g, 17.8 mmol), A2 (4.28 g, 10.9 mmol) and B1 (1.91 g, 7.23 mmol) were mixed with NMP (40.8 g) and reacted at 40°C for 12 hours. A polyamic acid solution (8) having a resin solid content concentration of 20% by mass was obtained. The Mn of the polyamide acid was 18,200 and the Mw was 58,800.

<Synthesis Example 9> To the polyamic acid solution (8) (30.0 g) obtained by the method of Synthesis Example 8, NMP was added and diluted to 6% by mass, and then acetic anhydride as an imidization catalyst was added. (3.70g) and pyridine (2.30g) were made to react at 60 degreeC for 3 hours. The reaction solution was poured into methanol (450 ml), and the resulting precipitate was collected by filtration. The precipitate was washed with methanol and dried under reduced pressure at 100°C to obtain a polyimide powder (9). The imidization rate of this polyimide was 52%, Mn was 16,500, and Mw was 45,800.

<Synthesis Example 10> D4 (1.52 g, 7.65 mmol), A5 (2.43 g, 6.46 mmol) and C1 (0.98 g, 6.46 mmol) were mixed with γ-BL (15.8 g), and reacted at 60°C for 4 hours Then, D1 (1.00 g, 5.10 mmol) and γ-BL (7.91 g) were added and reacted at 40° C. for 6 hours to obtain a polyamic acid solution (10) having a resin solid content concentration of 20 mass %. The Mn of the polyamide acid was 10,900 and the Mw was 37,800.

Table 1 shows the polyimide-based polymers obtained in the synthesis examples. In addition, in Table 1, *1 represents polyamide.

"Synthesis of polysiloxane-based polymer"<Synthesis example 11> ECS (28.3 g), E1 (4.10 g), and E3 (7.45 g) were mixed in a 200-ml four-neck reaction flask equipped with a thermometer and a reflux tube. ) and E5 (32.5 g) to prepare a solution of the alkoxysilane monomer. To this solution, a solution prepared by mixing ECS (14.2 g), water (10.8 g), and oxalic acid (0.70 g) as a catalyst in advance was added dropwise at 25° C. for 30 minutes, and further stirred at 25° C. 30 minutes. Then, after heating with an oil bath and refluxing for 30 minutes, a mixed solution of a methanol solution (1.20 g) containing 92 mass % of E4 (1.10 g) prepared in advance and ECS (0.90 g) was added. Furthermore, after making it reflux for 30 minutes, and standing to cool, the polysiloxane solution (1) whose _SiO2 conversion density|concentration is 12 mass % can be obtained.

<Synthesis Example 12> EC (29.2 g), E1 (4.10 g) and E5 (38.8 g) were mixed in a 200 ml four-necked reaction flask equipped with a thermometer and a reflux tube to prepare a mixture of alkoxysilane monomers. solution. To this solution, a solution prepared by mixing EC (14.6 g), water (10.8 g), and oxalic acid (0.50 g) as a catalyst in advance was added dropwise at 25° C. for 30 minutes, and further stirred at 25° C. 30 minutes. Then, after heating with an oil bath and refluxing for 30 minutes, a mixed solution of a methanol solution (1.20 g) and EC (0.90 g) having a content of 92 mass % of E4 (1.10 g) prepared in advance was added. Furthermore, after making it reflux for 30 minutes, and standing to cool, the polysiloxane solution (2) whose _SiO2 conversion density|concentration is 12 mass % can be obtained.

<Synthesis example 13> In a 200 ml four-neck reaction flask equipped with a thermometer and a reflux tube, EC (28.3 g), E2 (4.07 g), E3 (7.45 g) and E5 (32.5 g) were mixed to prepare alkane A solution of oxysilane monomer. To this solution, a solution prepared by mixing ECS (14.2 g), water (10.8 g), and oxalic acid (0.70 g) as a catalyst in advance was added dropwise at 25° C. for 30 minutes, and further stirred at 25° C. 30 minutes. Then, after heating with an oil bath and refluxing for 30 minutes, a mixed solution of a methanol solution (1.20 g) containing 92 mass % of E4 (1.10 g) prepared in advance and ECS (0.90 g) was added. Furthermore, after making it reflux for 30 minutes, and standing to cool, the polysiloxane solution (3) whose _SiO2 conversion density|concentration is 12 mass % can be obtained.

Table 2 shows the polysiloxane-based polymers obtained in the synthesis examples.

"Production of Liquid Crystal Alignment Agent" <Synthesis Example 14> To the polyamic acid solution (1) (5.50 g) obtained by the method of Synthesis Example 1, NMP (10.8 g) was added, and the mixture was stirred at 25°C for 1 hour. Then, BCS (6.07g) and PB (9.10g) were added, and it stirred at 25 degreeC for 4 hours, and the liquid crystal aligning agent (1) was obtained. Abnormalities such as turbidity and precipitation were not found in this liquid crystal aligning agent, and it was a homogeneous solution.

<Synthesis Example 15> To the polyimide powder (2) (1.10 g) obtained by the method of Synthesis Example 2, NMP (15.2 g) was added, and the mixture was stirred at 70°C for 24 hours and dissolved. Then, BCS (4.55g), PB (10.6g), Q1 (0.055g), and K1 (0.077g) were added, and it stirred at 25 degreeC for 4 hours, and liquid-crystal aligning agent (2) was obtained. Abnormalities such as turbidity and precipitation were not found in this liquid crystal aligning agent, and it was a homogeneous solution.

