TWI614554B - Liquid crystal display element, liquid crystal alignment treatment agent, and liquid crystal alignment film - Google Patents

Description

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

The present invention relates to a transflective liquid crystal display element which is in a transparent state when no voltage is applied, a scattering-type liquid crystal display element which is in a scattering state when a voltage is applied, a liquid crystal alignment treatment agent for obtaining the element, and a liquid crystal alignment film.

As a liquid crystal display element using a liquid crystal material, a TN (Twisted Nematic) mode has been put into practical use. In this mode, light is switched by the optical rotation characteristics of the liquid crystal, and when used as a liquid crystal display element, a polarizing plate must be used. However, it is known that the use of a polarizing plate makes the utilization efficiency of light low.

A liquid crystal display element having high utilization efficiency of light that does not use a polarizing plate has a liquid crystal display element that switches between a liquid crystal through state (also referred to as a transparent state) and a scattering state, and is generally known to use a polymer. Dispersed liquid crystal (also known as PDLC (Polymer Dispersed Liquid Crystal)) or polymer network type liquid crystal (also known as PNLC (Polymer Network Liquid Crystal)).

The liquid crystal display element is formed by providing a liquid crystal layer between a pair of substrates provided with electrodes, and is disposed between the pair of substrates In the liquid crystal composition, the liquid crystal composition is cured in a state in which liquid crystallinity is present in a part or all of the liquid crystal composition, and a liquid crystal display element is produced by a step of forming a cured composite of a liquid crystal and a polymerizable compound; The liquid crystal composition includes a polymerizable compound which is polymerized by at least one of an active energy ray and heat. The liquid crystal display element controls the penetration state and the scattering state of the liquid crystal by applying a voltage.

As a liquid crystal display element using PDLC or PNLC in the past When it is known that there is no applied voltage, since the liquid crystal molecules are oriented in a random direction, they are in a white turbid (scattering) state, and when a voltage is applied, the liquid crystals are arranged in the direction of the electric field, and the light penetrates into a normal type element in a penetrating state. However, in a normal type element, in order to obtain a penetrating state, a voltage is often applied, so that it is used in a transparent state, for example, in the case of use of a window glass, power consumption is large.

With respect to the normal type element, a reverse type element has been reported which is in a penetrating state when no voltage is applied and a scattering state when a voltage is applied (refer to Patent Documents 1 and 2).

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent No. 2885116

[Patent Document 2] Japanese Patent No. 4132424

In the case of a reverse type component, the liquid crystal must be aligned vertically, thus A liquid crystal alignment film (also referred to as a vertical liquid crystal alignment film) that vertically aligns the liquid crystals is used. At this time, since the liquid crystal alignment film is a film having high hydrophobicity, the adhesion between the liquid crystal layer and the liquid crystal alignment film is lowered. Therefore, in the liquid crystal composition used for the reverse type element, a large amount of a polymerizable compound (also referred to as a curing agent) for improving the adhesion between the liquid crystal layer and the liquid crystal alignment film must be introduced. However, when a large amount of a polymerizable compound is introduced, the vertical alignment property of the liquid crystal is hindered, and the transparency at the time of application of a voltage and the scattering property at the time of applying a voltage are largely lowered. Therefore, for the liquid crystal alignment film of the reverse type element, the vertical alignment of the liquid crystal must be high.

Here, the object of the present invention is to provide a combination of the above characteristics. Liquid crystal display element. That is, an object of the present invention is to provide a liquid crystal display device which has high vertical alignment property and good optical characteristics, that is, transparency at the time of no applied voltage and scattering characteristics at an applied voltage are good and the liquid crystal layer The adhesion to the vertical liquid crystal alignment film is high. Furthermore, the present invention provides a liquid crystal alignment film for obtaining the liquid crystal display element and a liquid crystal alignment treatment agent used for forming the liquid crystal alignment film.

As a result of intensive studies, the present inventors have found that a liquid crystal alignment treatment agent comprises a cellulose-based polymer having a specific structure and a polyimide-based polymer having a side chain of a specific structure, which has a liquid crystal alignment. The liquid crystal alignment film obtained by the treatment agent has high adhesion between the liquid crystal layer and the liquid crystal alignment film, and the liquid crystal has high vertical alignment property and good optical characteristics. In other words, it is possible to obtain a liquid crystal display element which is excellent in transparency when no voltage is applied and scattering characteristics when a voltage is applied.

The present invention has the following gist in the light of these findings.

(1) A liquid crystal display device in which a liquid crystal composition is disposed between two substrates each having an electrode, at least one of which has a liquid crystal alignment film, and is represented by a part or all of the liquid crystal composition A liquid crystal display device in which a cured product of a liquid crystal and a polymerizable compound is formed by curing in a liquid crystal state, and the liquid crystal composition contains a liquid crystal and a polymerizable polymerized by an active energy ray or heat. Compound; characterized by

The liquid crystal alignment film is formed of a liquid crystal alignment treatment agent containing the following components (A) and (B), and the component (A) is a cellulose-based polymer having a structure represented by the following formula [1].

(X ¹ , X ² , X ³ , X ⁴ , X ⁵ and X ⁶ are each independently represented by a group selected from at least one of the groups represented by the following formulas [1a] to [1m], n Is an integer from 100 to 1,000,000)

(X ⁷ and X ⁸ are each independently shown as a benzene ring or an alkyl group having 1 to 4 carbon atoms, and X ⁹ , X ¹⁰ , X ¹¹ , X ¹² , X ¹³ and X ¹⁴ are each independently represented as a benzene ring or a carbon number of 1~ 4 alkyl, m, n is shown as an integer from 0 to 3)

Component (B): a polyimide-based polymer selected from the group consisting of a polyimide precursor and a polyimine, and having a formula selected from the following formula [2-1] and formula [ 2-2] at least one of the groups formed by the structure shown,

(Y ^{1 is} shown as being selected from the group consisting of a single bond, -(CH ₂ ) _a - (a is an integer of 1 to 15), -O-, -CH ₂ O-, -COO-, and -OCO- 1; Y ^{2 is} shown as a single bond or -(CH ₂ ) _b - (b is an integer from 1 to 15); Y ^{3 is} shown to be selected from a single bond, -(CH ₂ ) _c - (c is 1 to 15) At least one of the group of integers, -O-, -CH ₂ O-, -COO-, and -OCO-; Y ⁴ is selected from the group consisting of a benzene ring, a cyclohexane ring, and a heterocyclic ring At least one divalent cyclic group or a divalent organic group having a carbon number of 17 to 51 having a steroid skeleton, and any hydrogen atom on the cyclic group may be an alkyl group having 1 to 3 carbon atoms and a carbon number of 1 Alkoxy group of ~3, fluorine-containing alkyl group having 1 to 3 carbon atoms, fluorine-containing alkoxy group having 1 to 3 carbon atoms or fluorine atom; Y ⁵ is selected from a benzene ring, a cyclohexane ring and a hetero At least one cyclic group in the group formed by the ring, any hydrogen atom on the cyclic group may have an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, and a carbon number of 1 to a fluorine-containing alkyl group of 3, a fluorine-containing alkoxy group having 1 to 3 carbon atoms or a fluorine atom; n is an integer of 0 to 4; and Y ⁶ is selected from an alkyl group having 1 to 18 carbon atoms and a carbon number a fluorine-containing alkyl group of 1 to 18, an alkoxy group having 1 to 18 carbon atoms, and a carbon number of 1 to 18 The alkoxy group into the at least one; ~ n-4 shown is an integer of 0) [Chem ^{5] -Y 7 -Y 8 [2-2} ]

(Y ^{7 is} shown to be selected from the group consisting of a single bond, -O-, -CH ₂ O-, -CONH-, -NHCO-, -CON(CH ₃ )-, -N(CH ₃ )CO-, -COO- and - At least one bonding group in the group formed by OCO-; Y ⁸ is an alkyl group having 8 to 22 carbon atoms or a fluorine-containing alkyl group having 6 to 18 carbon atoms).

(2) The liquid crystal display element according to the above (1), wherein the ratio of the component (A) to the component (B) is 0.1 to 9 by mass for the component (B). Share.

(3) The liquid crystal display device according to the above (1) or (2), wherein the polyamidimide polymer of the component (B) is selected from the group consisting of a polyimide precursor and a polyimine. At least one of them is obtained by using a diamine compound having a structure represented by the above formula [2-1] or formula [2-2] as a part of a raw material.

(4) The liquid crystal display device according to the above (3), wherein the diamine compound is a diamine compound represented by the following formula [2a].

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

(5) The liquid crystal display element according to any one of the above (1), wherein the polyamidene-based polymer of the component (B) is selected from the group consisting of a polyimide precursor and a polyimine. At least one of the group formed is obtained by using a tetracarboxylic acid component represented by the following formula [3] as a part of a raw material.

(Z ¹ is a structure selected from at least one selected from the group consisting of the structures represented by the following formulas [3a] to [3j])

(Z ² to Z ⁵ are each independently represented by a hydrogen atom, a methyl group, a chlorine atom or a benzene ring; and Z ⁶ and Z ⁷ are each independently represented as a hydrogen atom or a methyl group).

The liquid crystal display element of any one of the above-mentioned (1) to (5), wherein the liquid crystal alignment treatment agent further contains a solvent.

(7) The liquid crystal display device according to the above (6), wherein the solvent contains a solvent having a boiling point of less than 180 ° C and accounts for 50% by mass or more of the entire solvent.

(8) The liquid crystal display device according to the above (6) or (7), wherein the solvent further contains a solvent selected from the group consisting of cyclopentanone, cyclohexanone, and the solvent represented by the following formula [A1] and formula [A2]. At least one solvent in the group,

(A ^{1 is} shown as an alkyl group having 1 to 3 carbon atoms; and A ² is represented as an alkyl group having 1 to 3 carbon atoms).

(9) The liquid crystal display element according to any one of the above (6), wherein the solvent further contains one selected from the group consisting of 1-hexanol, cyclohexanol, 1,2-ethanediol, 1,2- A solvent of at least one selected from the group consisting of propylene glycol, propylene glycol monobutyl ether, ethylene glycol monobutyl ether, and dipropylene glycol dimethyl ether.

(10) The liquid crystal display element according to any one of the above (6), wherein the solvent further contains N-methyl-2-pyrrolidone and N-ethyl-2-pyrrolidone And at least one solvent selected from the group consisting of γ-butyrolactone and a solvent represented by the following formula [A3],

(A ^{3 is} shown as an alkyl group having 1 to 4 carbon atoms).

The liquid crystal display device of any one of the above-mentioned (1) to (10), wherein the liquid crystal alignment treatment agent further contains a compound selected from the group consisting of the following formulas [B1] to [B8] At least one of the groups formed by the foundation of the structure,

(B ¹ is a hydrogen atom or a benzene ring; B ² is a cyclic group selected from at least one selected from the group consisting of a benzene ring, a cyclohexane ring, and a hetero ring; and B ³ is selected from a carbon number of 1 to At least one of a group of 18 alkyl groups, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, and a fluorine-containing alkoxy group having 1 to 18 carbon atoms.

The liquid crystal display device according to any one of the above aspects, wherein the liquid crystal alignment agent further contains a generating agent selected from the group consisting of a photo-radical generating agent, a photo-acid generating agent, and light. At least one selected from the group consisting of alkali generators.

(13) The liquid crystal according to any one of (1) to (12) above A display element, wherein the substrate is a glass substrate or a plastic substrate.

(14) A liquid crystal alignment film which is used in a liquid crystal alignment film of the liquid crystal display element according to any one of the above (1) to (13), and which is subjected to liquid crystal alignment treatment containing the component (A) and the component (B) The agent is formed.

(15) The liquid crystal alignment film according to (14) above, wherein the film thickness is 5 to 500 nm.

(16) A liquid crystal alignment treatment agent for forming a liquid crystal alignment treatment agent for the liquid crystal alignment film of the above (14) or (15), comprising the component (A) and the component (B).

According to the present invention, by using the vertical liquid crystal alignment film of the present invention which is obtained from a liquid crystal alignment treatment agent comprising a cellulose-based polymer having a specific structure and a polyimine-based polymer having a side chain of a specific configuration, The adhesion between the liquid crystal layer and the vertical liquid crystal alignment film is high, and the vertical alignment of the liquid crystal is high, and the optical characteristics are good, that is, the transparency at the time of no applied voltage and the scattering characteristic at the applied voltage are good. Liquid crystal display element. In particular, the liquid crystal display element of the present invention can be suitably used as a reverse type element which is in a penetrating state when no voltage is applied and a scattering state when a voltage is applied, and can be used for display-oriented liquid crystal displays or to control light penetration. Dimming window or shutter element that penetrates and occludes.

[Best Mode for Carrying Out the Invention]

The liquid crystal alignment treatment agent used in the liquid crystal display device of the present invention contains the cellulose-based polymer of the component (A) and the polyamidimide-based polymer of the component (B).

<Cellulose Polymer>

The cellulose-based polymer of the component (A) in the present invention (hereinafter also referred to as It is a polymer of the structure of the following formula [1] as a specific cellulose type polymer.

In the formula [1], X ¹ , X ² , X ³ , X ⁴ , X ⁵ and X ⁶ are each independently represented by at least one selected from the group consisting of the structures represented by the following formulas [1a] to [1m]. Base.

n is shown as an integer from 100 to 1,000,000. Among them, n is preferably from 100 to 500,000 from the viewpoint of solubility of a specific cellulose polymer to a solvent or operability at the time of preparation as a liquid crystal alignment treatment agent. It is preferably from 100 to 100,000.

X ⁷ and X ⁸ are each independently represented by a benzene ring or an alkyl group having 1 to 4 carbon atoms (specifically, methyl group, ethyl group, n-propyl group, isopropyl group, butyl group, etc.). X ⁹ , X ¹⁰ , X ¹¹ , X ¹² , X ¹³ and X ¹⁴ are each independently represented by a benzene ring or an alkylene group having 1 to 4 carbon atoms (specifically, a methylene group, an exoethyl group, and an n-extension group C). Base, iso-propyl, butyl, etc.).

n is shown as an integer from 0 to 3. Among them, preferably 0 or 1 Integer.

m is shown as an integer from 0 to 3. Among them, an integer of 0 or 1 is preferred.

In the formula [1], X ¹ , X ² , X ³ , X ⁴ , X ⁵ and X ⁶ are each independently selected from the group of the formulae [1a] to [1m], but the basis of these may be one type. There are two or more types. In particular, it is preferable to use a plurality of kinds of two or more kinds of the cellulose-based polymer in terms of solubility in a solvent or coating property of a liquid crystal alignment treatment agent.

Further preferably, the formula [1a] and the formula [1b] to [1m] are used. It is particularly preferable to use the formula [1a] and the formula [1c], the formula [1d], the formula [1e], the formula [1h] or the formula [1i].

Specific examples of the specific cellulose-based polymer include the following, but are not limited thereto.

For example, cellulose, methyl cellulose, ethyl cellulose, propyl cellulose, butyl cellulose, methyl ethyl cellulose, cellulose acetate, cellulose propionate, hydroxymethyl cellulose, hydroxyl group Ethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, ethylhydroxyethylcellulose, hydroxybutylmethylcellulose, hydroxypropylmethylcellulose phthalate, methylamine Cellulose, ethylamino cellulose, propylamino cellulose, benzyl cellulose, benzoyl cellulose, cellulose acetate butyrate, cellulose acetate propionate, carboxymethyl cellulose, carboxy Methyl ethyl cellulose or carboxymethyl hydroxyethyl cellulose. Among them, preferred are methyl cellulose, ethyl cellulose, propyl cellulose, cellulose acetate, hydroxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxypropyl methyl cellulose. , ethyl hydroxyethyl cellulose, hydroxypropyl methyl cellulose phthalate, benzyl cellulose, cellulose acetate propionate, carboxymethyl ethyl cellulose or carboxymethyl hydroxyethyl cellulose . Further preferred are methylcellulose, ethylcellulose, cellulose acetate, hydroxymethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, ethylhydroxyethylcellulose Or hydroxypropylmethylcellulose phthalate or carboxymethylethylcellulose. Particularly preferred are methyl cellulose, ethyl cellulose, cellulose acetate, hydroxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, ethyl hydroxyethyl cellulose or hydroxypropyl methyl cellulose. Phthalates.

These cellulose derivatives are generally available. Again The method for introducing the group represented by the formula [1b] to [1m] is not particularly limited, and an existing method can be used.

For example, when introducing the formula [1b], a method of reacting cellulose with a benzyl chloride in the presence of a base; and introducing a compound of the formula [1c], reacting a cellulose with a halogen compound having X ⁷ in the presence of a base A method of reacting cellulose with an acid chloride compound having X ⁸ in the presence of a base or a method of reacting cellulose with acetic anhydride when introducing the formula [1d]; and introducing the fiber into the formula [1e]; a method of reacting a halogen with a halogen compound having X ⁹ -OH in the presence of a base; a method of reacting cellulose with a halogen compound having X ¹⁰ -COOH in the presence of a base when introducing the formula [1f]; 1 g] a method of reacting cellulose with a halogen compound having X ¹¹ -NH ₂ in the presence of a base; a method of reacting cellulose with phthalic acid when introducing the formula [1h]; introducing the formula [1i] A method of reacting cellulose with a halogen compound having X ¹² and a phthalic acid skeleton in the presence of a base; and introducing a method of reacting cellulose with maleic anhydride when introducing the formula [1k].

The specific cellulose-based polymer depends on the solubility of the specific cellulose-based polymer in the solvent or the coating property of the liquid crystal alignment treatment agent, and further the optical characteristics of the liquid crystal display element or the adhesion between the liquid crystal layer and the vertical liquid crystal alignment film. The characteristics can be used in combination of one type or two or more types.

<Polyimide-based polymer>

The component (B) in the present invention is a polyamidene-based polymer (also referred to as a specific polyimine-based polymer) having a selected from the following formula [2-1] and formula [2-2]. At least one of the groups formed by the illustrated structure (also referred to as a specific side chain structure).

In the formula [2-1], Y ¹ , Y ² , Y ³ , Y ⁴ , Y ⁵ , Y ⁶ and n are as defined above, but are preferably as follows.

Y ^{1 is} preferably a single bond, -(CH ₂ ) _a - (a is an integer of 1 to 15), -O-, -CH ₂ O- or from the viewpoint of availability of a raw material or ease of synthesis. -COO-. Further preferred is a single bond, -(CH ₂ ) _a - (a is an integer of 1 to 10), -O-, -CH ₂ O- or -COO-.

Y ^{2 is} preferably a single bond or -(CH ₂ ) _b - (b is an integer of 1 to 10).

From the viewpoint of easiness of synthesis, Y ^{3 is} preferably a single bond, -(CH ₂ ) _c - (c is an integer of 1 to 15), -O-, -CH ₂ O- or -COO-. Further preferred is a single bond, -(CH ₂ ) _c - (c is an integer of from 1 to 10), -O-, -CH ₂ O- or -COO-.

