KR20160034984A - Liquid-crystal display element, liquid-crystal alignment agent, and liquid-crystal alignment film - Google Patents

Abstract

A liquid crystal composition comprising a liquid crystal and a polymerizable compound polymerized by an active energy ray or heat is disposed between two substrates provided with electrodes and has a liquid crystal alignment film on at least one of the substrates, Wherein the liquid crystal alignment film is a liquid crystal alignment film obtained by curing the liquid crystal composition in a state in which the liquid crystal composition exhibits a liquid crystal property or a liquid crystal property of the liquid crystal composition, Wherein the liquid crystal alignment treatment agent is a liquid crystal alignment agent. Component (A): A cellulosic polymer having a specific structure. Component (B): at least one polyimide polymer selected from the group consisting of a polyimide precursor having a specific side chain and a polyimide.

Description

TECHNICAL FIELD [0001] The present invention relates to a liquid crystal display device, a liquid crystal alignment treatment agent, and a liquid crystal alignment film,

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

As a liquid crystal display device using a liquid crystal material, a TN (Twisted Nematic) mode has been put to practical use. In this mode, optical switching is performed using the optical rotation property of the liquid crystal, and it is necessary to use a polarizing plate when it is used as a liquid crystal display element. However, it is known that the use efficiency of light is lowered by using a polarizing plate.

There is a liquid crystal display element which does not use a polarizing plate and which has high utilization efficiency of light and which performs switching between the transmissive state (also referred to as a transparent state) and the scattered state of a liquid crystal, and generally, a polymer dispersed liquid crystal (Also referred to as PDLC (Polymer Dispersed Liquid Crystal)) or a polymer network liquid crystal (also referred to as Polymer Network Liquid Crystal (PNLC)).

A liquid crystal display element using these liquid crystal display elements comprises a liquid crystal composition comprising a liquid crystal layer between a pair of substrates provided with electrodes and containing a polymerizable compound polymerized by at least one of active energy rays and heat between the pair of substrates And a step of curing the liquid crystal composition in a state in which a part or the whole of the liquid crystal composition exhibits liquid crystallinity to form a cured product complex of a liquid crystal and a polymerizable compound. This liquid crystal display element controls the transmission state and the scattering state of the liquid crystal by application of a voltage.

In conventional liquid crystal display devices using PDLC or PNLC, since the liquid crystal molecules are oriented in a random direction when no voltage is applied, the liquid crystal display device is in a whitish (scattering) state. When voltage is applied, liquid crystal is arranged in the electric field direction, A normal type device is known which is in a transmissive state. However, in a normal type device, since it is necessary to always apply a voltage to obtain a transparent state, power consumption is increased when the device is used in a transparent state, for example, when used in a window glass.

A reverse type device has been reported in which the normal type device is in a transmitting state when no voltage is applied and is in a scattering state when a voltage is applied (see Patent Documents 1 and 2).

Japanese Patent Publication No. 2885116 Japanese Patent Publication No. 4132424

In the reverse type device, a liquid crystal alignment film (also referred to as a vertical liquid crystal alignment film) for vertically aligning the liquid crystal is used because the liquid crystal must be vertically aligned. 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, it is necessary to introduce a large amount of a polymerizable compound (also referred to as a curing agent) for enhancing the adhesion between the liquid crystal layer and the liquid crystal alignment film in the liquid crystal composition used for the reverse type device. However, when a large amount of a polymerizable compound is introduced, the vertical alignment property of the liquid crystal is impaired, and there is a problem that the transparency at the time of no voltage application and the scattering property at the time of voltage application are significantly lowered. Therefore, the liquid crystal alignment film used for the reverse type device needs to have a high vertical alignment property of the liquid crystal.

Therefore, an object of the present invention is to provide a liquid crystal display element having the above-mentioned characteristics. That is, an object of the present invention is to provide a liquid crystal display device which has a high vertical alignment property of liquid crystal, good optical characteristics, that is, transparency when no voltage is applied and scattering property upon voltage application, . The present invention also provides a liquid crystal alignment film for 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 the adhesion between a liquid crystal layer and a liquid crystal alignment film is improved by having a liquid crystal alignment film obtained from a liquid crystal alignment treatment agent containing a cellulose polymer having a specific structure and a polyimide polymer having a side chain of a specific structure A liquid crystal display element having a high liquid crystal alignment property and a high liquid crystal vertical alignment property and having good optical characteristics, that is, transparency when no voltage is applied and scattering property upon voltage application, can be obtained.

The present invention is based on this finding and has the following points.

(1) A liquid crystal composition comprising a liquid crystal and a polymerizable compound which is polymerized by an active energy ray or heat is disposed between two substrates provided with electrodes and has a liquid crystal alignment film on at least one of the substrates, A liquid crystal display element comprising a liquid crystal and a cured product composite of a polymerizable compound formed by curing a part or the whole of the composition in a state of exhibiting liquid crystallinity, wherein the liquid crystal alignment film contains the following components (A) and (B) Wherein the liquid crystal alignment treatment agent is a liquid crystal alignment agent.

Component (A): A cellulosic polymer having a structure represented by the following formula [1].

[Chemical Formula 1]

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

(2)

(3)

X ⁷ , and X ⁸ each independently represent a benzene ring or an alkyl group having 1 to 4 carbon atoms, X ⁹ , X ¹⁰ , X ¹¹ , X ¹² , X ^13, and X ¹⁴ each independently represent a benzene ring Or an alkylene group having 1 to 4 carbon atoms, and m and n each represent an integer of 0 to 3.)

Component (B): At least one compound selected from the group consisting of a polyimide precursor and a polyimide having at least one structure selected from the group consisting of structures represented by the following formulas [2-1] and [2-2] One kind of polyimide-based polymer.

[Chemical Formula 4]

(Y ¹ is at least a group 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 shows a longitudinal Y ² is a single bond or _{-. (CH 2) b -} . represents a (b is an integer of 1 ~ 15) Y ³ is a single _{bond, - (CH 2) c -} (c is 1, -O-, -CH ₂ O-, -COO- and -OCO-, Y ⁴ represents a benzene ring, a cyclohexane ring and a heterocyclic ring Or a divalent organic group having 17 to 51 carbon atoms having a steroid skeleton, and any hydrogen atom on the cyclic group may be substituted with an alkyl group having 1 to 3 carbon atoms, an alkyl group having 1 to 3 carbon atoms, 3 alkoxyl group, a fluorine-containing alkyl group having a carbon number of 1 to 3 of, or may be substituted with a fluorine-containing alkoxy group or a fluorine atom of 1 to 3 carbon atoms. Y ⁵ is a benzene ring, a cycloalkyl An alkyl group having 1 to 3 carbon atoms, an alkoxyl group having 1 to 3 carbon atoms, an alkoxyl group having 1 to 3 carbon atoms, and an aryl group having 1 to 3 carbon atoms. A fluorine-containing alkoxyl group having 1 to 3 carbon atoms, or a fluorine atom, n is an integer of 0 to 4. Y ⁶ is an alkyl group having 1 to 18 carbon atoms, a fluorine-containing An alkyl group, an alkoxyl group having 1 to 18 carbon atoms, and a fluorinated alkoxyl group having 1 to 18 carbon atoms, and n represents an integer of 0 to 4.)

[Chemical Formula 5]

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

(2) The liquid crystal display element described in (1) above, wherein the ratio of the component (A) to the component (B) is 0.1 to 9 parts by mass relative to 1 part by mass of the component (B).

(3) The polyimide polymer of the above component (B) is a polyimide precursor and a polyimide precursor obtained by using a diamine compound having a structure represented by the above formula [2-1] or [2-2] (1) or (2), wherein the liquid crystal display device is at least one selected from the group consisting of a liquid crystal cell, a liquid crystal cell, and a liquid crystal cell.

(4) The liquid crystal display element described in (3), wherein the diamine compound is a diamine compound represented by the following formula [2a].

[Chemical Formula 6]

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

(5) The polyimide-based polymer of component (B) is at least one selected from the group consisting of polyimide precursors and polyimides obtained by using a tetracarboxylic acid component represented by the following formula [3] The liquid crystal display element described in any one of (1) to (4) above, which is one type.

(7)

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

[Chemical Formula 8]

(Z ² to Z ⁵ each independently represent a hydrogen atom, a methyl group, a chlorine atom or a benzene ring, and Z ⁶ and Z ⁷ each independently represent a hydrogen atom or a methyl group.

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

(7) The liquid crystal display element described in (6) above, wherein the solvent contains a solvent having a boiling point of at least 50 mass% of the entire solvent of less than 180 占 폚.

(8) The process according to the above (6) or (7), wherein the solvent further comprises at least one solvent selected from the group consisting of cyclopentanone, cyclohexanone, the solvent represented by the following formula [A1] (7).

[Chemical Formula 9]

(A ¹ represents an alkyl group having 1 to 3 carbon atoms, and A ² represents an alkyl group having 1 to 3 carbon atoms.)

(9) The method according to any one of (1) to (9), wherein the solvent is 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 (6) to (8), wherein the liquid crystal display device further comprises at least one solvent selected from among the following.

(10) The positive resist composition as described in any one of (1) to (3) above, wherein the solvent is at least one selected from the group consisting of N-methyl-2-pyrrolidone, N- The liquid crystal display element described in any one of (6) to (9) above, which further contains a solvent.

[Chemical formula 10]

(A < ³ > represents an alkyl group having 1 to 4 carbon atoms)

(11) The liquid crystal alignment treating agent according to any one of (1) to (10), wherein the liquid crystal alignment treating agent contains a compound having at least one group selected from the group consisting of groups represented by the following formulas [B1] to [ A liquid crystal display element according to any one of the preceding claims.

(11)

(Wherein B ¹ represents a hydrogen atom or a benzene ring, B ² represents at least one cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring and a heterocyclic ring, B ³ represents an alkyl group having 1 to 18 carbon atoms, At least one member selected from the group consisting of a fluorine-containing alkyl group of 1 to 18 carbon atoms, an alkoxyl group of 1 to 18 carbon atoms, and a fluoro-containing alkoxyl group of 1 to 18 carbon atoms.

(12) The liquid crystal alignment agent according to any one of (1) to (11), wherein the liquid crystal alignment treatment agent contains at least one generator selected from the group consisting of a photo-radical generator, a photo-acid generator and a photo- Wherein the liquid crystal display element is a liquid crystal display element.

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

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

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

(16) A liquid crystal alignment treatment agent for forming the liquid crystal alignment film according to (14) or (15), which contains the above-mentioned components (A) and (B).

According to the present invention, by using a vertical liquid crystal alignment film obtained from a liquid crystal alignment treatment agent containing a cellulose polymer having a specific structure and a polyimide polymer having a specific structure side chain, adhesion between the liquid crystal layer and the vertical liquid crystal alignment film is high, Can provide a liquid crystal display element in which the liquid crystal has a high vertical orientation and good optical characteristics, that is, transparency when no voltage is applied and scattering characteristics upon voltage application. Particularly, the liquid crystal display element of the present invention can be suitably used for a reverse type element which is in a transmissive state when no voltage is applied and is in a scattering state when a voltage is applied, and a liquid crystal display for display purposes, Is used as a dimmer window or an optical shutter element for controlling blocking.

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

<Cellulose-Based Polymer>

The cellulose polymer (hereinafter also referred to as a specific cellulose polymer) as the component (A) in the present invention is a polymer having a structure represented by the following formula [1].

[Chemical Formula 12]

X ¹ , X ² , X ³ , X ⁴ , X ⁵ and X ⁶ each independently represent at least one group selected from the group consisting of the groups represented by the following formulas [1a] to [1m] Lt; / RTI &gt;

and n represents an integer of 100 to 1,000,000. Among them, n is preferably 100 to 500,000 from the viewpoints of solubility in a solvent of a specific cellulose-based polymer and handling property when it is prepared as a liquid crystal alignment treatment agent. More preferred is 100 to 100,000.