<Synthesis Example 16> To the polyamic acid solution (3) (3.80 g) obtained by the method of Synthesis Example 3, γ-BL (1.80 g) and PGME (27.4 g) were added, and the mixture was stirred at 25°C for 6 hours. A liquid crystal alignment treatment agent (3) can be obtained. Abnormalities such as turbidity and precipitation were not found in this liquid crystal aligning agent, and it was a homogeneous solution.

<Synthesis Example 17> To the polyamic acid solution (3) (3.80 g) obtained by the method of Synthesis Example 3, γ-BL (1.80 g), PGME (27.4 g) and Q1 (0.053 g) were added, The liquid crystal aligning agent (4) can be obtained by stirring for 6 hours at 25°C. Abnormalities such as turbidity and precipitation were not found in this liquid crystal aligning agent, and it was a homogeneous solution.

<Synthesis Example 18> To the polyamic acid solution (3) (3.80 g) obtained by the method of Synthesis Example 3, γ-BL (1.80 g), PGME (27.4 g), Q1 (0.053 g) and K2 were added (0.053 g) and stirred at 25°C for 6 hours to obtain a liquid crystal aligning agent (5). Abnormalities such as turbidity and precipitation were not found in this liquid crystal aligning agent, and it was a homogeneous solution.

<Synthesis Example 19> To the polyamic acid solution (4) (3.80 g) obtained by the method of Synthesis Example 4, γ-BL (1.80 g) and PGME (27.4 g) were added, and the mixture was stirred at 25°C for 6 hours. A liquid crystal alignment treatment agent (6) can be obtained. Abnormalities such as turbidity and precipitation were not found in this liquid crystal aligning agent, and it was a homogeneous solution.

<Synthesis Example 20> To the polyamic acid solution (4) (3.80 g) obtained by the method of Synthesis Example 4, γ-BL (0.19 g), PGME (29.1 g), Q1 (0.038 g), K2 were added (0.053g) and N1 (0.023g), it stirred at 25 degreeC for 6 hours, and the liquid crystal aligning agent (7) was obtained. Abnormalities such as turbidity and precipitation were not found in this liquid crystal aligning agent, and it was a homogeneous solution.

<Synthesis Example 21> To the polyamic acid solution (5) (3.80 g) obtained by the method of Synthesis Example 5, γ-BL (3.42 g), PGME (22.6 g), PB (3.23 g), and Q2 were added. (0.023g) and K1 (0.053g), it stirred at 25 degreeC for 6 hours, and the liquid crystal aligning agent (8) was obtained. Abnormalities such as turbidity and precipitation were not found in this liquid crystal aligning agent, and it was a homogeneous solution.

<Synthesis Example 22> To the polyamic acid solution (6) (3.80 g) obtained by the method of Synthesis Example 6, γ-BL (5.03 g), PGME (24.2 g), Q1 (0.076 g), K2 were added (0.076g) and N1 (0.015g), it stirred at 25 degreeC for 6 hours, and the liquid crystal aligning agent (9) was obtained. Abnormalities such as turbidity and precipitation were not found in this liquid crystal aligning agent, and it was a homogeneous solution.

<Synthesis Example 23> To the polyamic acid solution (7) (3.80 g) obtained by the method of Synthesis Example 7, γ-BL (6.65 g), PGME (19.4 g), PB (3.23 g), and Q2 were added. (0.038g) and K2 (0.076g), it stirred at 25 degreeC for 6 hours, and the liquid crystal aligning agent (10) was obtained. Abnormalities such as turbidity and precipitation were not found in this liquid crystal aligning agent, and it was a homogeneous solution.

<Synthesis Example 24> NMP (12.3 g) was added to the polyamic acid solution (8) (5.50 g) obtained by the method of Synthesis Example 8, followed by stirring at 25°C for 1 hour. Then, PB (13.7g), Q1 (0.033g), and K1 (0.055g) were added, and it stirred at 25 degreeC for 4 hours, and liquid-crystal aligning agent (11) was obtained. Abnormalities such as turbidity and precipitation were not found in this liquid crystal aligning agent, and it was a homogeneous solution.

<Synthesis Example 25> To the polyimide powder (9) (1.10 g) obtained by the method of Synthesis Example 9, NMP (15.2 g) was added, and the mixture was stirred at 70°C for 24 hours and dissolved. Then, BCS (3.03g), PB (12.1g), Q1 (0.055g), K2 (0.077g), and N1 (0.033g) were added, and it stirred at 25 degreeC for 4 hours, and liquid crystal aligning agent (12) was obtained. Abnormalities such as turbidity and precipitation were not found in this liquid crystal aligning agent, and it was a homogeneous solution.

<Synthesis Example 26> To the polyamic acid solution (10) (3.80 g) obtained by the method of Synthesis Example 10, γ-BL (1.80 g) and PGME (27.4 g) were added, and the mixture was stirred at 25°C for 4 hours. A liquid crystal alignment treatment agent (13) can be obtained. Abnormalities such as turbidity and precipitation were not found in this liquid crystal aligning agent, and it was a homogeneous solution.

