JPWO2018159637A1 - Compound, liquid crystal composition and liquid crystal display device - Google Patents

Abstract

The object of the present invention is achieved by using the compound of the following formula [1a] in a liquid crystal composition of a liquid crystal display device. The definitions of the symbols in the formula are as described in the specification.

Description

  The present invention relates to a novel compound, a liquid crystal composition containing the compound, and a transmission-scattering type liquid crystal display device obtained using the liquid crystal composition.

  TN (Twisted Nematic) mode liquid crystal alignment elements have been put to practical use. In this mode, it is necessary to use a polarizing plate in order to switch light using the optical rotation characteristics of the liquid crystal. When a polarizing plate is used, light use efficiency is reduced. As a liquid crystal display element not using a polarizing plate, a polymer dispersed liquid crystal (also referred to as PDLC (Polymer Dispersed Liquid Crystal)) that switches between a transmission state (also referred to as a transparent state) and a scattering state of the liquid crystal. And a polymer network type liquid crystal (also referred to as PNLC (Polymer Network Liquid Crystal)) are known.

  In these liquid crystal display devices, 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 of liquid crystal and a cured product of a polymerizable compound (for example, a polymer network) can be formed. In such a liquid crystal display element, the transmission state and the scattering state of the liquid crystal can be controlled by applying a voltage.

  Conventional liquid crystal display devices using PDLC or PNLC often become cloudy (scattering) because liquid crystal molecules are oriented in random directions when no voltage is applied, and liquid crystals are arranged in the direction of an electric field when voltage is applied. Then, light is transmitted to be in a transmission state (such a liquid crystal display element is also referred to as a normal type element). However, in the normal type element, it is necessary to always apply a voltage in order to obtain a transmission state. Therefore, when used in a transparent state in many cases, for example, in a window glass application, power consumption is low. growing. On the other hand, there has been proposed a liquid crystal display element (also referred to as a reverse type element) using a PDLC that becomes a transmission state when no voltage is applied and becomes a scattering state when a voltage is applied (see Patent Documents 1 and 2).

Japanese Patent No. 2885116 Japanese Patent No. 4132424

  The polymerizable compound in the liquid crystal composition forms a polymer network and obtains desired optical characteristics, and the role of the liquid crystal layer (composite of the liquid crystal and the cured product of the polymerizable compound) and the liquid crystal alignment film. There is a role to enhance the adhesion. The liquid crystal alignment film used for the reverse type element has a problem that the adhesion between the liquid crystal layer and the liquid crystal alignment film is low because the liquid crystal alignment film is highly hydrophobic in order to vertically align the liquid crystal. In order to increase the adhesion, it is necessary to make the polymer network denser. Therefore, it is necessary to introduce a large amount of a polymerizable compound into the liquid crystal composition of the reverse type device. However, when the polymer network is dense, the vertical alignment of the liquid crystal is hindered, and the transparency of the reverse type device when no voltage is applied and the scattering characteristics when the voltage is applied are deteriorated. Therefore, the polymerizable compound in the liquid crystal composition used for the reverse type element needs to be one that enhances the vertical alignment of the liquid crystal when forming the liquid crystal layer.

  Furthermore, since the reverse type element is sometimes used by being attached to the window glass of an automobile or an architectural building, the vertical alignment of the liquid crystal is maintained even in a severe environment exposed to high temperature, high humidity and light for a long time. It is necessary that it does not decrease and that the adhesion between the liquid crystal layer and the liquid crystal alignment film is high. Heretofore, a liquid crystal display device satisfying such a condition has not been found.

  The present invention has a high liquid crystal vertical alignment property and good optical properties, that is, good transparency when no voltage is applied and good scattering properties when a voltage is applied, and furthermore, adhesion between the liquid crystal layer and the liquid crystal alignment film. It is an object of the present invention to provide a liquid crystal display element capable of maintaining these characteristics even in an environment that is exposed to high temperature, high humidity and light irradiation for a long time.

The present inventor has made intensive studies to achieve the above object, and as a result, completed the present invention having the following gist.
That is, the present invention can be used for a liquid crystal composition of a liquid crystal display element. ~ 16.

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

T ¹ represents a structure selected from the following formulas [2-1a] to [2-7a]. T ² are a linear or branched alkylene group having 2 to 18 carbon atoms, ^{T 1} and ^{T 3} and not adjacent said alkylene group any _-CH 2 in the - is, -O -, - CO -, - It may be replaced by COO—, —OCO—, —CONH—, —NHCO—, —NH—, a benzene ring or a cyclohexane ring. T ³ represents a structure selected from the following formulas [1-1b] to [1-4b]. T ⁴ represents a single bond or an alkylene group having 1 to 24 carbon atoms, ^{T 3} and not adjacent said alkylene group any _-CH 2 in the - is, -O -, - CO -, - COO -, - OCO- , -CONH -, - NHCO -, - NH -, - CON (CH 3) -, - S- or -SO ₂ - may be replaced by. T ⁵ represents a divalent cyclic group selected from a benzene ring, a cyclohexane ring and a heterocyclic ring, or a divalent organic group having a steroid skeleton and having 17 to 51 carbon atoms, and an arbitrary hydrogen atom on the cyclic group is It may be substituted by an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxy group having 1 to 3 carbon atoms or a fluorine atom. T ⁶ represents a single bond, —O—, —OCH ₂ —, —CH ₂ O—, —COO—, or —OCO—. T ⁷ represents a cyclic group selected from a benzene ring, a cyclohexane ring, and a heterocyclic ring, and any hydrogen atom on the cyclic group is an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, It may be substituted with a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxy group having 1 to 3 carbon atoms, or a fluorine atom. T ⁸ is an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, or a fluorine-containing alkoxy group having 1 to 18 carbon atoms. Represents a group. mT shows the integer of 1-4. nT shows the integer of 0-4.

W ^A is a hydrogen atom or a benzene ring.

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

  2. The compound of the formula [1a] is represented by the following formula [1b] or [1c]. The compound according to the above.

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

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

  4. A liquid crystal composition including a liquid crystal and a polymerizable compound disposed between a pair of substrates having electrodes is provided with a liquid crystal layer cured by irradiating ultraviolet rays, and at least one of the substrates vertically aligns the liquid crystal. What is claimed is: 1. A liquid crystal display device comprising a liquid crystal alignment film for aligning, wherein the liquid crystal composition comprises at least one compound selected from the formulas [1a], [1b] and [1c]. .

  5. 3. the liquid crystal composition contains a compound of the following formula [2a]; 3. The liquid crystal display device according to item 1.

W ¹ represents a structure selected from the following formulas [2-1a] to [2-7a]. W ² is a single bond, -O -, - COO- or an -OCO-. W ³ represents a single bond or an alkylene group having 1 to 12 carbon atoms. W ⁴ represents a single bond, —O—, —COO—, or —OCO—. W ⁵ represents a benzene ring, a cyclohexane ring or a divalent organic group having 17 to 51 carbon atoms having a steroid skeleton. W ⁶ being a single _{bond, -CH 2 -, - CH 2} O -, - OCH 2 -, - O -, - COO -, - OCO -, - NHCO- or an -CONH-. W ⁷ represents a benzene ring or a cyclohexane ring. W ⁸ is an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, or a fluorine-containing alkoxy group having 1 to 18 carbon atoms. Represents a group. mW represents an integer of 0 to 4.

W ^A is a hydrogen atom or a benzene ring.

  6. 3. The liquid crystal alignment film is a liquid crystal alignment film obtained from a liquid crystal alignment agent containing a polymer having a side chain structure represented by the following formula [4-1a] or formula [4-2a]. Or 5. 3. The liquid crystal display device according to item 1.

X ¹ and ^{X 3} is a single _{bond, - (CH 2) a -} (a is an integer of _{1~15), - O -, -} CH 2 O -, - COO- or an -OCO-. X ² represents a single bond or — (CH ₂ ) _b — (b is an integer of 1 to 15). X ⁴ represents a divalent cyclic group selected from a benzene ring, a cyclohexane ring and a heterocyclic ring, or a divalent organic group having a steroid skeleton and having 17 to 51 carbon atoms, and an arbitrary hydrogen atom on the cyclic group is It may be substituted by an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxy group having 1 to 3 carbon atoms or a fluorine atom. X ⁵ represents at least one cyclic group selected from a benzene ring, a cyclohexane ring and a heterocyclic ring, and any hydrogen atom on these cyclic groups is an alkyl group having 1 to 3 carbon atoms, It may be substituted by an alkoxy group, 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. X ⁶ is an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, or a fluorine-containing alkoxy group having 1 to 18 carbon atoms. Represents a group. n shows the integer of 0-4.

X ⁷ is a single _{bond, -O -, - CH 2 O} -, - CONH -, - NHCO -, - CON (CH 3) -, - N (CH 3) CO -, - shows a COO- or -OCO- . X ⁸ represents a fluorine-containing alkyl group having 6 to 18 carbon alkyl group or C of 8-18 carbon atoms.

  7. 5. The liquid crystal alignment treatment agent contains at least one selected from an acrylic polymer, a methacrylic polymer, a novolak resin, a polyhydroxystyrene, a polyimide precursor, a polyimide, a polyamide, a polyester, a cellulose, and a polysiloxane. 3. The liquid crystal display device according to item 1.

  8. A polyimide precursor obtained by reacting a diamine component containing a diamine having a side chain structure of the formula [4-1a] or [4-2a] with a tetracarboxylic acid component, 6. Including polyimide obtained by imidizing a polyimide precursor 3. The liquid crystal display device according to item 1.

  9. 7. The diamine having the side chain structure of the formula [4-1a] or [4-2a] is represented by the following formula [4a]. 3. The liquid crystal display device according to item 1.

  X represents the structure of the formula [4-1a] or the formula [4-2a]. m shows the integer of 1-4.

  10. 7. The tetracarboxylic acid component is a tetracarboxylic dianhydride of the following formula [5]. Or 9. 3. The liquid crystal display device according to item 1.

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

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

  11. The liquid crystal alignment treatment agent is a polysiloxane obtained by polycondensation of an alkoxysilane of the following formula [A1], or an alkoxysilane of the formula [A1], and the following formulas [A2] and / or [A3] 6. Including polysiloxane obtained by polycondensation with alkoxysilane. 3. The liquid crystal display device according to item 1.

A ¹ represents a structure of the 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 shows the integer of 0-2. p shows the integer of 0-3. However, m + n + p is 4.

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

  12. 5. The liquid crystal alignment treatment agent contains a compound having at least one structure selected from the following formulas [b-1] to [b-11]. ~ 11. The liquid crystal display device according to any one of the above.

B ^A represents a hydrogen atom or a benzene ring. Each B ^B .about.B ^D represents an alkyl group having 1 to 5 carbon atoms.

  13. 5. The liquid crystal alignment treatment agent contains a compound having at least one selected from an epoxy group, an isocyanate group, an oxetane group, a cyclocarbonate group, a hydroxyl group, a hydroxyalkyl group and a lower alkoxyalkyl group. ~ 12. The liquid crystal display device according to any one of the above.

  14． The liquid crystal alignment treatment agent is 1-hexanol, cyclohexanol, 1,2-ethanediol, 1,2-propanediol, propylene glycol monobutyl ether, ethylene glycol monobutyl ether, dipropylene glycol dimethyl ether, cyclohexanone, cyclopentanone and 5. It contains at least one member selected from solvents represented by the formulas [D1] to [D3]. ~ 13. The liquid crystal display device according to any one of the above.

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

  15. 5. The liquid crystal alignment treatment agent contains at least one selected from N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, and γ-butyrolactone. ~ 14. The liquid crystal display device according to any one of the above.

  16. 3. the substrate is a plastic substrate; ~ 15. The liquid crystal display device according to any one of the above.

  According to the present invention, good optical properties, that is, good transparency when no voltage is applied and good scattering properties when a voltage is applied, high adhesion between the liquid crystal layer and the liquid crystal alignment film, high temperature and high humidity for a long time And a liquid crystal display element capable of maintaining these characteristics even in an environment exposed to light irradiation. 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, a dimming window or an optical shutter element for controlling transmission and blocking of light, and the like.

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

T ^1, from the viewpoint of adhesion between the liquid crystal layer and the liquid crystal alignment film of the liquid crystal display device, wherein [2-1a] ~ formula [2-4a] is preferred. More preferably, it is a formula [2-1a] or a formula [2-2a]. T ² is preferably a linear or branched alkylene group having 2 to 12 carbon atoms, and any —CH ₂ — of the alkylene group that is not adjacent to T ¹ and T ³ is —O— or —CO—. , -COO-, -OCO-, -CONH-, -NHCO-, or -NH-. More preferably, it is a linear or branched alkylene group having 2 to 8 carbon atoms. T ³ is preferably the formula [1-1b], the formula [1-2b] or the formula [1-4b] from the viewpoint of the optical characteristics of the liquid crystal display element. More preferably, 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 alkylene group that is not adjacent to T ³ is —O—, —CO—, —COO—, or —OCO. -, - CONH -, - NHCO -, - NH -, - CON (CH 3) -, - S- or -SO ₂ - may be replaced by. More preferably, it is a single bond or an alkylene group having 1 to 8 carbon atoms. T ⁵ is the optical characteristics of the liquid crystal display element point, benzene ring, cyclohexane ring, or a divalent organic group having 17 to 51 carbon atoms having a steroid skeleton is preferable. T ⁶ is preferably a single bond, —O—, —COO— or —OCO—. More preferably, it is a single bond. T ⁷ is the optical characteristics of the liquid crystal display element point, a benzene ring or a cyclohexane ring.