[Chemical Formula 13]

[Chemical Formula 14]

X ⁷ and X ⁸ each independently represent a benzene ring or an alkyl group having 1 to 4 carbon atoms (specifically, a methyl group, an ethyl group, a n-propyl group, an isopropyl group or a butyl group). X ⁹ , X ¹⁰ , X ¹¹ , X ¹² , X ¹³ and X ¹⁴ each independently represent a benzene ring or an alkylene group having 1 to 4 carbon atoms (specifically, a methylene group, an ethylene group, Propylene, butylene group, etc.).

and n represents an integer of 0 to 3. Among them, an integer of 0 or 1 is preferable.

m represents an integer of 0 to 3; Among them, an integer of 0 or 1 is preferable.

In the formula [1], X ¹ , X ² , X ³ , X ⁴ , X ⁵ and X ⁶ each independently represent a group selected from the formulas [1a] to [1m] Or two or more. Particularly, from the viewpoint of the solubility in a solvent of a specific cellulose polymer and the coating property of a liquid crystal alignment treatment agent, it is preferable to use two or more kinds thereof.

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

Specific examples of the specific cellulose polymer include, but are not limited to, the following.

For example, there may be mentioned cellulose derivatives such as cellulose, methylcellulose, ethylcellulose, propylcellulose, butylcellulose, methylethylcellulose, acetylcellulose, cellulose propionate, hydroxymethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, , Ethylhydroxyethylcellulose, hydroxybutylmethylcellulose, hydroxypropylmethylcellulose phthalate, methylaminocellulose, ethylaminocellulose, propylaminocellulose, benzylcellulose, tribenzoylcellulose, cellulose acetate butyrate, cellulose acetate propionate, Carboxymethylcellulose, carboxymethylethylcellulose, or carboxymethylhydroxyethylcellulose. Among them, mention may be made of methylcellulose, ethylcellulose, propylcellulose, acetylcellulose, hydroxymethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, ethylhydroxyethylcellulose, hydroxypropylmethylcellulose phthalate, benzyl Cellulose, cellulose acetate propionate, carboxymethylethylcellulose or carboxymethylhydroxyethylcellulose are preferred. More preferably, it is selected from the group consisting of methylcellulose, ethylcellulose, acetylcellulose, hydroxymethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, ethylhydroxyethylcellulose, hydroxypropylmethylcellulose phthalate or carboxymethyl Ethyl cellulose. Particularly preferred are methylcellulose, ethylcellulose, acetylcellulose, hydroxymethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, ethylhydroxyethylcellulose or hydroxypropylmethylcellulose phthalate.

These cellulose derivatives are generally available. The method of introducing groups represented by the formulas [1b] to [1m] is not particularly limited, and conventional methods can be used.

For example, when introducing the formula [1b], a method of reacting cellulose and benzyl chloride in the presence of an alkali,

When introducing the formula [1c], a method of reacting cellulose and a halogen compound having X ⁷ in the presence of an alkali,

In the case of introducing the formula [1d], a method of reacting cellulose with an acid chloride compound having X ⁸ in the presence of an alkali, a method of reacting cellulose with anhydrous acetic acid,

In the case of introducing the formula [1e], a method of reacting cellulose and a halogen compound having X ⁹ -OH in the presence of an alkali,

When introducing the formula [1f], a method of reacting cellulose and a halogen compound having X ¹⁰ -COOH in the presence of an alkali,

When introducing the formula [1 g], a method of reacting cellulose and a halogen compound having X ¹¹ -NH ₂ in the presence of an alkali,

In the case of introducing the formula [1h], a method of reacting cellulose and phthalic acid,

In the case of 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 an alkali,

In the case of introducing the formula [1k], a method of reacting cellulose and maleic anhydride can be mentioned.

The specific cellulose polymer may be one kind or two kinds or more depending on the solubility of the specific cellulose polymer in a solvent, the application property of the liquid crystal alignment treatment agent, furthermore, the optical characteristics of the liquid crystal display element and the adhesiveness of the liquid crystal layer and the vertical liquid crystal alignment film. Or more.

<Polyimide Polymer>

The component (B) in the present invention has at least one structure (also referred to as a specific side chain structure) selected from the group consisting of the structures represented by the following formulas [2-1] and [2-2] Based polymer (also referred to as a specific polyimide-based polymer).

[Chemical Formula 15]

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

Y ¹ represents a single bond, - (CH ₂ ) _a - (a is an integer of 1 to 15), -O-, -CH ₂ O-, or -COO-, in terms of the availability of raw materials or ease of synthesis. . More preferably, it 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).

Y ³ is preferably a single bond, - (CH ₂ ) _c - (c is an integer of 1 to 15), -O-, -CH ₂ O- or -COO- from the viewpoint of easiness of synthesis. More preferably, it is a single bond, - (CH ₂ ) _c - (c is an integer of 1 to 10), -O-, -CH ₂ O- or -COO-.

Y ⁴ is preferably an organic group having 17 to 51 carbon atoms having a benzene ring, a cyclohexane ring or a steroid skeleton from the viewpoint of ease of synthesis.

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 alkoxyl group having 1 to 18 carbon atoms, or a fluorinated alkoxyl group having 1 to 10 carbon atoms. More preferred are an alkyl group having 1 to 12 carbon atoms or an alkoxyl group having 1 to 12 carbon atoms. Especially preferred are alkyl groups having 1 to 9 carbon atoms or alkoxyl groups having 1 to 9 carbon atoms.

n is preferably 0 to 3 in view of the availability of raw materials and ease of synthesis. More preferred is 0 to 2.

Preferred combinations of Y ¹ , Y ² , Y ³ , Y ⁴ , Y ⁵ , Y ⁶ and n are described in International Patent Publication WO2011 / 132751 (published on October 27, 2011) (2-1) to (2-629) shown in FIG. In each table of the International Publication, Y ¹ to Y ⁶ in the present invention are represented as Y ¹ to Y ⁶ , and Y ¹ to Y ⁶ are read in place of Y ¹ to Y ⁶ . In (2-605) to (2-629) listed in the tables of International Publication, the organic group having a steroid skeleton and having a carbon number of 17 to 51 in the present invention is an organic group having a steroid skeleton and having a carbon number of 12 to 25 Organic groups having 12 to 25 carbon atoms having a steroid skeleton are replaced with organic groups having 17 to 51 carbon atoms having a steroid skeleton.

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

[Chemical Formula 16]

In the formula [2-2], Y ⁷ and Y ⁸ are as defined above, and among them, the following are preferable.

Y ⁷ is preferably a single bond, -O-, -CH ₂ O-, -CONH-, -CON (CH ₃ ) - or -COO- in view of the availability of raw materials and ease of synthesis. More preferably, it 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] in that a high and stable liquid crystal alignment property can be obtained.

The specific polyimide polymer in the present invention is at least one polymer selected from the group consisting of a polyimide precursor having a specific side chain structure and a polyimide. At this time, the polyimide precursor can be obtained by reacting the diamine component and the tetracarboxylic acid component, and the polyimide can be obtained by imidizing such a polyimide precursor.

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

[Chemical Formula 17]

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

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

The polyimide polymer is preferably obtained by the following formula [D] because the polyimide polymer is relatively easily obtained by using the tetracarboxylic acid dianhydride represented by the following formula [B] and the diamine compound represented by the following formula [C] Or a polyimide obtained by imidizing the polyamic acid is preferable. Among them, polyimide is preferably used for the specific polyimide polymer in view of the physical and chemical stability of the liquid crystal alignment film.

[Chemical Formula 18]

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

[Chemical Formula 19]

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

In addition, in conventional synthesis methods, the polymer of the formula [D] obtained in the above-mentioned formula [A] of A ¹ and A ² shown by a carbon number of 1 ~ 8 A ³ and A ⁴ represents an alkyl group, formula [A] in An alkyl group having 1 to 5 carbon atoms or an acetyl group may be introduced.

As a method for introducing a specific side chain structure into a specific polyimide polymer, it is preferable to use a diamine compound having a specific side chain structure as a part of the starting material. It is particularly preferable to use a diamine compound represented by the following formula [2a] (also referred to as a specific side chain diamine).

[Chemical Formula 20]

In formula [2a], Y represents at least one structure selected from the group consisting of structures represented by the formulas [2-1] and [2-2].

n represents an integer of 1 to 4; Among them, an integer of 1 is preferable.

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

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

[Chemical Formula 21]

(R ¹ are _{each, -O-, -OCH 2 -, -CH} 2 O-, -COOCH 2 -. And shows the coupler of at least one member selected from the group consisting of -CH ^₂ OCO- R ₂ are each, A linear or branched alkyl group having 1 to 22 carbon atoms, a linear or branched alkoxyl group having 1 to 22 carbon atoms, a linear or branched alkyl group having 1 to 22 carbon atoms and a linear chain having 1 to 22 carbon atoms Type or branched fluorine-containing alkoxyl group).

[Chemical Formula 22]

(R ³ is a group consisting of -COO-, -OCO-, -CONH-, -NHCO-, -COOCH ₂ -, -CH ₂ OCO-, -CH ₂ O-, -OCH ₂ - and -CH ₂ - R ⁴ represents a linear or branched alkyl group having 1 to 22 carbon atoms, a linear or branched alkoxyl group having 1 to 22 carbon atoms, a straight-chain or branched alkoxyl group having 1 to 22 carbon atoms, A branched or branched fluorine-containing alkyl group, and a linear or branched fluorine-containing alkoxyl group having 1 to 22 carbon atoms.)

(23)

(R ⁵ are each, -COO-, -OCO-, -CONH-, -NHCO- , -COOCH 2 -, -CH 2 OCO-, -CH 2 O-, -OCH 2 -, -CH 2 -, - O-, and -NH-, and R ⁶ is at least one group selected from the group consisting of a fluorine group, a cyano group, a trifluoromethyl group, a nitro group, an azo group, a formyl group, an acetyl group, And at least one member selected from the group consisting of a hydroxyl group.

&Lt; EMI ID =

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

(25)

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

(26)

(A ₄ represents a linear or branched alkyl group having 3 to 20 carbon atoms which may be substituted with a fluorine atom, A ₃ represents a 1,4-cyclohexylene group or a 1,4-phenylene group, A ₂ represents an oxygen * indicates the atom or -COO- (provided that combined hand provided with an "*" are combined and a _3). a ₁ is a bond hand provided with an oxygen atom or -COO- * (However, the "*" (CH ₂ ) &lt; / RTI &gt; a ₂ ). A ₁ represents an integer of 0 or 1; and a ₂ represents an integer of 2 to 10. and a ₃ represents an integer of 0 or 1.)

(27)

(28)

[Chemical Formula 29]

(30)

(31)

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

More preferred are the diamine compounds represented by the following formulas [2a-32] to [2a-36].

(32)

(R ¹ each represents -CH ₂ O-, and R ² each represents an alkyl group having 3 to 12 carbon atoms.)

(33)

(Each R ³ represents an alkyl group having 3 to 12 carbon atoms, and the cis-trans isomer of 1,4-cyclohexylene is a trans isomer, respectively)

Examples of the diamine compound having a specific side chain structure represented by the above formula [2-2] include diamine compounds represented by the following formulas [2a-37] to [2a-46].

(34)

(A &lt; ¹ &gt; represents an alkyl group having 1 to 22 carbon atoms or a fluorine-containing alkyl group, respectively).

(35)

(A ¹ is at least one kind of bonding group selected from the group consisting of -COO-, -OCO-, -CONH-, -NHCO-, -CH ₂ -, -O-, -CO- and -NH- A ² represents at least one kind 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.)

The use ratio of the specific side chain type diamine compound is preferably 10 to 80 mol% with respect to the total diamine component in view of the vertical alignment property of the liquid crystal in the liquid crystal display element and the adhesion between the liquid crystal layer and the liquid crystal alignment film. More preferred is 10 to 70 mol%.

The specific side chain-type diamine compound may be one kind or a combination of two or more kinds depending on the solubility of the specific polyimide polymer in a solvent, the vertical alignment of the liquid crystal when the liquid crystal alignment film is formed, and further, Two or more kinds can be mixed and used.

As the diamine component for producing a specific polyimide polymer, it is preferable to use a diamine compound (also referred to as a second diamine compound) represented by the following formula [2b].

(36)

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

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

(37)

a represents an integer of 0 to 4; Of these, an integer of 0 or 1 is preferable in view of availability of raw materials and ease of synthesis.

and b represents an integer of 0 to 4. Of these, an integer of 0 or 1 is preferable in view of availability of raw materials and ease of synthesis.