<Synthesis Example 27> To the polysiloxane solution (1) (7.50 g) obtained by the method of Synthesis Example 11, ECS (5.04 g), PGME (14.6 g) and PB (2.91 g) were added, and the mixture was heated to 25°C. After stirring for 6 hours, a liquid crystal aligning agent (14) can be obtained. Abnormalities such as turbidity and precipitation were not found in this liquid crystal aligning agent, and it was a homogeneous solution.

<Synthesis Example 28> To the polysiloxane solution (2) (7.50 g) obtained by the method of Synthesis Example 12, EC (2.13 g), BCS (17.5 g), PB (2.91 g), Q2 (0.045 g) were added g), K1 (0.018 g) and N1 (0.027 g), and stirred at 25° C. for 6 hours to obtain a liquid crystal aligning agent (15). Abnormalities such as turbidity and precipitation were not found in this liquid crystal aligning agent, and it was a homogeneous solution.

<Synthesis Example 29> To the polysiloxane solution (3) (7.50 g) obtained by the method of Synthesis Example 13, ECS (5.04 g), PGME (14.6 g) and PB (2.91 g) were added, and the mixture was heated to 25°C. After stirring for 6 hours, a liquid crystal aligning agent (16) can be obtained. Abnormalities such as turbidity and precipitation were not found in this liquid crystal aligning agent, and it was a homogeneous solution.

The liquid crystal alignment treatment agents obtained in the synthesis examples are shown in Tables 3 and 4. In addition, in Tables 3 and 4, the numbers in parentheses about the specific compound A, the specific crosslinking compound, and the specific generator added to the liquid crystal aligning agent represent the respective values relative to 100 parts by mass of the specific polymer. content.

"Production of the specific compound and liquid crystal composition of the present invention" In the following Examples 1 to 4, examples of specific compounds produced by a predetermined method are described. Moreover, in Example 5 - Example 12, the example of the liquid crystal composition using these specific compounds is described. The obtained liquid crystal composition can also be used for the manufacture and evaluation of the following liquid crystal display elements.

"Synthesis of Specific Compound" <Example 1> Specific Compound: Synthesis of T1

Compound (2) was added to a mixture of compound (1) (20.0 g, 67.9 mmol), dibutylhydroxytoluene (0.72 g, 3.27 mmol), pyridine (53.8 g) and toluene (150 g) at 25°C (karenzBEI: manufactured by Showa Denko Co., Ltd.) (19.5 g, 81.5 mmol), and stirred at 120° C. for 24 hours. After completion of the reaction, the solvent of the reaction solution was distilled off under reduced pressure. To the residue, toluene (200 g) was added, and the solvent was evaporated under reduced pressure (this operation was repeated twice). Methanol (300 g) was added to the residue, the mixture was stirred under ice-cooling (0° C.), and the precipitated solid was collected by filtration. The obtained solid was washed with methanol and dried to obtain a white crystal (T1) (yield: 31.5 g, yield: 86.7%). 1H-NMR (CDCl ₃ , σppm): 6.40-6.47(m, 2H), 6.09-6.18(m, 2H), 5.86-5.91(m, 2H), 5.00(broad, 1H), 4.37(d, 2H) , 4.30(d, 2H), 3.84(d, 2H), 1.65-1.80(m, 8H), 1.43(s, 3H), 1.19-1.34(m, 10H), 1.08-1.18(m, 3H), 0.76 -1.06(m, 14H)

<Example 2> Specific compound: Synthesis of T2

In a mixture of compound (3) (5.01 g, 17.9 mmol), dibutylhydroxytoluene (0.010 g, 0.046 mmol), diazabicycloundecene (0.27 g, 1.79 mmol) and toluene (50 g) , Compound (2) (same as above) (4.69 g, 19.6 mmol) was added at 25°C, and the mixture was stirred at 110°C for 48 hours. After the completion of the reaction, a dilute aqueous hydrochloric acid solution was added, followed by extraction and separation with chloroform. The chloroform layer was washed three times with a dilute aqueous hydrochloric acid solution and twice with water, and then anhydrous magnesium sulfate was added and dried. Then, the solvent in the chloroform layer was distilled off under reduced pressure, and methanol (30 g) was added to the obtained residue. The precipitated solid was taken out by filtration, and when it was dried, a thin yellow-white crystal (T2) was obtained (yield: 4.69 g, yield: 50.5%). 1H-NMR (CDCl ₃ , σppm): 6.39-6.47(m, 2H), 6.09-6.18 (m, 2H), 5.85-5.91(m, 2H), 4.96(broad, 1H), 4.43-4.54(m, 1H), 4.38(d, 2H), 4.29(d, 2H), 1.95-2.04(m, 2H), 1.64-1.81 (m, 6H), 1.42(s, 3H), 0.76-1.34(m, 26H)