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, from the viewpoint of the optical characteristics of the liquid crystal display element. More preferably, it is an alkyl group having 1 to 12 carbon atoms or an alkoxy group having 1 to 12 carbon atoms. mT is preferably 2 to 4 from the viewpoint of adhesion between the liquid crystal layer of the liquid crystal display element and the liquid crystal alignment film. More preferably, it is 2. nT is preferably from 0 to 3. More preferably, it is 0-2.

  The method for synthesizing the specific compound is not particularly limited, and for example, heating an isocyanate compound of the following formula [TA] and a compound of the following formulas [TA-1] to [TA-5] under a basic catalyst: Can be combined.

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

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

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

T ⁹ , T ¹¹ , T ¹⁷ and T ¹⁹ each represent the structures of the formulas [2-1a] to [2-7a]. Among them, formulas [2-1a] to [2-4a] are preferable from the viewpoint of adhesion between the liquid crystal layer of the liquid crystal display element and the liquid crystal alignment film. More preferably, it is a formula [2-1a] or a formula [2-2a]. T ¹⁰ and ^{T 18} is a straight or branched alkylene group having 2 to 12 carbon atoms. Among them, a linear or branched alkylene group having 2 to 8 carbon atoms is preferable.

T ¹² and ^{T 20} shows the structure of the formula [1-1b] ~ formula [1-4b]. Above all, formula [1-1b], formula [1-2b] or formula [1-4b] is preferable from the viewpoint of the optical characteristics of the liquid crystal display element. More preferably, the formula [1-1b] or the formula [1-2b]. T ¹³ and ^{T 21} represents 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, 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 from the viewpoint of optical characteristics of the liquid crystal display device. More preferably, it is an alkyl group having 1 to 12 carbon atoms or an alkoxy group having 1 to 12 carbon atoms. T ²² represents a divalent organic group having 17 to 51 carbon atoms having a steroid skeleton. pT shows the integer of 0-4. Especially, 0-3 are preferable. More preferably, it is 0-2.

  Specific examples of the specific compounds of the formulas [1b] and [1c] include the following formulas [1a-1] to [1a-16], and it is preferable to use these.

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

T ^D represents a structure selected from formula [1-1b] ~ formula [1-4b]. T ^E is a single bond, -O -, - COO- or an -OCO-. T ^F is a single _{bond, -CH 2 -, - O -} , - COO- or an -OCO-. ^TG represents an alkyl group having 1 to 12 carbon atoms or an alkoxy group having 1 to 12 carbon atoms. p8 and p9 each represent an integer of 0 to 7, and p8 + p9 represents an integer of 1 to 7. p10 shows the integer of 0-8. p11, p12 and p13 each represent an integer of 0 to 6, and p11 + p12 + p13 represents an integer of 1 to 6.

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

  Specific examples of the specific compounds of the formulas [1b] and [1c] are more preferably the formulas [1a-5], [1a-7], [1a-11], and [1a-15]. . Particularly preferably, from the viewpoint of the optical characteristics of the liquid crystal display device, the formula [1a-5], the formula [1a-7] or the formula [1a-15] is used.

  The use ratio of the specific compound is preferably 1 to 40 parts by mass with respect to 100 parts by mass of the liquid crystal in the liquid crystal composition from the viewpoint of the optical characteristics of the liquid crystal display device. More preferably, it is 1 to 30 parts by mass. Particularly preferably, it is 1 to 15 parts by mass. In addition, the specific compound can be used singly or as a mixture of two or more according to each property. 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 device of the present invention but also as a component of the liquid crystal composition of other liquid crystal display devices.

  The liquid crystal composition used for the liquid crystal display device of the present invention contains a liquid crystal, a polymerizable compound and the specific compound of the formula [1a]. As the liquid crystal, a nematic liquid crystal, a smectic liquid crystal, or a cholesteric liquid crystal can be used. Among them, those having a negative dielectric anisotropy are preferable. Further, from the viewpoints of low-voltage driving and scattering characteristics, those having large anisotropy of dielectric constant and large anisotropy of refractive index are preferable. Further, as the liquid crystal, two or more types of liquid crystals can be used according to the above-described physical properties of the phase transition temperature, the dielectric anisotropy, and the 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 electric resistance and a high voltage holding ratio (VHR). Therefore, the liquid crystal is preferably a fluorine-based or chlorine-based liquid crystal that has a high electric resistance and does not decrease VHR due to active energy rays such as ultraviolet rays.

  The liquid crystal display element can be 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 is obtained. In this liquid crystal display device, the direction of the director of the liquid crystal (the direction of alignment) changes by 90 degrees depending on whether or not a voltage is applied. Therefore, in this device, a higher contrast can be obtained by utilizing the difference in the light absorption characteristics of the dichroic dye, as compared with a conventional guest-host device in which switching is performed in random alignment and vertical alignment. In a guest-host type element in which a dichroic dye is dissolved, the liquid crystal becomes colored when the liquid crystal is oriented in the horizontal direction, and becomes opaque only in the scattering state. Therefore, it is also possible to obtain an element that switches from colorless and transparent when no voltage is applied to colored and opaque and colored and transparent when voltage is applied.

  In order to form a polymer network, a polymerizable compound may be introduced into a liquid crystal composition, and a polymerization reaction may be performed by irradiation with ultraviolet rays during the production of a liquid crystal display device, or the polymerizable compound may be preliminarily polymerized. May be introduced into the liquid crystal composition. However, even when a polymer is used, it is necessary to have a site that undergoes a polymerization reaction upon irradiation with ultraviolet rays. More preferably, the handling of the liquid crystal composition, that is, from the viewpoint of suppressing the increase in viscosity of the liquid crystal composition and the solubility in the liquid crystal, by introducing a polymerizable compound into the liquid crystal composition, ultraviolet light during device production. It is preferable that a polymerization reaction be caused by irradiation to form a polymer network.

  The polymerizable compound in the liquid crystal composition is not particularly limited as long as the polymerizable compound is dissolved in the liquid crystal.When the polymerizable compound is dissolved in the liquid crystal, a temperature at which a part or the whole of the liquid crystal composition exhibits a liquid crystal phase exists. Is required. Even when a part of the liquid crystal composition shows a liquid crystal phase, the liquid crystal display element is visually confirmed, and it is sufficient that the entire element has substantially uniform transparency and scattering characteristics.

  The polymerizable compound may be any compound that can be polymerized by ultraviolet rays. In that case, the polymerization may proceed in any reaction form to form a polymer network. Specific reaction types include radical polymerization, cationic polymerization, anionic polymerization and polyaddition reaction. Among them, the reaction type of the polymerizable compound is preferably radical polymerization from the viewpoint of the optical characteristics of the liquid crystal display device. At that time, as the polymerizable compound, the following radical type polymerizable compound or an oligomer thereof can be used. As described above, a polymer obtained by polymerizing these polymerizable compounds can also be used.

  Specific examples of these radical-type polymerizable compounds or oligomers thereof include the radical-type polymerizable compounds described on pages 69 to 71 of International Publication WO 2015/146987 (published on 2015.10.1). The proportion of the radical-type polymerizable compound or the oligomer thereof is from 70 to 120 parts by mass with respect to 100 parts by mass of the liquid crystal in the liquid crystal composition from the viewpoint of the adhesion between the liquid crystal layer of the liquid crystal display element and the liquid crystal alignment film. Is preferred. More preferably, it is 80 to 110 parts by mass. In addition, one of these radical polymerizable compounds may be used alone, or two or more of them may be used in combination according to each property.

  In order to promote the formation of a polymer network, a radical initiator (also referred to as a polymerization initiator) that generates radicals by ultraviolet rays is introduced into the liquid crystal composition for the purpose of promoting radical polymerization of the polymerizable compound. Is preferred. Specific examples include the radical initiators described on pages 71 to 72 of International Publication WO 2015/146987 (published on 2015.10.1). The usage ratio of the radical initiator is preferably 0.01 to 10 parts by mass with respect to 100 parts by mass of the liquid crystal in the liquid crystal composition, from the viewpoint of the adhesion between the liquid crystal layer of the liquid crystal display device and the liquid crystal alignment film. More preferably, it is 0.05 to 5 parts by mass. The radical initiator can be used singly or as a mixture of two or more, depending on each property.

  It is preferable to introduce a compound represented by the following formula [2a] (also referred to as an additive compound) into the liquid crystal composition used in the liquid crystal display device of the present invention in order to enhance the optical properties, particularly transparency, of the liquid crystal display device. In particular, it is preferable to use with a specific compound.

W ¹ represents a structure selected from the following formulas [2-1a] to [2-7a]. W ² is a single bond, -O -, - COO- or an -OCO-. W ³ represents a single bond or an alkylene group having 1 to 12 carbon atoms. W ⁴ represents a single bond, —O—, —COO—, or —OCO—. W ⁵ represents a benzene ring, a cyclohexane ring or a divalent organic group having 17 to 51 carbon atoms having a steroid skeleton. W ⁶ being a single _{bond, -CH 2 -, - CH 2} O -, - OCH 2 -, - O -, - COO -, - OCO -, - NHCO- or an -CONH-. W ⁷ represents a benzene ring or a cyclohexane ring. W ⁸ is an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, or a fluorine-containing alkoxy group having 1 to 18 carbon atoms. Represents a group. mW represents an integer of 0 to 4.

W ^A is a hydrogen atom or a benzene ring.

  More specifically, the compounds of the formula [2a] include the compounds of the following formulas [2a-1] to [2a-6]. These compounds are used in view of the optical characteristics of the liquid crystal display device. Is preferred.

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

W ^C is a single bond, -O -, - COO- or an -OCO-. W ^D is a single _{bond, -CH 2 -, - O -} , - COO- or an -OCO-. W ^E denotes an alkyl group or an alkoxy group having 1 to 12 carbon atoms having 1 to 12 carbon atoms. p3 represents an integer of 1 to 8.

W ^F is a single bond, -O -, - COO- or an -OCO-. p4 shows the integer of 0-8.

  Among the compounds of the formula [2a], the formula [2a-1], the formula [2a-2], the formula [2a-7] or the formula [2a-8] are particularly preferable from the viewpoint of the optical characteristics of the liquid crystal display device. preferable. More preferably, it is a formula [2a-1] or a formula [2a-2].

  The use ratio of the additive compound is preferably 1 to 30 parts by mass with respect to 100 parts by mass of the liquid crystal in the liquid crystal composition from the viewpoint of the optical characteristics of the liquid crystal display device. More preferably, it is 1 to 20 parts by mass, most preferably 1 to 15 parts by mass. Further, the additive compounds can be used singly or as a mixture of two or more kinds according to each property.

<Polymer>
As the liquid crystal alignment film in the liquid crystal display element of the present invention, a liquid crystal alignment film obtained from a liquid crystal alignment agent containing a polymer having a specific side chain structure represented by the following formula [4-1a] or [4-2a] is used. Is preferred.

X ¹ is a single _{bond, - (CH 2) a -} (a is an integer of _{1~15), - O -, -} CH 2 O -, - COO- or an -OCO-. From the standpoint of ease of the availability of raw materials and synthetic, single _{bond, - (CH 2) a -} (a is an integer of 1~15), - O -, - CH 2 O- or -COO -Is preferred. More preferably, a single _{bond, - (CH 2) a -} (a is an integer of 1 to _{10), - O -, - CH} 2 O- or -COO- in which. 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 preferable.

X ³ is a single _{bond, - (CH 2) a -} (a is an integer of _{1~15), - O -, -} CH 2 O -, - COO- or an -OCO-. Among them, for ease of synthesis, a single _{bond, - (CH 2) a -} (a is an integer of 1~15), - O -, - CH 2 O- or -COO- are preferred. More preferably, a single _{bond, - (CH 2) a -} (a is an integer of 1 to _{10), - O -, - CH} 2 O- or -COO- in which. X ⁴ represents a divalent cyclic group selected from a benzene ring, a cyclohexane ring and a heterocyclic ring, or a divalent organic group having a steroid skeleton and having 17 to 51 carbon atoms, and an arbitrary hydrogen atom on the cyclic group is It may be substituted by an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxy group having 1 to 3 carbon atoms or a fluorine atom. Among them, an organic group having 17 to 51 carbon atoms having a benzene ring, a cyclohexane ring or a steroid skeleton is preferable from the viewpoint of ease of synthesis.

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 may be an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, It may be substituted with a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxy group having 1 to 3 carbon atoms, or a fluorine atom. Among them, a benzene ring or a cyclohexane ring is preferred.

X ⁶ is an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, or a fluorine-containing alkoxy group having 1 to 18 carbon atoms. Represents a group. Among them, an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 18 carbon atoms or a fluorine-containing alkoxy group having 1 to 10 carbon atoms is preferable. More preferably, it is an alkyl group having 1 to 12 carbon atoms or an alkoxy group having 1 to 12 carbon atoms. Especially preferably, it is a C1-C9 alkyl group or a C1-C9 alkoxy group. n shows the integer of 0-4. Among these, 0 to 3 are preferable from the viewpoint of availability of raw materials and ease of synthesis. More preferably, it is 0-2.

Preferred combinations of X ^{1 to} X ⁶ and n are described in Tables 6 to 47 on pages 13 to 34 of International Publication WO2011 / 132751 (published on 2011.10.27) (2-1) to (2). -629). In each table of International Publication, ^X 1 to X ⁶ in the present invention is shown as Y1 to Y6, Y1 to ^Y6, it shall read X 1 to X ^6. In addition, in (2-605) to (2-629) described in each table of International Publication, the organic group having 17 to 51 carbon atoms having a steroid skeleton in the present invention is a compound having 12 to 12 carbon atoms having a steroid skeleton. Although shown as an organic group having 25, an organic group having 12 to 25 carbon atoms having a steroid skeleton is to be read as an organic group having 17 to 51 carbon atoms having a steroid skeleton.