W ¹ and W ² each independently represent a hydrocarbon group of 1 to 12 carbon atoms.

W ³ represents an alkyl group having 1 to 5 carbon atoms.

Specific examples of the second diamine compound are mentioned below, but the present invention is not limited thereto.

For example, there can be mentioned 2,4-dimethyl-m-phenylenediamine, 2,6-diaminotoluene, 2,4-diaminophenol, 3,5-diaminophenol, 3,5- Diaminobenzoic acid, 3,5-diaminobenzoic acid, 3,5-diaminobenzoic acid, 4-diaminobenzoic acid, 4,6-diaminoresorcinol, 2,4- ] To [2b-6].

(38)

[Chemical Formula 39]

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-diaminobenzoic acid, 3,5-diaminobenzoic acid, or a diamine compound represented by the formula [2b-1] to [2b-3].

More preferable examples thereof include 2,4-diaminophenol, 3,5-diaminophenol, 3,5-diaminobenzyl alcohol, 3,5-diaminobenzoic acid or the compounds represented by formulas [2b-1] to [2b-2] And the like.

The use ratio of the second diamine compound is preferably 10 to 90 mol% with respect to the total diamine component in view of the vertical alignment property of the liquid crystal in the liquid crystal display element and the adhesion between the liquid crystal layer and the liquid crystal alignment film. More preferred is 20 to 90 mol%. Especially preferred is 30 to 80 mol%.

The second diamine compound may be used alone or in combination of two or more types depending on the solubility of the specific polyimide polymer in a solvent, the vertical alignment of the liquid crystal when used as a liquid crystal alignment film, and further, Or more can be mixed and used.

As long as the effect of the present invention is not impaired, a diamine compound other than the specific side chain type diamine compound and the second diamine compound (also referred to as another diamine compound) may be used for the diamine component in order to produce the specific polyimide type polymer have. Specific examples of the other diamine compounds are mentioned below, but are not limited thereto.

For example, there may be mentioned m-phenylenediamine, p-phenylenediamine, 4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, Diaminobiphenyl, 3,3'-dihydroxy-4,4'-diaminobiphenyl, 3,3'-dicarboxy-4,4'-diaminobiphenyl, 3,3'- 3'-difluoro-4,4'-diaminobiphenyl, 3,3'-trifluoromethyl-4,4'-diaminobiphenyl, 3,4'-diaminobiphenyl, 3,3 Diaminobiphenyl, 2,2'-diaminobiphenyl, 2,3'-diaminobiphenyl, 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 3'- , 4'-diaminodiphenylmethane, 2,2'-diaminodiphenylmethane, 2,3'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 3,3'-diamino Diphenyl ether, 3,4'-diaminodiphenyl ether, 2,2'-diaminodiphenyl ether, 2,3'-diaminodiphenyl ether, 4,4'-sulfonyldi aniline, 3,3 ' (4-aminophenyl) silane, bis (3-aminophenyl) silane, dimethyl-bis Phenyl) silane, dimethyl-bis (3-aminophenyl) silane, 4,4'-thiodianiline, 3,3'- thiodianiline, 4,4'- diaminodiphenylamine, Aminodiphenylamine, 3,4'-diaminodiphenylamine, 2,2'-diaminodiphenylamine, 2,3'-diaminodiphenylamine, N-methyl (4,4'-diamino di (3,3'-diaminodiphenyl) amine, N-methyl (3,4'-diaminodiphenyl) amine, N-methyl (2,2'-diaminodiphenyl) Amine, N-methyl (2,3'-diaminodiphenyl) amine, 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 3,4'- diaminobenzophenone, Diaminobenzoquinone, 4-diaminonaphthalene, 2,2'-diaminobenzophenone, 2,3'-diaminobenzophenone, 1,5-diaminonaphthalene, 1,6-diaminonaphthalene, Diaminonaphthalene, 2,6-diaminonaphthalene, 2,8-diaminonaphthalene, 1,2-bis (4-aminophenyl) ) Ethane, 1,2-bis (3-aminophenyl) ethane, 1, Bis (4-aminophenyl) propane, 1,3-bis (3-aminophenyl) propane, 1,4- (4-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, Benzene, 1,3-bis (4-aminophenyl) benzene, 1,4-bis (4-aminophenoxy) benzene, - [1,4-phenylenebis (methylene)] dianiline, 4,4 '- [1,3-phenylenebis (methylene)] dianiline, 3,4' - [ Methylene)] dianiline, 3,4 '- [1,3-phenylenebis (methylene)] dianiline, 3,3' - [1,4-phenylenebis (methylene)] dianiline, - [1,3-phenylenebis (methylene)] dianiline, 1,4-phenylenebis [(4-aminophenyl (methanone)], Phenylenebis [(3-aminophenyl) methanone], 1,4-phenylenebis (4-amino Benzoate), 1,4-phenyl Bis (3-aminobenzoate), 1,3-phenylenebis (4-aminobenzoate), 1,3-phenylenebis (4-aminophenyl) isophthalate, bis (3-aminophenyl) isophthalate, N, N ' , N, N '- (1, 3-phenylene) bis (3-aminobenzamide), N, N' (3-aminophenyl) terephthalamide, N, N'-bis (4-aminophenyl) terephthalamide, N, N'- N, N'-bis (3-aminophenyl) isophthalamide, 9,10-bis (4-aminophenyl) anthracene, 4,4'-bis Bis [4- (4-aminophenoxy) phenyl] hexafluoro (2-hydroxyphenyl) Propane, 2,2'-bis (4- Bis (3-aminophenyl) hexafluoropropane, 2,2'-bis (3-aminophenyl) hexafluoropropane, 2,2'- Bis (4-aminophenyl) propane, 2,2'-bis (3-aminophenyl) propane, 2,2'- Propane, 1,3-bis (3-aminophenoxy) propane, 1,4-bis (4-aminophenoxy) butane, 1,4- Bis (4-aminophenoxy) pentane, 1,6-bis (3-aminophenoxy) pentane, Bis (4-aminophenoxy) heptane, 1,7-bis (4-aminophenoxy) heptane, (Aminophenoxy) octane, 1,9-bis (4-aminophenoxy) nonane, 1,9-bis , 10-bis (3-aminophenoxy) decane, 1,11-bis (4-aminophenoxy) undecane, 3-aminophenoxy) undecane, 1,12-bis (4-aminophenoxy) dodecane, 1,12-bis (4-amino-3-methylcyclohexyl) methane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, Diminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, and 1,12-diaminododecane. .

In addition, as long as the effect of the present invention is not impaired, diamine compounds represented by the following formulas [DA1] to [DA14] may be used.

(40)

(p represents an integer of 1 to 10).

(41)

(m represents an integer of 0 to 3).

(42)

(n represents an integer of 1 to 5)

(43)

(A ¹ and A ³ are, each independently, a single _{bond, -CH 2 -, -C 2 H} 4 -, -C (CH 3) 2 -, -CF 2 -, -C (CF 3) 2 -, -O-, -CO-, -NH-, -N (CH ₃ ) -, -CONH-, -NHCO-, -CH ₂ O-, -OCH ₂ -, -COO-, -OCO-, -CON CH ₃ ) - and -N (CH ₃ ) CO-, m ¹ and m ² each represent an integer of 0 to 4, and m ¹ + m ² represents M ³ and m ⁴ each represent an integer of 1 to 5, A ² represents a linear or branched alkyl group having 1 to 5 carbon atoms, m ⁵ represents an integer of 1 to 5, M ⁶ represents an integer of 1 to 4.)

(44)

(A ¹ is -O-, -NH-, -N (CH ₃ ) -, -CONH-, -NHCO-, -CH ₂ O-, -OCO-, -CON (CH ₃ ) ₃ ) CO-, A ² represents a single bond, an aliphatic hydrocarbon group of 1 to 20 carbon atoms, a non-aromatic cyclic hydrocarbon group or an aromatic hydrocarbon group, A ³ represents a single bond , -NH-, -N (CH ₃ ) -, -CONH-, -NHCO-, -COO-, -OCO-, -CON (CH ₃ ) -, -N (CH ₃ ) -O (CH ₂ ) _m - (m is an integer of 1 to 5), A ⁴ represents a nitrogen-containing aromatic heterocyclic ring, and n represents an integer of 1 to 4 Lt; / RTI &gt;

[Chemical Formula 45]

The other diamine compound may be used alone or in combination of two or more, depending on the solubility of the specific polyimide polymer in a solvent, the vertical alignment of the liquid crystal when used as a liquid crystal alignment film, and further, Can be used.

The tetracarboxylic acid component for producing the specific polyimide polymer includes a tetracarboxylic acid dianhydride represented by the following formula [3], a tetracarboxylic acid derivative thereof, a tetracarboxylic acid dihalide compound , A tetracarboxylic acid dialkyl ester compound or a tetracarboxylic acid dialkyl ester dihalide compound (all may be collectively referred to as a specific tetracarboxylic acid component) is preferably used.

(46)

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

(47)

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

Z ⁶ and Z ⁷ each independently represent a hydrogen atom or a methyl group.

Z ¹ in the formula [3] is a group represented by the formula [3a], the formula [3c], the formula [3d], the formula [3e] and the formula [3f] from the viewpoint of easiness of synthesis and ease of polymerization reactivity in the production of the polymer. ] Or the formula [3g]. More preferred are the formula [3a], the formula [3e], the formula [3f] or the formula [3g]. Especially preferred are the formula [3e], the formula [3f] or the formula [3g].

The use ratio of the specific tetracarboxylic acid component is preferably 1 mol% or more with respect to the total tetracarboxylic acid component. More preferred is 5 mol% or more. Particularly preferred is 10 mol% or more, and most preferably 15 to 90 mol% in view of optical characteristics in a liquid crystal display element.

When the specific tetracarboxylic acid component having the structure represented by the formula [3e], the formula [3f] or the formula [3g] is used, the amount of the tetracarboxylic acid component to be used is 20 mol% or more of the total tetracarboxylic acid component, A desired effect is obtained. More preferably, it is at least 30 mol%. Further, all of the specific tetracarboxylic acid component may be a tetracarboxylic acid component having a structure represented by the formula [3e], the formula [3f] or the formula [3g].

As long as the effect of the present invention is not impaired, other tetracarboxylic acid components other than the specific tetracarboxylic acid component may be used for the specific polyimide polymer.

Examples of other tetracarboxylic acid components include the following tetracarboxylic acid compounds, tetracarboxylic acid dianhydrides, dicarboxylic acid dihalide compounds, dicarboxylic acid dialkyl ester compounds and dialkyl ester dihalide compounds .

For example, pyromellitic acid, 2,3,6,7-naphthalenetetracarboxylic acid, 1,2,5,6-naphthalenetetracarboxylic acid, 1,4,5,8-naphthalenetetracarboxylic acid, 2,3,6,7-anthracene tetracarboxylic acid, 1,2,5,6-anthracene tetracarboxylic acid, 3,3 ', 4,4'-biphenyltetracarboxylic acid, 2,3,3 (3,4-dicarboxyphenyl) ether, 3,3 ', 4,4'-benzophenonetetracarboxylic acid, bis (3,4-dicarboxyphenyl) Bis (3,4-dicarboxyphenyl) propane, 1,1,1,3,3,3-hexafluoro-2,2 (3,4-dicarboxyphenyl) propane, bis (3,4-dicarboxyphenyl) dimethylsilane, bis (3,4-dicarboxyphenyl) diphenylsilane, 2,3,4,5- Carboxylic acid, 2,6-bis (3,4-dicarboxyphenyl) pyridine, 3,3 ', 4,4'-diphenylsulfone tetracarboxylic acid, 3,4,9,10- A carboxylic acid or 1,3-diphenyl-1,2,3,4-cyclobutanetetracar And the like.

The specific tetracarboxylic acid component and other tetracarboxylic acid component are preferably used in combination with other polyimide-based polymers such as solubility in a solvent of a specific polyimide-based polymer, vertical orientation of liquid crystal when used as a liquid crystal alignment film, , One kind or two or more kinds may be mixed and used.