From the viewpoint of easiness of synthesis, Y ^{4 is} preferably a benzene ring, a cyclohexane ring or an organic group having a carbon number of 17 to 51 having a steroid skeleton.

Y ^{5 is} preferably a benzene ring or a cyclohexane ring.

Y ^{6 is} preferably 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. Further, it is preferably an alkyl group having 1 to 12 carbon atoms or an alkoxy group having 1 to 12 carbon atoms. Particularly preferred are alkyl groups having 1 to 9 carbon atoms or alkoxy groups having 1 to 9 carbon atoms.

n is preferably 0 to 3 from the viewpoint of availability of raw materials or ease of synthesis. It is preferably 0 to 2.

Preferred combinations of Y ¹ , Y ² , Y ³ , Y ⁴ , Y ⁵ , Y ⁶ and n can be exemplified in Table 6 on pages 13 to 34 of International Publication WO2011/132751 (2011.10.27 publication). (2-1) to (2-629) described in Table 47 are the same combinations. In the tables of the International Publications, Y ¹ to Y ⁶ in the present invention are represented by Y1 to Y6, and Y1 to Y6 are interpreted as Y ¹ to Y ⁶ . Further, (2-605) to (2-629) described in the respective tables of the International Publications, the organic group having a steroid skeleton having a carbon number of 17 to 51 in the present invention has a carbon number of 12 having a steroid skeleton. The organic group of ~25 indicates that the organic group having a carbon number of 12 to 25 having a steroid skeleton can be interpreted as an organic group having a carbon number of 17 to 51 having a steroid skeleton.

Among them, it is preferably (2-25)~(2-96), (2-145)~(2-168), (2-217)~(2-240), (2-268)~(2 -315), a combination of (2-364)~(2-387), (2-436)~(2-483) or (2-603)~(2-615). Further preferably (2-49)~(2-96), (2-145)~(2-168), (2-217)~(2-240), (2-603)~(2-606 ), a combination of (2-607)~(2-609), (2-611), (2-612) or (2-624).

[化16]-Y ⁷ -Y ⁸ [2-2]

In the formula [2-2], Y ⁷ and Y ^{8 are} as defined above, but are preferably as follows.

Y ^{7 is} preferably a single bond, -O-, -CH ₂ O-, -CONH-, -CON(CH ₃ )- or -COO- from the viewpoint of availability of the raw material or ease of synthesis. Further preferred is a single bond, -O-, -CONH- or -COO-.

Y ^{8 is} preferably an alkyl group having 8 to 18 carbon atoms.

In the present invention, the specific side chain structure is preferably a structure represented by the formula [2-1] from the viewpoint of obtaining a high and stable vertical alignment of the liquid crystal.

The specific polyimine-based polymer in the present invention is a polymer having at least one selected from the group consisting of a polyimide intermediate and a polyimine having a specific side chain structure. In this case, a polyimine precursor can be obtained by reacting a diamine component with a tetracarboxylic acid component, and the polyamidene precursor can be imidized to obtain a polyimine.

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

(R ¹ is a tetravalent organic group; R ² is a divalent organic group; and A ¹ and A ² are each independently represented by a hydrogen atom or an alkyl group having 1 to 8 carbon atoms; and A ³ and A ⁴ are independently shown as A hydrogen atom, an alkyl group having 1 to 5 carbon atoms or an ethylene group; n is a positive integer).

The diamine component is a diamine compound having two primary or secondary amine groups in the molecule. Examples of the tetracarboxylic acid component include a tetracarboxylic acid compound, a tetracarboxylic dianhydride, a dihalogenated tetracarboxylic acid compound, a tetracarboxylic acid dialkyl ester compound, or a dihalogenated tetracarboxylic acid dialkyl ester compound.

By using a tetracarboxylic dianhydride represented by the following formula [B] and a diamine compound represented by the following formula [C] as a raw material, the polyimine-based polymer is preferred because it can be obtained relatively easily. It is a polyperonine having a repeating unit represented by the following formula [D] or a polyimine which is imidized with the polyphosphonium amide. Among the viewpoints of the physical and chemical stability of the liquid crystal alignment film, The polyimine-based polymer is preferably a polyimine.

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

(R ¹ and R ² system and the formula [A] are the same meaning as defined)

Further, an alkyl group having 1 to 8 carbon atoms of A ¹ and A ² represented by the formula [A] and a formula [A] can be introduced into the polymer of the formula [D] obtained above by a usual synthesis method. The alkyl group or the ethylidene group having a carbon number of 1 to 5 of A ³ and A ⁴ is shown.

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

In the formula [2a], Y is selected from the group consisting of the above formula [2-1] and the formula [2-2] A structure that makes at least one of the group formed.

n is shown as an integer from 1 to 4. Among them, an integer of 1 is preferred.

The specific side chain structure in the formula [2a] is preferably the structure shown in the formula [2-1] as described above.

Specifically, for example, a diamine compound represented by the following formula [2a-1] to formula [2a-31] can be mentioned.

(R ^{1 is} each a bond group selected from the group consisting of -O-, -OCH ₂ -, -CH ₂ O-, -COOCH ₂ -, and -CH ₂ OCO-, respectively. R ² shows It is a linear or branched fluorine-containing alkyl group selected from the group consisting of a linear or branched alkyl group having 1 to 22 carbon atoms, a linear or branched alkoxy group having 1 to 22 carbon atoms, and a carbon number of 1 to 22. And at least one of a group of linear or branched fluorine-containing alkoxy groups having 1 to 22 carbon atoms.

(R ^{3 is} shown as being selected from -COO-, -OCO-, -CONH-, -NHCO-, -COOCH ₂ -, -CH ₂ OCO-, -CH ₂ O-, -OCH ₂ -, and -CH ₂ - At least one bonding group in the group formed. R ⁴ is a linear or branched alkoxy group having a carbon number of 1 to 22 and a linear or branched alkoxy group having a carbon number of 1 to 22, respectively. And at least one of a linear or branched fluorine-containing alkyl group having 1 to 22 carbon atoms and a linear or branched fluorine-containing alkoxy group having 1 to 22 carbon atoms.

(R ^{5 is} shown as being selected from -COO-, -OCO-, -CONH-, -NHCO-, -COOCH ₂ -, -CH ₂ OCO-, -CH ₂ O-, -OCH ₂ -, -CH ₂ - a bonding group of at least one of -O- and -NH-, wherein R ⁶ is selected from the group consisting of a fluorine group, a cyano group, a trifluoromethyl group, a nitro group, an azo group, and a methyl group. At least one of the group consisting of an ethyl group, an ethoxy group and a hydroxyl group).

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

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

(A ₄ may be shown as the fluorine atom substituted 3 to 20 carbon atoms of straight-chain or branched alkyl group II.A ₃ shown is 1,4-cyclohexylene or 1,4-phenylene shown .A ₂ It is an oxygen atom or -COO-* (however, the bond with "*" is bonded to A ₃ ). A _{1 is} shown as an oxygen atom or -COO-* (however, the bond key with "*" is Bonded with (CH ₂ )a ₂ )). Also, a _{1 is} shown as an integer of 0 or 1. a ₂ is an integer of from 2 to 10 shows the. a _{3 is} shown as an integer of 0 or 1.)

Among them, from the viewpoint of optical characteristics in the liquid crystal display element, the formula [2a-1] to the formula [2a-6], the formula [2a-9] to the formula [2a-13] or the formula [2a- is preferable. 22]~ a diamine compound represented by the formula [2a-31].

Further, a diamine compound represented by the following formula [2a-32] to the formula [2a-36] is preferred.

(R ^{1 is} each shown as -CH ₂ O-. R ^{2 is} shown as an alkyl group having 3 to 12 carbon atoms, respectively).

(R ^{3 is} shown as an alkyl group having 3 to 12 carbon atoms, respectively, and the cis-trans isomerism of 1,4-cyclohexylene is a trans isomer).

In addition, as the diamine compound having a specific side chain structure represented by the above formula [2-2], a diamine compound represented by the following formula [2a-37] to [2a-46] can be exemplified.

(A ^{1 is} shown as an alkyl group having 1 to 22 carbon atoms or a fluorine-containing alkyl group, respectively).

(A ^{1 is} shown as a bond selected from at least one selected from the group consisting of -COO-, -OCO-, -CONH-, -NHCO-, -CH ₂ -, -O-, -CO-, and -NH-, respectively. The base group A ^{2 is} respectively selected from the group consisting of a linear or branched alkyl group having 1 to 22 carbon atoms and a linear or branched fluorine-containing alkyl group having 1 to 22 carbon atoms. 1 kind).

The proportion of the specific side chain type diamine compound is used as the liquid crystal From the viewpoint of the vertical alignment of the liquid crystal in the display element and the adhesion between the liquid crystal layer and the liquid crystal alignment film, it is preferably from 10 to 80 mol% based on the entire diamine component. It is preferably 10 to 70 mol%.

Further, the specific side chain type diamine is specified in view of the solubility in a solvent of a specific polyimine-based polymer, the vertical alignment of a liquid crystal when a liquid crystal alignment film is formed, and the optical characteristics of a liquid crystal display element. Compound can be mixed One type or two or more types are used.

As a diamine used to make a specific polyamidene-based polymer As the component, a diamine compound (also referred to as a second diamine compound) represented by the following formula [2b] is preferably used.

In the formula [2b], X is a substituent selected from at least one selected from the group consisting of the structures represented by the following formulas [2-1b] to [2-4b].

m is shown as an integer from 1 to 4. Among them, it is preferably 1.

a is shown as an integer from 0 to 4. Among them, from the viewpoint of availability of raw materials or ease of synthesis, an integer of 0 or 1 is preferable.

b is shown as an integer from 0 to 4. Among them, from the viewpoint of availability of raw materials or ease of synthesis, an integer of 0 or 1 is preferable.

W ¹ and W ² are each independently shown as a hydrocarbon group having 1 to 12 carbon atoms.

W ^{3 is} shown as an alkyl group having 1 to 5 carbon atoms.

Specific examples of the second diamine compound are as follows, but It is not limited to these examples.

For example, in addition to 2,4-dimethyl-m-phenylenediamine, 2,6-diaminotoluene, 2,4-diaminophenol, 3,5-diaminophenol, 3,5-diamine Alkyl benzyl alcohol, 2,4-diaminobenzyl alcohol, 4,6-diamino resorcinol, 2,4-diaminobenzoic acid, 2,5-diaminobenzoic acid or 3,5- Other than the diaminobenzoic acid, a diamine compound represented by the following formula [2b-1] to [2b-6] can be exemplified.

Among them, 2,4-diaminophenol, 3,5-diaminophenol, 3,5-diaminobenzyl alcohol, 2,4-diaminobenzyl alcohol, 4,6-diaminoresorcinol, 2,4-diaminobenzoic acid, 2,5-diaminobenzene Formic acid, 3,5-diaminobenzoic acid or a diamine compound represented by the formula [2b-1] to [2b-3].

Further preferred is 2,4-diaminophenol, 3,5-diaminophenol, 3,5-diaminobenzyl alcohol, 3,5-diaminobenzoic acid or the formula [2b-1]~[ 2b-2] shows a diamine compound or the like.

The ratio of use of the second diamine compound is preferably 10 in terms of the vertical alignment of the liquid crystal in the liquid crystal display element and the adhesion between the liquid crystal layer and the liquid crystal alignment film. ~90% by mole. It is preferably 20 to 90 mol%. Very good for 30~80 moles.

In addition, the second diamine compound is characterized by the solubility of the specific polyimine-based polymer in the solvent, the vertical alignment of the liquid crystal when the liquid crystal alignment film is formed, and the optical characteristics of the liquid crystal display element. It can be used in combination of 1 type or 2 types or more.

Used within the scope of not impairing the effects of the present invention A specific side chain type diamine compound and a diamine compound other than the second diamine compound (also referred to as another diamine compound) may be used for the diamine component of the specific polyimine-based polymer. Specific examples of the other diamine compound are as follows, but are not limited thereto.

For example, m-phenylenediamine, p-phenylenediamine, 4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,3' -dimethoxy-4,4'-diaminobiphenyl, 3,3'-dihydroxy-4,4'-diaminobiphenyl, 3,3'-dicarboxy-4,4'-di Aminobiphenyl, 3,3'-difluoro-4,4'-diaminobiphenyl, 3,3'-trifluoromethyl-4,4'-diaminobiphenyl, 3,4'- Diaminobiphenyl, 3,3'-diaminobiphenyl, 2,2'-diaminobiphenyl, 2,3'-diaminobiphenyl, 4,4'-diaminodiphenyl Methane, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 2,2'-diaminodiphenylmethane, 2,3'-diaminodi Phenylmethane, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 2,2'-diamine Diphenyl ether, 2,3'-diaminodiphenyl ether, 4,4'-sulfonyldiphenylamine, 3,3'-sulfonyldiphenylamine, bis(4-aminobenzene) Base) decane, bis(3-aminophenyl)decane, dimethyl-bis(4-aminophenyl)decane, dimethyl-bis(3-aminophenyl)decane, 4,4'- Thiodiphenylamine, 3,3'-thiodiphenylamine, 4,4'-diaminodiphenylamine, 3,3'-diaminodiphenylamine, 3,4'-diaminodi Phenylamine, 2,2'-diaminodiphenylamine, 2,3'-diaminodiphenylamine, N-methyl(4,4'-diaminodiphenyl)amine, N -Methyl (3,3'-diaminodiphenyl)amine, N-methyl(3,4'-diaminodiphenyl)amine, N-methyl (2,2'-diamino) Diphenyl)amine, N-methyl(2,3'-diaminodiphenyl)amine, 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone , 3,4'-diaminobenzophenone, 1,4-diaminonaphthalene, 2,2'-diaminobenzophenone, 2,3'-diaminobenzophenone, 1 , 5-diaminonaphthalene, 1,6-diaminonaphthalene, 1,7-diaminonaphthalene, 1,8-diaminonaphthalene, 2,5-diaminonaphthalene, 2,6-diamino Naphthalene, 2,7-diaminonaphthalene, 2,8-diaminonaphthalene, 1,2-bis(4-aminophenyl)ethane, 1,2-bis(3-aminophenyl)ethane Alkane, 1,3-bis(4-aminophenyl)propane, 1,3-bis(3-aminophenyl)propane, 1,4-bis(4-aminobenzene) Butane, 1,4-bis(3-aminophenyl)butane, bis(3,5-diethyl-4-aminophenyl)methane, 1,4-bis(4-aminobenzene) Oxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenyl)benzene, 1,3-bis(4-aminophenyl)benzene , 1,4-bis(4-aminobenzyl)benzene, 1,3-bis(4-aminophenoxy)benzene, 4,4'-[1,4-phenylene bis(methylene) )]Diphenylamine, 4,4'-[1,3-phenylenebis(methylene)]diphenylamine, 3,4'-[1,4-phenylenebis(methylene)]diphenylamine , 3,4'-[1,3-phenylenebis(methylene)]diphenylamine, 3,3'-[1,4-phenylenebis(methylene)]diphenylamine, 3,3 '-[1,3-Exophenylbis(methylene)]diphenylamine, 1,4-phenylene bis[(4-aminophenyl)methanone], 1,4-phenylene bis[ (3-aminophenyl) Methyl ketone], 1,3-phenylene bis[(4-aminophenyl)methanone], 1,3-phenylene bis[(3-aminophenyl)methanone], 1,4- Phenyl bis(4-aminobenzoate), 1,4-phenylene bis(3-aminobenzoate), 1,3-phenylene bis(4-aminobenzoic acid) Ester), 1,3-phenylene bis(3-aminobenzoate), bis(4-aminophenyl)terephthalate, bis(3-aminophenyl)-p-phenylene Formate, bis(4-aminophenyl)isophthalate, bis(3-aminophenyl)isophthalate, N,N'-(1,4-phenylene) Bis(4-aminobenzamide), N,N'-(1,3-phenylene)bis(4-aminobenzylamine), N,N'-(1,4-phenylene) Bis(3-aminobenzamide), N,N'-(1,3-phenylene)bis(3-aminobenzylamine), N,N'-bis(4-aminophenyl) Paraxylamine, N,N'-bis(3-aminophenyl)terephthalamide, N,N'-bis(4-aminophenyl)m-xylyleneamine, N , N'-bis(3-aminophenyl)m-xylyleneamine, 9,10-bis(4-aminophenyl)anthracene, 4,4'-bis(4-aminophenoxy) Diphenylanthracene, 2,2'-bis[4-(4-aminophenoxy)phenyl]propane, 2,2'-bis[4-(4-aminophenoxy)phenyl]hexa Fluoropropane, 2,2'-bis(4-aminophenyl) Fluoropropane, 2,2'-bis(3-aminophenyl)hexafluoropropane, 2,2'-bis(3-amino-4-methylphenyl)hexafluoropropane, 2,2'-double (4-Aminophenyl)propane, 2,2'-bis(3-aminophenyl)propane, 2,2'-bis(3-amino-4-methylphenyl)propane, 1,3 - bis(4-aminophenoxy)propane, 1,3-bis(3-aminophenoxy)propane, 1,4-bis(4-aminophenoxy)butane, 1,4- Bis(3-aminophenoxy)butane, 1,5-bis(4-aminophenoxy)pentane, 1,5-bis(3-aminophenoxy)pentane, 1,6 - bis(4-aminophenoxy)hexane, 1,6-bis(3-aminophenoxy)hexane, 1,7-bis(4-aminophenoxy)heptane, 1, 7-bis(3-amino group Phenoxy)heptane, 1,8-bis(4-aminophenoxy)octane, 1,8-bis(3-aminophenoxy)octane, 1,9-bis(4-amine Phenoxy)decane, 1,9-bis(3-aminophenoxy)decane, 1,10-bis(4-aminophenoxy)decane, 1,10-bis(3- Aminophenoxy)decane, 1,11-bis(4-aminophenoxy)undecane, 1,11-bis(3-aminophenoxy)undecane, 1,12-double (4-Aminophenoxy)dodecane, 1,12-bis(3-aminophenoxy)dodecane, bis(4-aminocyclohexyl)methane, bis(4-amino-3) -Methylcyclohexyl)methane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7 -diaminoheptane, 1,8-diaminooctane, 1,9-diaminodecane, 1,10-diaminodecane, 1,11-diaminoundecane or 1, 12-diaminododecane and the like.

Further, within the range that does not impair the effects of the present invention, The diamine compound represented by the following formula [DA1] to [DA14] is used.

(p is an integer from 1 to 10).

(m is shown as an integer from 0 to 3).

(n is shown as an integer from 1 to 5).

(A ¹ and A ³ are each independently selected from a single bond, -CH ₂ -, -C ₂ H ₄ -, -C(CH ₃ ) ₂ -, -CF ₂ -, -C(CF ₃ ) ₂ -, -O-, -CO-, -NH-, -N(CH ₃ )-, -CONH-, -NHCO-, -CH ₂ O-, -OCH ₂ -, -COO-, -OCO-, -CON( At least one bonding group in the group formed by CH ₃ )- and -N(CH ₃ )CO-, m ¹ and m ² are each an integer of 0 to 4, and m ¹ + m ^{2 is} shown as 1~ An integer of 4, m ³ and m ⁴ are each shown as an integer from 1 to 5. A ^{2 is} shown as a linear or branched alkyl group having a carbon number of 1 to 5. m ⁵ is an integer of 1 to 5. m ^{6 is} shown as An integer from 1 to 4).