  Among them, (2-25) to (2-96), (2-145) to (2-168), (2-217) to (2-240), (2-268) to (2-315) , (2-364) to (2-387), (2-436) to (2-483), or (2-603) to (2-615). More preferably, (2-49)-(2-96), (2-145)-(2-168), (2-217)-(2-240), (2-603)-(2-606) ), (2-607) to (2-609), (2-611), (2-612) or (2-624).

X ⁷ is a single _{bond, -O -, - CH 2 O} -, - CONH -, - NHCO -, - CON (CH 3) -, - N (CH 3) CO -, - shows a COO- or -OCO- . Among them, a single _{bond, -O -, - CH 2 O} -, - CONH -, - CON (CH 3) - or -COO- are preferred. More preferably, it is a single bond, -O-, -CONH- or -COO-. X ⁸ represents a fluorine-containing alkyl group having 6 to 18 carbon alkyl group or C of 8-18 carbon atoms. Among them, an alkyl group having 8 to 18 carbon atoms is preferable.

  As described above, the specific side chain structure in the invention is preferably Formula [4-1a] from the viewpoint that a high and stable vertical alignment of liquid crystal can be obtained.

  The specific polymer having a specific side chain structure is not particularly limited, but may be at least one polymer selected from an acrylic polymer, a methacrylic polymer, a novolak resin, a polyhydroxystyrene, a polyimide precursor, a polyimide, a polyamide, a polyester, a cellulose, and a polysiloxane. Coalescence is preferred. More preferably, it is a polyimide precursor, polyimide or polysiloxane. When a polyimide precursor or a polyimide (also collectively referred to as a polyimide-based polymer) is used as the specific polymer, a polyimide precursor or a polyimide obtained by reacting a diamine component with a tetracarboxylic acid component is preferable.

  The polyimide precursor has a structure represented by 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. A ³ and A ⁴ each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or an acetyl group. n shows a positive integer.

  The diamine component is a diamine having two primary or secondary amino groups in the molecule, and the tetracarboxylic acid component is a tetracarboxylic acid compound, a tetracarboxylic dianhydride, a tetracarboxylic dihalide compound, Examples thereof include carboxylic acid dialkyl ester compounds and tetracarboxylic acid dialkyl ester dihalide compounds.

  The polyimide-based polymer can be obtained relatively easily by using a tetracarboxylic dianhydride of the following formula [B] and a diamine of the following formula [C] as raw materials. A polyamic acid having a structural formula of a repeating unit or a polyimide obtained by imidizing the polyamic acid is preferable.

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

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

In addition, the polymer of the formula [D] obtained above is added to the polymer of the formula [D] obtained by an ordinary synthesis technique, and the alkyl group having 1 to 8 carbon atoms of A ¹ and A ^{2 in} the formula [A], and the polymer of the formula [A] It is also possible to introduce an alkyl group having 1 to 5 carbon atoms or an acetyl group of A ³ and A ⁴ .

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

X represents the structure of the formula [4-1a] or the formula [4-2a]. Further, details and preferred combinations of X ¹ , X ² , X ³ , X ⁴ , X ⁵ , X ⁶ and n in the formula [4-1a] are as in the formula [4-1a], and the formula [4a] -2a], details and preferred combinations of X ⁷ and X ⁸ are as described in the above formula [4-2a]. m shows the integer of 1-4. Above all, 1 is preferable. In the present invention, as described above, it is preferable to use the specific side chain type diamine having the 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] are described in the formula [2] described on pages 15 to 19 of International Publication WO2013 / 125595 (published on 2013.8.29). -1] to formula [2-6] and formula [2-9] to formula [2-36]. In the description of International Publication WO2013 / 125595, R ₂ in the formulas [2-1] to [2-3] and R ₄ in the formulas [2-4] to [2-6] are carbon atoms. It represents 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, or a fluorine-containing alkoxy group having 1 to 18 carbon atoms. A ₄ in Formula [2-13] represents a linear or branched alkyl group having 3 to 18 carbon atoms. In addition, _R 3 in the formula [2-4] to the formula [2-6] _{is, -O -, - CH 2 O} -, - COO- or an -OCO-.

  Among them, preferred diamines are those represented by the formulas [2-1] to [2-6], [2-9] to [2-13] or [2-22] described in International Publication WO2013 / 125595. ] To Formula [2-31]. More preferably, diamines represented by the following formulas [4a-32] to [4a-41] are preferable from the viewpoint of the optical characteristics of the liquid crystal display device.

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 isomer of 1,4-cyclohexylene is a trans isomer.

  Particularly preferred are diamines represented by the formulas [4a-35] to [4a-37], [4a-40] or [4a-41] from the viewpoint of the optical characteristics of the liquid crystal display device.

Specific examples of the specific side chain type diamine having a specific side chain structure represented by the formula [4-2a] include formulas [DA1] to formula [DA1] described on page 23 of International Publication WO2013 / 125595 (2013.8.29). [DA11]. In the description of International Publication WO2013 / 125595, _{A 1} in the formula [DA1] ~ formula [DA5] is an alkyl group or a fluorine-containing alkyl group having 6 to 18 carbon atoms having 8 to 22 carbon atoms.

  The use ratio of the specific side chain type diamine is preferably from 10 to 80 mol% based on the entire diamine component from the viewpoint of the optical characteristics of the liquid crystal display element and the adhesion between the liquid crystal layer and the liquid crystal alignment film. More preferably, it is 20 to 70 mol%. Further, the specific side chain type diamine can be used singly or as a mixture of two or more types according to each property.

<Second diamine>
The diamine component for producing the polyimide polymer preferably contains a diamine represented by the following formula [4b] (also referred to as a second diamine).

Y ¹ is a single _{bond, -O -, - NH -,} - N (CH 3) -, - CH 2 O -, - CONH -, - NHCO -, - CON (CH 3) -, - N (CH 3) CO-, -COO- or -OCO- is shown. Among them, a single _{bond, -O -, - CH 2 O} -, - CONH -, - COO- or -OCO- are preferred. More preferably, from easiness of the availability of raw materials and synthetic, single bond, -O -, - _CH 2 O- or -COO- in which.

Y ² represents a single bond, an alkylene group having 1 to 18 carbon atoms, or an organic group having 6 to 24 carbon atoms having a cyclic group selected from a benzene ring, a cyclohexane ring, and a heterocyclic ring; The atom is substituted with an alkyl group having 1 to 3 carbon atoms, an alkoxyl group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxyl group having 1 to 3 carbon atoms or a fluorine atom. Is also good. Among them, a single bond, an alkylene group having 1 to 12 carbon atoms, a benzene ring or a cyclohexane ring is preferable. More preferably, it is a single bond or an alkylene group having 1 to 12 carbon atoms in view of adhesion between the liquid crystal layer and the liquid crystal alignment film.

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- is shown. Among them, a single bond, -O-, -COO- or -OCO- is preferable. More preferably, it is a single bond or -OCO-. Y ⁴ represents a structure selected from the following formulas [4ba] to [4bi], and preferably formulas [4ba] to [4b-f]. Of these, formulas [4ba] to [4be] are preferable. More preferably, from the adhesion between the liquid crystal layer and the liquid crystal alignment film, the formula [4ba], the formula [4bb], the formula [4bd] or the formula [4be] is used.

Y ^A represents a hydrogen atom or a benzene ring. m shows the integer of 1-4. Especially, 1 or 2 is preferable. n shows the integer of 1-4. Above all, 1 is preferable.

  Specific examples of the second diamine include the following formulas [4b-1] to [4b-12], and it is preferable to use these.

  n1 represents an integer of 2 to 12.

  n2 shows the integer of 0-12. n3 represents an integer of 2 to 12.

  Specific examples of the second diamine include, among others, Formula [4b-1], Formula [4b-2], Formula [4b-5] to Formula [4b-7], Formula [4b-11], or Formula [4b] -12] is preferred. More preferably, formulas [4b-5] to [4b-7], [4b-11] or [4b-12] are used.

  The use ratio of the second diamine is preferably from 10 to 70 mol%, more preferably from 20 to 60 mol%, based on the entire diamine component, from the viewpoint of the optical characteristics of the liquid crystal display element and the adhesion between the liquid crystal layer and the liquid crystal alignment film. preferable. In addition, the second diamine can be used singly or as a mixture of two or more types according to each property.

<Third diamine>
The diamine component for producing the polyimide-based polymer preferably also contains a diamine of the following formula [4c] (also referred to as a third diamine).

  W represents a structure selected from the following formulas [4c-a] to [4cd]. m shows the integer of 1-4. Above all, 1 is preferable.

a shows the integer of 0-4. Among them, 0 or 1 is preferable from the viewpoint of availability of raw materials and ease of synthesis. b shows the integer of 0-4. Among them, 0 or 1 is preferable from the viewpoint of availability of raw materials and ease of synthesis. Each W ^A and ^{W B,} an alkyl group having 1 to 12 carbon atoms. W ^C represents an alkyl group having 1 to 5 carbon atoms.

  The following are specific examples of the third diamine. 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, and 3,5-diaminobenzoic acid. In addition, diamines of the following formulas [4c-1] and [4c-2] can be given.

  Specific examples of the third diamine include, among others, 2,4-diaminophenol, 3,5-diaminophenol, 3,5-diaminobenzyl alcohol, 2,4-diaminobenzyl alcohol, 4,6-diaminoresorcinol, Preferred are 2,4-diaminobenzoic acid, 2,5-diaminobenzoic acid, 3,5-diaminobenzoic acid, and the diamine of the formula [4c-1] or [4c-2]. More preferably, 2,4-diaminophenol, 3,5-diaminophenol, 3,5-diaminobenzyl alcohol, 3,5-diaminobenzyl alcohol, and the like, from the viewpoint of solubility of the polyimide polymer in a solvent and optical characteristics of a liquid crystal display device. -Diaminobenzoic acid or a formula [2a-1].

  Diamines other than the above-mentioned diamines (also referred to as other diamines) can be used as the diamine component for producing the polyimide-based polymer. More specifically, other diamine compounds described on pages 27 to 30 of International Publication WO2015 / 012368 (published on 2015.1.29), and the formula [DA1 To the formula [DA14]. In addition, other diamines can be used singly or in combination of two or more according to each property.

<Tetracarboxylic acid component>
Examples of the tetracarboxylic acid component for producing the polyimide polymer include a tetracarboxylic dianhydride represented by the following formula [5], a tetracarboxylic acid derivative of tetracarboxylic acid, a tetracarboxylic dihalide compound, and tetracarboxylic acid. It is preferable to use a dialkyl ester compound or a tetracarboxylic acid dialkyl ester dihalide compound (all are collectively referred to as a specific tetracarboxylic acid component).

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

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

  Among them, Z in the formula [5] represents the formula [5a], the formula [5c], the formula [5d], the formula [5d] from the viewpoint of easiness of synthesis and easiness of polymerization reactivity when producing a polymer. 5e], formula [5f], formula [5g], formula [5k] or formula [51] are preferable. More preferably, formula [5a], formula [5e], formula [5f], formula [5g], formula [5k], or formula [51]. Particularly preferably, from the viewpoint of the optical characteristics of the liquid crystal display element, the formula [5a], the formula [5e], the formula [5f], the formula [5g] or the formula [5l] are used.

  The use ratio of the specific tetracarboxylic acid component is preferably 1 mol% or more based on all the tetracarboxylic acid components. More preferably, it is at least 5 mol%. Particularly preferably, it is at least 10 mol%. Most preferably, it is 10 to 90 mol% from the viewpoint of the optical characteristics of the liquid crystal display device.

  As 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. Other tetracarboxylic acid components include the following tetracarboxylic acid compounds, tetracarboxylic dianhydrides, dicarboxylic dihalide compounds, dicarboxylic dialkyl ester compounds or dialkyl ester dihalide compounds.

  Specific examples thereof include other tetracarboxylic acid components described on pages 34 to 35 of International Publication WO2015 / 012368 (published on 2015.1.29). The specific tetracarboxylic acid component and other tetracarboxylic acid components can be used singly or as a mixture of two or more types according to each property. The method for synthesizing the polyimide polymer is not particularly limited. Usually, it is obtained by reacting a diamine component with a tetracarboxylic acid component. Specifically, the method described on pages 35 to 36 of International Publication WO2015 / 012368 (published on 2015.1.29) may be mentioned.

<Polyimide polymer and its production>
The reaction between the diamine component and the tetracarboxylic acid component is usually performed in a solvent containing the diamine component and the tetracarboxylic acid component. The solvent used at this time is not particularly limited as long as the produced polyimide precursor is dissolved. Specifically, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, γ-butyrolactone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide, or 1,3-dimethyl-imidazolide And non. In addition, when the solvent solubility of the polyimide precursor is high, methyl ethyl ketone, cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone, or a solvent represented by the following formulas [D1] to [D3] may be used. it can.

D ¹ and D ² represent an alkyl group having 1 to 3 carbon atoms. D ³ represents an alkyl group having 1 to 4 carbon atoms. These may be used alone or as a mixture. Furthermore, even if the solvent does not dissolve the polyimide precursor, it may be mixed with the above-mentioned solvent and used as long as the generated polyimide precursor does not precipitate. Further, since water in the organic solvent inhibits the polymerization reaction and further causes hydrolysis of the produced polyimide precursor, it is preferable to use a dehydrated organic solvent as the organic solvent.