The method for synthesizing the specific polyimide polymer in the present invention is not particularly limited. It is usually obtained by reacting a diamine component and a tetracarboxylic acid component. Generally, a method of reacting a tetracarboxylic acid component selected from the group consisting of a tetracarboxylic acid and a derivative thereof and a diamine component comprising one or more kinds of diamine compounds to obtain a polyamic acid . Specifically, there are a method of polycondensing a tetracarboxylic acid dianhydride and a primary or secondary diamine compound to obtain a polyamic acid, a method of dehydrating polycondensation reaction of a tetracarboxylic acid and a primary or secondary diamine compound, A method of obtaining an acid or a method of polycondensing a dicarboxylic acid dihalide and a primary or secondary diamine compound to obtain a polyamic acid is used.

To obtain the polyamide acid alkyl ester, polycondensation of a tetracarboxylic acid in which a carboxylic acid group is dialkyl esterified with a primary or secondary diamine compound, a method in which a carboxylic acid group is dialkyl esterified and a dicarboxylic acid dihalide And a primary or secondary diamine compound, or a method of converting a carboxyl group of a polyamic acid into an ester is used.

To obtain the polyimide, a method of converting the above polyamic acid or polyamide acid alkyl ester into a polyimide by ring closure is used.

The reaction of the diamine component and the tetracarboxylic acid component is usually carried out in a solvent. The solvent to be used at this time is not particularly limited as long as the resultant polyimide precursor dissolves. Specific examples of the solvent to be used in the reaction include, but are not limited to, the following examples.

For example, there may be mentioned N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone,? -Butyrolactone, N, N-dimethylformamide, 1,3-dimethyl-imidazolidinone, methyl ethyl ketone, 4-hydroxy-4-methyl-2-pentanone, or a solvent represented by the following formula [A3].

(48)

(A &lt; ³ &gt; represents an alkyl group having 1 to 4 carbon atoms)

When the solubility of the specific polyimide polymer in a solvent is high, cyclopentanone, cyclohexanone, a solvent represented by the following formula [A1] or formula [A2], and the like can be used.

(49)

(A ¹ represents an alkyl group having 1 to 3 carbon atoms, and A ² represents an alkyl group having 1 to 3 carbon atoms.)

These solvents may be used alone or in combination. The solvent may be a solvent that does not dissolve the polyimide precursor, or may be mixed with the solvent to the extent that the resulting polyimide precursor does not precipitate. In addition, the moisture in the solvent inhibits the polymerization reaction and further causes hydrolysis of the resulting polyimide precursor. Therefore, it is preferable that the solvent is dehydrated and dried.

When the diamine component and the tetracarboxylic acid component are reacted in a solvent, there is a method in which a solution in which a diamine component is dispersed or dissolved in a solvent is stirred and the tetracarboxylic acid component is added as it is or dispersed or dissolved in a solvent, A method of adding a diamine component to a solution in which a carboxylic acid component is dispersed or dissolved in a solvent, and a method of alternately adding a diamine component and a tetracarboxylic acid component. Any of these methods may be used.

When a plurality of the diamine component and the tetracarboxylic acid component are used in the reaction, they may be reacted in a preliminarily mixed state, or they may be sequentially reacted individually, or the low molecular weight compounds reacted individually may be mixed and reacted, . The polymerization temperature at that time may be any temperature within the range of -20 to 150 ° C, preferably -5 to 100 ° C. The reaction can be carried out at an arbitrary concentration, but if the concentration is too low, it becomes difficult to obtain a polymer having a high molecular weight. If the concentration is too high, the viscosity of the reaction liquid becomes too high, and uniform stirring becomes difficult. Therefore, the content is preferably 1 to 50% by mass, and more preferably 5 to 30% by mass. The reaction may be carried out at a high concentration in the initial stage, and then a solvent may be added.

In the polymerization reaction of the polyimide precursor, the ratio of the total molar number of the diamine component to the total molar number of the tetracarboxylic acid component is preferably 0.8 to 1.2. As in the case of a typical polycondensation reaction, the closer the molar ratio is to 1.0, the larger the molecular weight of the resulting polyimide precursor.

The polyimide in the present invention is a polyimide obtained by ring closure of the polyimide precursor. The closed rate (also referred to as the imidization rate) of the amidic acid group of the polyimide need not always be 100% As shown in FIG. Among them, in the present invention, from the viewpoint of the solubility in a solvent of the specific polyimide polymer and the optical characteristics of the liquid crystal display element, it is preferably 30 to 80%. More preferably, it is 40 to 70%. Particularly preferred is 40 to 60%.

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

The temperature at which the polyimide precursor is thermally imidized in a solution is preferably 100 to 400 ° C. More preferably, it is 120 to 250 ° C, and it is preferable to carry out water while removing water generated by the imidization reaction out of the system.

The catalyst imidation of the polyimide precursor can be carried out by adding a basic catalyst and an acid anhydride to the polyimide precursor solution and stirring at -20 to 250 ° C, preferably 0 to 180 ° C. The amount of the basic catalyst is 0.5 to 30 moles, preferably 2 to 20 moles, of the amide group, and the amount of the acid anhydride is 1 to 50 moles, preferably 3 to 30 moles, of the amide group.

Examples of the basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine, trioctylamine, and the like. Among them, pyridine is preferable since it has a suitable basicity for promoting the reaction.

Examples of the acid anhydride include acetic anhydride, trimellitic anhydride, and pyromellitic anhydride. Above all, use of acetic anhydride is preferable since purification after completion of the reaction becomes easy. The imidization rate by the catalyst imidization can be controlled by adjusting the catalyst amount, the reaction temperature, and the reaction time.

When the polyimide precursor or the polyimide is recovered from the polyimide precursor or polyimide reaction solution, the reaction solution may be put into a solvent and precipitated. Examples of the solvent used in the precipitation include methanol, ethanol, isopropyl alcohol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, toluene, benzene or water. The polymer precipitated by charging into the solvent can be recovered by filtration and then dried under normal pressure or reduced pressure at room temperature or by heating. In addition, when the polymer precipitated and recovered is redissolved in a solvent, and the operation of re-precipitation and recovery is repeated 2 to 10 times, impurities in the polymer can be reduced. As the solvent at this time, for example, alcohols, ketones, hydrocarbons and the like can be exemplified, and when three or more kinds of solvents selected from these solvents are used, the purification efficiency is further increased, which is preferable.

The molecular weight of the specific polyimide polymer is preferably from 5,000 to 500,000, more preferably from 5,000 to 500,000, in terms of weight average molecular weight measured by GPC (Gel Permeation Chromatography), in consideration of the strength of the vertical liquid crystal alignment film obtained therefrom, And more preferably 10,000 to 150,000.

In the present invention, the specific polyimide-based polymer is preferably a polyimide obtained by catalyzing the above-described polyimide precursor in view of the optical characteristics of the liquid crystal display element. The imidization rate at that time is preferably in the above-described range.

&Lt; Liquid crystal 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 coating solution containing a specific cellulose polymer based on component (A), a specific polyimide based polymer as component (B), and a solvent.

The ratio of the specific cellulose polymer to the specific polyimide polymer in the liquid crystal alignment treatment agent is preferably from 0.01 to 99 parts by mass when the proportion of the specific polyimide polymer is 1 part by mass. More preferred is 0.1 to 9 parts by mass. Particularly preferable is 0.1 to 3 parts by mass.

All the polymer components in the liquid crystal alignment treatment agent may be all of a specific cellulose polymer and a specific polyimide polymer, or may be mixed with other polymers. Examples of the other polymer include a polyimide polymer not containing a specific side chain structure. It is also possible to mix acrylic polymer, methacrylic polymer, novolac resin, polyhydroxystyrene, polyamide, polyester or polysiloxane.

At that time, the content of the other polymer is preferably 0.5 to 15 parts by mass with respect to 100 parts by mass of the total polymer containing the specific cellulose polymer and the specific polyimide polymer. More preferred is 1 to 10 parts by mass.

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

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

For example, there may be mentioned N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone,? -Butyrolactone, N, N-dimethylformamide, 1,3-dimethyl-imidazolidinone, methyl ethyl ketone, 4-hydroxy-4-methyl-2-pentanone or a solvent represented by the above formula [A3]. Among them, it is preferable to use N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone,? -Butyrolactone or a solvent represented by the above formula [A3].

When the solubility of the specific polyimide polymer in a solvent is high, it is preferable to use cyclopentanone, cyclohexanone, a solvent represented by the above formula [A1] or formula [A2] or the like.

It is preferable that the both solvents in the liquid crystal alignment treatment agent are 10 to 100% by mass of the total solvent contained in the liquid crystal alignment treatment agent. More preferably, it is 20 to 90% by mass. Particularly preferable is 30 to 80 mass%.

As long as the effect of the present invention is not impaired, a solvent (also referred to as a poor solvent) for improving the film property and surface smoothness of the vertical alignment film when the liquid crystal alignment treatment agent is applied can be used for the liquid crystal alignment treatment agent. Specific examples of the poor solvent are shown below, but the present invention is not limited to these examples.

Butanol, isobutyl alcohol, tert-butyl alcohol, 1-pentanol, 2-pentanol, 3-pentanol, 2-methyl-1-butanol, Butanol, neopentyl alcohol, 1-hexanol, 2-methyl-1-pentanol, 2-methyl- Butanol, 1-heptanol, 2-heptanol, 3-heptanol, 1-octanol, 2-octanol, 2-ethyl-1-hexanol, cyclohexanol, 1-methylcyclohexanol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,3-propanediol, Butanediol, 1,5-pentanediol, 2-methyl-2,4-pentanediol, 2-ethyl-1,3-hexanediol, dipropyl ether, dibutyl ether, dihexyl ether, dioxane, Ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, 1,2-butoxyethane, diethylene glycol dimethyl ether, Ethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dibutyl ether, 2-pentanone, 3-pentanone, 2-hexanone, 2-heptanone, 4- (2-ethylhexyl) acetate, ethylene glycol monoacetate, ethylene glycol diacetate, propylene carbonate, ethylene carbonate, 2- (methoxymethoxy) ethanol, ethylene glycol monobutyl Propylene glycol monobutyl ether, ethylene glycol monohexyl ether, ethylene glycol monohexyl ether, 2- (hexyloxy) ethanol, furfuryl alcohol, diethylene glycol, propylene glycol, propylene glycol monobutyl ether, 1- , Propylene glycol monomethyl ether acetate, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, tripropylene glycol mono Ethylene glycol monoacetate, ethylene glycol monoethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monoacetate, ethylene glycol diacetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, Diethyleneglycol monomethyl ether, triethyleneglycol monoethyl ether, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, acetic acid n (2-ethoxyethoxy) ethyl acetate, diethylene glycol acetate, triethylene glycol, triethylene glycol monomethyl ether, Propylene glycol monoethyl ether, propyleneglycol monoethyl ether, propyleneglycol monoethyl ether, propyleneglycol monoethyl ether, propyleneglycol monoethyl ether, butylpropyleneglycol monoethylether acetate, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, Propyl 3-methoxypropionate, 3-methoxypropyl Butyl lactate, sodium lactate, or a solvent represented by the above formulas [A1] to [A3], and the like can be given as examples of the lactic acid esters, such as methyl lactate, butyl lactate, methyl lactate, ethyl lactate, n-propyl lactate, Among them, 1-hexanol, cyclohexanol, 1,2-ethanediol, 1,2-propanediol, propylene glycol monobutyl ether, ethylene glycol monobutyl ether, dipropylene glycol dimethyl ether, A solvent represented by the formula [A3] or the like is preferably used.

These poor solvents are preferably 1 to 70% by mass of the total solvent contained in the liquid crystal alignment treatment agent. More preferably, it is 1 to 60% by mass. Especially preferred is 5 to 60 mass%.

The liquid crystal alignment treatment agent of the present invention may contain a compound having at least one group selected from the group consisting of groups represented by the following formulas [B1] to [B8] for the purpose of enhancing adhesion between the liquid crystal layer and the liquid crystal alignment layer (Also referred to as an adhesive compound).

The groups represented by the formulas [B1] to [B8] preferably have two or more groups in the compound.

(50)

(Wherein B ¹ represents a hydrogen atom or a benzene ring, B ² represents at least one cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring and a heterocyclic ring, B ³ represents an alkyl group having 1 to 18 carbon atoms, A fluorine-containing alkyl group having 1 to 18 carbon atoms, and an alkoxyl group having 1 to 18 carbon atoms.)