(A ^{1 is} shown to be selected from -O-, -NH-, -N(CH ₃ )-, -CONH-, -NHCO-, -CH ₂ O-, -OCO-, -CON(CH ₃ )- and - N (CH ₃₎ CO- group formed by the bonding of at least one kind of group .A ² is shown as a single bond, a carbon number of from 1 to 20 aliphatic hydrocarbon group, non-aromatic cyclic hydrocarbon group or an aromatic hydrocarbon group .A ³ It is shown to be selected from the group consisting of a single bond, -O-, -NH-, -N(CH ₃ )-, -CONH-, -NHCO-, -COO-, -OCO-, -CON(CH ₃ )-, -N ( CH ₃ ) CO- and -O(CH ₂ ) _m - (m is an integer of 1 to 5) of at least one bonding group in the group formed. A ⁴ is a nitrogen-containing aromatic heterocyclic ring. An integer from 1 to 4).

The other diamine compound may be mixed in one type depending on the solubility of the specific polyimine-based polymer in the solvent, the vertical alignment of the liquid crystal when the liquid crystal alignment film is formed, and the optical characteristics of the liquid crystal display element. Use two or more types.

a tetracarboxylic acid used to make a specific polyamidene-based polymer The tetracarboxylic dianhydride represented by the following formula [3], or the tetracarboxylic acid, the dihalogenated tetracarboxylic acid compound, the dicarboxylic acid dialkyl ester compound or the dihalogenated tetracarboxylic acid represented by the following formula [3] is preferably used. Acid dialkyl ester compounds (all also collectively referred to as specific tetracarboxylic acid components).

Z ¹ is a group selected from at least one selected from the group consisting of the structures represented by the following formulas [3a] to [3j].

Z ² to Z ⁵ are each independently represented by a hydrogen atom, a methyl group, a chlorine atom or a benzene ring.

Z ⁶ and Z ⁷ are each independently shown as a hydrogen atom or a methyl group.

Formula [3] Z ^1, the viewpoint of the easiness of the polymerization reaction of the easiness of synthesis or manufacture of the polymer, it is preferably of formula [. 3A], formula [. 3C], formula [3D], of formula [3e], formula [3f] or formula [3g]. Further preferred is the formula [3a], the formula [3e], the formula [3f] or the formula [3g]. Particularly preferred is the formula [3e], the formula [3f] or the formula [3g].

The proportion of the specific tetracarboxylic acid component to be used is preferably 1 mol% or more based on the total tetracarboxylic acid component. It is also preferably 5 mol% or more. It is particularly preferably 10 mol% or more, and is preferably 15 to 90 mol% from the viewpoint of optical characteristics in the liquid crystal display element.

When a specific tetracarboxylic acid component having a structure represented by the above formula [3e], formula [3f] or formula [3g] is used, the amount used is 20 mol% or more of the entire tetracarboxylic acid component. Get the desired effect. Also preferably 30 moles %the above. Further, all of the specific tetracarboxylic acid components may be a tetracarboxylic acid component having a structure represented by the formula [3e], the formula [3f] or the formula [3g].

Within a certain range without damaging the effects of the present invention Other tetracarboxylic acid components other than the specific tetracarboxylic acid component can also be used for the quinone imine polymer.

Examples of the other tetracarboxylic acid component include a tetracarboxylic acid compound, a tetracarboxylic dianhydride, a dihalogenated dicarboxylic acid compound, a dicarboxylic acid dialkyl ester compound or a dihalogenated dialkyl ester compound shown below.

For example, pyromellitic acid, 2,3,6,7-naphthalenetetracarboxylic acid, 1,2,5,6-naphthalenetetracarboxylic acid, 1,4,5,8-naphthalenetetracarboxylic acid, 2, 3 may be mentioned. ,6,7-nonanetetracarboxylic acid, 1,2,5,6-nonanetetracarboxylic acid, 3,3',4,4'-biphenyltetracarboxylic acid, 2,3,3',4'- Biphenyltetracarboxylic acid, bis(3,4-dicarboxyphenyl)ether, 3,3',4,4'-benzophenonetetracarboxylic acid, bis(3,4-dicarboxyphenyl)fluorene , bis(3,4-dicarboxyphenyl)methane, 2,2-bis(3,4-dicarboxyphenyl)propane, 1,1,1,3,3,3-hexafluoro-2,2- Bis(3,4-dicarboxyphenyl)propane, bis(3,4-dicarboxyphenyl)dimethyloxane, bis(3,4-dicarboxyphenyl)diphenylnonane, 2,3,4 , 5-pyridinetetracarboxylic acid, 2,6-bis(3,4-dicarboxyphenyl)pyridine, 3,3',4,4'-diphenylphosphonium tetracarboxylic acid, 3,4,9,10 - tetracarboxylic acid or 1,3-diphenyl-1,2,3,4-cyclobutanetetracarboxylic acid or the like.

Solvent dissolution of a specific polyamidene-based polymer The properties of the liquid crystal alignment film, the vertical alignment of the liquid crystal display film, and the optical characteristics of the liquid crystal display element, and the like, may be used in combination of one or two or more kinds of the tetracarboxylic acid component and the other tetracarboxylic acid component.

A method for synthesizing a specific polyamidene-based polymer of the present invention Do not limit. Usually, it is obtained by the reaction of a diamine component and a tetracarboxylic acid component. In general, a tetracarboxylic acid component selected from at least one selected from the group consisting of tetracarboxylic acids and derivatives thereof is reacted with a diamine component formed from one or more kinds of diamine compounds. The method of poly-proline. Specifically, a method of polycondensing a tetracarboxylic dianhydride with a diamine compound of a 1st or 2nd stage to obtain a poly-proline can be used; a tetracarboxylic acid and a diamine of a 1st or 2nd stage can be used. A method in which a compound is dehydrated and polycondensed to obtain a poly-proline acid; or a method in which a dihalogenated dicarboxylic acid is polycondensed with a diamine compound of a first or a second stage to obtain a poly-proline.

To obtain polyalkyl amide, use the following a method of polycondensing a tetracarboxylic acid obtained by esterifying a carboxylic acid dialkyl ester with a diamine compound of a first or second stage; a dihalogenated dicarboxylic acid obtained by esterifying a carboxylic acid dialkyl A method of polycondensation of a diamine compound of a grade 1 or 2; or a method of converting a carboxyl group of a polylysine to an ester.

In order to obtain a polyimine, a method of obtaining a polyimine by ring-closing the polyamic acid or polyalkyl amide may be used.

The reaction of the diamine component with the tetracarboxylic acid component is usually dissolved In the agent. The solvent to be used at this time is not particularly limited as long as it dissolves the produced polyimide precursor. Although specific examples of the solvent used for the reaction are listed below, the examples are not limited thereto.

For example, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, γ-butyrolactone, N,N-dimethylformamide, N,N-dimethyl group Acetamide, dimethyl hydrazine, 1,3-dimethyl-imidazolidinone, methyl ethyl ketone, 4-hydroxy-4-methyl-2-pentanone or the following formula [A3] Solvents, etc.

(A ^{3 is} shown as an alkyl group having 1 to 4 carbon atoms).

Further, when the solubility of the specific polyimine-based polymer in the solvent is high, a solvent such as cyclopentanone or cyclohexanone, a compound represented by the following formula [A1] or the formula [A2], or the like can be used.

(A ^{1 is} shown as an alkyl group having 1 to 3 carbon atoms, and A ² is represented as an alkyl group having 1 to 3 carbon atoms).

These solvents may be used singly or in combination. Further, even if it is a solvent which does not dissolve the polyimide precursor, it may be used in the above solvent in the range in which the produced polyimide precursor is not precipitated. Further, since the water in the solvent hinders the polymerization reaction and further causes hydrolysis of the produced polyimide precursor, the solvent is preferably used by dehydration.

When the diamine component and the tetracarboxylic acid component are reacted in a solvent, for example, a solution obtained by dispersing or dissolving a diamine component in a solvent may be used, and the tetracarboxylic acid component may be directly dispersed or dissolved in the solvent. a method of adding a solvent; conversely, a method of adding a diamine component in a solution in which a tetracarboxylic acid component is dispersed or dissolved in a solvent; and a diamine component and four are alternately added A method of a carboxylic acid component. These methods can be used.

Also, a plurality of diamine components or tetracarboxylic acid components are used respectively. When the reaction is carried out, the reaction can be carried out in a state of being mixed in advance, or the reaction can be carried out individually, and the low-molecular weight body of the individual reaction can be mixed and reacted to form a polymer. The polymerization temperature at this time may be any temperature of from -20 to 150 ° C, preferably from -5 to 100 ° C. Further, the reaction can be carried out at any concentration. However, when the concentration is too low, it is difficult to obtain a polymer having a high molecular weight. When the concentration is too high, the viscosity of the reaction liquid becomes too high, and it is difficult to uniformly stir. Therefore, it is preferably from 1 to 50% by mass, and more preferably from 5 to 30% by mass. The initial stage of the reaction can be carried out at a high concentration, and then a solvent is added.

In the polymerization reaction of the polyimine precursor, the ratio of the total number of moles of the diamine component to the total number of moles of the tetracarboxylic acid component is preferably from 0.8 to 1.2. As with the usual polycondensation reaction, the closer the molar ratio is to 1.0, the larger the molecular weight of the resulting polyimide precursor.

The polyimine in the present invention is a polyimine obtained by ring-closing the polyimine precursor, and a ring closure ratio (also referred to as a ruthenium rate) of the amidino group of the polyimide. It does not have to be 100%, and can be adjusted arbitrarily according to the purpose or purpose. In the present invention, from the viewpoint of the solubility of the specific polyamidene-based polymer to the solvent or the optical characteristics of the liquid crystal display device, it is preferably from 30 to 80%. It is preferably 40 to 70%. Very good for 40~60%.

As a method for imidating a polyimine precursor ruthenium, The ruthenium imidization of the ruthenium imidization of the solution of the polyimide precursor is directly heated or the catalyst is added to the solution of the polyimide precursor.

The temperature at which the polyimine precursor is thermally imidized in the solution is preferably from 100 to 400 °C. Further preferably, it is preferably from 120 to 250 ° C, and it is preferred to remove the water formed by the imidization reaction to the outside of the system.

The ruthenium imidization of the polyimide precursor can be stirred at -20 to 250 ° C, preferably 0 to 180 ° C by adding a basic catalyst and an acid anhydride to the solution of the polyimide precursor. Come on. The amount of the alkaline catalyst is 0.5 to 30 moles, preferably 2 to 20 moles, of the proline group, and the amount of the anhydride is 1 to 50 moles of the amidate group, preferably 3 ~30 moles.

As the basic catalyst, pyridine, triethylamine, trimethylamine, tributylamine or trioctylamine can be exemplified. Among them, pyridine is preferred because it has an appropriate basicity for allowing the reaction to proceed.

Examples of the acid anhydride include acetic anhydride, trimellitic anhydride, and pyromellitic anhydride. Among them, in the case of using acetic anhydride, purification after the completion of the reaction becomes easy, which is preferable. The imidization ratio of the imidization by the catalyst oxime can be controlled by adjusting the amount of the catalyst, the reaction temperature, and the reaction time.

When the produced polyimine precursor or polyimine is recovered from the reaction solution of the polyimine precursor or the polyimine, the reaction solution may be placed in a solvent to precipitate. Examples of the solvent used in the precipitation include methanol, ethanol, isopropanol, acetone, hexane, butyl cyanisol, heptane, methyl ethyl ketone, methyl isobutyl ketone, toluene, benzene or water. . The polymer which is charged and precipitated can be recovered by filtration, and dried at normal temperature or under reduced pressure under normal pressure or reduced pressure. Further, the polymer recovered by the precipitation is redissolved in the solvent, and the operation of repeating the reprecipitation recovery is repeated 2 to 10 times to reduce the impurities in the polymer. Examples of the solvent at this time include alcohols, When three or more solvents selected from the above are used in the ketones, hydrocarbons, and the like, the efficiency of purification can be further improved, which is preferable.

The molecular weight of the specific polyimine-based polymer, when considering the strength of the vertical liquid crystal alignment film obtained therefrom, the workability at the time of formation of the vertical liquid crystal alignment film, and the coating property, the weight measured by GPC (Gel Permeation Chromatography) method The average molecular weight is preferably from 5,000 to 1,000,000, more preferably from 10,000 to 150,000.

In the present invention, from the viewpoint of the optical characteristics of the liquid crystal display element, the specific polyimine-based polymer is preferably the above-mentioned polyimine which is imidized by the polyimide precursor catalyst. The ruthenium amination ratio at this time is preferably in the above range.

<Liquid alignment treatment agent>

The liquid crystal alignment treatment agent in the present invention is a coating solution for forming a liquid crystal alignment film, and is a specific cellulose-based polymer of the component (A), a specific polyamidene-based polymer of the component (B), and Solvent coating solution.

When the ratio of the specific cellulose-based polymer and the specific polyimine-based polymer in the liquid crystal alignment agent is 1 part by mass based on the ratio of the specific polyamidene-based polymer, the ratio of the specific cellulose-based polymer It is preferably 0.01 to 99 parts by mass. It is preferably 0.1 to 9 parts by mass. Particularly preferably 0.1 to 3 parts by mass.

All of the polymer components in the liquid crystal alignment agent can be All are specific cellulose-based polymers and specific polyamidene-based polymers, Other polymers than the other may be mixed. Examples of the polymer other than the polymer include a polyimide-based polymer which does not include a specific side chain structure. Further, an acrylic polymer, a methacrylic polymer, a phenol resin, polyhydroxystyrene, polyamine, polyester or polyoxyalkylene may be mixed.

In this case, the content of the polymer other than the polymer is preferably 0.5 to 15 parts by mass based on 100 parts by mass of the total polymer of the specific cellulose-based polymer and the specific polyimine-based polymer. Parts by mass. It is preferably 1 to 10 parts by mass.

In the liquid crystal alignment treatment agent, the solvent content can be appropriately selected from the viewpoint of the coating method of the liquid crystal alignment treatment agent or the so-called desired film thickness. In the viewpoint of forming a uniform vertical liquid crystal alignment film by coating, the content of the solvent in the liquid crystal alignment treatment agent is preferably from 50 to 99.9% by mass. It is preferably 60 to 99% by mass. Particularly good is 65 to 99% by mass.

The solvent used in the liquid crystal alignment agent, as long as it is The solvent (also referred to as a good solvent) for dissolving the specific cellulose polymer and the specific polyamidene polymer is not particularly limited. Specific examples of the good solvent are listed below, but are not limited thereto.

For example, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, γ-butyrolactone, N,N-dimethylformamide, N,N-dimethyl B Hydrazine, dimethyl hydrazine, 1,3-dimethyl-imidazolidinone, methyl ethyl ketone, 4-hydroxy-4-methyl-2-pentanone or a solvent represented by the above formula [A3] . Among them, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, γ-butyrolactone or a solvent represented by the above formula [A3] is preferably used.

Further, when the solubility of the specific polyimine-based polymer in a solvent is high, a solvent such as cyclopentanone or cyclohexanone, the above formula [A1] or the formula [A2] can be used.

The good solvent in the liquid crystal alignment treatment agent is preferably from 10 to 100% by mass based on the total amount of the solvent contained in the liquid crystal alignment treatment agent. It is preferably 20 to 90% by mass. Particularly good is 30 to 80% by mass.

Liquid crystal alignment within a range that does not impair the effects of the present invention A solvent (also referred to as a weak solvent) for improving the coating property or surface smoothness of the vertical liquid crystal alignment film when the liquid crystal alignment treatment agent is applied can be used as the treatment agent. Specific examples of the weak solvent are listed below, but are not limited thereto.

For example, ethanol, isopropanol, 1-butanol, 2-butanol, isobutanol, tert-butanol, 1-pentanol, 2-pentanol, 3-pentanol, 2-methyl-1- may be mentioned Butanol, isoamyl alcohol, tert-pentanol, 3-methyl-2-butanol, neopentyl alcohol, 1-hexanol, 2-methyl-1-pentanol, 2-methyl-2-pentanol , 2-ethyl-1-butanol, 1-heptanol, 2-heptanol, 3-heptanol, 1-octanol, 2-octanol, 2-ethyl-1-hexanol, cyclohexanol, 1-methylcyclohexanol, 2-methylcyclohexanol, 3-methylcyclohexanol, 1,2-ethanediol, 1,2-propanediol, 1,3-propanediol, 1,2-butane Alcohol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,5-pentanediol, 2-methyl-2,4-pentanediol, 2-B -1,3-hexanediol, dipropyl ether, dibutyl ether, dihexyl ether, dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl Ether, 1,2-butoxyethane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dibutyl ether, 2 -pentanone, 3-pentanone, 2-hexanone, 2-heptanone, 4-heptanone, 3-ethoxybutyl acetate, 1-methylpentyl acetate, 2-ethylbutyl Base B Acid ester, 2-ethylhexyl acetate, ethylene glycol monoacetate, ethylene glycol diacetate, propyl carbonate, ethyl carbonate, 2-(methoxymethoxy)ethanol, Ethylene glycol monobutyl ether, ethylene glycol monoisoamyl ether, ethylene glycol monohexyl ether, 2-(hexyloxy)ethanol, furan methanol, diethylene glycol, propylene glycol, propylene glycol monobutyl ether, 1 -(butoxyethoxy)propanol, propylene glycol monomethyl ether acetate, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, tripropylene glycol monomethyl ether, ethylene glycol monomethyl Ethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monoacetate, ethylene glycol diacetate, diethylene glycol monoethyl Ethyl ether acetate, diethylene glycol monobutyl ether acetate, 2-(2-ethoxyethoxy) ethyl acetate, diethylene glycol acetate, triethylene glycol, three Ethylene glycol monomethyl ether, triethylene glycol monoethyl ether, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether, methyl pyruvate , ethyl pyruvate, methyl 3-methoxypropionate, 3- Methyl ethyl oxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, propyl 3-methoxypropionate, 3-methoxy Butyl propionate, methyl lactate, ethyl lactate, n-propyl lactate, n-butyl lactate, isoamyl lactate or a solvent represented by the above formula [A1] to formula [A3]. Among them, 1-hexanol, cyclohexanol, 1,2-ethanediol, 1,2-propanediol, propylene glycol monobutyl ether, ethylene glycol monobutyl ether, dipropylene glycol dimethyl ether can be preferably used. Or a solvent represented by the above formula [A1] to formula [A3].

These weak solvents are preferably from 1 to 70% by mass based on the total amount of the solvent contained in the liquid crystal alignment agent. It is preferably from 1 to 60% by mass. Very good is 5 to 60% by mass.