<Example 3> Specific compound: Synthesis of T3

In a mixture of compound (4) (10.0 g, 30.4 mmol), dibutylhydroxytoluene (0.02 g, 0.091 mmol), diazabicycloundecene (0.46 g, 3.04 mmol) and toluene (100 g) , Compound (2) (same as above) (9.47 g, 39.6 mmol) was added at 25°C, and the mixture was stirred at 110°C for 72 hours. After the completion of the reaction, a dilute aqueous hydrochloric acid solution was added, followed by extraction and separation with chloroform. The chloroform layer was washed three times with a dilute aqueous hydrochloric acid solution and twice with water, and then anhydrous magnesium sulfate was added and dried. Then, the solvent in the chloroform layer was distilled off under reduced pressure, and isopropanol (150 g) was added to the obtained residue. Then, it heated to 40 degreeC, and filtered. The obtained filtrate was distilled off under reduced pressure, methanol (150 g) was added to the residue, and the precipitated solid was collected by filtration. When the obtained solid was subjected to silica gel column chromatography (eluent: chloroform), white crystals (T3) were obtained (yield: 2.26 g, yield: 13.0%). 1H-NMR (CDCl ₃ , σppm): 7.15-7.20(m, 2H), 6.98-7.04 (m, 2H), 6.43-6.50(m, 2H), 6.12-6.21(m, 2H), 5.88-5.93( m, 2H), 5.42(broad, 1H), 4.43(d, 2H), 4.36(d, 2H), 2.32-2.48 (m, 1H), 1.69-1.92(m, 8H), 1.50(s, 3H) , 0.93-1.46(m, 19H), 0.88(t, 3H)

<Example 4> Specific compound: Synthesis of T4

In compound (5) (cholesterol) (10.0 g, 25.9 mmol), dibutylhydroxytoluene (0.014 g, 0.064 mmol), diazabicycloundecene (0.39 g, 2.59 mmol) and toluene (100 g) To the mixture, compound (2) (same as above) (7.42 g, 31.0 mmol) was added at 25°C, and the mixture was stirred at 110°C for 10 hours. After completion of the reaction, the solvent was distilled off under reduced pressure, and the obtained residue was subjected to silica gel column chromatography (eluent: chloroform). To the solid obtained by the treatment, methanol (300 g) was added, and the mixture was stirred under ice-cooling (0° C.), and when the precipitated solid was filtered, white crystals (T4) were obtained (yield: 5.23 g, yield: 35.4 %). 1H-NMR (CDCl ₃ , σppm): 6.40-6.48(m, 2H), 6.10-6.19 (m, 2H), 5.86-5.91(m, 2H), 5.35-5.40(m, 1H), 4.94(broad, 1H), 4.41-4.52(m, 1H), 4.38(d, 2H), 4.30(d, 2H), 2.22-2.39(m, 2H), 1.77-2.05(m, 5H), 0.88-1.68(m, 15H), 1.43(s, 3H), 1.00(s, 3H), 0.91(d, 3H), 0.87(d, 3H), 0.86(d, 3H), 0.67(s, 3H)

"Preparation of liquid crystal composition" <Example 5> L1 (5.50g), T1 (0.50g), R1 (1.00g), R2 (1.20g), R3 (1.50g) and P1 (0.30g) were mixed to obtain a It stirred for 6 hours at 25 degreeC, and obtained the liquid crystal composition (1).

<Example 6> L1 (5.50 g), T1 (1.00 g), R1 (0.50 g), R2 (1.20 g), R3 (1.50 g) and P1 (0.30 g) were mixed and stirred at 25°C for 6 hours to obtain Liquid crystal composition (2).

<Example 7> L1 (5.50g), T1 (0.50g), W1 (0.30g), R1 (0.70g), R2 (1.20g), R3 (1.50g) and P1 (0.30g) were mixed to 25 The mixture was stirred for 6 hours to obtain a liquid crystal composition (3).

<Example 8> L1 (5.50 g), T2 (0.70 g), R1 (0.80 g), R2 (1.20 g), R3 (1.50 g) and P1 (0.30 g) were mixed and stirred at 25°C for 6 hours to obtain Liquid crystal composition (4).

<Example 9> L1 (5.50 g), T3 (0.30 g), R1 (1.20 g), R2 (1.20 g), R3 (1.50 g) and P1 (0.30 g) were mixed. The mixture was stirred at 25°C for 6 hours to obtain a liquid crystal composition (5).

<Example 10> L1 (5.50 g), T4 (0.30 g), R1 (1.20 g), R2 (1.20 g), R3 (1.50 g) and P1 (0.30 g) were mixed and stirred at 25°C for 6 hours to obtain Liquid crystal composition (6).

<Example 11> L1 (5.50g), T1 (0.30g), T4 (0.20g), R1 (1.00g), R2 (1.20g), R3 (1.50g) and P1 (0.30g) were mixed to 25 The mixture was stirred for 6 hours to obtain a liquid crystal composition (7).

<Example 12> L1 (5.50 g), T1 (0.30 g), T3 (0.20 g), W1 (0.20 g), R1 (0.80 g), R2 (1.20 g), R3 (1.50 g) and P1 ( 0.30 g), and stirred at 25° C. for 6 hours to obtain a liquid crystal composition (8).

<Comparative Example 30> L1 (5.50 g), R1 (1.50 g), R2 (1.20 g), R3 (1.50 g) and P1 (0.30 g) were mixed and stirred at 25°C for 6 hours to obtain a liquid crystal composition (9) .

"Production of liquid crystal display element (glass substrate)" The liquid crystal alignment treatment agent obtained by the method of the aforementioned synthesis example was subjected to pressure filtration with a membrane filter having a pore size of 1 μm. The obtained solution was spin-coated on ITO on a 100×100 mm glass substrate (length: 100 mm, width: 100 mm, thickness: 0.7 mm) with ITO electrodes that had been washed with pure water and IPA (isopropyl alcohol). On the surface, heat treatment was performed at 100°C for 5 minutes on a hot plate and 210°C for 30 minutes by a thermal cycle type clean oven to obtain an ITO substrate with a liquid crystal alignment film with a film thickness of 100 nm.