As a more specific adhesive compound, it is preferable to use a compound represented by the following formula [6].

(51)

In the formula [6], M ¹ represents at least one structure selected from the group consisting of the structures represented by the following formulas [a-1] to [a-7]. Among them, the structure represented by the formula [a-1], the formula [a-2], the formula [a-3], the formula [a- 5] or the formula [a- 6] . More preferably, it is a structure represented by the formula [a-1], the formula [a-3], the formula [a-5] or the formula [a-6].

(52)

A ¹ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. Among them, a hydrogen atom or an alkyl group having 1 to 2 carbon atoms is preferable from the viewpoint of ease of production of the adhesive compound. More preferred is a hydrogen atom or a methyl group.

A ² represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. Among them, a hydrogen atom or an alkyl group having 1 to 2 carbon atoms is preferable from the viewpoint of ease of production of the adhesive compound. More preferred is a hydrogen atom or a methyl group.

A ³ , A ⁵ , A ⁶ and A ⁹ each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. Among them, a hydrogen atom or an alkyl group having 1 to 2 carbon atoms is preferable from the viewpoint of ease of production of the adhesive compound. More preferred is a hydrogen atom or a methyl group.

A ⁴ , A ⁷ and A ⁸ each independently represent an alkylene group having 1 to 3 carbon atoms. Among them, an alkylene group having 1 to 2 carbon atoms is preferable in view of ease of production of the adhesive compound.

In formula [6], M ² represents a single bond, -CH ₂ -, -O-, -NH-, -N (CH ₃ ) -, -CONH-, -NHCO-, -CH ₂ O-, -OCH ₂ -, -COO-, -OCO-, -CON (CH ₃ ) - and -N (CH ₃ ) CO-. Among them, from the viewpoint of easiness of synthesis of the adhesive compound, a single bond, -CH ₂ -, -O-, -NH-, -CONH-, -NHCO-, -CH ₂ O-, -OCH ₂ -, -COO -, -OCO-, -CON (CH ₃ ) - or -N (CH ₃ ) CO-. More 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 formula [6], M ³ represents an alkylene group having 1 to 20 carbon atoms, - (CH ₂ -CH ₂ -O) _p - (p represents an integer of 1 to 10), - (CH ₂ -O-) _q - (q represents an integer of 1 to 10), and an organic group having a benzene ring or cyclohexane ring of 6 to 20 carbon atoms. Any of the -CH ₂ - groups of the alkylene group may be replaced by -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- and hydrogen atoms bonded to arbitrary carbon atoms May be substituted with a hydroxyl group (OH group), a carboxyl group (COOH group) or a halogen atom. Among them, an alkylene group having 1 to 20 carbon atoms, - (CH ₂ -CH ₂ -O) _p - (p represents an integer of 1 to 10), - (CH ₂ - O-) _q - (q represents an integer of 1 to 10), or a structure represented by the following formulas [c-1] to [c-5]. More preferably, the alkylene group having 1 to 15 carbon atoms, - (CH ₂ -CH ₂ -O) _p - (p represents an integer of 1 to 10), - (CH ₂ -O-) _q - C-4] or the formula [c-5] shown below. [C-1] Particularly preferred are alkylene groups of 1 to 15 carbon atoms, - (CH ₂ -CH ₂ -O) _p - (p represents an integer of 1 to 10), formula [c-1] Is a structure represented by the formula [c-5].

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

In the formula [6], M ⁵ represents a structure of at least one member selected from the group consisting of structures represented by the formula [B1] ~ [B8]. Among them, the structure represented by the formula [B1], the formula [B2] or the formula [B6] is preferable from the viewpoint of easiness of synthesis of the adhesive compound. More preferred is a structure represented by the formula [B1] or the formula [B2].

In the formula [6], n represents an integer of 1 to 3. Among them, 1 or 2 is preferable from the viewpoint of easiness of synthesis of the adhesive compound. More preferred is 1.

In the formula [6], m represents an integer of 1 to 3. Among them, 1 or 2 is preferable from the viewpoint of easiness of synthesis of the adhesive compound.

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

(54)

(n represents an integer of 1 to 10, and m represents an integer of 1 to 10.)

Examples of the adhesive compound further include the following compounds.

(Meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, tri (meth) acryloyloxyethoxy trimethylol propane or glycerin (Meth) acrylate, polyglycidyl ether poly (meth) acrylate, and other compounds having three polymerizable unsaturated groups such as ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate and tetraethylene glycol di Acrylate, propylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, neopentyl glycol di (meth) Acrylate, ethylene oxide bisphenol A type di (meth) acrylate, propylene oxide bisphenol type di (meth) acrylate, 1,6-hexanediol di (Meth) acrylate, glycerin di (meth) acrylate, pentaerythritol di (meth) acrylate, ethylene glycol diglycidyl ether di (meth) acrylate, diethylene glycol diglycidyl ether di A compound having two polymerizable unsaturated groups in the molecule, such as phthalic acid diglycidyl ester di (meth) acrylate or hydroxypivalic acid neopentyl glycol di (meth) acrylate, in addition to 2-hydroxyethyl (Meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2- 2-hydroxypropyl phthalate, 3-chloro-2-hydroxypropyl (meth) acrylate, glycerin mono (meth) acrylate, 2- (meth) acryloyloxyethyl phosphate or N-methylol Met) arc Polymerizable unsaturated group of the amides and the like can be mentioned compounds having one molecule.

The content of the adhesive compound in the liquid crystal alignment treatment agent is preferably 0.1 to 150 parts by mass with respect to 100 parts by mass of all the polymer components. More preferable is 0.1 to 100 parts by mass with respect to 100 parts by mass of all the polymer components in that the crosslinking reaction proceeds to exhibit the intended effect. Particularly preferable is 1 to 50 parts by mass.

The adhesive compound may be used alone or in combination of two or more thereof, depending on the properties such as the vertical alignment of the liquid crystal when the liquid crystal alignment film is formed as a vertical liquid crystal alignment film, and further, the optical characteristics of the liquid crystal display device.

The liquid crystal alignment treatment agent of the present invention may contain at least one generator (also referred to as a generator) selected from the group consisting of a photo-radical generator, a photo-acid generator and a photo-base generator for the purpose of enhancing adhesion between the liquid crystal layer and the liquid crystal alignment film ) Is preferably introduced.

The photo radical generator is not particularly limited as long as it generates radicals by ultraviolet rays. Butyl peroxy-iso-butyrate, 2,5-dimethyl-2,5-bis (benzoyldioxy) hexane, 1,4-bis [ (Propoxy) benzene, di-tert-butyl peroxide, 2,5-dimethyl-2,5-bis (tert- butyldioxy) hexene hydroperoxide, Tert-butyl hydroperoxide, 1,1-bis (tert-butyldioxy) -3,3,5-trimethylcyclohexane, butyl-4,4- Butyldioxy) valerate, cyclohexanone peroxide, 2,2 ', 5,5'-tetra (tert-butylperoxycarbonyl) benzophenone, 3,3', 4,4'- Peroxycarbonyl) benzophenone, 3,3 ', 4,4'-tetra (tert-amylperoxycarbonyl) benzophenone, 3,3', 4,4'-tetra (tert-hexylperoxycarbonyl ) Benzophenone, 3,3'-bis (tert-butylperoxycarbonyl) -4,4'-dicarboxybenzophenone, tert-butylperoxybenzoate or di- Organic peroxides such as benzoin methyl, benzoin ethyl, and terephthalate; quinones such as 9,10-anthraquinone, 1-chloro anthraquinone, 2-chloro anthraquinone, octamethylanthraquinone, Benzoin derivatives such as ether, alpha -methylbenzoin or alpha-phenylbenzoin, and the like.

The photoacid generator and photobase generator are not particularly limited as far as they generate an acid or a base by ultraviolet rays. For example, a triazine compound, an acetophenone derivative compound, a disulfone compound, a diazomethane compound, a sulfonic acid derivative compound, a diaryl iodonium salt, a triarylsulfonium salt, a triarylphosphonium salt or an iron arene complex have.

More specifically, there may be mentioned, for example, diphenyliodonium chloride, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium mesylate, diphenyliodonium tosylate, diphenyliodonium bromide, diphenyliodonium (P-tert-butylphenyl) iodonium hexafluorophosphate, diphenyliodonium hexafluoroantimonate, diphenyliodonium hexafluoroarsenate, bis (p- Phenylphenyl) iodonium mesylate, bis (p-tert-butylphenyl) iodonium tosylate, bis (p-tert- butylphenyl) iodonium trifluoromethanesulfonate, bis (P-chlorophenyl) iodonium chloride, bis (p-chlorophenyl) iodonium tetrafluoroborate, triphenylsulfonium chloride, tri Pe Tri (p-methoxyphenyl) sulfonium tetrafluoroborate, tri (p-methoxyphenyl) sulfonium hexafluorophosphate, tri (p-ethoxyphenyl) sulfonium tetrafluoroborate (P-methoxyphenyl) phosphonium tetrafluoroborate, tri (p-methoxyphenyl) phosphonium hexafluorophosphonate, tri (p-methoxyphenyl) phosphonium chloride, triphenylphosphonium chloride, triphenylphosphonium bromide, (2-nitrobenzyl) oxy] carbonylhexane-1,6-diamine], nitrobenzylcyclohexylcarbamate, di (methoxybenzyl) hexamethylene dicarbazole Mate, bis [[(2-nitrobenzyl) oxy] carbonylhexane-1,6-diamine], nitrobenzylcyclohexylcarbamate or di (methoxybenzyl) hexamethylene dicarbamate.

Above all, it is preferable to use a photo-radical generator in the generator of the present invention in that the adhesiveness between the liquid crystal layer and the liquid crystal alignment film can be efficiently increased.

The content of the generating agent in the liquid crystal alignment treatment agent is preferably 0.01 to 50 parts by mass with respect to 100 parts by mass of all the polymer components. More preferably, it is 0.01 to 30 parts by mass based on 100 parts by mass of all the polymer components in that the crosslinking reaction proceeds to exhibit the desired effect. Particularly preferable is 0.1 to 20 parts by mass.

The generating agent may be used alone or in combination of two or more thereof, depending on the properties such as the vertical alignment of the liquid crystal when used as the vertical liquid crystal alignment film, and furthermore, the optical characteristics of the liquid crystal display element.

The liquid crystal alignment treatment agent in the present invention may contain a compound having at least one substituent selected from the group consisting of a compound having an epoxy group, an isocyanate group, an oxetane group or a cyclocarbonate group, a hydroxyl group, a hydroxyalkyl group and a lower alkoxyalkyl group (Collectively referred to as a crosslinking compound) is preferably introduced. At this time, it is necessary to have two or more of these substituents in the crosslinkable compound.

Examples of the crosslinkable compound having an epoxy group or an isocyanate group include bisphenol acetone glycidyl ether, phenol novolak epoxy resin, cresol novolak epoxy resin, triglycidyl isocyanurate, tetraglycidylaminodiphenylene, (Aminoethyl) cyclohexane, tetraphenyl glycidyl ether ethane, triphenyl glycidyl ether ethane, bisphenol hexafluoroacetate di Glycidyl ether, 1,3-bis (1- (2,3-epoxypropoxy) -1-trifluoromethyl-2,2,2-trifluoromethyl) benzene, 4,4- 2- (4- (2,3-epoxypropoxy) phenyl) -2- (4-methylphenyl) Bis (4- (1- (4- (2,3-epoxypropoxy) phenyl) ethyl) phenyl) propane or 1,3- ) Phenyl) -1- (4- (1- (4- (2,3-epoxypropoxy) phenyl) -1-methylethyl) phenyl) ethyl) phenoxy) -2-propanol.

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

(55)

Specific examples thereof include crosslinkable compounds represented by the formulas [4a] to [4k] shown on pages 58 to 59 of International Publication WO2011 / 132751 (published on October 27, 2011).

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

(56)

Specifically, there can be mentioned the crosslinkable compounds represented by the formulas [5-1] to [5-42] listed on pages 76 to 82 of International Publication WO2012 / 014898 (published on Feb. 2, 2012).