In the liquid crystal alignment treatment agent of the present invention, liquid crystal is improved For the purpose of adhesion between the layer and the liquid crystal alignment film, it is preferred to introduce a compound having at least one selected from the group consisting of the structures represented by the following formulas [B1] to [B8] (also referred to as adhesion). Sex compound).

The basis of the structure shown in the formula [B1] to the formula [B8] is preferably two or more of the compounds.

(B ¹ is a hydrogen atom or a benzene ring, and B ² is a cyclic group selected from at least one of a group consisting of a benzene ring, a cyclohexane ring, and a hetero ring, and B ³ is selected from a carbon number of 1 to At least one of a group of 18 alkyl groups, a fluorine-containing alkyl group having 1 to 18 carbon atoms, and an alkoxy group having 1 to 18 carbon atoms.

As a more specific adhesive compound, it is preferred to use the following a compound of the formula [6].

In the formula [6], M ¹ is a structure selected from at least one selected from the group consisting of the structures represented by the following formulas [a-1] to [a-7]. Among them, from the viewpoint of easiness of production of the adhesion compound, it is preferably of the formula [a-1], the formula [a-2], the formula [a-3], the formula [a-5] or the formula. [a-6] The structure shown. Further, it is preferably a structure represented by the formula [a-1], the formula [a-3], the formula [a-5] or the formula [a-6].

A ¹ is represented by a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. Among them, from the viewpoint of easiness of production of the adhesion compound, a hydrogen atom or an alkyl group having 1 to 2 carbon atoms is preferable. Further preferred is a hydrogen atom or a methyl group.

A ² is represented by a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. Among them, from the viewpoint of easiness of production of the adhesion compound, a hydrogen atom or an alkyl group having 1 to 2 carbon atoms is preferable. Further preferred is a hydrogen atom or a methyl group.

A ³ , A ⁵ , A ⁶ and A ⁹ are each independently represented by a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. Among them, from the viewpoint of easiness of production of the adhesion compound, a hydrogen atom or an alkyl group having 1 to 2 carbon atoms is preferable. Further preferred is a hydrogen atom or a methyl group.

A ⁴ , A ⁷ and A ⁸ are each independently shown as an alkylene group having 1 to 3 carbon atoms. Among them, from the viewpoint of easiness of production of the adhesion compound, an alkylene group having 1 to 2 carbon atoms is preferable.

In the formula [6], M ² is selected from a single bond, -CH ₂ -, -O-, -NH-, -N(CH ₃ )-, -CONH-, -NHCO-, -CH ₂ O-, At least one bonding group of -OCH ₂ -, -COO-, -OCO-, -CON(CH ₃ )-, and -N(CH ₃ )CO-. Among them, from the viewpoint of easiness of synthesis of the adhesion compound, a single bond, -CH ₂ -, -O-, -NH-, -CONH-, -NHCO-, -CH ₂ O- is preferred. , -OCH ₂ -, -COO-, -OCO-, -CON(CH ₃ )- or -N(CH ₃ )CO-. Further preferred is a single bond, -CH ₂ -, -O-, -NH-, -CONH-, -CH ₂ O-, -OCH ₂ -, -COO- or -OCO-. Particularly preferred is a single bond, -O-, -CONH-, -OCH ₂ -, -COO- or -OCO-.

In the formula [6], M ³ is selected from an alkyl group having 1 to 20 carbon atoms, -(CH ₂ -CH ₂ -O) _p - (p is an integer of 1 to 10), -(CH ₂ - O-) _q - (q is an integer of 1 to 10), and at least one of the group consisting of an organic group having a benzene ring or a cyclohexane ring having 6 to 20 carbon atoms. At this time, any -CH ₂ - group of the above alkylene group may be via -COO-, -OCO-, -CONH-, NHCO-, -CO-, -S-, -SO ₂ -, -CF ₂ -, -C(CF ₃ ) ₂ -, -Si(CH ₃ ) ₂ -, -OSi(CH ₃ ) ₂ - or -Si(CH ₃ ) ₂ O- is substituted, and a hydrogen atom bonded to any carbon atom may be Substituted by a hydroxyl group (OH group), a carboxyl group (COOH group) or a halogen atom. Among them, from the viewpoint of easiness of production of the adhesion compound, an alkylene group having 1 to 20 carbon atoms and -(CH ₂ -CH ₂ -O) _p - (p is shown as 1 to 10) is preferred. The integer is), -(CH ₂ -O-) _q - (q is an integer of 1 to 10), or a structure represented by the following formula [c-1] to formula [c-5]. Further preferred is an alkylene group having 1 to 15 carbon atoms, -(CH ₂ -CH ₂ -O) _p - (p is an integer of 1 to 10), and -(CH ₂ -O-) _q - (q is shown The structure is an integer of 1 to 10, and is represented by the following formula [c-1], formula [c-3], formula [c-4], or formula [c-5]. Particularly preferred are an alkylene group having 1 to 15 carbon atoms, -(CH ₂ -CH ₂ -O) _p - (p is an integer of 1 to 10), a formula [c-1], a formula [c-4] or The configuration shown in the formula [c-5].

In the formula [6], M ⁴ is a bond group selected from at least one selected from the group consisting of a single bond, -CH ₂ -, -OCH ₂ -, and -O-CH ₂ -CH ₂ -. Among them, from the viewpoint of easiness of synthesis of the adhesion compound, a structure represented by a single bond, -CH ₂ - or -OCH ₂ - is preferred.

In the formula [6], M ⁵ is a structure selected from at least one selected from the group consisting of the structures represented by the above formulas [B1] to [B8]. Among them, from the viewpoint of easiness of synthesis of the adhesion compound, the structure represented by the formula [B1], the formula [B2] or the formula [B6] is preferable. Further, it is preferably a structure represented by the formula [B1] or the formula [B2].

In the formula [6], n is shown as an integer from 1 to 3. Among them, from the viewpoint of easiness of synthesis of the adhesion compound, it is preferably 1 or 2. It is also preferably 1.

In the formula [6], m is shown as an integer from 1 to 3. Among them, from the viewpoint of easiness of synthesis of the adhesion compound, it is preferably 1 or 2.

In the present invention, it is preferred to use an adhesive compound selected from the group consisting of A compound of at least one selected from the group consisting of the compounds represented by the following formula [6-1] and formula [6-5].

(n is shown as an integer from 1 to 10, and m is an integer from 1 to 10).

Further, examples of the adhesion compound include the following.

For example, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, tris (meth) propylene methoxy ethoxy trihydroxyl a propane or glycerol polyglycidyl ether poly(meth) acrylate or the like having three polymerizable unsaturated groups in the molecule; more, such as ethylene glycol di(meth) acrylate or diethylene glycol (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, Butanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, ethylene oxide bisphenol A di(meth)acrylate, propylene oxide bisphenol type di(methyl) Acrylate, 1,6-hexanediol di(meth)acrylate, Gan Oil di(meth)acrylate, pentaerythritol di(meth)acrylate, ethylene glycol diglycidyl ether di(meth)acrylate, diethylene glycol diglycidyl di(meth)acrylate, adjacent a compound having two polymerizable unsaturated groups in the molecule, such as diglycidyl phthalate di(meth) acrylate or hydroxytrimethyl acetic acid neopentyl glycol di(meth) acrylate; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-phenoxy-2-hydroxypropyl (methyl) Acrylate, 2-(methyl)propenyloxy-2-hydroxypropyl phthalate, 3-chloro-2-hydroxypropyl (meth) acrylate, glycerol mono(meth)acrylic acid A compound having one polymerizable unsaturated group in the molecule, such as an ester, 2-(meth)acryloyloxyethyl phosphate or N-methylol (meth) acrylamide.

The content of the adhesion compound in the liquid crystal alignment agent The amount is preferably 0.1 to 150 parts by mass based on 100 parts by mass of the total polymer component. The viewpoint of the effect of the crosslinking reaction and exhibiting the purpose is preferably 0.1 to 100 parts by mass based on 100 parts by mass of the total polymer component. Very good is 1 to 50 parts by mass.

In addition, the adhesive compound may be used alone or in combination of two or more kinds in accordance with the characteristics of the vertical alignment of the liquid crystal in the case of the vertical liquid crystal alignment film and the optical characteristics of the liquid crystal display element.

In the liquid crystal alignment treatment agent of the present invention, liquid crystal is improved For the purpose of adhesion between the layer and the liquid crystal alignment film, it is preferred to introduce at least one type of production agent (also referred to as a production agent) selected from the group consisting of a photo-radical generator, a photoacid generator, and a photobase generator. .

The photoradical generating agent is not particularly limited as long as it can generate a radical by ultraviolet rays.

For example, tert-butylperoxy-iso-phthalate, 2,5-dimethyl-2,5-bis(benzylidenedioxy)hexane, 1,4-double [α-(tert-butyldioxy)-iso-propoxy]benzene, di-tert-butyl peroxide, 2,5-dimethyl-2,5-bis(tert-butyl Oxy)hexene hydroperoxide, α-(iso-propylphenyl)-iso-propyl hydroperoxide, 2,5-dimethylhexane, tert-butyl hydroperoxide, 1 , 1-bis(tert-butyldioxy)-3,3,5-trimethylcyclohexane, butyl-4,4-bis(tert-butyldioxy)valerate, cyclohexyl Ketone peroxide, 2,2',5,5'-tetra(tert-butylperoxycarbonyl)benzophenone, 3,3',4,4'-tetra(tert-butylperoxy Carbonyl)benzophenone, 3,3',4,4'-tetra(tert-pentylperoxycarbonyl)benzophenone, 3,3',4,4'-tetra(tert-hexylperoxy) Carbocarbonyl)benzophenone, 3,3'-bis(tert-butylperoxycarbonyl)-4,4'-dicarboxybenzophenone, tert-butylperoxybenzoate or two Organic peroxides such as -tert-butyldiperoxyisophthalate; 9,10-anthracene, 1-chloroindole, 2-chloroindole, octamethylguanidine, 1,2 - benzopyrene A benzoin derivative such as benzoin methyl, benzoin ethyl ether, α-methylbenzoin or α-phenylbenzoin.

The photoacid generator and the photobase generator are not particularly limited as long as they can generate an acid or an alkali by ultraviolet rays. For example, a triazine type compound, an acetophenone derivative compound, a diterpene type compound, a diazomethane type compound, a sulfonic acid derivative compound, a diaryl sulfonium salt, a triaryl sulfonium salt, a triaryl sulfonium salt, or an iron aromatic hydrocarbon can be mentioned. Complex and so on.

More specifically, for example, diphenylphosphonium chloride, Diphenylsulfonium trifluoromethanesulfonate, diphenylsulfonium mesylate, diphenylphosphonium p-toluenesulfonate, diphenylphosphonium bromide, diphenylphosphonium tetrafluoroborate, diphenyl Hexafluorodecanoate, diphenylphosphonium hexafluoroarsenate, bis(p-tert-butylphenyl)phosphonium hexafluorophosphate, bis(p-tert-butylphenyl)indole mesylate , bis(p-tert-butylphenyl)fluorene p-toluenesulfonate, bis(p-tert-butylphenyl)fluorene trifluoromethanesulfonate, bis(p-tert-butylphenyl)fluorene Tetrafluoroborate, bis(p-tert-butylphenyl)phosphonium chloride, bis(p-chlorophenyl)phosphonium chloride, bis(p-chlorophenyl)phosphonium tetrafluoroborate, triphenyl Base metal chloride, triphenylsulfonium bromide, tris(p-methoxyphenyl)phosphonium tetrafluoroborate, tris(p-methoxyphenyl)phosphonium hexafluorophosphate, tris(p-B Oxyphenyl) fluorene tetrafluoroborate, triphenylphosphonium chloride, triphenylphosphonium bromide, tris(p-methoxyphenyl)phosphonium tetrafluoroborate, tris(p-methoxy Phenyl)phosphonium hexafluorophosphate, tris(p-ethoxyphenyl)phosphonium tetrafluoroborate, bis[[(2-nitrobenzyl)oxy]carbonylhexane-1,6-diamine ], nitrobenzylcyclohexylamine formate, di(a) Oxybenzyl)hexamethylenediamine formate, bis[[(2-nitrobenzyl)oxy]carbonylhexane-1,6-diamine], nitrobenzylcyclohexylaminecarboxylic acid Ester or bis(methoxybenzyl)hexamethylenediamine formate, and the like.

Among them, the agent in the present invention can be efficiently From the viewpoint of improving the adhesion between the liquid crystal layer and the liquid crystal alignment film, a photo radical generating agent is preferably used.

The content of the generating agent in the liquid crystal alignment agent is preferably 0.01 to 50 by mass based on 100 parts by mass of the total polymer component. Share. The viewpoint of the effect of the crosslinking reaction and exhibiting the purpose is preferably 0.01 to 30 parts by mass based on 100 parts by mass of the total polymer component. Particularly preferably 0.1 to 20 parts by mass.

In addition, the agent may be used in combination of one or two or more kinds in accordance with the characteristics of the vertical alignment of the liquid crystal in the case of the vertical liquid crystal alignment film and the optical characteristics of the liquid crystal display element.

In the liquid crystal alignment treatment agent of the present invention, it is preferably introduced a compound having an epoxy group, an isocyanate group, an oxetane group or a cyclic carbonate group; having at least one selected from the group consisting of a hydroxyl group, a hydroxyalkyl group and a lower alkoxyalkyl group; A compound of one type of substituent (also collectively referred to as a crosslinkable compound). In this case, these substituents must have two or more of the crosslinkable compounds.

As a crosslinkable compound having an epoxy group or an isocyanate group For example, bisphenol acetone glycidyl ether, phenol novolac epoxy resin, cresol novolac epoxy resin, triglycidyl isocyanurate, tetraglycidylamine diphenylene, tetraglycidyl group - M-xylylenediamine, tetraglycidyl-1,3-bis(aminoethyl)cyclohexane, tetraphenyl glycidyl ether ethane, triphenyl glycidyl ether ethane, bisphenol hexafluoroethyl Bisphenol hexafluoroacetodiglycidyl ether, 1,3-bis(1-(2,3-epoxypropoxy)-1-trifluoromethyl-2,2,2-trifluoromethyl) Benzene, 4,4-bis(2,3-epoxypropoxy)octafluorobiphenyl, triglycidyl-p-aminophenol, tetraglycidyl-m-xylenediamine, 2-(4- (2,3-epoxypropoxy)phenyl)-2-(4-(1,1-bis(4-(2,3-epoxypropoxy)phenyl)ethyl)phenyl Propane or 1,3-double (4-(1-(4-) (2,3-epoxypropoxy)phenyl)-1-(4-(1-(4-(2,3-epoxypropoxy)phenyl)-1-methylethyl) Phenyl)ethyl)phenoxy)-2-propanol and the like.

A crosslinkable compound having an oxetane group, for example, a crosslinkable compound having at least two oxetanyl groups represented by the following formula [4A].

Specifically, for example, the crosslinkable compound represented by the formula [4a] to [4k] described on pages 58 to 59 of International Publication WO2011/132751 (2011.10.27 publication).

The crosslinkable compound having a cyclic carbonate group is, for example, a crosslinkable compound having at least two cyclic carbonate groups represented by the following formula [5A].

Specifically, for example, the crosslinkable compound represented by the formula [5-1] to [5-42] described on pages 76 to 82 of International Publication WO2012/014898 (published in 2012.2.2).

As having a group selected from a hydroxyl group and an alkoxy group A crosslinkable compound having one less substituent, for example, an amino group-containing resin having a hydroxyl group or an alkoxy group, for example, a melamine resin, a urea resin, a guanamine resin, an acetylene urea-formaldehyde resin, and a butylene group Guanamine-A An aldehyde resin or a vinyl urea-formaldehyde resin or the like. Specifically, the hydrogen atom of the amine group may be a melamine derivative, a benzoguanamine derivative, an acetylene urea or the like substituted with a methylol group and/or an alkoxymethyl group. The melamine derivative or the benzoguanamine derivative may be present in the form of a dimer or a trimer. These components are preferably those having an average of 3 or more and 6 or less hydroxymethyl groups or alkoxymethyl groups per unit of the triazine ring.

Derived as such a melamine derivative or benzoguanamine For example, commercially available triazine rings are MX-750 substituted by an average of 3.7 methoxymethyl groups per unit, and the triazine ring is averaged 5.8 methoxy groups per unit. Methyl-substituted MW-30 (above, manufactured by Sanwa-Chemical Co., Ltd.), Cymel 300, 301, 303, 350, 370, 771, 325, 327, 703, 712, etc., methoxymethylated melamine, Cymel 235, Methoxymethylated butoxymethylated melamine of 236, 238, 212, 253, 254, etc., butoxymethylated melamine of Cymel 506, 508, etc., carboxylated methoxyl of Cymel 1141 Basic isobutoxymethylated melamine, Cymel 1123-like methoxymethylated ethoxymethylated benzoguanamine, Cymel 1123-10-like methoxymethylated butoxymethylated benzene Indoleamine, Cymel 1128-like butoxymethylated benzoguanamine, Cymel 1125-80 carboxyl group-containing methoxymethylated ethoxymethylated benzoguanamine (manufactured by Mitsui Cyanamid Co., Ltd.). Further, examples of the acetylene urea include a butoxymethylated acetylene urea such as Cymel 1170, a methylolated acetylene urea such as Cymel 1172, and a methoxymethylolated acetylene urea such as Powderlink 1174.

As a benzene or phenolic compound having a hydroxyl group or an alkoxy group, For example, 1,3,5-paraxyl (methoxymethyl)benzene, 1,2,4-para(isopropoxymethyl)benzene, 1,4-bis(sec-butoxymethyl) Benzene, 2,6-dihydroxymethyl-p-tert-butylphenol, and the like.

More specifically, for example, the crosslinkable compound represented by the formula [6-1] to the formula [6-48] described on pages 62 to 66 of International Publication WO2011/132751 (2011.10.27 publication). .

The content of the crosslinkable compound in the liquid crystal alignment agent is preferably 0.1 to 100 parts by mass based on 100 parts by mass of the total polymer component. The viewpoint of the effect of the crosslinking reaction and exhibiting the purpose is preferably 0.1 to 50 parts by mass based on 100 parts by mass of the total polymer component. Particularly preferred is 1 to 30 parts by mass.

In addition, the crosslinkable compound may be used alone or in combination of two or more kinds in accordance with the characteristics of the vertical alignment of the liquid crystal and the optical characteristics of the liquid crystal display element.

In the present invention, as a function of promoting electric power in a vertical liquid crystal alignment film The compound [M1]~[M156] described in pages 69 to 73 of International Publication WO2011/132751 (2011.10.27 publication) may be added to the liquid crystal alignment treatment agent. The nitrogen-containing heterocyclic amine compound shown. The amine compound may be added directly to the liquid crystal alignment agent. However, it is preferred to dilute it to a solution having a concentration of 0.1 to 10% by mass, preferably 1 to 7% by mass, in an appropriate solvent. The solvent is not particularly limited as long as it is a solvent capable of dissolving the specific cellulose polymer and the specific polyimine polymer.