Two obtained ITO substrates with a liquid crystal alignment film were prepared, and a spacer of 8 μm was placed on the liquid crystal alignment film surface of one of the substrates. After that, the liquid crystal composition obtained by the method of the above-mentioned embodiment was dropped on the surface of the liquid crystal alignment film on which the spacer was coated by the ODF (One Drop Filling) method, and then, the other side was The interface of the liquid crystal alignment film of the substrate is attached in an opposite manner to obtain the liquid crystal display element before the treatment.

The liquid crystal display element before the treatment was irradiated with ultraviolet rays for an irradiation time of 45 seconds using a metal halide lamp with an illuminance of 20 mW/cm ² to cut off a wavelength of 350 nm or less. At this time, the temperature in the irradiation apparatus when irradiating ultraviolet rays to the liquid crystal cell was controlled to 25°C. Thereby, a liquid crystal display element (glass substrate) can be obtained.

"Production of liquid crystal display element (plastic substrate)" The liquid crystal alignment treatment agent obtained in the aforementioned synthesis example was subjected to pressure filtration with a membrane filter having a pore size of 1 μm. The obtained solution was bar-coated on a 150×150 mm ITO electrode-attached PET (polyethylene terephthalate) substrate (length: 150 mm, width: 150 mm, thickness: 0.2 mm) that had been washed with pure water. mm) on the ITO surface, and heat treatment at 120° C. for 2 minutes in a thermal cycle type clean oven to obtain an ITO substrate with a liquid crystal alignment film with a film thickness of 100 nm.

Two obtained ITO substrates with a liquid crystal alignment film were prepared, and a spacer of 8 μm was coated on the liquid crystal alignment film surface of one of the substrates. Then, on the liquid crystal alignment film surface of the substrate on which the spacers have been coated, the liquid crystal composition obtained by the method of the above-mentioned embodiment is dropped by the ODF method, and then, the liquid crystal alignment film interface of the other substrate is formed. Lamination was performed so that it may be opposed, and the liquid crystal display element before a process was obtained. The liquid crystal display element before the treatment was irradiated with ultraviolet rays by the same method as the above-mentioned "production of liquid crystal display element (glass substrate)" to obtain a liquid crystal display element (plastic substrate).

"Production of liquid crystal display element (corresponding relationship with the examples)" As shown in Tables 5 to 7 or 8 to 10 below, use any one of the aforementioned liquid crystal alignment agents (1) to (16) and With any one of the aforementioned liquid crystal compositions (1) to (9), the liquid crystal display elements of Examples 1A to 20A and Comparative Examples 1A to 4A were produced. Examples 1A to 2A, 14A to 15A and 19A and Comparative Examples 1A and 4A are liquid crystal display elements made of glass substrates. Examples 3A to 13A, 16A to 18A and 20A and Comparative Examples 2A and 3A use plastic substrates The produced liquid crystal display element.

"Evaluation of Optical Properties (Transparency and Scattering Properties)" The evaluation of the transparency without applied voltage is carried out by measuring the transmittance of the liquid crystal display element (glass substrate and plastic substrate) under the state of no applied voltage. Specifically, UV-3600 (manufactured by Shimadzu Corporation) was used as a measuring apparatus, and the temperature was 25° C. and the scanning wavelength was measured under the conditions of 300 to 800 nm. At this time, in the case of a liquid crystal display element (glass substrate), the above-mentioned glass substrate with ITO electrodes was used as a control group (reference example), and in the case of a liquid crystal display element (plastic substrate), it was used. The above-mentioned PET substrate with an ITO electrode was carried out. In the evaluation, the transmittance at a wavelength of 550 nm was used as a reference, and the one with the higher transmittance was evaluated as excellent in transparency.

Moreover, as the stability test of the high temperature and high humidity environment of a liquid crystal display element, the measurement after storing in the constant temperature and humidity tank of temperature 80 degreeC and humidity 90%RH for 36 hours was also performed. Specifically, with respect to the transmittance (initial value) immediately after the production of the liquid crystal display element, the lower ratio of the transmittance after storage in a constant temperature and humidity chamber is evaluated as excellent in this evaluation.

Furthermore, as a stability test to light irradiation of a liquid crystal display element, a desktop UV curing device (HCT3B28HEX-1) (manufactured by SEN LIGHT) was also used, and it was measured after irradiating ultraviolet rays of 5 J/cm ² in conversion of 365 nm. Specifically, with respect to the transmittance immediately after the production of the liquid crystal display element (initial value), the lower ratio of the transmittance after ultraviolet irradiation was evaluated as excellent in this evaluation.

The evaluation of the scattering characteristics when a voltage is applied is carried out by visually observing the alignment state of the liquid crystal with an external AC drive of 30V for the liquid crystal display element (glass substrate and plastic substrate). Specifically, a liquid crystal display element that is cloudy, that is, one whose scattering properties can be obtained, is evaluated as excellent in this evaluation (in the table, it shows good).