Examples of the crosslinkable compound having at least one substituent selected from the group consisting of a hydroxyl group and an alkoxyl group include an amino resin having a hydroxyl group or an alkoxyl group such as a melamine resin, a urea resin, a guanamine resin, a glycol Urea-formaldehyde resin, succinylamide-formaldehyde resin or ethylene urea-formaldehyde resin. Specifically, a melamine derivative in which the hydrogen atom of the amino group is substituted with a methylol group and / or an alkoxymethyl group, a benzoguanamine derivative, glycoluril and the like can be used. The melamine derivative or the benzoguanamine derivative may be present as a dimer or trimer. These groups preferably have 3 to 6 on average of methylol groups or alkoxymethyl groups per one triazine ring.

Examples of such melamine derivatives or benzoguanamine derivatives include, for example, MX-750 in which a methoxymethyl group is substituted in an average of 3.7 methoxymethyl groups per one triazine ring of a commercially available product, methoxymethyl groups per one triazine ring are substituted on an average of 5.8 Methomethylated melamines such as MW-30 (manufactured by Sanwa Chemical Co.), Cymel 300, 301, 303, 350, 370, 771, 325, 327, 703 and 712, Cymel 235, 236, Methoxymethylated butoxymethylated melamines such as Cymel® 212, 253 and 254, butoxymethylated melamines such as Cymel 506 and 508, carboxyl-containing methoxymethylated isobutoxymethylated melamines such as Cymel 1141, methoxymethylated Ethoxymethylated benzoguanamine, methoxymethylated butoxymethylated benzoguanamine such as Cymel 1123-10, butoxymethylated benzoguanamine such as Cymel 1128, carboxyl group containing methoxymethyl such as Cymel 1125-80 (Manufactured by Mitsui Cyanamid Co., Ltd.); and the like. Examples of the glycoluril include butoxymethylated glycoluril such as Cymel 1170; methylol glycoluril such as Cymel 1172; methoxymethylolglycoluril such as Powderlink 1174; and the like.

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

More specifically, there can be mentioned the crosslinkable compounds represented by the formulas [6-1] to [6-48], which are listed on pages 62 to 66 of International Publication WO2011 / 132751 (published on October 27, 2011) .

The content of the crosslinkable compound in the liquid crystal alignment treatment agent is preferably 0.1 to 100 parts by mass with respect to 100 parts by mass of all the polymer components. More preferable is 0.1 to 50 parts by mass with respect to 100 parts by mass of all the polymer components in that the crosslinking reaction proceeds to exhibit the intended effect. Particularly preferable is 1 to 30 parts by mass.

The crosslinkable compound may be used alone or in combination of two or more thereof, depending on the properties such as the vertical alignment of the liquid crystal when used as a vertical liquid crystal alignment film, and furthermore, the optical characteristics of the liquid crystal display device.

In the present invention, as a compound promoting the charge transfer in the vertical liquid crystal alignment film and accelerating the charge leakage of the device, there is a compound represented by the formula (1) shown on page 69 to page 73 of International Publication WO2011 / 132751 M1] to [M156] may be added to the liquid crystal alignment treatment agent. The amine compound may be directly added to the liquid crystal alignment treatment agent, but it is preferable to add the amine compound in an appropriate solvent at a concentration of 0.1 to 10% by mass, preferably 1 to 7% by mass. The solvent is not particularly limited as long as it is a solvent for dissolving the above-mentioned specific cellulose polymer and specific polyimide polymer.

As long as the effect of the present invention is not impaired, a compound which improves the uniformity of the thickness of the vertical liquid crystal alignment film and the surface smoothness when the liquid crystal alignment treatment agent is applied can be used for the liquid crystal alignment treatment agent. Further, a compound improving the adhesion between the vertical liquid crystal alignment film and the substrate may be used.

Examples of the compound that improves the uniformity of the thickness of the vertical liquid crystal alignment film and the surface smoothness include a fluorine-based surfactant, a silicon-based surfactant, and a nonionic surface-active agent.

More specifically, for example, EF301, EF303 and EF352 (manufactured by TOKEM PRODUCTS CO., LTD.), Megafac F171, F173 and R-30 (manufactured by Dainippon Ink and Chemicals, Inc.), FLORAD FC430 and FC431 (Available from Asahi Glass Co., Ltd.), Asahi Guard AG710, Surfron S-382, SC101, SC102, SC103, SC104, SC105 and SC106 (manufactured by Asahi Glass Co., Ltd.).

The content of the surfactant in the liquid crystal alignment treatment agent is preferably 0.01 to 2 parts by mass based on 100 parts by mass of all the polymer components. More preferred is 0.01 to 1 part by mass.

Specific examples of the compound which improves the adhesion between the vertical liquid crystal alignment film and the substrate include the following functional silane-containing compounds and epoxy group-containing compounds.

For example, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N- (2-aminoethyl) -3 3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, N-ethoxy (2-aminoethyl) Aminopropyltriethoxysilane, N-trimethoxysilylpropyltriethoxysilane, N-trimethoxysilylpropyltriethoxysilane, N-trimethoxysilylpropyltriethoxysilane, N-trimethoxysilylpropyltriethoxysilane, Amine, 10-trimethoxysilyl-1,4,7-triazadecane, 10-triethoxysilyl-1,4,7-triazadecane, 9-trimethoxysilyl-3,6-diazanonyl Acetate, 9-triethoxysilyl-3,6-diazanonyl acetate, N-benzyl-3-aminopropyltrimethoxysilane, N-benzyl-3-aminopropyltriethoxysilane, N- Bis (oxyethylene) -3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N- Aminopropyltriethoxysilane, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neo Pentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5,6 Tetraglycidyl-2,4-hexanediol, N, N, N ', N', -tetraglycidyl-m-xylylenediamine, 1,3-bis (N, N-diglycidylamino Methyl) cyclohexane or N, N, N ', N', -tetraglycidyl-4,4'-diaminodiphenylmethane and the like.

It is also preferable that the adhesion of the liquid crystal alignment treatment agent to these substrates is improved and the content of the compound is 0.1 to 30 parts by mass based on 100 parts by mass of all the polymer components. More preferred is 1 to 20 parts by mass. If the amount is less than 0.1 part by mass, the effect of improving the adhesion can not be expected. If the amount is more than 30 parts by mass, the storage stability of the liquid crystal alignment treatment agent may be deteriorated.

As long as the effect of the present invention is not impaired in addition to the above-mentioned compounds other than the above-mentioned compounds, the liquid crystal alignment treatment agent of the present invention may be added with a dielectric substance or a conductive substance for the purpose of changing electric properties such as dielectric constant and conductivity of the vertical liquid crystal alignment film You can.

&Lt; Liquid crystal composition &

The liquid crystal composition in the present invention is a liquid crystal composition containing at least a polymerizable compound which undergoes polymerization reaction by liquid crystal and ultraviolet rays.

For the liquid crystal, nematic liquid crystal, smectic liquid crystal or cholesteric liquid crystal can be used. Among them, it is preferable to have a negative dielectric anisotropy. In view 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. Two or more kinds of liquid crystals can be mixed and used depending on the respective physical properties of phase transition temperature, dielectric anisotropy and refractive index anisotropy.

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

The liquid crystal display element may also be a guest host type element by dissolving a dichroic dye in the liquid crystal composition. In this case, a device which is transparent when voltage is not applied and which absorbs (scattering) when voltage is applied is obtained. In this liquid crystal display element, the direction (alignment direction) of the director of the liquid crystal is changed by 90 degrees depending on the presence or absence of voltage application. Therefore, this liquid crystal display element can obtain a high contrast as compared with the conventional guest host type device which performs switching in the random orientation and the vertical orientation by utilizing the difference in the light absorbing characteristics of the dichroic dye. In the guest host type device in which the dichroic dye is dissolved, the liquid crystal becomes colored when aligned in the horizontal direction, and becomes opaque only in the scattered state. Therefore, it is possible to obtain a device which is switched from a colorless transparent state to a colorless opaque state or a colored transparent state when no voltage is applied by applying a voltage.

The polymerizable compound may be any one capable of forming a cured product (for example, a polymer network) of a liquid crystal composition by polymerization reaction with ultraviolet rays. At this time, the monomer of the 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 that undergoes polymerization reaction by ultraviolet rays. More preferably, from the viewpoint of the handling of the liquid crystal composition, that is, the suppression of the high viscosity of the liquid crystal composition and the solubility in liquid crystals, the monomer is introduced into the liquid crystal composition and the polymerization reaction is conducted by irradiation of ultraviolet rays A method of forming a cured product is preferable.

The polymerizable compound may be any compound as long as it is dissolved in a liquid crystal. However, when the polymerizable compound is dissolved in the liquid crystal, it is necessary that a temperature at which a part or the whole of the liquid crystal composition exhibits a liquid crystal phase exists. Even if a part of the liquid crystal composition shows a liquid crystal phase, the liquid crystal display element can be confirmed by mass spectroscopy as long as substantially uniform transparency and scattering characteristics can be obtained in the entire device.

The polymerizable compound may be any compound that causes polymerization reaction by ultraviolet rays, and at that time, the polymerization may proceed in any reaction type to form a cured product (cured composite) of the liquid crystal composition. Specific examples of the reaction include radical polymerization, cation polymerization, anionic polymerization, or a polymerization reaction.

Among them, the reaction type of the polymerizable compound is preferably a radical polymerization. At this time, as the polymerizable compound, the following radical type polymerizable compound (monomer) and its oligomer can be used. As described above, polymers obtained by polymerizing these monomers may also be used.

Examples of the monofunctional polymerizable compound include monofunctional compounds such as 2-ethylhexyl acrylate, butyl ethyl acrylate, butoxy ethyl acrylate, 2-cyano ethyl acrylate, benzyl acrylate, cyclohexyl acrylate, Acrylate, N, N-dimethylaminoethyl acrylate, dicyclopentanyl acrylate, dicyclopentenyl acrylate, N, N-dimethylaminoethyl acrylate, Acrylate, phenoxyethyleneglycol acrylate, 2-ethylhexyl acrylate, 2-ethylhexyl acrylate, 2-ethylhexyl acrylate, 2-ethylhexyl acrylate, 2-ethylhexyl acrylate, glycidyl acrylate, tetrahydrofurfuryl acrylate, isobornyl acrylate, isodecyl acrylate, lauryl acrylate, , 2,2-trifluoroethyl acrylate, 2,2,3,3,3-pentafluoropropyl acrylate, 2,2,3,3-tetrafluoropropyl 2-ethylhexyl methacrylate, butyl ethyl methacrylate, butoxy ethyl methacrylate, 2-cyanoethyl methacrylate, 2-ethylhexyl methacrylate, Hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2-ethoxyethyl acrylate, N, N-diethylaminoethyl methacrylate, N , N-dimethylaminoethyl methacrylate, dicyclopentanyl methacrylate, dicyclopentenyl methacrylate, glycidyl methacrylate, tetrahydrofurfuryl methacrylate, isobornyl methacrylate, isodecyl methacrylate Acrylate, methacrylate, acrylate, methacrylate, acrylate, methacrylate, acrylate, methacrylate, 3-Te La fluoro may be a methacrylate or the like of 2,2,3,4,4,4- hexafluoro-butyl methacrylate monomer and a oligomer thereof.