Moreover, liquid crystal alignment processing is performed within a range that does not impair the effects of the present invention. In the agent, a compound which improves the uniformity of the film thickness or the surface smoothness of the vertical liquid crystal alignment film when the liquid crystal alignment agent is applied can be used. Further, a compound which enhances the adhesion between the vertical liquid crystal alignment film and the substrate can also be used.

As the uniformity or table of the film thickness of the vertical liquid crystal alignment film Examples of the compound having improved surface smoothness include a fluorine-based surfactant, a polyfluorene-based surfactant, and a nonionic surfactant.

More specifically, for example, EFTOP EF301, EF303, EF352 (above, manufactured by TOHKEM PRODUCTS), MEGAFAC F171, F173, R-30 (above, manufactured by Dainippon Ink Co., Ltd.), FLUORAD FC430, FC431 (above Sumitomo 3M) Company system), ASAHI GUARD AG710, SURFLON S-382, SC101, SC102, SC103, SC104, SC105, SC106 (above is manufactured by Asahi Glass Co., Ltd.).

In addition, the content of the surfactant in the liquid crystal alignment agent is preferably 0.01 to 2 parts by mass based on 100 parts by mass of the total polymer component. It is preferably 0.01 to 1 part by mass.

As the adhesion between the vertical liquid crystal alignment film and the substrate is improved Specific examples of the compound include, for example, a functional decane-containing compound or an epoxy group-containing compound described below.

For example: 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 2-aminopropyltrimethoxydecane, 2-aminopropyltriethoxydecane, N -(2-Aminoethyl)-3-aminopropyltrimethoxydecane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxydecane, 3-ureido Propyltrimethoxydecane, 3-ureidopropyltriethoxydecane, N-ethoxylate Carbonyl-3-aminopropyltrimethoxydecane, N-ethoxycarbonyl-3-aminopropyltriethoxydecane, N-triethoxydecylpropyltriethylenetriamine, N-trimethyl Oxidylalkyl propyl triethylene triamine, 10-trimethoxydecyl-1,4,7-triazadecane, 10-triethoxydecyl-1,4,7-triazaindene Alkane, 9-trimethoxydecyl-3,6-diazaindolyl acetate, 9-triethoxydecyl-3,6-diazaindolyl acetate, N-benzyl- 3-Aminopropyltrimethoxydecane, N-benzyl-3-aminopropyltriethoxydecane, N-phenyl-3-aminopropyltrimethoxydecane, N-phenyl-3 -Aminopropyltriethoxydecane, N-bis(extended oxyethyl)-3-aminopropyltrimethoxydecane, N-bis(exooxyethyl)-3-aminopropyltriethyl Oxydecane, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5,6-tetraglycidyl Base-2,4-hexanediol, N,N,N',N',-tetraglycidyl-m-xylylenediamine, 1,3-bis(N,N-diglycidylamino) Base) cyclohexane or N, N, N', N', -tetraglycidyl-4, 4'-diaminodiphenylmethane, and the like.

Moreover, in the liquid crystal alignment treatment agent, these are dense with the substrate The content of the compound having an improved property is preferably 0.1 to 30 parts by mass based on 100 parts by mass of the total polymer component. It is preferably from 1 to 20 parts by mass. When the amount is less than 0.1 part by mass, the effect of improving the adhesion cannot be expected. If the amount is more than 30 parts by mass, the storage stability of the liquid crystal alignment agent may be deteriorated.

In the liquid crystal alignment treatment agent of the present invention, in addition to the above, The dielectric material or the conductive material may be added for the purpose of changing the electrical properties such as the dielectric constant or the conductivity of the vertical liquid crystal alignment film as long as the effect of the present invention is not impaired.

<Liquid crystal composition>

The liquid crystal composition of the present invention contains at least a liquid crystal and a polymerizable compound which is polymerized by ultraviolet rays.

As the liquid crystal, a nematic liquid crystal, a smectic liquid crystal or a cholesteric liquid crystal can be used. Among them, those with negative dielectric anisotropy are preferred. Further, from the viewpoint of low voltage driving and scattering characteristics, it is preferable that the anisotropy of the dielectric constant is large and the anisotropy of the refractive index is large. Further, in view of various physical property values of the phase transition temperature, the dielectric anisotropy, and the refractive index anisotropy, two or more kinds of liquid crystals may be used in combination.

In order to make the liquid crystal display element as a TFT (Thin Film The active element driving such as Transistor requires high liquid crystal resistance and high voltage maintenance ratio (also called VHR). Therefore, the liquid crystal is preferably a fluorine-based or chlorine-based liquid crystal having a high electric resistance and a VHR which is not lowered by an active energy ray such as ultraviolet rays.

Further, the liquid crystal display element can also dissolve a dichroic dye in the liquid crystal composition to produce a host-guest element. In this case, an element which is transparent when no voltage is applied and which absorbs (scatters) when a voltage is applied can be obtained. Further, in the liquid crystal display device, the direction of the director of the liquid crystal (the direction of alignment) is changed by 90 degrees due to the presence or absence of voltage. Therefore, the liquid crystal display element is a difference in the light absorption characteristics of the dichroic dye, and is random. High contrast is achieved when the alignment is compared to previous host-type components that switch between vertical alignment. Further, the host-guest element in which the dichroic dye is dissolved becomes opaque when the liquid crystal is aligned in the horizontal direction, and becomes opaque only in the scattering state. Therefore, it is also possible to obtain an element which is switched to a color opaque and colored transparent state by colorless transparency without an applied voltage.

As the polymerizable compound, it can be used by ultraviolet rays. The polymerization reaction is carried out to form a cured product of a liquid crystal composition (for example, a polymer network). In this case, a monomer of a polymerizable compound may be introduced into the liquid crystal composition, or a polymer obtained by previously polymerizing the monomer may be introduced into the liquid crystal composition. However, even in the case of a polymer, it is necessary to have a site where the polymerization reaction is carried out by ultraviolet rays. Further, in view of the operation of the liquid crystal composition, that is, the suppression of the high viscosity of the liquid crystal composition or the solubility to the liquid crystal, the monomer is introduced into the liquid crystal composition by liquid crystal display. A method of irradiating ultraviolet rays during the production of the element to cause polymerization and formation of a cured product is preferred.

Further, the polymerizable compound may be any compound as long as it can be dissolved in the liquid crystal. However, when the polymerizable compound is dissolved in the liquid crystal, it is necessary to have a temperature at which a part or the whole of the liquid crystal composition exhibits a liquid crystal phase. In the case where a liquid crystal phase is present in a part of the liquid crystal composition, it is sufficient that the liquid crystal display element is visually recognized to have substantially the same transparency and scattering characteristics in the entire element.

Polymeric compounds, as long as they are caused by ultraviolet rays The compound to be polymerized may be used. In this case, it is possible to carry out polymerization in any reaction form to form a cured product (hardened composite) of the liquid crystal composition. Make Specific reaction forms include, for example, radical polymerization, cationic polymerization, anionic polymerization, or polyaddition reaction.

Among them, the reaction form of the polymerizable compound is preferably a radical polymerization. In this case, as the polymerizable compound, the following radical type polymerizable compound (monomer) and an oligomer thereof can be used. Further, as described above, a polymer which has been polymerized to react with such monomers can also be used.

As a monofunctional polymerizable compound, for example, 2-ethylhexyl acrylate, butyl ethyl acrylate, butoxyethyl acrylate, 2-cyanoethyl acrylate, benzyl acrylate, cyclohexyl acrylate, hydroxyethyl acrylate, 2- Hydroxypropyl acrylate, 2-ethoxyethyl acrylate, N,N-diethylaminoethyl acrylate, N,N-dimethylaminoethyl acrylate, dicyclopentanyl acrylate Ester, dicyclopentenyl acrylate, glycidyl acrylate, tetrahydrofurfuryl acrylate, isobornyl acrylate, isodecyl acrylate, lauryl acrylate, morpholine acrylate, phenoxyethyl Acrylate, phenoxy diethylene glycol acrylate, 2,2,2-trifluoroethyl acrylate, 2,2,3,3,3-pentafluoropropyl acrylate, 2,2,3,3 -tetrafluoropropyl acrylate, 2,2,3,4,4,4-hexafluorobutyl acrylate, 2-ethylhexyl methacrylate, butyl ethyl methacrylate, butoxy B Methyl methacrylate, 2-cyanoethyl methacrylate, benzyl methacrylate, cyclohexyl methacrylate, hydroxyethyl methacrylate, 2-hydroxypropyl methyl Acrylate, 2-ethoxyethyl acrylate, N,N-diethylaminoethyl methacrylate, N,N-dimethylaminoethyl methacrylate, dicyclopentanyl Methacrylate, dicyclopentenyl methacrylate, glycidyl methacrylate Ester, tetrahydrofurfuryl methacrylate, isobornyl methacrylate, isodecyl methacrylate, lauryl methacrylate, morpholine methacrylate, phenoxyethyl methacrylate , phenoxy diethylene glycol methacrylate, 2,2,2-trifluoroethyl methacrylate, 2,2,3,3-tetrafluoropropyl methacrylate or 2,2,3 , a monomer such as 4,4,4-hexafluorobutyl methacrylate, and the like.

As the difunctional polymerizable compound, for example, 4,4'-dipropylene oxime oxime, 4,4'-dipropylene decyloxy dimethyl hydrazine, 4,4'-dipropylene decyloxydiethyl hydrazine, 4,4'-dipropylene fluorene Oxydipropyl fluorene, 4,4'-dipropylene decyloxydibutyl fluorene, 4,4'-dipropylene decyloxydipentyl fluorene, 4,4'-dipropylene decyloxydihexyl fluorene , 4,4'-dipropenyloxydifluoroantimony, 2,2,3,3,4,4-hexafluoropentanediol-1,5-diacrylate, 1,1,2,2,3 ,3-hexafluoropropyl-1,3-diacrylate, diethylene glycol dimethacrylate, 1,4-butanediol dimethacrylate, 1,3-butanediol dimethacrylate Ester, 1,6-hexanediol dimethacrylate, neopentyl glycol dimethacrylate, tetraethylene glycol dimethacrylate, 4,4'-biphenyldiacrylate, diethyl Diethylstilbestrol diacrylate, 1,4-bisacryloxybenzene, 4,4'-bispropenyloxy diphenyl ether, 4,4'-bispropenyloxy diphenylmethane, 3,9- [1,1-Dimethyl-2-propenyloxyethyl]-2,4,8,10-tetraspiro[5,5]undecane, α,α'-bis[4-propene oxime Phenyl]-1,4-diisopropylbenzene, 1,4-bisacryloxytetrafluorobenzene, 4,4'-bispropene oxime Octafluorobiphenyl, diethylene glycol acrylate, 1,4-butanediol diacrylate, 1,3-butanediol diacrylate, dicyclopentane diacrylate, glycerin diacrylate, 1 ,6-hexanediol diacrylate, neopentyl glycol diacrylate, tetraethylene glycol dipropylene Ethyl ester, 1,9-nonanediol diacrylate, polyethylene glycol diacrylate, polypropylene glycol diacrylate, 1,9-nonanediol dimethacrylate, polyethylene glycol dimethacrylate Ester or polypropylene glycol dimethacrylate, and such oligomers.

As the polyfunctional polymerizable compound, for example, Trimethylolpropane triacrylate, pentaerythritol tetraacrylate, pentaerythritol triacrylate, ditrimethylolpropane tetraacrylate, dipentaerythritol hexaacrylate, dipentaerythritol monohydroxypentaacrylate, trimethylolpropane trimethyl Acrylate, pentaerythritol tetramethacrylate, pentaerythritol trimethacrylate, ditrimethylolpropane tetramethacrylate, dipentaerythritol hexamethacrylate, dipentaerythritol monohydroxypentamethacrylate or 2, 2,3,3,4,4-hexafluoropentanediol-1,5-dimethacrylate, and such oligomers.

The above-mentioned radical type polymerizable compound may be used in combination of one or two or more kinds depending on the optical properties of the liquid crystal display element or the adhesion between the liquid crystal layer and the vertical liquid crystal alignment film.

For the purpose of promoting radical polymerization of a polymeric compound, In the liquid crystal composition, a radical initiator (polymerization initiator) which generates a radical by ultraviolet rays is preferably introduced.

Specific examples thereof include tert-butylperoxy-iso-phthalate, 2,5-dimethyl-2,5-bis(benzylidenedioxy)hexane, and 1 , 4-bis[α-(tert-butyldioxy)-iso-propoxy]benzene, di-tert-butyl peroxide, 2,5-dimethyl-2,5-double (tert -butyldioxy)hexene hydroperoxide, α-(iso-propylphenyl)-iso-propyl hydroperoxide, 2,5-di Methyl hexane, tert-butyl hydroperoxide, 1,1-bis(tert-butyldioxy)-3,3,5-trimethylcyclohexane, butyl-4,4-double (tert-butyldioxy)pentanoate, cyclohexanone peroxide, 2,2',5,5'-tetra(tert-butylperoxycarbonyl)benzophenone, 3,3' , 4,4'-tetra(tert-butylperoxycarbonyl)benzophenone, 3,3',4,4'-tetra(tert-pentylperoxycarbonyl)benzophenone, 3, 3',4,4'-tetra(tert-hexylperoxycarbonyl)benzophenone, 3,3'-bis(tert-butylperoxycarbonyl)-4,4'-dicarboxydiphenyl Organic peroxides such as ketone, tert-butylperoxybenzoate or di-tert-butyldiperoxyisophthalate; 9,10-anthracene, 1-chloropurine, Anthraquinones such as 2-chloropurine, octamethylguanidine, 1,2-benzopyrene; benzoin derivatives such as benzoin methyl, benzoin ethyl ether, α-methylbenzoin or α-phenylbenzoin Wait.

These radical initiators may be used in combination of one or two or more kinds depending on the optical properties of the liquid crystal display element or the adhesion between the liquid crystal layer and the vertical liquid crystal alignment film.

As the polymerizable compound, the following ionic type can also be used. Polymeric compound. Specifically, it is a compound having a crosslinking-forming group selected from at least one selected from the group consisting of a hydroxyl group, a hydroxyalkyl group, and a lower-order alkoxyalkyl group.

More specifically, for example, a hydrogen atom of an amine group is a melamine derivative, a benzoguanamine derivative, or an acetylene urea substituted with a methylol group, an alkoxymethyl group or both. These melamine derivatives or benzoguanamine derivatives may be oligomers. Moreover, it is preferred that these components have an average of three or more and less than one unit per triazine ring. 6 hydroxymethyl or alkoxymethyl groups.

Derived as such a melamine derivative or benzoguanamine Specific examples of the product include, for example, a commercially available triazine ring of MX-750 substituted by an average of 3.7 methoxymethyl groups per unit; an average of 5.8 methoxy groups per unit of the triazine ring a methyl group-substituted MW-30 (above, manufactured by Sanwa-Chemical Co., Ltd.), a methoxymethylated melamine of Cymel 300, 301, 303, 350, 370, 771, 325, 327, 703, 712, etc.; Cymel 235 Methoxymethylated butoxymethylated melamine of 236, 238, 212, 253, 254, etc.; butoxymethylated melamine of Cymel 506, 508, etc.; carboxylated methoxyl of Cymel 1141 Methylated isobutoxymethylated melamine; Cymel 1123-like methoxymethylated ethoxymethylated benzoguanamine; Cymel 1123-10-like methoxymethylated butoxymethylation Benzoylamine; Cymel 1128-like butoxymethylated benzoguanamine; Cymel 1125-80 carboxyl-containing methoxymethylated ethoxymethylated benzoguanamine (above, Mitsui Cyanamid) . Further, examples of the acetylene urea include a butoxymethylated acetylene urea such as Cymel 1170 and a methylolated acetylene urea such as Cymel 1172.

As a benzene or phenolic compound having a hydroxyl group or an alkoxy group, For example, 1,3,5-glycol (methoxymethoxy)benzene, 1,2,4-para(isopropoxymethoxy)benzene, 1,4-bis(sec-butoxymethyl) Oxy)benzene, 2,6-dihydroxymethyl-p-tert-butylphenol, and the like.

Further, as the ionic polymerizable compound, it may be used. A compound having an epoxy group or an isocyanate group and having a crosslink to form a group.

Specifically, for example, bisphenol acetone glycidyl ether, phenol novolac Epoxy resin, cresol novolac epoxy resin, triglycidyl isocyanurate, tetraphenyl glycosyl diphenylene, tetraglycidyl-m-xylene diamine, tetrahydration Glyceryl-1,3-bis(aminoethyl)cyclohexane, tetraphenyl glycidyl ether ethane, triphenyl glycidyl ether ethane, bisphenol hexafluoroacetamodi diglycidyl ether, 1,3 -bis(1-(2,3-epoxypropoxy)-1-trifluoromethyl-2,2,2-trifluoromethyl)benzene, 4,4-bis(2,3-epoxy) Propyloxy)octafluorobiphenyl, triglycidyl-p-aminophenol, tetraglycidyl meta-xylenediamine, 2-(4-(2,3-epoxypropoxy)phenyl )-2-(4-(1,1-bis(4-(2,3-epoxypropoxy)phenyl)ethyl)phenyl)propane, 1,3-bis(4-(1-) (4-(2,3-Epoxypropoxy)phenyl)-1-(4-(1-(4-(2,3-epoxypropoxyphenyl)-1-methyl) Phenyl)ethyl)phenoxy)-2-propanol and the like.

When an ionic polymerizable compound is used, the polymerization is promoted For the purpose of the reaction, an ion initiator which generates an acid or a base by ultraviolet rays can also be introduced. Specifically, a triazine compound, an acetophenone derivative compound, a dioxon compound, a diazomethane compound, a sulfonic acid derivative compound, a diarylsulfonium salt, a triarylsulfonium salt, a triarylsulfonium salt or Iron aromatic hydrocarbon complexes and the like.

More specifically, for example, diphenylphosphonium chloride, diphenylsulfonium trifluoromethanesulfonate, diphenylsulfonium methanesulfonate, diphenylsulfonium p-toluenesulfonate, diphenylphosphonium bromide , diphenylphosphonium tetrafluoroborate, diphenylphosphonium hexafluoroantimonate, diphenylphosphonium hexafluoroarsenate, bis(p-tert-butylphenyl)phosphonium hexafluorophosphate, double (p-tert-butylphenyl) indolyl sulfonate, bis(p-tert-butylphenyl)fluorene p-toluenesulfonate, bis(p-tert-butyl Phenyl)indole trifluoromethanesulfonate, bis(p-tert-butylphenyl)phosphonium tetrafluoroborate, bis(p-tert-butylphenyl)phosphonium chloride, bis(p-chlorobenzene) Base) bismuth chloride, bis(p-chlorophenyl)phosphonium tetrafluoroborate, triphenylphosphonium chloride, triphenylphosphonium bromide, tris(p-methoxyphenyl)phosphonium tetrafluoroborate Ester, tris(p-methoxyphenyl)phosphonium hexafluorophosphate, tris(p-ethoxyphenyl)phosphonium tetrafluoroborate, triphenylphosphonium chloride, triphenylphosphonium bromide, three (p-methoxyphenyl)phosphonium tetrafluoroborate, tris(p-methoxyphenyl)phosphonium hexafluorophosphate, tris(p-ethoxyphenyl)phosphonium tetrafluoroborate, double [[(2-Nitrobenzyl)oxy]carbonylhexane-1,6-diamine], nitrobenzylcyclohexylamine formate, bis(methoxybenzyl)hexamethylenediamine Formate, bis[[(2-nitrobenzyl)oxy]carbonylhexane-1,6-diamine], nitrobenzylcyclohexylamine formate or bis(methoxybenzyl)hexa Methylene diamine formate and the like.