Moreover, as the stability test of the high temperature and high humidity environment of a liquid crystal display element, the observation after storing in the constant temperature and humidity tank of temperature 80 degreeC and humidity 90%RH for 36 hours was also performed. Specifically, a liquid crystal display element that is cloudy, that is, one whose scattering properties can be obtained, is evaluated as excellent in this evaluation (in the table, it shows good).

Furthermore, as a stability test to light irradiation of a liquid crystal display element, a desktop UV curing device (HCT3B28HEX-1) (manufactured by SEN LIGHT) was also used, and 5 J/cm ² of ultraviolet rays were irradiated at 365 nm and observed. Specifically, a liquid crystal display element that is cloudy, that is, one whose scattering properties can be obtained, is evaluated as excellent in this evaluation (in the table, it shows good).

The evaluation results of transmittance (%) and scattering properties after the liquid crystal display element is fabricated (initial stage), after storage in a constant temperature and humidity tank (constant temperature and humidity), and after ultraviolet irradiation (ultraviolet light) are summarized in Tables 5 to 7.

"Assessment of the Adhesion between the Liquid Crystal Layer and the Liquid Crystal Alignment Film" The evaluation of the adhesion between the liquid crystal layer and the liquid crystal alignment film is performed by measuring the liquid crystal display element (glass substrate and plastic substrate) at a temperature of 80°C and a humidity of 90% RH. It was stored in a constant temperature and humidity tank for 36 hours, and the presence or absence of air bubbles in the liquid crystal display element and the peeling of the element were confirmed (as a stability test of a liquid crystal display element in a high temperature and high humidity environment). Specifically, when no air bubbles were found in the element and no peeling of the element occurred (the liquid crystal layer and the liquid crystal alignment film were in a state of peeling), the evaluation was evaluated as excellent (in the table, good).

In addition, the liquid crystal display element was confirmed by irradiating ultraviolet rays of 5 J/cm ² in conversion of 365 nm using a desktop UV curing device (HCT3B28HEX-1) (manufactured by SEN LIGHT Co., Ltd.) Irradiation stability test). Specifically, when no air bubbles were found in the element and no peeling of the element occurred, it was evaluated as excellent in this evaluation (in the table, it is indicated as good).

The results (adhesion) of the liquid crystal layer and the liquid crystal alignment film after storage in a constant temperature and humidity tank (constant temperature and humidity) and after ultraviolet irradiation (ultraviolet rays) are shown in Tables 8 to 10.

<Examples 1A to 20A and Comparative Examples 1A to 4A> As shown in Tables 5 to 10 below, evaluation of optical properties (transparency and scattering properties) and evaluation of the adhesion between the liquid crystal layer and the liquid crystal alignment film were performed. The results of these evaluations are shown in Tables 5 to 10.

In addition, in the evaluation of the optical properties (scattering properties and transparency) and the evaluation of the adhesion between the liquid crystal layer and the liquid crystal alignment film in Examples 3A to 10A, Example 16A, Example 18A and Example 20A, in addition to the above In addition to the standard test, as an emphasis test, the evaluation was performed by storing in a constant temperature and humidity tank with a temperature of 80°C and a humidity of 90%RH for 72 hours (other conditions were the same as those described above).

*1：於元件內可發現極少量的氣泡。 　　*2：於元件內可發現少量的氣泡(較*1為多)。 　　*3：於元件內發現氣泡(較*2為多)。

*1: A very small amount of air bubbles can be found in the element. *2: A small amount of air bubbles (more than *1) can be found in the element. *3: Air bubbles were found in the element (more than *2).

As can be seen from the above, compared with the comparative examples, the liquid crystal display elements of the examples have favorable optical properties, that is, the liquid crystal display elements having good transparency after storage in a constant temperature and humidity chamber and after ultraviolet irradiation. Furthermore, even in a liquid crystal display element with a high adhesion between the liquid crystal layer and the liquid crystal alignment film, even when exposed to such a harsh environment, no peeling was found in the liquid crystal display element, and only a very small amount of air bubbles were found in the liquid crystal display element. In particular, these characteristics are good even when a plastic substrate is used as the substrate of the liquid crystal display element. Specifically, in the comparison under the same conditions, Example 1A and Comparative Example 1A, Comparative Example 3A and Comparative Example 2A, Comparative Example 17A and Comparative Example 3A, and Comparative Example 20A and Comparative Example 4A were compared.

When the amount of the specific compound added to the liquid crystal composition increases, the transmittance of the liquid crystal display element becomes high. Specifically, in the comparison under the same conditions, Example 8A was compared with Example 9A. Moreover, when an additive compound is added to a liquid crystal composition in addition to a specific compound, the transmittance|permeability of an element becomes high. Specifically, in the comparison under the same conditions, Example 6A was compared with Example 7A.

Among the specific side chain structure in the specific polymer of the liquid crystal aligning agent, if the diamine with the specific side chain structure of the formula [4-1a] is used, the difference is the same as when the diamine with the formula [4-2a] is used. In comparison, the transmittance of the liquid crystal display element will be higher. Furthermore, even after being stored for a long time in a constant temperature and humidity tank, the transparency was high. In addition, even in the evaluation of the adhesion between the liquid crystal layer and the liquid crystal alignment film, if the diamine of the formula [4-1a] is used, the adhesion is high even after being stored in a constant temperature and humidity tank for a long time. result. Specifically, in comparison under the same conditions, Example 3A was compared with Example 16A, and Example 18A was compared with Example 20A.