  Polyimide is a polyimide obtained by ring-closing a polyimide precursor. In this polyimide, the ring-closure rate of amic acid groups (also referred to as imidation rate) does not necessarily need to be 100%, and depends on the application and purpose. It can be prepared arbitrarily. Above all, from the viewpoint of solubility of the polyimide polymer in the solvent, 30 to 80% is preferable. More preferably, it is 40 to 70%.

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

<Production of siloxane polymer>
When a polysiloxane is used for the specific polymer, a polysiloxane obtained by polycondensing an alkoxysilane of the following formula [A1], or an alkoxysilane of the formula [A1], and the following formula [A2] and / or the formula [A1] It is preferable to use a polysiloxane (collectively referred to as a polysiloxane polymer) obtained by polycondensing the alkoxysilane of A3].

  An alkoxysilane of the formula [A1]:

A ¹ represents a structure of the formula [4-1a] or formula [4-2a]. Further, details and preferred combinations of X ¹ , X ² , X ³ , X ⁴ , X ⁵ , X ⁶ and n in the formula [4-1a] are as in the formula [4-1a], and the formula [4a] -2a], details and preferred combinations of X ⁷ and X ⁸ are as described in the above formula [4-2a]. Above all, the structure represented by the formula [4-1a] is preferable because a high and stable vertical alignment of the liquid crystal can be obtained. A ² represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. Among them, a hydrogen atom or an alkyl group having 1 to 3 carbon atoms is preferable. A ³ represents an alkyl group having 1 to 5 carbon atoms. Among them, an alkyl group having 1 to 3 carbon atoms is preferable from the viewpoint of polycondensation reactivity.

  m represents an integer of 1 or 2. Among them, 1 is preferable from the viewpoint of ease of synthesis. n shows the integer of 0-2. p shows the integer of 0-3. Among them, 1 to 3 are preferable from the viewpoint of the reactivity of polycondensation. More preferably, it is 2 or 3. m + n + p is 4.

  Specific examples of the alkoxysilane of the formula [A1] include those of the formulas [2a-1] to [2a-32] described on pages 17 to 21 of WO2015 / 008846 (published on 2015.1.22). Alkoxysilane is mentioned. Among them, alkoxysilanes of the formulas [2a-9] to [2a-21], [2a-25] to [2a-28] or [2a-32] in the same publication are preferable. The alkoxysilane of the formula [A1] can be used singly or in combination of two or more, depending on each property.

  An alkoxysilane of the formula [A2]:

B ¹ represents shows a vinyl group, an epoxy group, an amino group, a mercapto group, an isocyanate group, methacryl group, acryl group, an organic group having 2 to 12 carbon atoms and having at least one selected from a ureido group, and a cinnamoyl group. Among them, an organic group having a vinyl group, an epoxy group, an amino group, a methacryl group, an acryl group, or a ureide group is preferable from the viewpoint of availability. More preferably, it is an organic group having a methacryl group, an acrylic group or a ureide group. B ² represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. Among them, a hydrogen atom or an alkyl group having 1 to 3 carbon atoms is preferable. B ³ represents an alkyl group having 1 to 5 carbon atoms. Among them, an alkyl group having 1 to 3 carbon atoms is preferable from the viewpoint of polycondensation reactivity.

  m represents an integer of 1 or 2. Among them, 1 is preferable from the viewpoint of ease of synthesis. n shows the integer of 0-2. p shows the integer of 0-3. Among them, 1 to 3 are preferable from the viewpoint of the reactivity of polycondensation. More preferably, it is 2 or 3. m + n + p is 4.

  Specific examples of the alkoxysilane of the formula [A2] include specific examples of the alkoxysilane of the formula [2b] described on pages 21 to 24 of International Publication WO2015 / 008846 (published on 2015.1.22). Among them, allyltriethoxysilane, allyltrimethoxysilane, diethoxymethylvinylsilane, dimethoxymethylvinylsilane, triethoxyvinylsilane, vinyltrimethoxysilane, vinyltris (2-methoxyethoxy) silane, 3- (triethoxysilyl) propyl methacrylate, 3- (trimethoxysilyl) propyl acrylate, 3- (trimethoxysilyl) propyl methacrylate, 3-glycidyloxypropyl (dimethoxy) methylsilane, 3-glycidyloxypropyl (diethoxy) methylsilane, 3-glycidyloxypropyltrimethoxysilane or 2 -(3,4-Epoxycyclohexyl) ethyltrimethoxysilane is preferred. The alkoxysilane of the formula [A2] can be used singly or in combination of two or more, depending on each property.

  The alkoxysilane of the formula [A3]:

D ¹ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. Among them, a hydrogen atom or an alkyl group having 1 to 3 carbon atoms is preferable. D ² represents an alkyl group having 1 to 5 carbon atoms. Among them, an alkyl group having 1 to 3 carbon atoms is preferable from the viewpoint of polycondensation reactivity. n shows the integer of 0-3.

  Specific examples of the alkoxysilane of the formula [A3] include the specific examples of the alkoxysilane of the formula [2c] described on pages 24 to 25 of WO2015 / 008846 (published on 2015.1.22).

  In the formula [A3], examples of the alkoxysilane in which n is 0 include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, and tetrabutoxysilane, and the alkoxysilane of the formula [A3] includes these alkoxysilanes. Preferably, silane is used. The alkoxysilane of the formula [A3] can be used singly or as a mixture of two or more, depending on each property.

  The polysiloxane-based polymer is obtained by polycondensing an alkoxysilane of the formula [A1] or an alkoxysilane of the formula [A1] and an alkoxysilane of the formula [A2] and / or the formula [A3]. It is a polysiloxane obtained by polycondensation. That is, the polysiloxane polymer is a polysiloxane obtained by polycondensation of only the alkoxysilane of the formula [A1], and a polysiloxane obtained by polycondensation of two types of alkoxysilanes of the formula [A1] and the formula [A2]. A siloxane, a polysiloxane obtained by polycondensing two types of alkoxysilanes of the formulas [A1] and [A3], and three types of alkoxysilanes of the formulas [A1], [A2] and [A3] Any one of polysiloxanes obtained by condensation.

  Among them, polysiloxanes obtained by polycondensing a plurality of types of alkoxysilanes are preferable from the viewpoint of polycondensation reactivity and solubility of the polysiloxane polymer in a solvent. That is, a polysiloxane obtained by polycondensing two types of alkoxysilanes of the formulas [A1] and [A2], and a polysiloxane obtained by polycondensing two types of alkoxysilanes of the formulas [A1] and [A3]. It is preferable to use any one of siloxane and polysiloxane obtained by polycondensing three types of alkoxysilanes of the formulas [A1], [A2] and [A3].

  When a plurality of types of alkoxysilanes are used when producing a polysiloxane-based polymer, the usage ratio of the alkoxysilane of the formula [A1] is preferably 1 to 40 mol%, and more preferably 1 to 30 mol% in all the alkoxysilanes. Is more preferred. Further, the usage ratio of the alkoxysilane of the formula [A2] is preferably from 1 to 70 mol%, more preferably from 1 to 60 mol% in all the alkoxysilanes. Further, the usage ratio of the alkoxysilane of the formula [A3] is preferably from 1 to 99 mol%, more preferably from 1 to 80 mol%, in all the alkoxysilanes.

  The method for polycondensing the polysiloxane polymer is not particularly limited. Specifically, the method described on pages 26 to 29 of International Publication WO2015 / 008846 (published on 2015.1.22) may be mentioned.

  In the case of using a plurality of types of alkoxysilanes of the formula [A1], [A2] or [A3] in the polycondensation reaction for producing a polysiloxane polymer, use a mixture in which a plurality of types of alkoxysilanes are mixed in advance. The reaction may be performed while sequentially adding a plurality of types of alkoxysilanes.

  In the present invention, the solution of the polysiloxane polymer obtained by the above method may be used as the specific polymer as it is, or, if necessary, the solution of the polysiloxane polymer obtained by the above method may be used. It may be used as a specific polymer after concentration, dilution by adding a solvent, or substitution with another solvent.

  The solvent used for dilution (also referred to as an additional solvent) may be the solvent used for the polycondensation reaction or another solvent. The additive solvent is not particularly limited as long as the polysiloxane-based polymer is uniformly dissolved, and one or more kinds can be arbitrarily selected. Examples of the additive solvent include, in addition to the solvent used in the above-mentioned polycondensation reaction, ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone, and ester solvents such as methyl acetate, ethyl acetate and ethyl lactate.

  Furthermore, when a polysiloxane-based polymer and another polymer are used as the specific polymer, before mixing the other polymer with the polysiloxane-based polymer, the polysiloxane-based polymer is subjected to a polycondensation reaction. It is preferred that the generated alcohol be distilled off at normal pressure or reduced pressure.

<Liquid crystal aligning agent>
The liquid crystal alignment treating agent of the present invention is a solution for forming a liquid crystal alignment film, and contains a specific polymer having a specific side chain structure of the formula [4-1a] or the formula [4-2a] and a solvent. Solutions are preferred. All the polymer components in the liquid crystal alignment treatment agent may be all specific polymers, or may be mixed with other polymers. At that time, the content of the other polymer is 0.5 to 15 parts by mass, preferably 1 to 10 parts by mass with respect to 100 parts by mass of the specific polymer. As other polymers, the above-mentioned polymers having no specific side chain structure of the formula [4-1a] or the formula [4-2a] can be mentioned.

  The content of the solvent in the liquid crystal alignment treatment agent can be appropriately selected from the viewpoint of a method of applying the liquid crystal alignment treatment agent and obtaining a desired 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 agent is preferably 50 to 99.9% by mass. More preferably, it is 60 to 99% by mass. Particularly preferably, it is 65 to 99% by mass.

<Solvent>
The solvent used for the liquid crystal alignment treatment agent is not particularly limited as long as the solvent dissolves the specific polymer. Among them, when the specific polymer is a polyimide precursor, polyimide, polyamide or polyester, or, when the solubility of the acrylic polymer, methacrylic polymer, novolak resin, polyhydroxystyrene, cellulose or polysiloxane in the solvent is low, the following: It is preferable to use a solvent (also referred to as a solvent A) as shown in the following.

  For example, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, dimethyl sulfoxide, γ-butyrolactone, 1,3-dimethyl-imidazolidinone, methyl ethyl ketone , Cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone and the like. Among them, it is preferable to use N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone or γ-butyrolactone. These may be used alone or as a mixture.

  When the specific polymer is an acrylic polymer, a methacrylic polymer, a novolak resin, polyhydroxystyrene, cellulose or polysiloxane, further, the specific polymer is a polyimide precursor, a polyimide, a polyamide or a polyester, and the specific polymer When the solubility in a solvent is high, a solvent as shown below (also referred to as a solvent B) can be used.

  Specific examples of the solvent B include the solvent B described on pages 58 to 60 of International Publication WO2014 / 171493 (published by 2014.10.23). Among them, 1-hexanol, cyclohexanol, 1,2-ethanediol, 1,2-propanediol, propylene glycol monobutyl ether, ethylene glycol monobutyl ether, dipropylene glycol dimethyl ether, cyclohexanone, cyclopentanone or formula [D1] to It is preferable to use a solvent of the formula [D3].

  When these solvents B are used, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone or γ-butyrolactone of the solvents A is used in combination for the purpose of improving the coating property of the liquid crystal alignment treatment agent. Preferably, it is used. More preferably, γ-butyrolactone is used in combination.

  Since these solvents B can enhance the coating property and surface smoothness of the liquid crystal alignment film when applying the liquid crystal alignment treatment agent, when a polyimide precursor, polyimide, polyamide or polyester is used for the specific polymer. It is preferable to use it in combination with the solvent A. At that time, the solvent B is preferably contained in an amount of 1 to 99% by mass of the entire solvent contained in the liquid crystal alignment treatment agent. Especially, 10-99 mass% is preferable. More preferably, it is 20 to 95% by mass.

<Specific compound A>
The compound having at least one structure selected from the following formulas [b-1] to [b-11] (also referred to as a specific compound A) is included in the liquid crystal alignment treatment agent from the viewpoint of the optical characteristics of the liquid crystal display element. Is preferably introduced.

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

  Specific examples of the specific compound A include the following formulas [b-1a] to [b-24a], and their use is preferable.

k1 represents an integer of 1 to 12. Among them, 1 to 8 are preferable from the viewpoint of the optical characteristics of the liquid crystal display element. k2 represents an integer of 0 to 4. Above all, 1 or 2 is preferable from the viewpoint of the optical characteristics of the liquid crystal display element. K ^a is a single _{bond, -O -, - CH 2 O} -, - CONH -, - NHCO -, - CON (CH 3) -, - N (CH 3) CO -, - COO- or -OCO- the Show. Among them, -O- or -COO- is preferable from the viewpoint of availability of raw materials and ease of synthesis.

^Kb represents a C1-C18 alkyl group, a C1-C18 fluorine-containing alkyl group, a C1-C18 alkoxyl group or a C1-C18 fluorine-containing alkoxyl group. Among them, an alkyl group having 1 to 12 carbon atoms or an alkoxyl group having 1 to 12 carbon atoms is preferable. More preferably, it is an alkyl group having 1 to 8 carbon atoms or an alkoxyl group having 1 to 8 carbon atoms.

k3 represents an integer of 1 to 12. Among them, 1 to 8 are preferable from the viewpoint of the optical characteristics of the liquid crystal display element. K ^c is a single _{bond, - (CH 2) c -} (c is an integer of _{1~15), - O -, -} CH 2 O -, - COO- or an -OCO-. Among them, -COO- or -OCO- is preferable from the viewpoint of availability of raw materials and ease of synthesis. ^The K ^d, a single _{bond, -O -, - CH 2 O} -, - CONH -, - NHCO -, - CON (CH 3) -, - N (CH 3) CO -, - COO- or -OCO- the Show. Among them, -O- or -COO- is preferable from the viewpoint of availability of raw materials and ease of synthesis.