In the present invention, as the polymerizable compound, a radical type polymerizable compound is preferably used from the viewpoint of optical characteristics of the liquid crystal display device.

The amount of the polymerizable compound introduced into the liquid crystal composition is not When the amount of the polymerizable compound introduced is large, the polymerizable compound is not dissolved in the liquid crystal, or the temperature at which the liquid crystal composition does not exhibit the liquid crystal phase, and the change in the transparent state and the scattering state of the device is small, and optical characteristics are obtained. Getting worse. In addition, when the amount of introduction of the polymerizable compound is small, the hardenability of the liquid crystal layer is lowered, and the adhesion between the liquid crystal layer and the liquid crystal alignment film is lowered, and the alignment of the liquid crystal is liable to be disordered with respect to the mechanical external pressure. Therefore, the amount of the polymerizable compound to be introduced is preferably 100 parts by mass based on the liquid crystal. 1 to 50 parts by mass. It is preferably 5 to 40 parts by mass. Particularly good is 11 to 30 parts by mass.

In addition, the amount of introduction of the radical initiator or the ion initiator to promote the reaction of the polymerizable compound is not particularly limited, and is preferably 0.01 to 10 parts by mass based on 100 parts by mass of the liquid crystal. It is preferably 0.05 to 5 parts by mass. Particularly preferred is 0.05 to 3 parts by mass.

<Vertical liquid crystal alignment film and method for producing liquid crystal display element>

The substrate to be used for the liquid crystal display element is not particularly limited as long as it is a substrate having high transparency, and a plastic substrate such as an acrylic substrate, a polycarbonate substrate or a PET (polyethylene terephthalate) substrate can be used as the glass substrate. Such a film can be used as a substrate or the like. When a liquid crystal display element is used as a reverse type element for a dimming window or the like, a plastic substrate or a film is preferred. Further, from the viewpoint of simplification of the process, it is preferable to use 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, or the like is formed. . Further, in the case of a reflective reverse type element, a single-sided substrate or a substrate on which a metal such as aluminum or a dielectric multilayer film is formed may be used.

The liquid crystal display element of the present invention, at least one of the substrates It is a vertical liquid crystal alignment film having vertical alignment of liquid crystal molecules. This vertical liquid crystal alignment film is obtained by applying a liquid crystal alignment treatment agent onto a substrate, baking it, and performing an alignment treatment by rubbing treatment or light irradiation. However, in the present invention, even if there is no such alignment treatment, it can be used as a vertical liquid crystal alignment film. use.

The coating method of the liquid crystal alignment treatment agent is not particularly limited, and industrially, there are screen printing, offset printing, letterpress printing, ink jet method, dipping method, roll coating method, slit coating method, and spinner method. Or a spray method or the like, which is suitable for the film thickness of the vertical liquid crystal alignment film depending on the type or purpose of the substrate.

After the liquid crystal alignment treatment agent is applied onto the substrate, The heating means such as a heating plate, a heat cycle type oven, or an IR (infrared) type oven is used at a temperature of 30 to 300 ° C, preferably 30 to 250 ° C depending on the type of the substrate or the solvent used in the liquid crystal alignment treatment agent. The solvent was evaporated to form a vertical liquid crystal alignment film. In particular, when a plastic substrate is used as the substrate, it is preferably treated at a temperature of 30 to 150 °C.

When the thickness of the vertical liquid crystal alignment film after firing is too thick, it is disadvantageous in terms of power consumption of the liquid crystal display element. If the thickness is too thin, the reliability of the element is lowered. Therefore, it is preferably 5 to 500 nm. It is preferably 10 to 300 nm, and particularly preferably 10 to 250 nm.

The liquid crystal composition used for the liquid crystal display element is like the liquid crystal composition described above, and a spacer for controlling an electrode gap (also referred to as a gap) of the liquid crystal display element may be introduced.

The method of injecting the liquid crystal composition is not particularly limited, and For example, the following method. In other words, when a glass substrate is used as the substrate, one of the vertical liquid crystal alignment films is prepared, and the sealing agent is applied to the four sheets of the single-sided substrate, and then the surface of the vertical liquid crystal alignment film is made inside. In a manner, an empty cell is fabricated by bonding the substrate on the other side. then, For example, a method in which a liquid crystal composition is injected into a unit cell is obtained by injecting a liquid crystal composition under reduced pressure from a portion where the sealant is not applied. When a plastic substrate or a film is used as the substrate, for example, one of the vertical liquid crystal alignment films is prepared, and the liquid crystal composition is dropped by an ODF (One Drop Filling) method or an inkjet method on the single-sided substrate. Then, the substrate on the other side is bonded to obtain a method in which the liquid crystal composition is injected into the unit cell.

In the liquid crystal display device of the present invention, since the adhesion between the liquid crystal layer and the vertical liquid crystal alignment film is high, it is not necessary to apply a sealant to the four sheets of the substrate.

The gap of the liquid crystal display element can be controlled by a spacer or the like. This method can be exemplified by a method of introducing a spacer having a desired size into the liquid crystal composition, a method of using a substrate having a columnar spacer of a desired size, and the like. Further, when a plastic or a film substrate is used as the substrate and the substrate is bonded by a laminator, the gap can be controlled without introducing a spacer.

The size of the gap of the liquid crystal display element is preferably 1 to 100 μm. It is preferably 2 to 50 μm. Very good is 5~20μm. When the gap is too small, the contrast of the liquid crystal display element is lowered. When the gap is too large, the driving voltage of the liquid crystal display element becomes high.

The liquid crystal display device of the present invention is obtained by curing a liquid crystal composition in a state in which liquid crystallinity is present in a part or all of the liquid crystal composition, and forming a cured product of a liquid crystal and a polymerizable compound. The curing of the liquid crystal composition is carried out by injecting the liquid crystal composition into at least one of ultraviolet light irradiation and heating.

As a light source of the ultraviolet irradiation device used at this time, for example, for example, Metal halide lamp or high pressure mercury lamp. Further, the wavelength of the ultraviolet light is preferably from 250 to 400 nm. It is preferably 310 to 370 nm. Further, at the time of heat treatment, the temperature is preferably from 40 to 120 °C. It is preferably 60 to 80 ° C. Further, both the ultraviolet treatment and the heat treatment can be performed simultaneously, and the heat treatment can be performed after the ultraviolet treatment. In the present invention, the hardening of the liquid crystal composition is preferably carried out only by ultraviolet treatment.

As described above, comprising a specific cellulose-based polymer and A liquid crystal alignment treatment agent for a specific polyimine-based polymer to obtain a vertical liquid crystal alignment film, and a liquid crystal layer using the vertical liquid crystal alignment film has high adhesion between the liquid crystal layer and the liquid crystal alignment film, and further, vertical alignment of the liquid crystal The film has a high optical property and is excellent in optical characteristics, that is, a liquid crystal display element which is excellent in transparency when no voltage is applied and scattering characteristics when a voltage is applied. In particular, the device can be suitably used in a reverse type element which is in a penetrating state when no voltage is applied and a scattering state when a voltage is applied, and is suitable as a liquid crystal display for display purposes or to control light penetration. And the dimming window or shutter element of the occlusion. As the substrate at this time, a plastic substrate or a film is preferably used.

Moreover, the liquid crystal display element of the present invention is used for a liquid crystal display element of a transportation machine and a transportation machine for automobiles, railways, airplanes, etc., and specifically, can be suitably used for a dimming window or indoor that controls penetration and interruption of light. Mirror light gate components, etc. In particular, since the transparency at the time of no applied voltage and the scattering characteristics at the time of applying a voltage are good, when the element is used for a glass window of a vehicle, the light at night is compared with the case of using a conventional reverse type element. The efficiency of taking in is high, and the glare effect from external light is also prevented from becoming high. Therefore, you can enter Improve the safety of driving a vehicle or the comfort of riding in one step. Moreover, when the element is produced by a film and is adhered to a glass window of a vehicle, it is less likely to cause poor adhesion or deterioration due to low adhesion between the liquid crystal layer and the vertical liquid crystal alignment film, and the conventional reverse type element In comparison, the reliability of this component becomes higher.

Furthermore, the liquid crystal display device of the present invention can also be used for a light guide plate of a display device such as an LCD (Liquid Crystal Display) or an OLED (Organic Light-emitting Diode) display, or a back plate of a transparent display using the display. Specifically, when the screen is displayed on the transparent display in which the transparent display and the element are combined, the entry of light from the back surface can be suppressed by the element. At this time, when the component is displayed on the screen on the transparent display, the applied voltage becomes a scattering state, and the screen can be displayed clearly, and after the screen is displayed, it becomes a transparent state without an applied voltage.

[Examples]

The invention is illustrated in more detail in the following examples, but is not limited thereto. Further, the abbreviations of the compounds used in the synthesis examples, examples, and comparative examples are as follows.

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

(Polymerizable compound) R1: a compound represented by the following formula [R1]

(Photoinitiator) P1: a compound represented by the following formula [P1]

(specific cellulose polymer)

CE-1: hydroxyethyl cellulose (manufactured by WAKO)

CE-2: hydroxypropylmethylcellulose phthalate (ACROS)

(specific side chain type diamine compound)

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

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

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

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

A5: 1,3-diamino-4-octadecyloxybenzene (the following formula [A5])

(2nd diamine compound)

B1: 3,5-diaminobenzoic acid (the following formula [B1])

B2: a compound represented by the following formula [B2]

(other diamine compounds)

C1: p-phenylenediamine (the following formula [C1])

C2: m-phenylenediamine (the following formula [C2])

(tetracarboxylic acid component)

D1:1, 2,3,4-cyclobutane tetracarboxylic dianhydride (Formula [D1] below)

D2: Bicyclo[3,3,0]octane-2,4,6,8-tetracarboxylic dianhydride (Formula [D2] below)

D3: tetracarboxylic dianhydride represented by the following formula [D3]

D4: tetracarboxylic dianhydride represented by the following formula [D4]

(generating agent)

S1: a compound represented by the following formula [S1]

S2: a compound represented by the following formula [S2]

(adhesive compound)

M1: a compound represented by the following formula [M1]

M2: a compound represented by the following formula [M2]

M3: a compound represented by the following formula [M3]

(crosslinkable compound)

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

(solvent)

NMP: N-methyl-2-pyrrolidone

NEP: N-ethyl-2-pyrrolidone

γ-BL: γ-butyrolactone

PGME: propylene glycol monomethyl ether

ECS: ethylene glycol monoethyl ether

BCS: ethylene glycol monobutyl ether

PB: propylene glycol monobutyl ether

EC: diethylene glycol monoethyl ether

"Measurement of molecular weight of polyamidene-based polymers"

The molecular weight of the polyimine precursor and the polyimine is a normal temperature gel permeation chromatography (GPC) device (GPC-101) (manufactured by Showa Denko Co., Ltd.) and a column (KD-803, KD-805, Shodex). Company system), as measured below.

Column temperature: 50 ° C

Dissolution: N,N'-dimethylformamide (additive is lithium bromide-hydrate (LiBr.H ₂ O) is 30 mmol / L (liter), phosphoric acid. Anhydrous crystal (o-phosphoric acid) is 30 mmol / L, Tetrahydrofuran (THF) is 10ml/L)

Flow rate: 1.0ml/min

Standard sample for the production of calibration lines: 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) (Polymer) Laboratories company).

"Determination of the imidization rate of polyamidiamine"

5(草野科學公司製))，添加重氫化二甲基亞碸(DMSO-d6，0.05質量%TMS(四甲基矽烷)混合品)(0.53ml)，施加超音波使完全溶解。將此溶液使用NMR測定機(JNW-ECA500)(JEOL公司製)測定500MHz的質子NMR。醯亞胺化率係以來 自醯亞胺化前後結構未變化的質子作為基準質子而決定，使用此質子之波峰累積值與來自於9.5~10.0ppm附近所出現的醯胺酸的NH基之質子波峰累積值，使用下述式求出。 20 mg of polyimine powder was placed in an NMR sampling tube stand (NMR sampling tube stand,

5 (manufactured by Kusano Scientific Co., Ltd.), a solution of dimethyl hydrazine (DMSO-d6, 0.05% by mass of TMS (tetramethyl decane)) (0.53 ml) was added thereto, and ultrasonic waves were applied to completely dissolve. This solution was measured for proton NMR at 500 MHz using an NMR measuring machine (JNW-ECA500) (manufactured by JEOL Co., Ltd.). The ruthenium imidization rate is determined by using protons whose structure has not changed before and after imidization as a reference proton, and the peak value of the proton is used and the proton of the NH group derived from valeric acid which is present near 9.5 to 10.0 ppm. The peak cumulative value was obtained by the following formula.

醯 imidization rate (%) = (1-α.x/y) × 100

In the above formula, x is the proton peak cumulative value of the NH group derived from proline, y is the peak cumulative value of the reference proton; α is the relative proline acid when the polyproline (0%) The ratio of the number of reference protons of one NH matrix.

"Synthesis of Polyimine Polymers" <Synthesis Example 1>

D1 (3.32 g, 16.9 mmol), A1 (3.26 g, 8.57 mmol), B1 (1.04 g, 6.84 mmol) and C2 (0.19 g, 1.76 mmol) were mixed in NEP (23.4 g) to make at 40 ° C After reacting for 8 hours, a polyamic acid solution (1) having a resin solid content concentration of 25% by mass was obtained. The polyamine has a number average molecular weight of 23,200 and a weight average molecular weight of 70,100.

<Synthesis Example 2>

D2 (4.29 g, 17.1 mmol), A2 (6.76 g, 17.1 mmol) and B1 (2.61 g, 17.1 mmol) were mixed in NMP (33.9 g), and the reaction was carried out at 50 ° C for 2 hours, then D1 (3.29) was added. g, 16.8 mmol) and NMP (17.0 g) were reacted at 40 ° C for 6 hours. A polyamic acid solution (2) having a resin solid content concentration of 25% by mass was obtained. The polyamine had a number average molecular weight of 23,800 and a weight average molecular weight of 69,500.

<Synthesis Example 3>

In the polyamic acid solution (2) (30.5 g) obtained in Synthesis Example 2, NMP was added and diluted to 6 mass%, and then acetic anhydride (3.90 g) and pyridine (2.41 g) as a ruthenium catalyst were added. The reaction was allowed to proceed at 70 ° C for 2 hours. This reaction solution was poured into methanol (460 ml), and the obtained precipitate was obtained by filtration. This precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (3). The polyimine had a hydrazine imidation ratio of 61%, a number average molecular weight of 21,900, and a weight average molecular weight of 59,900.

<Synthesis Example 4>

D2 (2.96 g, 11.9 mmol), A3 (5.11 g, 11.8 mmol), B1 (1.79 g, 11.8 mmol) and B2 (1.20 g, 5.89 mmol) were mixed in NMP (28.9 g) to make at 80 ° C After reacting for 5 hours, D1 (3.38 g, 17.7 mmol) and NMP (14.4 g) were added, and the reaction was allowed to proceed at 40 ° C for 8 hours to obtain a polyamic acid solution having a resin solid concentration of 25% by mass.

After the NMP was added to the obtained polyamic acid solution (30.0 g) to be diluted to 6 mass%, acetic anhydride (3.85 g) and pyridine (2.40 g) as a ruthenium amide catalyst were added thereto, and the mixture was added at 50 ° C. Reaction for 2 hours. Dissolve this reaction The liquid was poured into methanol (460 ml), and the obtained precipitate was obtained by filtration. This precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (4). The polyimine had a hydrazine imidation ratio of 57%, a number average molecular weight of 19,100, and a weight average molecular weight of 55,800.

<Synthesis Example 5>

D2 (2.80 g, 11.2 mmol), A4 (3.32 g, 6.72 mmol), B1 (1.70 g, 11.2 mmol), B2 (0.46 g, 2.24 mmol) and C1 (0.25 g, 2.24 mmol) in NMP (21.4 g) After mixing and reacting at 80 ° C for 5 hours, D1 (2.15 g, 11.0 mmol) and NMP (10.7 g) were added, and the reaction was carried out at 40 ° C for 6 hours to obtain a polymer having a resin solid concentration of 25% by mass. Proline solution.

After the NMP was added and diluted to 6 mass%, the obtained poly-proline acid solution (30.5 g) was added, and acetic anhydride (4.05 g) and pyridine (2.50 g) as a ruthenium-imidation catalyst were added, and the mixture was made at 50 °C. Reaction for 2 hours. This reaction solution was poured into methanol (460 ml), and the obtained precipitate was obtained by filtration. This precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (5). The polyimine had a hydrazine imidation ratio of 51%, a number average molecular weight of 17,800, and a weight average molecular weight of 50,200.

<Synthesis Example 6>

D3 (6.10 g, 27.2 mmol), A2 (6.51 g, 16.5 mmol), B1 (1.25 g, 8.24 mmol) and B2 (0.56 g, 2.76 mmol) were mixed in NMP (43.3 g) to make at 40 ° C Reaction for 10 hours, To a polyamic acid solution having a resin solid concentration of 25% by mass.

After adding NMP to 6% by mass of the obtained polyamidic acid solution (30.0 g), acetic anhydride (4.00 g) and pyridine (2.50 g) as a ruthenium amide catalyst were added at 70 ° C. The reaction was allowed to proceed for 2 hours. This reaction solution was poured into methanol (460 ml), and the obtained precipitate was obtained by filtration. This precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (6). The polyimine had a hydrazine imidation ratio of 61%, a number average molecular weight of 17,500, and a weight average molecular weight of 49,900.

<Synthesis Example 7>

D3 (6.10 g, 27.2 mmol), A4 (4.07 g, 8.25 mmol) and B1 (2.92 g, 19.3 mmol) were mixed in NMP (39.3 g), and the reaction was carried out at 40 ° C for 5 hours to obtain a resin solid concentration. It is a 25% by mass polylysine solution.

After the NMP was added to the obtained polyamic acid solution (30.0 g) to be diluted to 6 mass%, acetic anhydride (4.55 g) and pyridine (2.50 g) as a ruthenium amide catalyst were added thereto, and the mixture was added at 50 ° C. Reaction for 3 hours. This reaction solution was poured into methanol (460 ml), and the obtained precipitate was obtained by filtration. This precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (7). The polyimine had a hydrazine imidation ratio of 55%, a number average molecular weight of 18,100, and a weight average molecular weight of 49,400.