Moreover, when using the 2nd diamine in a specific polymer, even after storing in a constant temperature and humidity tank for a long time, the adhesiveness of a liquid crystal layer and a liquid crystal alignment film will become high. Specifically, in the comparison under the same conditions, Example 3A was compared with Example 6A.

Furthermore, when the specific compound A is added to a liquid crystal aligning agent, the transmittance of a liquid crystal display element becomes high. Specifically, Example 3A was compared with Example 4A. Moreover, when a specific crosslinkable compound is added, the adhesiveness of a liquid crystal layer and a liquid crystal alignment film becomes high. Furthermore, when the specific compound A, the specific crosslinkable compound, and the specific generator are added, the transmittance of the liquid crystal display element and the adhesion between the liquid crystal layer and the liquid crystal alignment film become high. Specifically, Example 7A was compared with Example 10A. [Industrial Availability]

By using a liquid crystal composition containing a compound with a specific structure, good optical properties can be obtained, that is, the transparency when no voltage is applied and the scattering properties when voltage is applied are good, and the liquid crystal layer and the liquid crystal alignment film are dense. It is a liquid crystal display element that can maintain these characteristics even in harsh environments such as high temperature and high humidity or exposure to light for a long time.

In addition, the liquid crystal display element of the present invention can be suitably used as a normal type element, which becomes a transparent state when no voltage is applied, and becomes a scattering state when a voltage is applied. Therefore, the device can be used in a liquid crystal display for display purposes, and can be used in a dimming window or a light shutter device for controlling the blocking and transmission of light. In the substrate of the normal type device, the Use a plastic substrate.

Further, the specific compound of the present invention can be used not only as a component of the liquid crystal composition of the liquid crystal display element of the present invention, but also as a component of the liquid crystal composition of other liquid crystal display elements.

Claims (15)

A compound of the following formula [1b] or formula [1c],

T ⁹ , T ¹¹ , T ¹⁷ and T ¹⁹ each represent a structure selected from the following formulae [2-1a] to [2-7a], and T ¹⁰ and T ¹⁸ represent a straight chain having 2 to 12 carbon atoms Shape or branched alkylene, ^T12 and T20 represent ^the structure selected from the following formula [1-1b] ~ formula [ ^1-4b ], ^T13 and T21 represent a single bond or carbon number 1-8 alkylene groups, T ¹⁴ and T ¹⁵ represent benzene ring or cyclohexane ring, T ¹⁶ represents alkyl or alkoxy with carbon number 1-12, T ²² represents carbon number with steroid skeleton Divalent organic group of 17~51, pT represents an integer of 0~4,

W ^A represents a hydrogen atom or a benzene ring;

T ^B represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. A liquid crystal composition containing the compound of claim 1. A liquid crystal display element comprising a liquid crystal layer, wherein the liquid crystal layer is cured by irradiating ultraviolet rays to a liquid crystal composition comprising a liquid crystal and a polymerizable compound disposed between a pair of substrates having electrodes, and at least one of the substrates is cured. The liquid crystal alignment film provided with the vertical alignment of liquid crystal is characterized in that the liquid crystal composition contains the compound according to claim 1. The liquid crystal display element according to claim 3, wherein the liquid crystal composition comprises the compound of the following formula [2a],

W ¹ represents a structure selected from the following formulas [2-1a] to [2-7a], W ² represents a single bond, -O-, -COO- or -OCO-, and W ³ represents a single bond Or alkylidene with carbon number 1~12, W ⁴ represents single bond, -O-, -COO- or -OCO-, W ⁵ represents benzene ring, cyclohexane ring or carbon number 17~ with steroid skeleton Divalent organic group of 51, W ⁶ represents a single bond, -CH ₂ -, -CH ₂ O-, -OCH ₂ -, -O-, -COO-, -OCO-, -NHCO- or -CONH- , W ⁷ represents a benzene ring or a cyclohexane ring, W ⁸ represents an alkyl group with a carbon number of 1 to 18, an alkenyl group with a carbon number of 2 to 18, a fluorine-containing alkyl group with a carbon number of 1 to 18, and a carbon number of 1 to 18. 18 alkoxy group or fluorine-containing alkoxy group with carbon number 1~18, mW represents an integer of 0~4,

^WA represents a hydrogen atom or a benzene ring. The liquid crystal display element according to claim 3, wherein the liquid crystal alignment film is a liquid crystal alignment obtained from a liquid crystal alignment treatment agent containing a polymer having a side chain structure of the following formula [4-1a] or formula [4-2a] membrane,