K ^e is an alkyl group, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxyl group or a fluorine-containing alkoxyl group having 1 to 18 carbon atoms having 1 to 18 carbon atoms having 1 to 18 carbon atoms. Among them, an alkyl group having 1 to 12 carbon atoms or an alkoxyl group having 1 to 12 carbon atoms is preferable. More preferably, it is an alkyl group having 1 to 8 carbon atoms or an alkoxyl group having 1 to 8 carbon atoms.

k4 represents an integer of 0 to 4. Above all, 1 or 2 is preferable from the viewpoint of the optical characteristics of the liquid crystal display element. K ^f is an alkyl group, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxyl group or a fluorine-containing alkoxyl group having 1 to 18 carbon atoms having 1 to 18 carbon atoms having 1 to 18 carbon atoms. Among them, an alkyl group having 1 to 12 carbon atoms or an alkoxyl group having 1 to 12 carbon atoms is preferable. More preferably, it is an alkyl group having 1 to 8 carbon atoms or an alkoxyl group having 1 to 8 carbon atoms.

k5 represents an integer of 1 to 12. Among them, 1 to 8 are preferable from the viewpoint of the optical characteristics of the liquid crystal display element. k6 represents an integer of 0 to 4. Above all, 1 or 2 is preferable from the viewpoint of the optical characteristics of the liquid crystal display element. K ^g represents an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxyl group having 1 to 18 carbon atoms, or a fluorine-containing alkoxyl group having 1 to 18 carbon atoms. Among them, an alkyl group having 1 to 12 carbon atoms or an alkoxyl group having 1 to 12 carbon atoms is preferable. More preferably, it is an alkyl group having 1 to 8 carbon atoms or an alkoxyl group having 1 to 8 carbon atoms.

K ^h is a single _{bond, - (CH 2) c -} (c is an integer of _{1~15), - O -, -} CH 2 O -, - COO- or an -OCO-. Among them, -COO- or -OCO- is preferable from the viewpoint of availability of raw materials and ease of synthesis. K ⁱ denotes an alkyl group, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxyl group or a fluorine-containing alkoxyl group having 1 to 18 carbon atoms having 1 to 18 carbon atoms having 1 to 18 carbon atoms. Among them, an alkyl group having 1 to 12 carbon atoms or an alkoxyl group having 1 to 12 carbon atoms is preferable. More preferably, it is an alkyl group having 1 to 8 carbon atoms or an alkoxyl group having 1 to 8 carbon atoms.

k7 represents an integer of 1 to 12. Among them, 1 to 8 are preferable from the viewpoint of the optical characteristics of the liquid crystal display element. K ^j is a single _{bond, - (CH 2) c -} (c is an integer of _{1~15), - O -, -} CH 2 O -, - COO- or an -OCO-. Among them, -COO- or -OCO- is preferable from the viewpoint of availability of raw materials and ease of synthesis.

K ^k represents an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxyl group having 1 to 18 carbon atoms, or a fluorine-containing alkoxyl group having 1 to 18 carbon atoms. Among them, an alkyl group having 1 to 12 carbon atoms or an alkoxyl group having 1 to 12 carbon atoms is preferable. More preferably, it is an alkyl group having 1 to 8 carbon atoms or an alkoxyl group having 1 to 8 carbon atoms.

  Specific examples of the specific compound A include, among others, formula [b-1a], formula [b-2a], formula [b-7a], formula [b-8a], formula [b-10a], and formula [b- 11a], formula [b-13a], formula [b-14a], formula [b-16a] or formula [b-17a].

  The proportion of the specific compound A in the liquid crystal alignment treatment agent is preferably 0.1 to 30 parts by mass with respect to 100 parts by mass of the specific polymer from the viewpoint of the optical characteristics of the liquid crystal display device. More preferably, it is 0.5 to 20 parts by mass. Particularly preferably, it is 1 to 10 parts by mass. In addition, the specific compound A can be used singly or as a mixture of two or more according to each property.

<Specific crosslinkable compound>
The liquid crystal alignment agent has a compound having at least one selected from an epoxy group, an isocyanate group, an oxetane group, a cyclocarbonate group, a hydroxy group, a hydroxyalkyl group and a lower alkoxyalkyl group in order to increase the film strength of the resin film. It is preferable to introduce (generically referred to as a specific crosslinking compound). At that time, these compounds need to have two or more in the compound.

  Specific examples of the crosslinkable compound having an epoxy group or an isocyanate group include a crosslinkable compound having an epoxy group or an isocyanate group described on pages 63 to 64 of International Publication WO2014 / 171493 (published on 2014.10.23). No.

  Specific examples of the crosslinkable compound having an oxetane group include the crosslinkable compounds represented by the formulas [4a] to [4k] described on pages 58 to 59 of WO2011 / 132751 (2011.10.27). No.

  Specific examples of the crosslinkable compound having a cyclocarbonate group include the formulas [5-1] to [5-42] described on pages 76 to 82 of WO2012 / 014898 (2012.2.2 publication). Crosslinkable compounds.

  Specific examples of the crosslinkable compound having a hydroxyl group, a hydroxyalkyl group and a lower alkoxyalkyl group include melamine derivatives or benzoguanamine derivatives described on pages 65 to 66 of International Publication WO 2014/171493 (2014.10.23). And the crosslinkable compounds of formulas [6-1] to [6-48] described on pages 62 to 66 of WO2011 / 132751 (published on 2011.10.27).

  The content of the specific crosslinking compound in the liquid crystal alignment treatment agent is preferably from 0.1 to 100 parts by mass based on 100 parts by mass of all the polymer components. More preferably, the amount is 0.1 to 50 parts by mass with respect to 100 parts by mass of all the polymer components, in order for the cross-linking reaction to proceed and express the desired effect. Particularly preferably, it is 1 to 30 parts by mass.

<Specific generator>
It is preferable to introduce at least one type of generator (also referred to as a specific generator) selected from a photoradical generator, a photoacid generator and a photobase generator into the liquid crystal alignment treatment agent. Specific examples of the specific generator include the specific generators described on pages 54 to 56 of International Publication WO 2014/171493 (published on 2014.10.23). Above all, it is preferable to use a photo-radical generator as the specific generator from the viewpoint of adhesion between the liquid crystal layer of the liquid crystal display element and the liquid crystal alignment film.

<Specific adhesive compound>
The liquid crystal alignment treatment agent has at least one structure selected from the following formulas [e-1] to [e-8] for the purpose of enhancing the adhesion between the liquid crystal layer of the liquid crystal display element and the vertical liquid crystal alignment film. It is preferable to introduce a compound (also referred to as a specific adhesive compound).

E ^A is a hydrogen atom or a benzene ring. E ^B represents at least one cyclic group selected from hexane ring and heterocyclic benzene ring, cyclohexane. E ^C denotes an alkyl group, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxy group or a fluorine-containing alkoxy group having 1 to 18 carbon atoms having 1 to 18 carbon atoms having 1 to 18 carbon atoms.

  Specific examples of the specific adhesive compound include a compound of the formula [6] described on pages 43 to 46 of International Publication WO2015 / 012368 (published on 2015.1.29). Further, adhesive compounds described on pages 61 to 63 of International Publication WO2014 / 171493 (published on 2014.10.23) can also be used.

  The content of the specific adhesive compound in the liquid crystal alignment agent is preferably 0.1 to 150 parts by mass with respect to 100 parts by mass of all polymer components. More preferably, the amount is 0.1 to 100 parts by mass with respect to 100 parts by mass of all the polymer components so that the crosslinking reaction proceeds and the desired effect is exhibited. Particularly preferably, it is 1 to 50 parts by mass.

  The liquid crystal alignment treatment agent is described on pages 69 to 73 of International Publication WO2011 / 132751 (2011.10.27 publication) in order to promote charge transfer in the liquid crystal alignment film and promote charge removal of the device. Alternatively, a nitrogen-containing heterocyclic amine compound of the formulas [M1] to [M156] can be added. This amine compound may be added directly to the liquid crystal alignment treatment agent, but is preferably added after a solution having a concentration of 0.1 to 10% by mass, preferably 1 to 7% by mass in a suitable solvent. The solvent is not particularly limited as long as it is an organic solvent that dissolves the specific polymer.

<Compound that improves uniformity of film thickness and surface smoothness of liquid crystal alignment film>
As the liquid crystal alignment treatment agent, a compound that improves the uniformity of the film thickness and the surface smoothness of the liquid crystal alignment film when the liquid crystal alignment treatment agent is applied can be used as long as the effects of the present invention are not impaired. Further, a compound or the like for improving the adhesion between the liquid crystal alignment film and the substrate can be used.

  Examples of the compound that improves the uniformity of the film thickness and the surface smoothness of the liquid crystal alignment film include a fluorine-based surfactant, a silicone-based surfactant, and a nonion-based surfactant. Specific examples include surfactants described on page 67 of International Publication WO2014 / 171493 (published on 2014.10.23). Further, the use ratio thereof is preferably 0.01 to 2 parts by mass, more preferably 0.01 to 1 part by mass, based on 100 parts by mass of all the polymer components contained in the liquid crystal alignment treatment agent. .

  Specific examples of the compound for improving the adhesion between the liquid crystal alignment film and the substrate include compounds described on pages 67 to 69 of International Publication WO2014 / 171493 (published on 2014.10.23). Further, the usage ratio is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass, based on 100 parts by mass of all the polymer components contained in the liquid crystal alignment treatment agent. In addition to the compounds other than those described above, a dielectric substance or a conductive substance for changing electric properties such as a dielectric constant and conductivity of the liquid crystal alignment film may be added to the liquid crystal alignment treatment agent.

<Method for producing liquid crystal alignment film and liquid crystal display element>
The substrate used for the liquid crystal display element is not particularly limited as long as it is a substrate having high transparency. In addition to a glass substrate, a plastic substrate such as an acrylic substrate, a polycarbonate substrate, a PET (polyethylene terephthalate) substrate, and a film made of such a film are used. Can be used. When the element is used as a reverse type element for a light control window or the like, a plastic substrate or a film is preferable. Further, from the viewpoint of simplification of the process, a substrate on which an ITO (Indium Tin Oxide) electrode, an IZO (Indium Zinc Oxide) electrode, an IGZO (Indium Gallium Zinc Oxide) electrode, an organic conductive film, etc. are formed for driving a liquid crystal. It is preferable to use In the case of a reflection type reverse type element, a silicon wafer or a substrate on which a metal such as aluminum or a dielectric multilayer film is formed can be used as long as only one substrate is used.

  In the liquid crystal display device, at least one of the substrates has a liquid crystal alignment film for vertically aligning liquid crystal molecules. This liquid crystal alignment film can be obtained by applying a liquid crystal alignment treatment agent on a substrate, baking it, and performing an alignment treatment by rubbing treatment or light irradiation. However, in the case of the liquid crystal alignment film in the present invention, it can be used without these alignment treatments. The method of applying the liquid crystal alignment treatment agent is not particularly limited, but industrially, there are screen printing, offset printing, flexographic printing, an inkjet method, a dip method, a roll coater method, a slit coater method, a spinner method, a spray method, and the like. It can be appropriately selected according to the type of the substrate and the intended thickness of the liquid crystal alignment film.

  After the liquid crystal aligning agent is applied on the substrate, it is heated by a heating means such as a hot plate, a heat circulating oven, or an IR (infrared) oven depending on the type of the substrate and the solvent used for the liquid crystal aligning agent. The solvent can be evaporated at a temperature of 300 ° C., preferably 30 to 250 ° C. to form a liquid crystal alignment film. In particular, when a plastic substrate is used as the substrate, the treatment is preferably performed at a temperature of 30 to 150 ° C.

  If the thickness of the liquid crystal alignment film after firing is too large, it is disadvantageous in terms of power consumption of the liquid crystal display element, and if too thin, the reliability of the element may be reduced. It is more preferably from 10 to 300 nm, particularly preferably from 10 to 250 nm. The liquid crystal composition used for the liquid crystal display element is the liquid crystal composition as described above, and a spacer for controlling an electrode gap (also referred to as a gap) of the liquid crystal display element can be introduced therein.

  The method for injecting the liquid crystal composition is not particularly limited, and examples thereof include the following method. That is, when a glass substrate is used as a substrate, a pair of substrates on which a liquid crystal alignment film is formed is prepared, and a sealant is applied to four pieces of one side of the substrate except for a part thereof. An empty cell in which the substrate on the other side is bonded to the inside is produced. Then, there is a method in which a liquid crystal composition is injected under reduced pressure from a place where the sealant is not applied to obtain a liquid crystal composition injection cell. When a plastic substrate or a film is used as the substrate, a pair of substrates having a liquid crystal alignment film formed thereon is prepared, and a liquid crystal composition is formed on one of the substrates by an ODF (One Drop Filling) method, an inkjet method, or the like. Is dropped, and then the other substrate is attached to obtain a liquid crystal composition injection 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 not necessary to apply a sealant to four pieces of the substrate.