Examples of the bifunctional polymerizable compound include 4,4'-diacryloyloxystilbene, 4,4'-diacryloyloxydimethylstilbene, 4,4'-diacryloyloxydiethyl Styrene, 4,4'-diacryloyloxydipropylstyrene benzene, 4,4'-diacryloyloxydibutylstyrene benzene, 4,4'-diacryloyloxy dipentylstyrene benzene, 4,4'- Diacryloyloxydihexyl stilbene, 4,4'-diacryloyloxydifluorostilbene, 2,2,3,3,4,4-hexafluoropentanediol-1,5-diacrylate , 1,1,2,2,3,3-hexafluoropropyl-1,3-diacrylate, diethylene glycol dimethacrylate, 1,4-butanediol dimethacrylate, 1,3-butylene Hexanediol dimethacrylate, neopentyl glycol dimethacrylate, tetraethylene glycol dimethacrylate, 4,4'-biphenyl diacrylate, diethylstilbestroldiacrylate, 1,6-hexanediol dimethacrylate, 1,4-bisacryloyloxybenzene, 4,4'-bis Acryloyloxydiphenyl ether, 4,4'-bisacryloyloxydiphenylmethane, 3,9- [1,1-dimethyl-2-acryloyloxyethyl] -2,4,8,10-tetraspiro [5,5] undecane, α, α'-bis [4-acryloyloxyphenyl] -1,4-diisopropylbenzene, 1,4-bisacryloyloxytetrafluorobenzene, '-Bis acryloyloxyoctafluorobiphenyl, diethylene glycol acrylate, 1,4-butanediol diacrylate, 1,3-butylene glycol diacrylate, dicyclopentanyl diacrylate, glycerol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, tetraethylene glycol diacrylate, 1,9-nonanediol diacrylate, polyethylene glycol diacrylate, polypropylene glycol diacrylate, 1,9 - nonadiolydimethacrylate, polyethylene glycol dimethacrylate or polypropylene glycol dimethacrylate Acrylates, oligomers thereof, and the like.

Examples of the multifunctional polymerizable compound include trimethylolpropane triacrylate, pentaerythritol tetraacrylate, pentaerythritol triacrylate, ditrimethylolpropane tetraacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexaacrylate, Trimethylolpropane trimethacrylate, pentaerythritol tetramethacrylate, pentaerythritol tetramethacrylate, ditrimethylolpropane tetramethacrylate, dipentaerythritol hexamethacrylate, dipentaerythritol pentaacrylate, , Dipentaerythritol monohydroxypentamethacrylate or 2,2,3,3,4,4-hexafluoropentanediol-1,5-dimethacrylate, and oligomers thereof, and the like.

These radical type polymerizable compounds may be used alone or in combination of two or more thereof depending on the optical characteristics of the liquid crystal display element and the adhesiveness between the liquid crystal layer and the vertical liquid crystal alignment film.

In the liquid crystal composition, it is preferable to introduce a radical initiator (also referred to as a polymerization initiator) which generates a radical by ultraviolet rays for the purpose of promoting radical polymerization of the polymerizable compound.

Specific examples thereof include tert-butylperoxy-iso-butyrate, 2,5-dimethyl-2,5-bis (benzoyldioxy) hexane, 1,4-bis [ Propyloxy) -iso-propoxy] benzene, di-tert-butyl peroxide, 2,5-dimethyl-2,5-bis (tert- butyldioxy) hexene hydroperoxide, propyl hydroperoxide, 2,5-dimethylhexane, tert-butyl hydroperoxide, 1,1-bis (tert-butyldioxy) -3,3,5-trimethylcyclohexane, butyl- (Tert-butyldioxy) valerate, cyclohexanone peroxide, 2,2 ', 5,5'-tetra (tert-butylperoxycarbonyl) benzophenone, 3,3', 4,4'-tetra (tert-butylperoxycarbonyl) benzophenone, 3,3 ', 4,4'-tetra (tert-amylperoxycarbonyl) benzophenone, 3,3', 4,4'- Butylperoxycarbonyl) -4,4'-dicarboxybenzophenone, tert-butylperoxybenzoate or di-tert-butylperoxycarbonyl) benzophenone, 3,3'-bis (tert- Organic peroxides such as dipentaerythritol, dipentaerythritol triacetate, and dipiperoxyisophthalate; quinones such as 9,10-anthraquinone, 1-chloro anthraquinone, 2-chloro anthraquinone, octamethylanthraquinone, and 1,2-benzanthraquinone; Benzoin derivatives such as ethyl ether,? -Methylbenzoin or? -Phenylbenzoin, and the like.

These radical initiators may be used alone or in combination of two or more, depending on the optical characteristics of the liquid crystal display element and the adhesiveness between the liquid crystal layer and the vertical liquid crystal alignment film.

As the polymerizable compound, the following ionic polymerizable compound may be used. Specifically, it is a compound having at least one crosslinking group selected from the group consisting of a hydroxyl group, a hydroxyalkyl group and a lower alkoxyalkyl group.

More specifically, a melamine derivative in which the hydrogen atom of the amino group is substituted with a methylol group, an alkoxymethyl group, or both, a benzoguanamine derivative, or glycoluril. These melamine derivatives and benzoguanamine derivatives may be oligomers. It is preferable that they have an average of 3 or more and 6 or fewer methylol groups or alkoxymethyl groups per one triazine ring.

Specific examples of such melamine derivatives and benzoguanamine derivatives include, for example, MX-750 in which an average of 3.7 methoxymethyl groups is substituted per one triazine ring of a commercial product; an average of methoxymethyl groups per one triazine ring is 5.8 Methionine methylated melamins such as MW-30 (manufactured by Sanwa Chemical Co., Ltd.), CYMEL 300, 301, 303, 350, 370, 771, 325, 327, 703 and 712, CYMEL 235, 236 and 238 , 212, 253 and 254, methoxymethylated butoxymethylated melamines such as Cymel 506 and 508, carboxy-containing methoxymethylated isobutoxymethylated melamines such as Cymel 1141, Ethoxymethylated ethoxymethylated benzoguanamine, methoxymethylated butoxymethylated benzoguanamine such as Cymel 1123-10, butoxymethylated benzoguanamine such as Cymel 1128, carboxyl such as Cymel 1125-80 There may be mentioned; in the methoxy-methylation ethoxy methylated benzoguanamine (above, Mitsui Cytec keusa Ltd.). Examples of glycoluril include butoxymethylated glycoluril such as Cymel 1170 and methylol glycoluryl such as Cymel 1172. [

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

As the ionic polymerizable compound, a compound containing an epoxy group or an isocyanate group and having a crosslinking group may be used.

Specific examples thereof include bisphenol acetone glycidyl ether, phenol novolak epoxy resin, cresol novolac epoxy resin, triglycidyl isocyanurate, tetraglycidyl aminodiphenylene, tetraglycidyl-m (Aminoethyl) cyclohexane, tetraphenyl glycidyl ether ethane, triphenyl glycidyl ether ethane, bisphenol hexafluoroacetated diglycidyl ether, 1 , 3-bis (1- (2,3-epoxypropoxy) -1-trifluoromethyl-2,2,2-trifluoromethyl) benzene, 4,4- 2- (4- (2,3-epoxypropoxy) phenyl) -2- (4- (1,1,1) -tetrahydroxyphenyl) Bis (4- (1- (4- (2,3-epoxypropoxy) phenyl) ethyl) phenyl) propane, 1,3- (4- (1- (4- (2,3-epoxypropoxyphenyl) -1-methylethyl) phenyl) Phenoxy) -2-propanol, and the like.

When an ionic polymerizable compound is used, an ionic initiator that generates an acid or a base by ultraviolet rays may be introduced for the purpose of promoting the polymerization reaction. Specifically, a triazine-based compound, an acetophenone derivative compound, a disulfone-based compound, a diazomethane-based compound, a sulfonic acid derivative compound, a diaryliodonium salt, a triarylsulfonium salt, a triarylphosphonium salt or an iron arene complex can be used have. More specifically, there may be mentioned, for example, diphenyliodonium chloride, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium mesylate, diphenyliodonium tosylate, diphenyliodonium bromide, diphenyliodonium (P-tert-butylphenyl) iodonium hexafluorophosphate, diphenyliodonium hexafluoroantimonate, diphenyliodonium hexafluoroarsenate, bis (p- Phenylphenyl) iodonium mesylate, bis (p-tert-butylphenyl) iodonium tosylate, bis (p-tert- butylphenyl) iodonium trifluoromethanesulfonate, bis (P-chlorophenyl) iodonium chloride, bis (p-chlorophenyl) iodonium tetrafluoroborate, triphenylsulfonium chloride, tri Pe Tri (p-methoxyphenyl) sulfonium tetrafluoroborate, tri (p-methoxyphenyl) sulfonium hexafluorophosphate, tri (p-ethoxyphenyl) sulfonium tetrafluoroborate (P-methoxyphenyl) phosphonium tetrafluoroborate, tri (p-methoxyphenyl) phosphonium hexafluorophosphonate, tri (p-methoxyphenyl) phosphonium chloride, triphenylphosphonium chloride, triphenylphosphonium bromide, (2-nitrobenzyl) oxy] carbonylhexane-1,6-diamine], nitrobenzylcyclohexylcarbamate, di (methoxybenzyl) hexamethylene dicarbazole Mate, bis [[(2-nitrobenzyl) oxy] carbonylhexane-1,6-diamine], nitrobenzylcyclohexylcarbamate or di (methoxybenzyl) hexamethylene dicarbamate.

In the present invention, as the polymerizable compound, it is preferable to use a radical type polymerizable compound in view of the optical characteristics of the liquid crystal display element.

The amount of the polymerizable compound to be introduced into the liquid crystal composition is not particularly limited. However, when the amount of the polymerizable compound introduced is large, the polymerizable compound does not dissolve in the liquid crystal, the liquid crystal composition shows no liquid crystal phase, And the change of the scattering state becomes small, so that the optical characteristics are deteriorated. When the introduction amount of the polymerizable compound is small, the curability of the liquid crystal layer is lowered, and further, the adhesion between the liquid crystal layer and the liquid crystal alignment film is lowered, and the alignment property of the liquid crystal is liable to be disturbed against mechanical external pressure. Therefore, the introduction amount of the polymerizable compound is preferably 1 to 50 parts by mass with respect to 100 parts by mass of the liquid crystal. And more preferably 5 to 40 parts by mass. Especially preferred is 11 to 30 parts by mass.

The amount of the radical initiator or ionic initiator that promotes the reaction of the polymerizable compound is not particularly limited, but it is preferably 0.01 to 10 parts by mass based on 100 parts by mass of the liquid crystal. More preferred is 0.05 to 5 parts by mass. Particularly preferable is 0.05 to 3 parts by mass.

&Lt; Vertical Liquid Crystal Orientation Film and Manufacturing Method of Liquid Crystal Display Element &gt;

The substrate used for the liquid crystal display element is not particularly limited as long as it is a substrate having high transparency. In addition to the glass substrate, a plastic substrate such as an acrylic substrate, a polycarbonate substrate, a PET (polyethylene terephthalate) substrate and the like can be used . When a liquid crystal display element is used as a reverse type element and used as a flashlight or the like, a plastic substrate or a film is preferable. From the viewpoint of simplifying 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) Do. In the case of a reflection type reverse-type device, a substrate on which a metal such as a silicon wafer or aluminum or a dielectric multilayer film is formed can be used as long as it is a substrate on one side.

In the liquid crystal display element of the present invention, at least one of the substrates has a vertical liquid crystal alignment film for vertically aligning the liquid crystal molecules. This vertical liquid crystal alignment film can be obtained by coating and firing a liquid crystal alignment treatment agent on a substrate, followed by orientation treatment by rubbing treatment, light irradiation, or the like. However, in the present invention, these alignment treatments can be used as a vertical liquid crystal alignment film.

There are no particular restrictions on the method of applying the liquid crystal alignment treatment agent, and examples thereof include screen printing, offset printing, flexographic printing, inkjet method, dip method, roll coater method, slit coater method, spinner method, It can be appropriately selected depending on the type of substrate and the intended thickness of the vertical liquid crystal alignment film.

After the liquid crystal alignment treatment agent is applied onto the substrate, the liquid crystal alignment treatment agent is applied by a heating means such as a hot plate, a heat circulation type oven or an IR (infrared) type oven to 30 to 300 The solvent may be evaporated at a temperature of 30 to 250 ° C, preferably 30 to 250 ° C, to form a vertical liquid crystal alignment film. Particularly, when a plastic substrate is used for the substrate, it is preferable to perform the treatment at a temperature of 30 to 150 캜.

When the thickness of the vertical liquid crystal alignment layer after firing is too large, the power consumption of the liquid crystal display element is disadvantageously deteriorated. When the thickness is too thin, the reliability of the device may deteriorate. More preferably 10 to 300 nm, and particularly preferably 10 to 250 nm.