<Synthesis Example 8>

D4 (5.14 g, 17.1 mmol), A3 (7.41 g, 17.1 mmol), B1 (2.08 g, 13.7 mmol) and B2 (0.69 g, 3.42 mmol) were mixed in NMP (37.3 g) to make 40 ° C After reacting for 8 hours, D1 (3.29 g, 16.8 mmol) and NMP (18.6 g) were added, and the reaction was allowed to proceed at 25 ° C for 10 hours to obtain a polyamic acid solution having a resin solid concentration of 25% by mass.

After adding NMP to 6% by mass of the obtained polyamidic acid solution (30.0 g), acetic anhydride (7.20 g) and pyridine (2.25 g) as a ruthenium catalyst were added at 40 ° C. The reaction was allowed to proceed for 1.5 hours. This reaction solution was poured into methanol (460 ml), and the obtained precipitate was obtained by filtration. This precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (8). The polyimine had a hydrazine imidation ratio of 71%, a number average molecular weight of 17,600, and a weight average molecular weight of 39,900.

<Synthesis Example 9>

D2 (4.29 g, 17.1 mmol), A5 (6.45 g, 17.1 mmol) and B1 (2.61 g, 17.1 mmol) were mixed in NMP (33.3 g), and the reaction was carried out at 50 ° C for 2 hours, then D1 (3.29) was added. g, 16.8 mmol) and NMP (16.6 g) were reacted at 40 ° C for 6 hours to obtain a polyamic acid solution having a resin solid concentration of 25% by mass.

In the obtained polyaminic acid solution (30.0 g), NMP was added and diluted to 6 mass%, and then acetic anhydride was added as a ruthenium catalyst. (3.90 g) and pyridine (2.45 g) were reacted at 70 ° C for 2 hours. This reaction solution was poured into methanol (460 ml), and the obtained precipitate was obtained by filtration. This precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (9). The polyimine had a hydrazine imidation ratio of 60%, a number average molecular weight of 18,500, and a weight average molecular weight of 56,900.

<Synthesis Example 10>

D2 (4.29 g, 17.1 mmol) and B1 (5.22 g, 34.3 mmol) were mixed in NMP (25.6 g), and the reaction was carried out at 50 ° C for 2 hours, then D1 (3.29 g, 16.8 mmol) and NMP (12.8) were added. g), the reaction was allowed to proceed at 40 ° C for 6 hours to obtain a polyamic acid solution (10) having a resin solid concentration of 25% by mass. The polyamine has a number average molecular weight of 26,400 and a weight average molecular weight of 80,900.

<Synthesis Example 11>

In the polyamic acid solution (10) (30.0 g) obtained in Synthesis Example 10, NMP was added and diluted to 6 mass%, and acetic anhydride (3.85 g) and pyridine (2.45 g) as a ruthenium catalyst were added. The reaction was allowed to proceed at 70 ° C for 2 hours. This reaction solution was poured into methanol (460 ml), and the obtained precipitate was obtained by filtration. This precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (11). The polyimine had a hydrazine imidation ratio of 60%, a number average molecular weight of 22,100, and a weight average molecular weight of 62,900.

The polyimine-based polymers obtained in Synthesis Examples 1 to 11 were prepared and shown in Table 1.

"Modulation of liquid crystal composition" (Liquid crystal composition (1))

L1 (11.5 g), R1 (1.73 g), and P1 (0.12 g) were mixed, and after heating (110 ° C), it was cooled to 25 ° C to obtain a liquid crystal composition (1).

(Liquid crystal composition (2))

L1 (12.0 g), R1 (2.40 g), and P1 (0.12 g) were mixed, and after heating (110 ° C), the mixture was cooled to 25 ° C to obtain a liquid crystal composition (2).

"Production of Liquid Crystal Display Element (Glass Substrate)"

The liquid crystal alignment treatment agent of the examples or the comparative examples described later was pressure-filtered through a membrane filter having a pore diameter of 1 μm. The obtained solution was spin-coated on an ITO surface of an ITO electrode glass substrate (length: 100 mm, width: 100 mm, thickness: 0.7 mm) of 100 × 100 mm washed with pure water and IPA (isopropyl alcohol). The film was heat-treated at 100 ° C for 2 minutes on a hot plate, and further heat-treated at 210 ° C for 10 minutes using a heat cycle type clean oven to obtain an ITO substrate with a liquid crystal alignment film having a film thickness of 100 nm. Two pieces of the obtained ITO substrate with the liquid crystal alignment film were prepared, and a spacer of 6 μm was applied to the liquid crystal alignment film surface of one of the substrates. Then, the liquid crystal composition is dropped on the liquid crystal alignment film surface of the substrate by the ODF (One Drop Filling) method, and then bonded to the liquid crystal alignment film interface of the other substrate. Liquid crystal display element before processing.

In the liquid crystal display device before the treatment, a metal halide lamp having an illuminance of 60 mW was used, and a wavelength of 350 nm or less was removed, and irradiation with ultraviolet rays of 7 J/cm ² in terms of 365 nm was performed. At this time, the temperature in the irradiation apparatus when irradiating ultraviolet rays on the element was controlled to 25 °C. Thereby, a liquid crystal display element (reverse type element) can be obtained.

"Production of Liquid Crystal Display Devices (Plastic Substrate)"

The liquid crystal alignment treatment agent of the example described later was pressure-filtered through a membrane filter having a pore diameter of 1 μm. The obtained solution was applied to a PET (polyethylene terephthalate) substrate with an ITO electrode of 150 × 150 mm washed with pure water using a bar coater (length: 150 mm, width: 150 mm, thickness). The ITO surface of 0.2 mm) was heat-treated at 100 ° C for 2 minutes on a hot plate, and further heat-treated at 150 ° C for 1 minute using a heat cycle type clean oven to obtain an ITO substrate with a liquid crystal alignment film having a film thickness of 100 nm. Two pieces of the obtained ITO substrate with the liquid crystal alignment film were prepared, and a spacer of 6 μm was applied to the liquid crystal alignment film surface of one of the substrates. Then, the liquid crystal composition is dropped on the liquid crystal alignment film surface of the substrate by the ODF method, and then bonded to the liquid crystal alignment film interface of the other substrate to obtain a liquid crystal display before the treatment. element.

In the liquid crystal display device before the treatment, a metal halide lamp having an illuminance of 60 mW was used, and a wavelength of 350 nm or less was removed, and irradiation with ultraviolet rays of 7 J/cm ² in terms of 365 nm was performed. At this time, the temperature in the irradiation apparatus when irradiating ultraviolet rays on the element was controlled to 25 °C. Thereby, a liquid crystal display element (reverse type element) can be obtained.

"Evaluation of Liquid Crystal Display Components" (liquid crystal alignment)

Liquid crystal alignment of liquid crystal display elements (reverse type elements) of glass substrates and plastic substrates, using a polarizing microscope (ECLIPSE E600WPOL) (manufactured by Nikon Co., Ltd.) observed and confirmed whether or not the liquid crystal was vertically aligned. Specifically, the liquid crystal was a vertical alignment, and it was evaluated as excellent in this evaluation.

Then, the element whose evaluation of the liquid crystal alignment property was completed was stored in a high temperature bath at a temperature of 100 ° C for 336 hours. After storage, the liquid crystal alignment property was evaluated under the same conditions as described above. Specifically, the liquid crystal alignment property was not observed to be scattered, and the liquid crystal uniform alignment was excellent in the evaluation.

The evaluation results of the liquid crystal alignment of the liquid crystal display element (reverse type element) of the glass substrate and the plastic substrate were collectively shown in Tables 5 to 7.

(Optical characteristics (transparency and scattering characteristics))

The evaluation of the optical characteristics (transparency and scattering characteristics) of the liquid crystal display element (reverse type element) of the glass substrate and the plastic substrate was carried out as follows.

The transparency at the time of no applied voltage is measured by measuring the transmittance of an element having no applied voltage state. Specifically, the measurement apparatus used UV-3600 (manufactured by Shimadzu Corporation) at a temperature of 25 ° C, and the control group used the above-mentioned ITO electrode glass substrate (PET substrate for evaluation of a plastic substrate) and a scanning wavelength of 300 to 800 nm. Transmittance. The transmittance was evaluated at a wavelength of 450 nm, and the higher the transmittance, the better in this evaluation.

The scattering characteristics at the time of applying a voltage were carried out by visually observing the alignment state of the liquid crystal by applying 40 V to the element by AC driving. Specifically, the component is white turbid, that is, the scatter characteristic is available, which is evaluated in this evaluation. Excellent price.

The results of the optical characteristics (transparency and scattering characteristics) of the liquid crystal display element (reverse type element) of the glass substrate and the plastic substrate were summarized and shown in Tables 8 to 10.

(Adhesion between liquid crystal layer and liquid crystal alignment film)

The evaluation of the adhesion between the liquid crystal layer of the liquid crystal display element (reverse type element) of the glass substrate and the plastic substrate and the liquid crystal alignment film was carried out as follows.

Specifically, the device was stored in a high-temperature, high-humidity bath at a temperature of 80 ° C and a humidity of 90 RH for 96 hours, and the presence or absence of bubbles in the device and the peeling of the device were confirmed. At this time, in the case where no bubbles were observed in the element and peeling of the element was not caused (the state in which the liquid crystal layer and the liquid crystal alignment film were peeled off), it was excellent in the evaluation.

The results of the adhesion between the liquid crystal layer of the liquid crystal display element (reverse type element) of the glass substrate and the plastic substrate and the liquid crystal alignment film are shown in Tables 8 to 10.

<Example 1>

NEP (22.7 g), BCS (20.8 g), and CE-2 (1.00 g) were added to the polyamic acid solution (1) (7.43 g) having a solid content concentration of 25% by mass of the resin obtained in Synthesis Example 1. Stir at 50 ° C for 5 hours. Then, M2 (0.286 g) and K1 (0.286 g) were added to the solution, and the mixture was stirred at 25 ° C for 2 hours to obtain a liquid crystal alignment treatment agent (1). It was confirmed that the liquid crystal alignment agent did not detect abnormalities such as turbidity or precipitation, and was uniformly dissolved. liquid.

A liquid crystal display device (glass substrate) was produced using the obtained liquid crystal alignment treatment agent (1) and liquid crystal composition (1), and various evaluations were performed.

<Example 2>

NMP (27.3 g), BCS (25.5 g), and CE-2 (1.05 g) were added to the polyamic acid solution (2) (9.80 g) having a solid content concentration of 25% by mass of the resin obtained in Synthesis Example 2. The mixture was stirred at 50 ° C for 5 hours to obtain a liquid crystal alignment treatment agent (2). It was confirmed that this liquid crystal alignment treatment agent was not found to have an abnormality such as turbidity or precipitation, and was a uniform solution.

A liquid crystal display element (glass substrate) was produced using the obtained liquid crystal alignment treatment agent (2) and liquid crystal composition (1), and various evaluations were performed.

<Example 3>

A liquid crystal display element (glass substrate) was produced using the liquid crystal alignment treatment agent (2) and the liquid crystal composition (2) obtained in Example 2, and various evaluations were performed.

<Example 4>

NMP (35.4 g) and BCS (24.2 g) were added to the polyimine powder (3) (2.33 g) obtained in Synthesis Example 3, and the mixture was stirred at 70 ° C for 24 hours to be dissolved. Then, CE-2 (1.00 g) was added to the solution, and the mixture was stirred at 50 ° C for 5 hours to obtain a liquid crystal alignment treatment agent (3). It was confirmed that the liquid crystal alignment agent did not detect abnormalities such as turbidity or precipitation, and was uniformly dissolved. liquid.

A liquid crystal display element (glass substrate) was produced using the obtained liquid crystal alignment treatment agent (3) and liquid crystal composition (1), and various evaluations were performed.

<Example 5>

A liquid crystal display element (glass substrate) was produced using the liquid crystal alignment treatment agent (3) and the liquid crystal composition (2) obtained in Example 4, and various evaluations were performed.

<Example 6>

NEP (32.8 g) and PB (18.2 g) were added to the polyimine powder (3) (1.86 g) obtained in Synthesis Example 3, and the mixture was stirred at 70 ° C for 24 hours to be dissolved. Then, CE-2 (1.10 g) was added to the solution, and the mixture was stirred at 50 ° C for 5 hours. Further, S2 (0.143 g), M2 (0.429 g) and K1 (0.286 g) were added to the solution, and the mixture was stirred at 25 ° C for 2 hours to obtain a liquid crystal alignment treatment agent (4). It was confirmed that this liquid crystal alignment treatment agent was not found to have an abnormality such as turbidity or precipitation, and was a uniform solution.

A liquid crystal display element (glass substrate) was produced using the obtained liquid crystal alignment treatment agent (4) and liquid crystal composition (1), and various evaluations were performed.

<Example 7>

γ-BL (6.40 g) and PGME (42.5 g) were added to the polyimine powder (3) (1.65 g) obtained in Synthesis Example 3, and the mixture was stirred at 70 ° C for 24 hours to be dissolved. Then, CE-2 (1.10g) was added to the solution. Stir at 50 ° C for 5 hours. Further, S2 (0.138 g) and M1 (0.550 g) were added to the solution, and the mixture was stirred at 25 ° C for 2 hours to obtain a liquid crystal alignment treatment agent (5). It was confirmed that this liquid crystal alignment treatment agent was not found to have an abnormality such as turbidity or precipitation, and was a uniform solution.

A liquid crystal display device (glass substrate, plastic substrate) was produced using the obtained liquid crystal alignment treatment agent (5) and liquid crystal composition (1), and various evaluations were performed.

<Example 8>

NEP (34.0 g), BCS (12.4 g) and PB (14.6 g) were added to the polyimine powder (4) (2.55 g) obtained in Synthesis Example 4, and the mixture was stirred at 70 ° C for 24 hours to be dissolved. Then, CE-1 (0.85 g) was added to the solution, and the mixture was stirred at 50 ° C for 5 hours. Further, S1 (0.170 g) and M2 (0.170 g) were added to the solution, and the mixture was stirred at 25 ° C for 2 hours to obtain a liquid crystal alignment treatment agent (6). It was confirmed that this liquid crystal alignment treatment agent was not found to have an abnormality such as turbidity or precipitation, and was a uniform solution.

A liquid crystal display element (glass substrate) was produced using the obtained liquid crystal alignment treatment agent (6) and liquid crystal composition (1), and various evaluations were performed.

<Example 9>

γ-BL (12.8 g) and PGME (43.2 g) were added to the polyimine powder (4) (2.04 g) obtained in Synthesis Example 4, and the mixture was stirred at 70 ° C for 24 hours to be dissolved. Then, CE-2 (1.10 g) was added to the solution, and the mixture was stirred at 50 ° C for 5 hours. Add S1 (0.314g) to this solution. Further, M2 (0.314 g) was stirred at 25 ° C for 2 hours to obtain a liquid crystal alignment treatment agent (7). It was confirmed that this liquid crystal alignment treatment agent was not found to have an abnormality such as turbidity or precipitation, and was a uniform solution.

A liquid crystal display device (glass substrate, plastic substrate) was produced using the obtained liquid crystal alignment treatment agent (7) and liquid crystal composition (2), and various evaluations were performed.

<Example 10>

γ-BL (12.7 g), PGME (36.1 g), and ECS (5.50 g) were added to the polyimine powder (4) (2.70 g) obtained in Synthesis Example 4, and the mixture was stirred at 70 ° C for 24 hours to dissolve. . Then, CE-1 (0.30 g) was added to the solution, and the mixture was stirred at 50 ° C for 5 hours. Further, S2 (0.210 g), M3 (0.450 g) and K1 (0.450 g) were added to the solution, and the mixture was stirred at 25 ° C for 2 hours to obtain a liquid crystal alignment treatment agent (8). It was confirmed that this liquid crystal alignment treatment agent was not found to have an abnormality such as turbidity or precipitation, and was a uniform solution.

A liquid crystal display device (glass substrate, plastic substrate) was produced using the obtained liquid crystal alignment treatment agent (8) and liquid crystal composition (1), and various evaluations were performed.

<Example 11>

γ-BL (7.20 g), PGME (44.7 g) and EC (5.90 g) were added to the polyimine powder (5) (1.95 g) obtained in Synthesis Example 5, and the mixture was stirred at 70 ° C for 24 hours to dissolve. . Then add this solution CE-2 (1.30 g) was stirred at 50 ° C for 5 hours. Further, M2 (0.325 g) and K1 (0.488 g) were added to the solution, and the mixture was stirred at 25 ° C for 2 hours to obtain a liquid crystal alignment treatment agent (9). It was confirmed that this liquid crystal alignment treatment agent was not found to have an abnormality such as turbidity or precipitation, and was a uniform solution.

A liquid crystal display element (glass substrate, plastic substrate) was produced using the obtained liquid crystal alignment treatment agent (9) and liquid crystal composition (1), and various evaluations were performed.

<Example 12>

γ-BL (16.2 g) and PGME (43.0 g) were added to the polyimine powder (5) (1.83 g) obtained in Synthesis Example 5, and the mixture was stirred at 70 ° C for 24 hours to be dissolved. Then, CE-2 (1.50 g) was added to the solution, and the mixture was stirred at 50 ° C for 5 hours. Further, S2 (0.500 g) and M3 (0.167 g) were added to the solution, and the mixture was stirred at 25 ° C for 2 hours to obtain a liquid crystal alignment treatment agent (10). It was confirmed that this liquid crystal alignment treatment agent was not found to have an abnormality such as turbidity or precipitation, and was a uniform solution.

A liquid crystal display device (glass substrate, plastic substrate) was produced using the obtained liquid crystal alignment treatment agent (10) and liquid crystal composition (2), and various evaluations were performed.

<Example 13>

NEP (38.9 g) and PB (19.5 g) were added to the polyimine powder (5) (2.60 g) obtained in Synthesis Example 5, and the mixture was stirred at 70 ° C for 24 hours to be dissolved. Then, CE-1 (0.65g) was added to the solution to 50 Stir at ° C for 5 hours. Further, S2 (0.033 g), M2 (0.975 g) and K1 (0.163 g) were added to the solution, and the mixture was stirred at 25 ° C for 2 hours to obtain a liquid crystal alignment treatment agent (11). It was confirmed that this liquid crystal alignment treatment agent was not found to have an abnormality such as turbidity or precipitation, and was a uniform solution.

A liquid crystal display element (glass substrate) was produced using the obtained liquid crystal alignment treatment agent (11) and liquid crystal composition (1), and various evaluations were performed.

<Example 14>

γ-BL (14.9 g) and PGME (39.9 g) were added to the polyimine powder (6) (1.55 g) obtained in Synthesis Example 6, and the mixture was stirred at 70 ° C for 24 hours to be dissolved. Then, CE-2 (1.55 g) was added to the solution, and the mixture was stirred at 50 ° C for 5 hours. Further, M2 (0.620 g) and K1 (0.155 g) were added to the solution, and the mixture was stirred at 25 ° C for 2 hours to obtain a liquid crystal alignment treatment agent (12). It was confirmed that this liquid crystal alignment treatment agent was not found to have an abnormality such as turbidity or precipitation, and was a uniform solution.