  The gap of the liquid crystal display element can be controlled by the spacer or the like. Examples of the method include a method of introducing a spacer having a target size into a liquid crystal composition and a method of using a substrate having a column spacer having a target size, as described above. In the case where a plastic or film substrate is used as a substrate and the substrates are laminated by lamination, the gap can be controlled without introducing a spacer.

  The gap of the liquid crystal display device is preferably from 1 to 100 μm, more preferably from 1 to 50 μm. Particularly preferably, it is 2 to 30 μm. If the gap is too small, the contrast of the device decreases, and if it is too large, the driving voltage of the device increases.

  In the liquid crystal display element of the present invention, the liquid crystal composition is cured in a state where a part or the whole of the liquid crystal composition exhibits liquid crystallinity, thereby forming a cured product composite (liquid crystal layer) of liquid crystal and a polymerizable compound. can get. The curing of the liquid crystal composition is performed by irradiating the liquid crystal composition injection cell with ultraviolet rays. As a light source of the ultraviolet irradiation device used at that time, for example, a metal halide lamp or a high-pressure mercury lamp is used. The wavelength of the ultraviolet light is preferably from 250 to 400 nm. Especially, 310-370 nm is preferable. In addition, heat treatment may be performed after irradiation with ultraviolet light. The temperature at that time is 40 to 120 ° C, preferably 40 to 80 ° C.

  Hereinafter, the present invention will be described in more detail with reference to Examples, but it should not be construed that the invention is limited thereto. Abbreviations used below are as follows.

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

  <Additive compound>

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

  <Polymerizable compound>

  R3: Blemmer TA-604AU (manufactured by NOF CORPORATION)

  <Radical initiator>

"Compounds used for liquid crystal alignment treatment agent"
<Specific side chain type diamine>

  <Second diamine>

  <Third diamine>

  <Other diamines>

  <Specific tetracarboxylic acid component>

  <Monomer for producing polysiloxane polymer>

E2: octadecyltriethoxysilane E3: 3-methacryloxypropyltrimethoxysilane 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 monoethyl ether EC: diethylene glycol monoethyl ether

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

"Measurement of imidation rate of polyimide polymer"
20 mg of the polyimide powder is placed in an NMR (nuclear magnetic resonance) sample tube (NMR sampling tube standard, φ5 (manufactured by Kusano Science)), and deuterated dimethyl sulfoxide (DMSO-d6, 0.05% by mass TMS (tetramethylsilane)) (Mixture) (0.53 ml) was added, and the mixture was completely dissolved by sonication. The solution was measured for proton NMR at 500 MHz using an NMR measuring device (JNW-ECA500) (manufactured by JEOL Datum). The imidation ratio is determined based on a proton derived from a structure that does not change before and after imidation as a reference proton, and a peak integrated value of this proton and a proton peak derived from the NH group of the amic acid appearing around 9.5 ppm to 10.0 ppm. It was determined by the following equation using the integrated value.
Imidation ratio (%) = (1−α · x / y) × 100
(X is the integrated value of the proton peak derived from the NH group of the amic acid, y is the integrated value of the peak of the reference proton, α is the reference proton for one NH group proton of the amic acid in the case of polyamic acid (imidation ratio is 0%) Is the number ratio.)

"Synthesis of polyimide-based polymer"
<Synthesis example 1>
D2 (2.13 g, 8.50 mmol), A1 (4.91 g, 12.9 mmol), C1 (0.98 g, 6.46 mmol) and D1 (0.23 g, 2.15 mmol) were converted to NMP (28.7 g). After mixing at 80 ° C. for 4 hours, D1 (2.50 g, 12.8 mmol) and NMP (14.3 g) were added, and the mixture was reacted at 40 ° C. for 6 hours. % Polyamic acid solution (1) was obtained. The number average molecular weight (also referred to as Mn) of this polyamic acid was 17,300, and the weight average molecular weight (also referred to as Mw) was 56,200.

<Synthesis Example 2>
NMP was added to the polyamic acid solution (1) (30.0 g) obtained by the method of Synthesis Example 1 to dilute to 6% by mass, and then acetic anhydride (3.70 g) and pyridine (2.30 g) were used as imidation catalysts. ) Was added and reacted at 60 ° C. for 2.5 hours. This reaction solution was poured into methanol (450 ml), and the obtained precipitate was separated by filtration. This precipitate was washed with methanol and dried under reduced pressure at 100 ° C. to obtain a polyimide powder (2). The imidation ratio 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 in γ-BL (16.1 g), After reacting for 1 hour, D1 (1.00 g, 5.10 mmol) and γ-BL (8.06 g) were added, and the mixture was reacted at 40 ° C. for 6 hours. ) Got. Mn of this polyamic acid was 12,500 and Mw was 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 in γ-BL (18.1 g), After reacting for 1 hour, D1 (1.00 g, 5.10 mmol) and γ-BL (9.03 g) were added, and the mixture was reacted at 40 ° C. for 6 hours to obtain a polyamic acid solution (4%) having a resin solid content concentration of 20% by mass. ) Got. Mn of this polyamic acid was 11,100 and Mw was 37,600.

<Synthesis example 5>
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) were converted to γ-BL (16. 7g) and reacted at 60 ° C. for 4 hours. Then, D1 (1.30 g, 6.63 mmol) and γ-BL (8.33 g) were added, and the mixture was reacted at 40 ° C. for 6 hours. A polyamic acid solution (5) having a concentration of 20% by mass was obtained. Mn of this polyamic acid was 11,300 and Mw was 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) was mixed in γ-BL (16.6 g) and reacted at 60 ° C. for 4 hours. Then, D1 (1.50 g, 7.65 mmol) and γ-BL (8.29 g) were added. The reaction was carried out at 40 ° C. for 6 hours to obtain a polyamic acid solution (6) having a resin solid content of 20% by mass. Mn of this polyamic acid was 10,900 and 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 converted to γ-BL (18. 3g), and reacted at 60 ° C. for 4 hours. Then, D1 (1.00 g, 5.10 mmol) and γ-BL (9.16 g) were added, and the mixture was reacted at 40 ° C. for 6 hours. A polyamic acid solution (7) having a concentration of 20% by mass was obtained. Mn of this polyamic acid was 10,500 and 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 in NMP (40.8 g) and reacted at 40 ° C. for 12 hours. Thus, a polyamic acid solution (8) having a resin solid content of 20% by mass was obtained. Mn of this polyamic acid was 18,200 and Mw was 58,800.

<Synthesis example 9>
NMP was added to the polyamic acid solution (8) (30.0 g) obtained by the method of Synthesis Example 8 to dilute to 6% by mass, and then acetic anhydride (3.70 g) and pyridine (2.30 g) were used as imidation catalysts. ) And reacted at 60 ° C. for 3 hours. This reaction solution was poured into methanol (450 ml), and the obtained precipitate was separated by filtration. This precipitate was washed with methanol and dried under reduced pressure at 100 ° C. to obtain a polyimide powder (9). The imidation ratio 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 in γ-BL (15.8 g), After reacting for 1 hour, D1 (1.00 g, 5.10 mmol) and γ-BL (7.91 g) were added, and the mixture was reacted at 40 ° C. for 6 hours. ) Got. Mn of this polyamic acid was 10,900 and Mw was 37.800.

  Table 1 shows the polyimide polymers obtained in the synthesis examples. In Table 1, * 1 represents polyamic acid.

"Synthesis of polysiloxane polymer"
<Synthesis Example 11>
ECS (28.3 g), E1 (4.10 g), E3 (7.45 g) and E5 (32.5 g) were mixed in a 200 ml four-neck reaction flask equipped with a thermometer and a reflux tube. A solution of the alkoxysilane monomer was prepared. To this solution, a solution previously prepared by mixing ECS (14.2 g), water (10.8 g), and oxalic acid (0.70 g) as a catalyst was added dropwise at 25 ° C. over 30 minutes. Then, the mixture was further stirred at 25 ° C. for 30 minutes. Thereafter, the mixture was heated and refluxed for 30 minutes using an oil bath, and a previously prepared methanol solution (1.20 g) containing 92% by mass of E4 (1.10 g) and ECS (0.90 g) were prepared. ) Was added. After further reflux for 30 minutes, the mixture was allowed to cool to obtain a polysiloxane solution (1) having a concentration of 12% by mass in terms of SiO ₂ .

<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 solution of alkoxysilane monomer. did. A solution previously prepared by mixing EC (14.6 g), water (10.8 g), and oxalic acid (0.50 g) as a catalyst was dropped into this solution at 25 ° C. over 30 minutes. Then, the mixture was further stirred at 25 ° C. for 30 minutes. Thereafter, the mixture was heated and refluxed for 30 minutes using an oil bath, and a previously prepared methanol solution (1.20 g) containing 92% by mass of E4 (1.10 g) and EC (0.90 g) were prepared. Was added. After further refluxing for 30 minutes, the mixture was allowed to cool to obtain a polysiloxane solution (2) having a concentration in terms of SiO ₂ of 12% by mass.

<Synthesis Example 13>
ECS (28.3 g), E2 (4.07 g), E3 (7.45 g) and E5 (32.5 g) were mixed in a 200 ml four-necked reaction flask equipped with a thermometer and a reflux tube. A solution of the alkoxysilane monomer was prepared. To this solution, a solution previously prepared by mixing ECS (14.2 g), water (10.8 g), and oxalic acid (0.70 g) as a catalyst was added dropwise at 25 ° C. over 30 minutes. Then, the mixture was further stirred at 25 ° C. for 30 minutes. Thereafter, the mixture was heated and refluxed for 30 minutes using an oil bath, and a previously prepared methanol solution (1.20 g) containing 92% by mass of E4 (1.10 g) and ECS (0.90 g) were prepared. ) Was added. After further refluxing for 30 minutes, the mixture was allowed to cool to obtain a polysiloxane solution (3) having a concentration in terms of SiO ₂ of 12% by mass.

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

"Manufacture of liquid crystal alignment agent"
<Synthesis Example 14>
NMP (10.8 g) was added to the polyamic acid solution (1) (5.50 g) obtained by the method of Synthesis Example 1, and the mixture was stirred at 25 ° C. for 1 hour. Thereafter, BCS (6.07 g) and PB (9.10 g) were added, and the mixture was stirred at 25 ° C. for 4 hours to obtain a liquid crystal alignment agent (1). No abnormality such as turbidity or precipitation was observed in this liquid crystal alignment treatment agent, and the solution was a uniform solution.

<Synthesis Example 15>
NMP (15.2 g) was added to the polyimide powder (2) (1.10 g) obtained by the method of Synthesis Example 2 and dissolved by stirring at 70 ° C. for 24 hours. Thereafter, BCS (4.55 g), PB (10.6 g), Q1 (0.055 g) and K1 (0.077 g) were added, and the mixture was stirred at 25 ° C. for 4 hours to obtain a liquid crystal alignment agent (2). Was. No abnormality such as turbidity or precipitation was observed in this liquid crystal alignment treatment agent, and the solution was a uniform solution.

<Synthesis Example 16>
Γ-BL (1.80 g) and PGME (27.4 g) were added to the polyamic acid solution (3) (3.80 g) obtained by the method of Synthesis Example 3, and the mixture was stirred at 25 ° C. for 6 hours. An alignment agent (3) was obtained. No abnormality such as turbidity or precipitation was observed in this liquid crystal alignment treatment agent, and the solution was a uniform 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, and the mixture was added at 25 ° C. The mixture was stirred for 6 hours to obtain a liquid crystal alignment agent (4). No abnormality such as turbidity or precipitation was observed in this liquid crystal alignment treatment agent, and the solution was a uniform 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 (0.053 g) ) And stirred at 25 ° C. for 6 hours to obtain a liquid crystal alignment treatment agent (5). No abnormality such as turbidity or precipitation was observed in this liquid crystal alignment treatment agent, and the solution was a uniform 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. An alignment agent (6) was obtained. No abnormality such as turbidity or precipitation was observed in this liquid crystal alignment treatment agent, and the solution was a uniform 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 (0.053 g) ) And N1 (0.023 g) were added, and the mixture was stirred at 25 ° C. for 6 hours to obtain a liquid crystal aligning agent (7). No abnormality such as turbidity or precipitation was observed in this liquid crystal alignment treatment agent, and the solution was a uniform 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 (0.023 g) ) And K1 (0.053 g) were added and stirred at 25 ° C. for 6 hours to obtain a liquid crystal alignment agent (8). No abnormality such as turbidity or precipitation was observed in this liquid crystal alignment treatment agent, and the solution was a uniform 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 (0.076 g) ) And N1 (0.015 g) were added, and the mixture was stirred at 25 ° C. for 6 hours to obtain a liquid crystal aligning agent (9). No abnormality such as turbidity or precipitation was observed in this liquid crystal alignment treatment agent, and the solution was a uniform 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 (0.038 g) ) And K2 (0.076 g) were added, and the mixture was stirred at 25 ° C for 6 hours to obtain a liquid crystal aligning agent (10). No abnormality such as turbidity or precipitation was observed in this liquid crystal alignment treatment agent, and the solution was a uniform 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, and the mixture was stirred at 25 ° C. for 1 hour. Thereafter, PB (13.7 g), Q1 (0.033 g) and K1 (0.055 g) were added, and the mixture was stirred at 25 ° C. for 4 hours to obtain a liquid crystal alignment agent (11). No abnormality such as turbidity or precipitation was observed in this liquid crystal alignment treatment agent, and the solution was a uniform solution.