X ¹ and X ³ each represent a single bond, -(CH ₂ ) _a - (a is an integer of 1 to 15), -O-, -CH ₂ O-, -COO- or -OCO-; X ² represents Single bond or -(CH ₂ ) _b - (b is an integer from 1 to 15); X ⁴ represents a divalent cyclic group selected from a benzene ring, a cyclohexane ring and a heterocyclic ring or a carbon with a steroid skeleton A divalent organic group of 17-51, and any hydrogen atom on the aforementioned cyclic group can be an alkyl group with 1-3 carbon atoms, an alkoxy group with 1-3 carbon atoms, or a group containing 1-3 carbon atoms. A fluoroalkyl group, a fluorine-containing alkoxy group having 1 to 3 carbon atoms or a fluorine atom is substituted; X ⁵ represents at least one cyclic group selected from a benzene ring, a cyclohexane ring and a heterocyclic ring, and these Any hydrogen atom on the cyclic group can be an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, or a fluorine-containing alkyl group having 1 to 3 carbon atoms. Oxygen or fluorine atom substitution; X ⁶ represents alkyl with 1-18 carbons, alkenyl with 2-18 carbons, fluorine-containing alkyl with 1-18 carbons, alkoxy with 1-18 carbons or Fluorine-containing alkoxy with 1 to 18 carbon atoms; n is an integer of 0 to 4; ─X ⁷ ─X ⁸ [4-2a] X ⁷ represents a single bond, -O-, -CH ₂ O-, -CONH -, -NHCO-, -CON(CH ₃ )-, -N(CH ₃ )CO-, -COO- or -OCO-; X ⁸ represents an alkyl group with a carbon number of 8~18 or an alkyl group with a carbon number of 6~18 Fluoroalkyl. The liquid crystal display element according to claim 5, wherein the liquid crystal alignment treatment agent is selected from the group consisting of acrylic polymers, methacrylic polymers, phenolic resins, polyhydroxystyrene, polyimide precursors, polyimide, polyimide At least one of amide, polyester, cellulose and polysiloxane. The liquid crystal display element according to claim 6, wherein the liquid crystal alignment treatment agent comprises a polyimide precursor obtained by the reaction of a diamine component and a tetracarboxylic acid component or the polyimide precursor is imidized The said diamine component contains the diamine which has the side chain structure of the said formula [4-1a] or formula [4-2a]. The liquid crystal display element according to claim 7, wherein the diamine having the side chain structure of the aforementioned formula [4-1a] or formula [4-2a] is represented by the following formula [4a],

X represents the structure of the aforementioned formula [4-1a] or formula [4-2a], and m represents an integer of 1 to 4. The liquid crystal display element according to claim 7, wherein the tetracarboxylic acid component is a tetracarboxylic dianhydride of the following formula [5],

Z represents a structure selected from the following formulas [5a] to [51],

Each of Z ¹ to Z ⁴ represents a hydrogen atom, a methyl group, a chlorine atom or a benzene ring, and each of Z ⁵ and Z ⁶ represents a hydrogen atom or a methyl group. The liquid crystal display element of claim 6, wherein the liquid crystal alignment treatment agent comprises a polysiloxane obtained by polycondensation of an alkoxysilane of the following formula [A1], or a polysiloxane obtained by polycondensing an alkoxysilane of the formula [A1] Polysiloxane obtained by polycondensation of silane and alkoxysilane of formula [A2] and/or formula [A3], (A ¹ ) _m Si(A ² ) _n (OA ³ ) _p [A1] A ¹ represents the structure of the aforementioned formula [4-1a] or formula [4-2a], A ² represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, A ³ represents an alkyl group having 1 to 5 carbon atoms, m represents an integer of 1 or 2, n represents an integer from 0 to 2, p represents an integer from 0 to 3, but m+n+p is 4, (B ¹ ) _m Si(B ² ) _n (OB ³ ) _p [A2] B ¹ represents at least one carbon number selected from vinyl group, epoxy group, amine group, mercapto group, isocyanate group, methacrylic group, acrylic group, urea group and cinnamic acid group. 12 is an organic group, B ² represents a hydrogen atom or an alkyl group with 1 to 5 carbon atoms, B ³ represents an alkyl group with 1 to 5 carbon atoms, m represents an integer of 1 or 2, and n represents an integer of 0 to 2. Integer, p represents an integer from 0 to 3, but m+n+p is 4, (D ¹ ) _n Si(OD ² ) _4-n [A3] D ¹ represents a hydrogen atom or a carbon number of 1 to 5 For the alkyl group, D ² represents an alkyl group having 1 to 5 carbon atoms, and n represents an integer of 0 to 3. The liquid crystal display element according to claim 5, wherein the liquid crystal aligning agent contains a compound having at least one structure selected from the following formulae [b-1] to [b-11],

B ^A represents a hydrogen atom or a benzene ring, and B ^B to B ^D each represent an alkyl group having 1 to 5 carbon atoms. The liquid crystal display element according to claim 5, wherein the liquid crystal alignment treatment agent contains at least one selected from the group consisting of epoxy groups, isocyanate groups, oxetanyl groups, cyclic carbonate groups, hydroxyl groups, hydroxyalkyl groups, and low molecular weight groups. alkoxy Alkyl compounds. The liquid crystal display element according to claim 5, wherein the liquid crystal alignment treatment agent contains a substance selected from the group consisting of 1-hexanol, cyclohexanol, 1,2-ethylene glycol, 1,2-propylene glycol, propylene glycol monobutyl ether, ethylene glycol At least one of alcohol monobutyl ether, dipropylene glycol dimethyl ether, cyclohexanone, cyclopentanone, and solvents of the following formulas [D1] to [D3],

D ¹ and D ² represent an alkyl group having 1 to 3 carbon atoms, and D ³ represents an alkyl group having 1 to 4 carbon atoms. The liquid crystal display element according to claim 5, wherein the liquid crystal alignment treatment agent contains at least one selected from the group consisting of N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone and γ-butyrolactone kind. The liquid crystal display element according to any one of claims 3 to 14, wherein the substrate is a plastic substrate.