A liquid crystal display device (glass substrate, plastic substrate) was produced using the obtained liquid crystal alignment treatment agent (12) and liquid crystal composition (1), and various evaluations were performed.

<Example 15>

NEP (33.5 g), PB (20.0 g) and EC (6.10 g) were added to the polyimine powder (6) (2.33 g) obtained in Synthesis Example 6, and the mixture was stirred at 70 ° C for 24 hours to be dissolved. Then, add CE-2 to this solution. (1.00 g), stirred at 50 ° C for 5 hours. Further, S1 (0.233 g) and K1 (0.333 g) were added to the solution, and the mixture was stirred at 25 ° C for 2 hours to obtain a liquid crystal alignment treatment agent (13). It was confirmed that this liquid crystal alignment treatment agent was not found to have an abnormality such as turbidity or precipitation, and was a uniform solution.

A liquid crystal display element (glass substrate) was produced using the obtained liquid crystal alignment treatment agent (13) and liquid crystal composition (2), and various evaluations were performed.

<Example 16>

γ-BL (20.1 g), PGME (36.1 g) and ECS (6.40 g) were added to the polyimine powder (7) (2.45 g) obtained in Synthesis Example 7, and stirred at 70 ° C for 24 hours to dissolve. . Then, CE-2 (1.05 g) was added to the solution, and the mixture was stirred at 50 ° C for 5 hours. Further, M2 (0.875 g) and K1 (0.350 g) were added to the solution, and the mixture was stirred at 25 ° C for 2 hours to obtain a liquid crystal alignment treatment agent (14). It was confirmed that this liquid crystal alignment treatment agent was not found to have an abnormality such as turbidity or precipitation, and was a uniform solution.

A liquid crystal display device (glass substrate, plastic substrate) was produced using the obtained liquid crystal alignment treatment agent (14) and liquid crystal composition (2), and various evaluations were performed.

<Example 17>

NEP (26.8 g), BCS (24.7 g) and EC (5.80 g) were added to the polyimine powder (7) (2.40 g) obtained in Synthesis Example 7, and the mixture was stirred at 70 ° C for 24 hours to be dissolved. Then, add CE-1 to this solution. (0.80 g), stirred at 50 ° C for 5 hours. Further, S2 (0.032 g), M3 (0.320 g) and K1 (0.160 g) were added to the solution, and the mixture was stirred at 25 ° C for 2 hours to obtain a liquid crystal alignment treatment agent (15). It was confirmed that this liquid crystal alignment treatment agent was not found to have an abnormality such as turbidity or precipitation, and was a uniform solution.

A liquid crystal display element (glass substrate) was produced using the obtained liquid crystal alignment treatment agent (15) and liquid crystal composition (1), and various evaluations were performed.

<Example 18>

NMP (32.7 g) and BCS (25.1 g) were added to the polyimine powder (8) (1.95 g) obtained in Synthesis Example 8, and the mixture was stirred at 70 ° C for 24 hours to be dissolved. Then, CE-2 (1.30 g) was added to the solution, and the mixture was stirred at 50 ° C for 5 hours to obtain a liquid crystal alignment treatment agent (16). It was confirmed that this liquid crystal alignment treatment agent was not found to have an abnormality such as turbidity or precipitation, and was a uniform solution.

A liquid crystal display element (glass substrate) was produced using the obtained liquid crystal alignment treatment agent (16) and liquid crystal composition (1), and various evaluations were performed.

<Example 19>

γ-BL (10.1 g) and PGME (45.9 g) were added to the polyimine powder (8) (2.04 g) obtained in Synthesis Example 8, and the mixture was stirred at 70 ° C for 24 hours to be dissolved. Then, CE-2 (1.10 g) was added to the solution, and the mixture was stirred at 50 ° C for 5 hours. Add S2 to this solution (0.094 g), M2 (0.628 g) and K1 (0.314 g) were stirred at 25 ° C for 2 hours to obtain a liquid crystal alignment treatment agent (17). It was confirmed that this liquid crystal alignment treatment agent was not found to have an abnormality such as turbidity or precipitation, and was a uniform solution.

A liquid crystal display device (glass substrate, plastic substrate) was produced using the obtained liquid crystal alignment agent (17) and liquid crystal composition (1), and various evaluations were performed.

<Example 20>

NEP (38.2 g) and PB (19.5 g) were added to the polyimine powder (9) (1.95 g) obtained in Synthesis Example 9, and the mixture was stirred at 70 ° C for 24 hours to be dissolved. Then, CE-2 (1.30 g) was added to the solution, and the mixture was stirred at 50 ° C for 5 hours. Further, S1 (0.098 g), M1 (0.488 g) and K1 (0.325 g) were added to the solution, and the mixture was stirred at 25 ° C for 2 hours to obtain a liquid crystal alignment treatment agent (18). It was confirmed that this liquid crystal alignment treatment agent was not found to have an abnormality such as turbidity or precipitation, and was a uniform solution.

A liquid crystal display element (glass substrate) was produced using the obtained liquid crystal alignment treatment agent (18) and liquid crystal composition (2), and various evaluations were performed.

<Comparative Example 1>

NMP (16.8 g) and BCS (16.5 g) were added to a polyamic acid solution (10) (10.5 g) having a solid content concentration of 25% by mass of the resin obtained in Synthesis Example 10, and stirred at 25 ° C for 5 hours to obtain Liquid crystal alignment treatment agent (19). It was confirmed that the liquid crystal alignment agent was found to be turbid or precipitated. Often, it is a homogeneous solution.

A liquid crystal display element (glass substrate) was produced using the obtained liquid crystal alignment treatment agent (19) and liquid crystal composition (1), and various evaluations were performed.

<Comparative Example 2>

NMP (23.5 g) and BCS (15.7 g) were added to the polyimine powder (11) (2.50 g) obtained in Synthesis Example 11 and stirred at 70 ° C for 24 hours to obtain a liquid crystal alignment treatment agent (20). It was confirmed that this liquid crystal alignment treatment agent was not found to have an abnormality such as turbidity or precipitation, and was a uniform solution.

A liquid crystal display element (glass substrate) was produced using the obtained liquid crystal alignment treatment agent (20) and liquid crystal composition (1), and various evaluations were performed.

<Comparative Example 3>

NMP (16.0 g) and BCS (15.7 g) were added to a polyamic acid solution (2) (10.0 g) having a solid content concentration of 25% by mass of the resin obtained in Synthesis Example 2, and stirred at 25 ° C for 5 hours to obtain Liquid crystal alignment treatment agent (21). It was confirmed that this liquid crystal alignment treatment agent was not found to have an abnormality such as turbidity or precipitation, and was a uniform solution.

A liquid crystal display element (glass substrate) was produced using the obtained liquid crystal alignment treatment agent (21) and liquid crystal composition (1), and various evaluations were performed.

<Comparative Example 4>

A liquid crystal display device (glass substrate) was produced using the liquid crystal alignment treatment agent (21) and the liquid crystal composition (2) obtained in Comparative Example 3, and various evaluations were carried out.

<Comparative Example 5>

NMP (24.0 g) and BCS (16.0 g) were added to the polyimine powder (3) (2.55 g) obtained in Synthesis Example 3, and the mixture was stirred at 70 ° C for 24 hours to obtain a liquid crystal alignment treatment agent (22). It was confirmed that this liquid crystal alignment treatment agent was not found to have an abnormality such as turbidity or precipitation, and was a uniform solution.

A liquid crystal display element (glass substrate) was produced using the obtained liquid crystal alignment treatment agent (22) and liquid crystal composition (1), and various evaluations were performed.

<Comparative Example 6>

A liquid crystal display device (glass substrate) was produced using the liquid crystal alignment treatment agent (22) and the liquid crystal composition (2) obtained in Comparative Example 5, and various evaluations were carried out.

<Comparative Example 7>

NMP (22.8 g) and BCS (15.2 g) were added to CE-2 (2.00 g), and the mixture was stirred at 50 ° C for 5 hours to obtain a liquid crystal alignment treatment agent (23). It was confirmed that this liquid crystal alignment treatment agent was not found to have an abnormality such as turbidity or precipitation, and was a uniform solution.

A liquid crystal display element (glass substrate) was produced using the obtained liquid crystal alignment treatment agent (23) and liquid crystal composition (1), and various evaluations were performed.

<Examples 1 to 20, and Comparative Examples 1 to 7>

The liquid crystal alignment treatment agents obtained in the above examples and comparative examples are shown in Tables 2 to 4 below.

Further, as shown in the following Tables 5 to 10, the liquid crystal alignment treatment agents (1) to (23) obtained in the above examples and comparative examples, and the liquid crystal composition (1) or (2), are used. The production of the liquid crystal display element (glass substrate, plastic substrate) and the evaluation of the liquid crystal display element (liquid crystal alignment, optical characteristics (transparency and scattering characteristics), and adhesion between the liquid crystal layer and the liquid crystal alignment film) are performed.

Further, in the evaluation of the liquid crystal display elements of Examples 4, 6, 18 and 19 (the adhesion between the liquid crystal layer and the vertical liquid crystal alignment film), in addition to the above-mentioned standard test, the temperature was also 80 ° C and the humidity was 90 RH. Evaluation of 168 hours of storage in a high-temperature and high-humidity tank of % (other conditions are the same as those described above) as an emphasis test. As a result, in Examples 6 and 19, no bubbles were observed in the element, but in Examples 4 and 18, a small amount of bubbles were observed in the element.

As can be seen from the above results, compared with the liquid crystal display of the comparative example In the liquid crystal display device of the embodiment, the liquid crystal layer has high adhesion to the liquid crystal alignment film, and the liquid crystal has high vertical alignment and good optical characteristics, that is, transparency and applied voltage without an applied voltage. Scattering Sex is good.

On the other hand, in the liquid crystal display device of the comparative example, the adhesion between the liquid crystal layer and the liquid crystal alignment film is poor, and after being stored in the high temperature and high humidity bath, bubbles are observed in the element or between the liquid crystal layer and the liquid crystal alignment film. Peeling occurred. Further, after storage in a high temperature bath, the disorder of liquid crystal alignment due to insufficient vertical alignment of the liquid crystal can be seen.

Specifically, examples including component (A) (specific cellulose-based polymer) and comparative examples not containing component (A), that is, Example 2 and Comparative Example 3, Example 3, and Comparative Example 4. In the comparison between Example 4 and Comparative Example 5 and Example 5 and Comparative Example 6, it was confirmed that the difference was clear.

Further, in Comparative Example 1 and Comparative Example 2 in which a polyimide-based polymer having no specific side chain structure was used, and in Comparative Example 7 in which only a specific cellulose-based polymer was contained, the liquid crystal was not vertically aligned.

In addition, when a generating agent, an adhesive compound, and a crosslinkable compound are introduced into the liquid crystal alignment treatment agent, the liquid crystal display element is more excellent in adhesion to the vertical liquid crystal alignment film. Specifically, in the comparison between Example 4 and Example 6, and the comparison with Example 18 and Example 19, it was confirmed that the difference was clear.

[Industry Utilization]

The liquid crystal display device of the present invention can be suitably used in a reverse type element which is in a penetrating state when no voltage is applied and a scattering state when a voltage is applied, and is suitable for a liquid crystal display for display purposes, and further controls A dimming window or shutter element that penetrates and blocks light. Moreover, when the liquid crystal display element of the present invention is produced as a plastic substrate such as a film substrate, it can be used by being adhered to a glass substrate or a window glass used as a support.

The entire contents of the specification, the scope of the application, and the abstract of the Japanese Patent Application No. 2013-154864, filed on Jan.

Claims (16)

A liquid crystal display device in which a liquid crystal composition is disposed between two substrates on which an electrode is provided, at least one of the substrates has a liquid crystal alignment film, and a part or all of the liquid crystal composition exhibits liquid crystallinity. a liquid crystal display device in which a cured product of a liquid crystal and a polymerizable compound is formed by curing, and the liquid crystal composition contains a liquid crystal and a polymerizable compound polymerized by an active energy ray or heat; The liquid crystal alignment film is formed of a liquid crystal alignment agent containing the following components (A) and (B), and the component (A) is a cellulose polymer having a structure represented by the following formula [1]. (X ¹ , X ² , X ³ , X ⁴ , X ⁵ and X ⁶ are each independently represented by a group selected from at least one of the groups represented by the following formulas [1a] to [1m], n Is an integer from 100 to 1,000,000) (X ⁷ and X ⁸ are each independently shown as a benzene ring or an alkyl group having 1 to 4 carbon atoms, and X ⁹ , X ¹⁰ , X ¹¹ , X ¹² , X ¹³ and X ¹⁴ are each independently represented as a benzene ring or a carbon number of 1~ 4 alkylene, m, n is an integer of 0 to 3) Component (B): Polyimine polymerization selected from at least one of a group consisting of a polyimide precursor and a polyimine And a structure having at least one selected from the group consisting of the structures represented by the following formulas [2-1] and [2-2], (Y ^{1 is} shown as being selected from the group consisting of a single bond, -(CH ₂ ) _a - (a is an integer of 1 to 15), -O-, -CH ₂ O-, -COO-, and -OCO- 1; Y ^{2 is} shown as a single bond or -(CH ₂ ) _b - (b is an integer from 1 to 15); Y ^{3 is} shown to be selected from a single bond, -(CH ₂ ) _c - (c is 1 to 15) At least one of the group of integers, -O-, -CH ₂ O-, -COO-, and -OCO-; Y ⁴ is selected from the group consisting of a benzene ring, a cyclohexane ring, and a heterocyclic ring At least one divalent cyclic group or a divalent organic group having a carbon number of 17 to 51 having a steroid skeleton, and any hydrogen atom on the cyclic group may be an alkyl group having 1 to 3 carbon atoms and a carbon number of 1 Alkoxy group of ~3, fluorine-containing alkyl group having 1 to 3 carbon atoms, fluorine-containing alkoxy group having 1 to 3 carbon atoms or fluorine atom; Y ⁵ is selected from a benzene ring, a cyclohexane ring and a hetero At least one cyclic group in the group formed by the ring, any hydrogen atom on the cyclic group may have an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, and a carbon number of 1 to a fluorine-containing alkyl group of 3, a fluorine-containing alkoxy group having 1 to 3 carbon atoms or a fluorine atom; n is an integer of 0 to 4; and Y ⁶ is selected from an alkyl group having 1 to 18 carbon atoms and a carbon number a fluorine-containing alkyl group of 1 to 18, an alkoxy group having 1 to 18 carbon atoms, and a carbon number of 1 to 18 At least one of the group formed by the fluoroalkoxy group; n is an integer of 0 to 4) [Chemical 5]-Y ⁷ -Y ⁸ [2-2] (Y ⁷ is selected from a single bond, -O- Bonding of at least one of -CH ₂ O-, -CONH-, -NHCO-, -CON(CH ₃ )-, -N(CH ₃ )CO-, -COO-, and -OCO- The group Y ⁸ is represented by an alkyl group having 8 to 22 carbon atoms or a fluorine-containing alkyl group having 6 to 18 carbon atoms. The liquid crystal display element of claim 1, wherein the ratio of the component (A) to the component (B) is 0.1 to 9 parts by mass based on 1 part by mass of the component (B). The liquid crystal display element according to claim 1 or 2, wherein the polyamidimide polymer of the component (B) is at least one selected from the group consisting of a polyimide precursor and a polyimine. A diamine compound having a structure represented by the above formula [2-1] or formula [2-2] is used as a part of a raw material. The liquid crystal display element of claim 3, wherein the diamine compound is a diamine compound represented by the following formula [2a], (Y is a structure selected from at least one selected from the group consisting of the structures represented by the above formulas [2-1] and [2-2]; n is an integer of 1 to 4). The liquid crystal display element according to claim 1 or 2, wherein the polyamidimide polymer of the component (B) is at least one selected from the group consisting of a polyimide precursor and a polyimine. The tetracarboxylic acid component represented by the following formula [3] is used as a part of a raw material, (Z ¹ is a structure selected from at least one selected from the group consisting of the structures represented by the following formulas [3a] to [3j]) (Z ² to Z ⁵ are each independently represented by a hydrogen atom, a methyl group, a chlorine atom or a benzene ring; and Z ⁶ and Z ⁷ are each independently represented as a hydrogen atom or a methyl group). The liquid crystal display element of claim 1 or 2, wherein the liquid crystal alignment treatment agent further contains a solvent. The liquid crystal display device of claim 6, wherein the solvent contains a solvent having a boiling point of less than 180 ° C and 50% by mass or more of the entire solvent. The liquid crystal display element according to claim 7, wherein the solvent further contains at least one solvent selected from the group consisting of cyclopentanone, cyclohexanone, and a solvent represented by the following formula [A1] and formula [A2]. (A ^{1 is} shown as an alkyl group having 1 to 3 carbon atoms; and A ² is represented as an alkyl group having 1 to 3 carbon atoms). The liquid crystal display element of claim 7, wherein the solvent is further Containing a group selected from the group consisting of 1-hexanol, cyclohexanol, 1,2-ethanediol, 1,2-propanediol, propylene glycol monobutyl ether, ethylene glycol monobutyl ether, and dipropylene glycol dimethyl ether At least one solvent. The liquid crystal display element of claim 7, wherein the solvent further comprises a group selected from the group consisting of N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, γ-butyrolactone, and the following formula [A3] a solvent of at least one of the group of solvents shown, (A ^{3 is} shown as an alkyl group having 1 to 4 carbon atoms). The liquid crystal display element of claim 1 or 2, wherein the liquid crystal alignment treatment agent further contains a compound having at least one selected from the group consisting of the structures represented by the following formulas [B1] to [B8] Kind, (B ¹ is a hydrogen atom or a benzene ring; B ² is a cyclic group selected from at least one selected from the group consisting of a benzene ring, a cyclohexane ring, and a hetero ring; and B ³ is selected from a carbon number of 1 to At least one of a group of 18 alkyl groups, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, and a fluorine-containing alkoxy group having 1 to 18 carbon atoms. The liquid crystal display device of claim 1 or 2, wherein the liquid crystal alignment treatment agent further comprises a generating agent selected from the group consisting of a photo radical generating agent, a photoacid generator, and a photobase generator; Kind. The liquid crystal display element of claim 1 or 2, wherein the substrate is a glass substrate or a plastic substrate. A liquid crystal alignment film which is used in a liquid crystal alignment film of a liquid crystal display element according to any one of claims 1 to 13, and which is formed of a liquid crystal alignment treatment agent containing the component (A) and the component (B). The liquid crystal alignment film of claim 14, wherein the film thickness is 5 to 500 nm. A liquid crystal alignment treatment agent for forming a liquid crystal alignment treatment agent for a liquid crystal alignment film of claim 14 or 15, and comprising the above-mentioned component (A) and component (B).