<Synthesis Example 25>
NMP (15.2 g) was added to the polyimide powder (9) (1.10 g) obtained by the method of Synthesis Example 9 and dissolved by stirring at 70 ° C. for 24 hours. Thereafter, BCS (3.03 g), PB (12.1 g), Q1 (0.055 g), K2 (0.077 g) and N1 (0.033 g) were added, and the mixture was stirred at 25 ° C. for 4 hours to align the liquid crystal. A treating agent (12) was obtained. No abnormality such as turbidity or precipitation was observed in this liquid crystal alignment treatment agent, and the solution was a uniform 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 6 hours. An alignment agent (13) was obtained. No abnormality such as turbidity or precipitation was observed in this liquid crystal alignment treatment agent, and the solution was a uniform solution.

<Synthesis Example 27>
ECS (5.04 g), PGME (14.6 g) and PB (2.91 g) were added to the polysiloxane solution (1) (7.50 g) obtained by the method of Synthesis Example 11, and the mixture was heated at 25 ° C. for 6 hours. The mixture was stirred to obtain a liquid crystal alignment agent (14). No abnormality such as turbidity or precipitation was observed in this liquid crystal alignment treatment agent, and the solution was a uniform solution.

<Synthesis example 28>
In 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), K1 (0.018 g) and N1 (0.027 g) were added, and the mixture was stirred at 25 ° C. for 6 hours to obtain a liquid crystal alignment treatment agent (15). No abnormality such as turbidity or precipitation was observed in this liquid crystal alignment treatment agent, and the solution was a uniform solution.

<Synthesis example 29>
ECS (5.04 g), PGME (14.6 g) and PB (2.91 g) were added to the polysiloxane solution (3) (7.50 g) obtained by the method of Synthesis Example 13, and the mixture was added at 25 ° C. for 6 hours. The mixture was stirred to obtain a liquid crystal alignment agent (16). No abnormality such as turbidity or precipitation was observed in this liquid crystal alignment treatment agent, and the solution was a uniform solution.

  Tables 3 and 4 show the liquid crystal aligning agents obtained in the synthesis examples. In Tables 3 and 4, the values in parentheses for the specific compound A, the specific crosslinking compound, and the specific generator added to the liquid crystal alignment treatment agent are the contents with respect to 100 parts by mass of each specific polymer. Is shown.

"Production of specific compound and liquid crystal composition of the present invention"
In Examples 1 to 4 below, examples of specific compounds produced by a predetermined method are described. In Examples 5 to 12, examples of liquid crystal compositions using these specific compounds will be described. The obtained liquid crystal composition is also used for production of a liquid crystal display element described below and its evaluation.

"Synthesis of specific compounds"
<Example 1>
Specific compound: Synthesis of T1

Compound (1) (20.0 g, 67.9 mmol), dibutylhydroxytoluene (0.72 g, 3.27 mmol), pyridine (53.8 g) and toluene (150 g) were added to a mixture of compound (2) at 25 ° C. ) (Karenz BEI: manufactured by Showa Denko KK) (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. Toluene (200 g) was added to the residue, and the solvent was distilled off under reduced pressure (this operation was repeated twice). Methanol (300 g) was added to the residue, and the mixture was stirred under ice cooling (0 ° C.), and the precipitated solid was collected by filtration. The obtained solid was washed with methanol (50 g) and dried to obtain a white crystal (T1) (amount: 31.5 g, yield: 86.7%).
1H-NMR (CDCl ₃ , σ ppm): 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

To 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), At 25 ° C, compound (2) (same as above) (4.69 g, 19.6 mmol) was added, and the mixture was stirred at 110 ° C for 48 hours. After the completion of the reaction, a diluted hydrochloric acid aqueous solution was added, and the mixture was extracted and separated with chloroform. The chloroform layer was washed three times with a dilute hydrochloric acid aqueous solution and twice with water, and dried by adding anhydrous magnesium sulfate. Thereafter, the solvent of the chloroform layer was distilled off under reduced pressure, and methanol (30 g) was added to the obtained residue. The precipitated solid was collected by filtration and dried to obtain pale yellowish white crystals (T2) (amount: 4.69 g, yield: 50.5%).
1H-NMR (CDCl ₃ , σ ppm): 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

To 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), At 25 ° C, compound (2) (same as above) (9.47 g, 39.6 mmol) was added, and the mixture was stirred at 110 ° C for 72 hours. After the completion of the reaction, a diluted hydrochloric acid aqueous solution was added, and the mixture was extracted and separated with chloroform. The chloroform layer was washed three times with a dilute hydrochloric acid aqueous solution and twice with water, and dried by adding anhydrous magnesium sulfate. Thereafter, the solvent of the chloroform layer was distilled off under reduced pressure, and isopropyl alcohol (150 g) was added to the obtained residue. Then, it heated at 40 degreeC and performed filtration. The obtained filtrate was distilled off under reduced pressure, methanol (150 g) was added to the residue, and the precipitated solid was taken out by filtration. The obtained solid was subjected to silica gel column chromatography (eluent: chloroform) to give a white crystal (T3) (amount: 2.26 g, yield: 13.0%).
1H-NMR (CDCl ₃ , σ ppm): 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

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) Compound (2) (same as above) (7.42 g, 31.0 mmol) was added to the mixture 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). Methanol (300 g) was added to the solid obtained by the treatment, the mixture was stirred under ice cooling (0 ° C.), and the precipitated solid was filtered. As a result, white crystals (T4) (yield: 5.23 g, yield: 35) .4%).
1H-NMR (CDCl ₃ , σ ppm): 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>
Mix L1 (5.50 g), T1 (0.50 g), R1 (1.00 g), R2 (1.20 g), R3 (1.50 g) and P1 (0.30 g), and at 25 ° C. for 6 hours The mixture was stirred to obtain a liquid crystal composition (1).

<Example 6>
Mix 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), and at 25 ° C. for 6 hours The mixture was stirred to obtain a liquid crystal composition (2).

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

Example 8
Mix 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), and at 25 ° C. for 6 hours The mixture was stirred to obtain a liquid crystal composition (4).

<Example 9>
Mix 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), and at 25 ° C. for 6 hours The mixture was stirred to obtain a liquid crystal composition (5).

<Example 10>
Mix 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) and at 25 ° C. for 6 hours The mixture was stirred to obtain a liquid crystal composition (6).

<Example 11>
Mix L1 (5.50 g), T1 (0.30 g), T4 (0.20 g), R1 (1.00 g), R2 (1.20 g), R3 (1.50 g) and P1 (0.30 g) Then, the mixture was stirred at 25 ° C. 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>
A mixture of L1 (5.50 g), R1 (1.50 g), R2 (1.20 g), R3 (1.50 g) and P1 (0.30 g) was stirred at 25 ° C. for 6 hours to obtain a liquid crystal composition. (9) was obtained.

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

  Two ITO substrates with the obtained liquid crystal alignment film were prepared, and an 8 μm spacer was applied to the liquid crystal alignment film surface of one of the substrates. Thereafter, the liquid crystal composition obtained by the method of the above-described embodiment is dropped on the surface of the liquid crystal alignment film on which the spacer is applied by the ODF (One Drop Filling) method, and then the liquid crystal alignment of the other substrate is performed. Lamination was performed so that the film interfaces faced each other, and a liquid crystal display element before processing was obtained.

The liquid crystal display element before this treatment was irradiated with ultraviolet rays for 45 seconds using a metal halide lamp with an illuminance of 20 mW / cm ² while cutting the wavelength of 350 nm or less. At that time, the temperature in the irradiation device when the liquid crystal cell was irradiated with ultraviolet rays was controlled at 25 ° C. Thus, a liquid crystal display device (glass substrate) was obtained.

"Production of liquid crystal display element (plastic substrate)"
The liquid crystal aligning agent obtained in the above synthesis example was subjected to pressure filtration with a membrane filter having a pore diameter of 1 μm. The obtained solution was applied with a bar coater on the ITO surface of a 150 × 150 mm PET (polyethylene terephthalate) substrate with ITO electrodes (length: 150 mm, width: 150 mm, thickness: 0.2 mm) washed with pure water. Then, a heat treatment was performed at 120 ° C. for 2 minutes in a heat circulation type clean oven to obtain an ITO substrate having a liquid crystal alignment film having a thickness of 100 nm.

  Two ITO substrates with the obtained liquid crystal alignment film were prepared, and an 8 μm spacer was applied to the liquid crystal alignment film surface of one of the substrates. Thereafter, the liquid crystal composition obtained by the method of the above embodiment is dropped on the surface of the liquid crystal alignment film coated with the spacer of the substrate by the ODF method, and then the liquid crystal alignment film interface of the other substrate is opposed. To obtain a liquid crystal display element before processing. The liquid crystal display element before this treatment was irradiated with ultraviolet rays in the same manner as in “Preparation of liquid crystal display element (glass substrate)” to obtain a liquid crystal display element (plastic substrate).

"Production of liquid crystal display element (correspondence relationship with example)"
As shown in Tables 5 to 7 or 8 to 10 below, any one of the liquid crystal alignment treatment agents (1) to (16) and any one of the liquid crystal compositions (1) to (9) were used. The liquid crystal display elements of Examples 1A to 20A and Comparative Examples 1A to 4A were produced using the same. Examples 1A to 2A, 14A to 15A and 19A and Comparative Examples 1A and 4A are liquid crystal display devices manufactured using a glass substrate, and Examples 3A to 13A, 16A to 18A and 20A and Comparative Examples 2A and 3A Is a liquid crystal display element manufactured using a plastic substrate.

"Evaluation of optical properties (transparency and scattering properties)"
For evaluation of the transparency when no voltage was applied, the transmittance of a liquid crystal display element (glass substrate and plastic substrate) in a state where no voltage was applied was measured. Specifically, the measurement was performed using UV-3600 (manufactured by Shimadzu Corporation) as a measuring device under the conditions of a temperature of 25 ° C. and a scan wavelength of 300 to 800 nm. At this time, in the case of a liquid crystal display device (glass substrate), the glass substrate with the ITO electrode is used as a reference (reference example), and in the case of a liquid crystal display device (plastic substrate), the above PET substrate with the ITO electrode is used. went. The evaluation was based on the transmittance at a wavelength of 550 nm, and the higher the transmittance, the better the transparency.

  In addition, as a stability test of the liquid crystal display element in a high-temperature and high-humidity environment, measurement was performed after storing the liquid crystal display element in a constant temperature and humidity chamber at a temperature of 80 ° C. and a humidity of 90% RH for 36 hours. Specifically, the lower the rate of decrease in transmittance after storage in a thermo-hygrostat relative to the transmittance (initial value) immediately after production of the liquid crystal display element, the better the evaluation.

Further, as a stability test for light irradiation of the liquid crystal display element, measurement after irradiation with ultraviolet rays of 5 J / cm ^{2 in} terms of 365 nm using a desktop UV curing device (HCT3B28HEX-1) (manufactured by Senlight) was also performed. went. Specifically, the lower the rate of decrease in transmittance after ultraviolet irradiation with respect to the transmittance (initial value) immediately after production of the liquid crystal display element, the better the evaluation.

  For the evaluation of the scattering characteristics at the time of applying a voltage, 30 V was applied to a liquid crystal display element (glass substrate and plastic substrate) by AC driving, and the alignment state of the liquid crystal was visually observed. Specifically, a liquid crystal display element which became cloudy, that is, a liquid crystal display element having a scattering property was determined to be excellent in this evaluation (good display in the table).

  In addition, as a stability test of the liquid crystal display element in a high-temperature and high-humidity environment, observation was performed after the liquid crystal display element was stored in a thermo-hygrostat at a temperature of 80 ° C. and a humidity of 90% RH for 36 hours. Specifically, a liquid crystal display element which became cloudy, that is, a liquid crystal display element having a scattering property was determined to be excellent in this evaluation (good display in the table).

Further, as a stability test of the liquid crystal display element against light irradiation, observation after irradiating ultraviolet rays of 5 J / cm ^{2 in} terms of 365 nm using a tabletop UV curing device (HCT3B28HEX-1) (manufactured by Senlight) was also conducted. went. Specifically, a liquid crystal display element which became cloudy, that is, a liquid crystal display element having a scattering property was determined to be excellent in this evaluation (good display in the table).

  Tables 5 to 7 show the evaluation results of the transmittance (%) immediately after production of the liquid crystal display element (initial stage), after storage in a thermo-hygrostat (constant thermo-humidity) and after irradiation with ultraviolet light (ultraviolet light), and scattering characteristics.

"Evaluation of adhesion between liquid crystal layer and liquid crystal alignment film"
To evaluate the adhesion between the liquid crystal layer and the liquid crystal alignment film, the liquid crystal display device (glass substrate and plastic substrate) was stored in a constant temperature and humidity chamber at a temperature of 80 ° C. and a humidity of 90% RH for 36 hours. The presence or absence of air bubbles and peeling of the element were confirmed (as a stability test of the liquid crystal display element in a high temperature and high humidity environment). Specifically, a sample in which no air bubbles were observed in the element and no separation of the element (a state in which the liquid crystal layer and the liquid crystal alignment film were separated) occurred was judged to be excellent in this evaluation (in the table). Good display).

In addition, the liquid crystal display device was checked using a table-top UV curing device (HCT3B28HEX-1) (manufactured by Senlight Co., Ltd.) after irradiating it with ultraviolet rays of 5 J / cm ^{2 in} 365 nm conversion (light of the liquid crystal display device). As a test for stability against irradiation). Specifically, a sample in which no air bubbles were observed in the element and the element did not peel was evaluated as excellent in this evaluation (good display in the table).

  Tables 8 to 10 show the results of adhesion (adhesion) between the liquid crystal layer and the liquid crystal alignment film after storage in a thermo-hygrostat (constant temperature and humidity) and after irradiation with ultraviolet light (ultraviolet light).

<Examples 1A to 20A and Comparative Examples 1A to 4A>
As shown in Tables 5 to 10 below, evaluation of optical characteristics (transparency and scattering characteristics) and evaluation of adhesion between a liquid crystal layer and a 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 characteristics (scattering characteristics 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, the standard test described above was used. In addition, as an emphasis test, evaluation was also performed when stored in a thermo-hygrostat at a temperature of 80 ° C. and a humidity of 90% RH for 72 hours (other conditions are the same as those described above).

＊１：素子内に極少量の気泡が見られた。
＊２：素子内に少量の気泡が見られた（＊１よりも多い）。
＊３：素子内に気泡が見られた（＊２よりも多い）。

* 1: A very small amount of bubbles was observed in the device.
* 2: A small amount of air bubbles were observed in the device (more than * 1).
* 3: Bubbles were observed in the device (more than * 2).

  As can be seen from the above, the liquid crystal display device of the example was a liquid crystal display device having better optical characteristics, that is, better transparency after storage in a thermo-hygrostat and irradiation with ultraviolet light, as compared with the comparative example. Furthermore, the liquid crystal display element has a high adhesion between the liquid crystal layer and the liquid crystal alignment film. Even after being exposed to the harsh environment, the liquid crystal display element does not peel off, and only a very small amount of air bubbles can be seen. Did not. In particular, these characteristics were good even when a plastic substrate was used as the substrate of the liquid crystal display element. Specifically, in the comparison under the same conditions, the comparison between Example 1A and Comparative Example 1A, the comparison between Example 3A and Comparative Example 2A, the comparison between Example 17A and Comparative Example 3A, and the example 20A And Comparative Example 4A.

  When the amount of the specific compound added to the liquid crystal composition was increased, the transmittance of the liquid crystal display device was increased. Specifically, in the comparison under the same conditions, Example 8A and Example 9A are compared. Further, when an additive compound was added to the liquid crystal composition in addition to the specific compound, the transmittance of the device was increased. Specifically, in the comparison under the same conditions, the comparison between Example 6A and Example 7A is made.

  When the diamine having the specific side chain structure of the formula [4-1a] is used in the specific side chain structure in the specific polymer of the liquid crystal aligning agent, the diamine having the formula [4-2a] is used. In comparison, the transmittance of the liquid crystal display element was increased. Furthermore, even after storing in a thermo-hygrostat for a long time, high transparency was obtained. Also, in the evaluation of the adhesion between the liquid crystal layer and the liquid crystal alignment film, when the diamine of the formula [4-1a] is used, the result shows that the adhesion is high even after being stored in a thermo-hygrostat for a long time. became. Specifically, in the comparison under the same conditions, a comparison between Example 3A and Example 16A, and a comparison between Example 18A and Example 20A.

  In addition, when the second diamine was used as the specific polymer, the result was that the adhesion between the liquid crystal layer and the liquid crystal alignment film was high even after being stored in a thermo-hygrostat for a long time. Specifically, in the comparison under the same conditions, Example 3A and Example 6A are compared.

  Furthermore, when the specific compound A was added to the liquid crystal alignment treatment agent, the transmittance of the liquid crystal display element was increased. Specifically, this is a comparison between Example 3A and Example 4A. In addition, when the specific crosslinking compound was added, the adhesion between the liquid crystal layer and the liquid crystal alignment film was increased. Further, when the specific compound A, the specific crosslinking compound and the specific generator were added, the transmittance of the liquid crystal display element and the adhesion between the liquid crystal layer and the liquid crystal alignment film were increased. Specifically, it is a comparison between Example 7A and Example 10A.

  By using a liquid crystal composition containing a compound having a specific structure, good optical properties, that is, transparency when no voltage is applied and good scattering properties when a voltage is applied, and furthermore, the liquid crystal layer and the liquid crystal alignment film A liquid crystal display element having high adhesion and capable of maintaining these characteristics even in a harsh environment exposed to high temperature, high humidity, or light irradiation for a long time can be obtained.

  Further, the liquid crystal display device of the present invention can be suitably used for a normal type device which becomes a transparent state when no voltage is applied and becomes a scattering state when a voltage is applied. This element can be used for a liquid crystal display for display purposes, furthermore, for a light control window or an optical shutter element for controlling the blocking and transmission of light. A substrate can be used.

  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 device of the present invention, but also as a component of the liquid crystal composition of other liquid crystal display devices.

Claims (16)

A compound of the following formula [1a]:

T ¹ represents a structure selected from the following formulas [2-1a] to [2-7a]. T ² are a linear or branched alkylene group having 2 to 18 carbon atoms, ^{T 1} and ^{T 3} and not adjacent said alkylene group any _-CH 2 in the - is, -O -, - CO -, - It may be replaced by COO—, —OCO—, —CONH—, —NHCO—, —NH—, a benzene ring or a cyclohexane ring. T ³ represents a structure selected from the following formulas [1-1b] to [1-4b]. T ⁴ represents a single bond or an alkylene group having 1 to 24 carbon atoms, ^{T 3} and not adjacent said alkylene group any _-CH 2 in the - is, -O -, - CO -, - COO -, - OCO- , -CONH -, - NHCO -, - NH -, - CON (CH 3) -, - S- or -SO ₂ - may be replaced by. T ⁵ represents a divalent cyclic group selected from a benzene ring, a cyclohexane ring and a heterocyclic ring, or a divalent organic group having a steroid skeleton and having 17 to 51 carbon atoms, and an arbitrary hydrogen atom on the cyclic group is It may be substituted by an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxy group having 1 to 3 carbon atoms or a fluorine atom. T ⁶ represents a single bond, —O—, —OCH ₂ —, —CH ₂ O—, —COO—, or —OCO—. T ⁷ represents a cyclic group selected from a benzene ring, a cyclohexane ring, and a heterocyclic ring, and any hydrogen atom on the cyclic group is an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, It may be substituted with a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxy group having 1 to 3 carbon atoms, or a fluorine atom. T ⁸ is an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, or a fluorine-containing alkoxy group having 1 to 18 carbon atoms. Represents a group. mT shows the integer of 1-4. nT shows the integer of 0-4.

W ^A is a hydrogen atom or a benzene ring.

T ^B is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. The compound according to claim 1, wherein the compound of the formula [1a] is the following formula [1b] or [1c].

T ⁹ , T ¹¹ , T ¹⁷ and T ¹⁹ each represent a structure selected from the formulas [2-1a] to [2-7a]. T ¹⁰ and ^{T 18} is a straight or branched alkylene group having 2 to 12 carbon atoms. T ¹² and ^{T 20} represents a structure selected from the formula [1-1b] ~ formula [1-4b]. T ¹³ and ^{T 21} represents a single bond or an alkylene group having 1 to 8 carbon atoms. T ¹⁴ and T ¹⁵ represent a benzene ring or a cyclohexane ring. T ¹⁶ represents an alkyl group or an alkoxy group having 1 to 12 carbon atoms. T ²² represents a divalent organic group having 17 to 51 carbon atoms having a steroid skeleton. pT shows the integer of 0-4.   A liquid crystal composition containing at least one compound selected from the formulas [1a], [1b] and [1c]. A liquid crystal composition including a liquid crystal and a polymerizable compound disposed between a pair of substrates having electrodes is provided with a liquid crystal layer cured by irradiating ultraviolet rays, and at least one of the substrates vertically aligns the liquid crystal. A liquid crystal display device comprising a liquid crystal alignment film for aligning,
A liquid crystal display device wherein the liquid crystal composition contains at least one compound selected from the formulas [1a], [1b] and [1c]. The liquid crystal display device according to claim 4, wherein the liquid crystal composition includes a compound represented by the following formula [2a].

W ¹ represents a structure selected from the following formulas [2-1a] to [2-7a]. W ² is a single bond, -O -, - COO- or an -OCO-. W ³ represents a single bond or an alkylene group having 1 to 12 carbon atoms. W ⁴ represents a single bond, —O—, —COO—, or —OCO—. W ⁵ represents a benzene ring, a cyclohexane ring or a divalent organic group having 17 to 51 carbon atoms having a steroid skeleton. W ⁶ being a single _{bond, -CH 2 -, - CH 2} O -, - OCH 2 -, - O -, - COO -, - OCO -, - NHCO- or an -CONH-. W ⁷ represents a benzene ring or a cyclohexane ring. W ⁸ is an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, or a fluorine-containing alkoxy group having 1 to 18 carbon atoms. Represents a group. mW represents an integer of 0 to 4.

W ^A is a hydrogen atom or a benzene ring. The liquid crystal alignment film according to claim 4 or 5, wherein the liquid crystal alignment film is a liquid crystal alignment film obtained from a liquid crystal alignment agent containing a polymer having a side chain structure represented by the following formula [4-1a] or formula [4-2a]. The liquid crystal display element as described in the above.

X ¹ and ^{X 3} is a single _{bond, - (CH 2) a -} (a is an integer of _{1~15), - O -, -} CH 2 O -, - COO- or an -OCO-. X ² represents a single bond or — (CH ₂ ) _b — (b is an integer of 1 to 15). X ⁴ represents a divalent cyclic group selected from a benzene ring, a cyclohexane ring and a heterocyclic ring, or a divalent organic group having a steroid skeleton and having 17 to 51 carbon atoms, and an arbitrary hydrogen atom on the cyclic group is It may be substituted by an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxy group having 1 to 3 carbon atoms or a fluorine atom. X ⁵ represents at least one cyclic group selected from a benzene ring, a cyclohexane ring and a heterocyclic ring, and any hydrogen atom on these cyclic groups is an alkyl group having 1 to 3 carbon atoms, It may be substituted by an alkoxy group, 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. X ⁶ is an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, or a fluorine-containing alkoxy group having 1 to 18 carbon atoms. Represents a group. n shows the integer of 0-4.

X ⁷ is a single _{bond, -O -, - CH 2 O} -, - CONH -, - NHCO -, - CON (CH 3) -, - N (CH 3) CO -, - shows a COO- or -OCO- . X ⁸ represents a fluorine-containing alkyl group having 6 to 18 carbon alkyl group or C of 8-18 carbon atoms.   The liquid crystal display according to claim 6, wherein the liquid crystal alignment treatment agent contains at least one selected from an acrylic polymer, a methacrylic polymer, a novolak resin, a polyhydroxystyrene, a polyimide precursor, a polyimide, a polyamide, a polyester, a cellulose, and a polysiloxane. element.   A polyimide precursor obtained by reacting a diamine component containing a diamine having a side chain structure of the formula [4-1a] or [4-2a] with a tetracarboxylic acid component, The liquid crystal display device according to claim 7, comprising a polyimide obtained by imidizing a polyimide precursor. The liquid crystal display device according to claim 8, wherein the diamine having a side chain structure represented by the formula [4-1a] or the formula [4-2a] is represented by the following formula [4a].

X represents the structure of the formula [4-1a] or the formula [4-2a]. m shows the integer of 1-4.
The liquid crystal display device according to claim 8, 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 [5l].

Z ^{1 to} Z ⁴ each represent a hydrogen atom, a methyl group, a chlorine atom or a benzene ring. Z ⁵ and Z ⁶ each represent a hydrogen atom or a methyl group.
The liquid crystal alignment treatment agent is a polysiloxane obtained by polycondensation of an alkoxysilane of the following formula [A1], or an alkoxysilane of the formula [A1], and the following formulas [A2] and / or [A3] The liquid crystal display device according to claim 7, comprising a polysiloxane obtained by polycondensing an alkoxysilane.

A ¹ represents a structure of the 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 shows the integer of 0-2. p shows the integer of 0-3. However, m + n + p is 4.

B ¹ represents shows a vinyl group, an epoxy group, an amino group, a mercapto group, an isocyanate group, methacryl group, acryl group, an organic group having 2 to 12 carbon atoms and having at least one selected from a ureido group, and a cinnamoyl group. B ² represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. B ³ represents an alkyl group having 1 to 5 carbon atoms. m represents an integer of 1 or 2. n shows the integer of 0-2. p shows the integer of 0-3. However, 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. n shows the integer of 0-3.
The liquid crystal alignment treatment agent according to any one of claims 6 to 11, wherein the liquid crystal alignment treatment agent comprises a compound having at least one structure selected from the following formulas [b-1] to [b-11]. Liquid crystal display element.

B ^A represents a hydrogen atom or a benzene ring. Each B ^B .about.B ^D represents an alkyl group having 1 to 5 carbon atoms.
The liquid crystal aligning agent contains a compound having at least one selected from an epoxy group, an isocyanate group, an oxetane group, a cyclocarbonate group, a hydroxyl group, a hydroxyalkyl group and a lower alkoxyalkyl group. The liquid crystal display element according to any one of the above.
The liquid crystal alignment treatment agent is 1-hexanol, cyclohexanol, 1,2-ethanediol, 1,2-propanediol, propylene glycol monobutyl ether, ethylene glycol monobutyl ether, dipropylene glycol dimethyl ether, cyclohexanone, cyclopentanone and The liquid crystal display device according to any one of claims 6 to 13, comprising at least one selected from solvents represented by the formulas [D1] to [D3].

D ¹ and D ² represent an alkyl group having 1 to 3 carbon atoms. D ³ represents an alkyl group having 1 to 4 carbon atoms.
The liquid crystal alignment treatment agent according to any one of claims 6 to 14, wherein the agent comprises at least one selected from N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, and γ-butyrolactone. Liquid crystal display element.
  The liquid crystal display device according to any one of claims 4 to 15, wherein the substrate is a plastic substrate.