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

The method of injecting the liquid crystal composition is not particularly limited, and for example, the following method can be used. That is, when a glass substrate is used as a substrate, a pair of substrates on which a vertical liquid crystal alignment film is formed are prepared, and four portions of the substrate on one side are coated with a sealant except for a part, So that the substrate on the other side is bonded to produce an empty cell. A method of injecting the liquid crystal composition under reduced pressure from a place not coated with a sealant to obtain a liquid crystal composition injection cell. When a plastic substrate or a film is used as a substrate, a pair of substrates on which a vertical liquid crystal alignment film is formed are prepared, a liquid crystal composition is dropped onto one of the substrates by an ODF (One Drop Filling) method or an inkjet method, And thereafter, the substrate on the other side is bonded to obtain a liquid crystal composition injection cell.

Since the liquid crystal display element of the present invention has high adhesion between the liquid crystal layer and the vertical liquid crystal alignment film, it is not necessary to apply a sealant to the four sides of the substrate.

The gap of the liquid crystal display element can be controlled by the above-described spacer or the like. The method includes a method of introducing a spacer of a desired size into the liquid crystal composition as described above, a method of using a substrate having a column spacer of a desired size, and the like. Further, in the case where the plastic or film substrate is used for the substrate and the substrate is laminated by lamination, the gap can be controlled without introducing the spacer.

The size of the gap of the liquid crystal display element is preferably 1 to 100 mu m. More preferred is 2 to 50 占 퐉. And particularly preferably from 5 to 20 mu m. When the gap is too small, the contrast of the liquid crystal display element is deteriorated. When the gap is too large, the driving voltage of the liquid crystal display element is high.

The liquid crystal display element of the present invention is obtained by curing a liquid crystal composition in a state in which a part or the whole of the liquid crystal composition exhibits liquid crystallinity and forming a cured product complex of a liquid crystal and a polymerizable compound. The curing of the liquid crystal composition is carried out by the treatment of at least one of irradiation of ultraviolet rays and heating to the liquid crystal composition injection cell.

Examples of the light source of the ultraviolet irradiation device used at this time include a metal halide lamp or a high-pressure mercury lamp. The wavelength of ultraviolet rays is preferably 250 to 400 nm. More preferred is 310 to 370 nm. In the case of heat treatment, the temperature is preferably 40 to 120 ° C. More preferred is 60 to 80 占 폚. The ultraviolet ray treatment and the heat treatment may be carried out simultaneously, or the ultraviolet ray treatment may be performed before the heat treatment. In the present invention, the curing of the liquid crystal composition is preferably performed only by ultraviolet ray treatment.

As described above, in a liquid crystal display device using a vertical liquid crystal alignment film obtained from a liquid crystal alignment treatment agent containing a specific cellulose polymer and a specific polyimide polymer, adhesion between the liquid crystal layer and the liquid crystal alignment film is high, and further, It becomes a liquid crystal display element having a high and good optical characteristic, that is, transparency when voltage is not applied and scattering property upon voltage application. Particularly, the device can be suitably used for a reverse type device which is in the transmissive state when the voltage is not applied and is in the scattering state when the voltage is applied. The liquid crystal display for display purposes, It is useful as a dimmer window or an optical shutter element to be controlled. As the substrate at this time, it is preferable to use a plastic substrate or a film.

The liquid crystal display element of the present invention may be applied to a liquid crystal display element used for transportation equipment and transportation equipment such as an automobile, a railroad, an airplane and the like, specifically, a dimmer window for controlling the transmission and blocking of light, And the like. Particularly, since this device is excellent in transparency when voltage is not applied and scattering property at the time of voltage application, when used for a window glass of a vehicle, compared to the case of using a conventional reverse type device, And the effect of preventing glare from external light is also enhanced. Therefore, it is possible to further improve the safety when the vehicle is operated and the comfort during riding. When the device is used as a film and attached to a glass window of a vehicle, defects or deterioration, which is a factor of low adhesion between the liquid crystal layer and the vertical liquid crystal alignment film, hardly occurs, and reliability is higher than that of the conventional reverse type device.

Further, the liquid crystal display element of the present invention can be used for a light guide plate of a display device such as an LCD (Liquid Crystal Display) or OLED (Organic Light-Emitting Diode) display, or a transparent display using these displays. Specifically, when the transparent display and the present device are combined to perform screen display on the transparent display, the incoming light from the back surface can be suppressed by the present device. At this time, when the screen is displayed on the transparent display, the device becomes a scattered state by applying a voltage, and the screen display can be clarified. After the screen display is finished, the voltage becomes transparent without any change.

Example

Hereinafter, the present invention will be described in further detail with reference to examples, but the present invention is not limited to these examples. The abbreviations of the compounds used in Synthesis Examples, Examples and Comparative Examples are as follows.

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

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

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

(57)

(Specific cellulosic polymer)

CE-1: Hydroxyethyl cellulose (Wako)

CE-2: Hydroxypropyl methylcellulose phthalate (ACROS)

(Specific side chain type diamine compound)

A1 Synthesis of 1,3-diamino-4- [4- (trans-4-n-heptylcyclohexyl) phenoxy]

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

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

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

A5: 1,3-Diamino-4-octadecyloxybenzene (represented by the following formula [A5]):

(58)

[Chemical Formula 59]

(60)

(Second diamine compound)

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

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

(61)

(Other diamine compound)

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

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

(62)

(Tetracarboxylic acid component)

D1: 1,2,3,4-Cyclobutane tetracarboxylic acid dianhydride (the following formula [D1])

D2: bicyclo [3,3,0] octane-2,4,6,8-tetracarboxylic acid dianhydride (the following formula [D2])

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

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

(63)

(Generator)

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

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

&Lt; EMI ID =

(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]

(65)

(Crosslinkable compound)

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

(66)

(menstruum)

NMP: N-methyl-2-pyrrolidone

NEP: N-ethyl-2-pyrrolidone

? -BL:? -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

&Quot; Molecular weight measurement of polyimide polymer &quot;

The molecular weights of the polyimide precursor and polyimide were measured using a room temperature gel permeation chromatography (GPC) apparatus (GPC-101) (manufactured by Showa Denko K.K.), a column (KD-803, KD-805) , And measurement was carried out as follows.

Column temperature: 50 ° C

30 mmol / L of lithium bromide-hydrate (LiBr.H ₂ O), 30 mmol / L of phosphoric acid-anhydrous crystal (o-phosphoric acid) as the additive, N, N'-dimethylformamide Furan (THF) of 10 ml / l)

Flow rate: 1.0 ml / min

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

&Quot; Measurement of imidization rate of polyimide &quot;

(DMSO-d6, 0.05 mass% TMS (tetramethylsilane) mixture) of polyimide powder was placed in an NMR (nuclear magnetic resonance) sample tube (NMR sampling tube standard, Product) (0.53 ml) was added, and completely dissolved by ultrasonic wave. This solution was measured for proton NMR at 500 MHz with an NMR measuring instrument (JNW-ECA500) (manufactured by Nippon Denshoku). A proton originating from a structure which does not change before and after imidization is defined as a reference proton and the proton peak integrated value derived from the NH group of the amide acid appearing in the vicinity of 9.5 to 10.0 ppm By using the following equation.

Imidization ratio (%) = (1 -? X / y) x 100

In the above formula, x is the proton peak integrated value derived from the NH group of the amide acid, y is the peak integrated value of the reference proton, and? Is the NH of the amide acid in the case of the polyamic acid (the imidization rate is 0% The ratio of the number of reference protons to one protopertone.

&Quot; Synthesis of polyimide polymer &quot;

&Lt; Synthesis Example 1 &

(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 obtain a polyamic acid solution (1) having a resin solid content concentration of 25 mass%. This polyamic acid had a number average molecular weight of 23,200 and a weight average molecular weight of 70,100.

&Lt; 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) 16.8 mmol) and NMP (17.0 g) were added and reacted at 40 占 폚 for 6 hours to obtain a polyamic acid solution (2) having a resin solid content concentration of 25 mass%. The polyamic acid had a number average molecular weight of 23,800 and a weight average molecular weight of 69,500.

&Lt; Synthesis Example 3 &

NMP was added to the polyamic acid solution (2) (2) (2) obtained in Synthesis Example 2 to dilute to 6 mass%, acetic anhydride (3.90 g) and pyridine (2.41 g) The reaction was carried out at 70 DEG C for 2 hours. The reaction solution was poured into methanol (460 ml), and the resulting precipitate was separated by filtration. The precipitate was washed with methanol, and dried at 100 ° C under reduced pressure to obtain a polyimide powder (3). The imidization ratio of the polyimide was 61%, the number average molecular weight was 21,900, and the weight average molecular weight was 59,900.

&Lt; Synthesis Example 4 &

(1.9 g, 11.8 mmol) and B2 (1.20 g, 5.89 mmol) were mixed in NMP (28.9 g) and heated at 80 &lt; 0 &gt; C for 5 h After the reaction, D1 (3.38 g, 17.7 mmol) and NMP (14.4 g) were added and reacted at 40 DEG C for 8 hours to obtain a polyamic acid solution having a resin solid content concentration of 25 mass%.

To the obtained polyamic acid solution (30.0 g) was added NMP and diluted to 6 mass%. Acetic anhydride (3.85 g) and pyridine (2.40 g) were added as imidation catalysts and reacted at 50 ° C for 2 hours . The reaction solution was poured into methanol (460 ml), and the resulting precipitate was separated by filtration. The precipitate was washed with methanol and dried under reduced pressure at 100 ° C to obtain a polyimide powder (4). The imidization ratio of the polyimide was 57%, the number average molecular weight was 19,100, and the weight average molecular weight was 55,800.

&Lt; Synthesis Example 5 &

NMP (21.4 g) was added to 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) , D1 (2.15 g, 11.0 mmol) and NMP (10.7 g) were added, and the mixture was allowed to react at 40 DEG C for 6 hours to obtain a polyamic acid having a resin solid content concentration of 25 mass% Solution.

NMP was added to the resulting polyamidic acid solution (30.5 g) to dilute it to 6 mass%, acetic anhydride (4.05 g) and pyridine (2.50 g) were added as imidation catalysts and reacted at 50 ° C for 2 hours . This reaction solution was poured into methanol (460 ml), and the resulting precipitate was separated by filtration. The precipitate was washed with methanol and dried under reduced pressure at 100 ° C to obtain a polyimide powder (5). The imidization ratio of the polyimide was 51%, the number average molecular weight was 17,800, and the weight average molecular weight was 50,200.

&Lt; Synthesis Example 6 &

Was added in NMP (43.3 g) and stirred at 40 &lt; 0 &gt; C for 10 h To obtain a polyamic acid solution having a resin solid content concentration of 25 mass%.

NMP was added to the resultant polyamic acid solution (30.0 g), diluted to 6 mass%, acetic anhydride (4.00 g) and pyridine (2.50 g) were added as imidation catalysts and reacted at 70 ° C for 2 hours . This reaction solution was poured into methanol (460 ml), and the resulting precipitate was separated by filtration. The precipitate was washed with methanol, and dried at 100 ° C under reduced pressure to obtain a polyimide powder (6). The imidization ratio of the polyimide was 61%, the number average molecular weight was 17,500, and the weight average molecular weight was 49,900.

&Lt; Synthesis Example 7 &

The reaction was carried out at 40 占 폚 for 5 hours to obtain a resin solid concentration of 25 mass%, and the mixture was stirred at room temperature for 2 hours. % Polyamic acid solution.

NMP was added to the resulting polyamic acid solution (30.0 g), diluted to 6 mass%, acetic anhydride (4.55 g) and pyridine (2.50 g) were added as an imidation catalyst and reacted at 50 ° C for 3 hours . This reaction solution was poured into methanol (460 ml), and the resulting precipitate was separated by filtration. The precipitate was washed with methanol, and dried at 100 ° C under reduced pressure to obtain a polyimide powder (7). The imidization ratio of the polyimide was 55%, the number average molecular weight was 18,100, and the weight average molecular weight was 49,400.

&Lt; Synthesis Example 8 &

B3 (0.69 g, 3.42 mmol) was mixed in NMP (37.3 g) and stirred at 40 &lt; 0 &gt; C for 8 h After the reaction, D1 (3.29 g, 16.8 mmol) and NMP (18.6 g) were added and reacted at 25 DEG C for 10 hours to obtain a polyamic acid solution having a resin solid content concentration of 25 mass%.

To the obtained polyamic acid solution (30.0 g) was added NMP and diluted to 6 mass%. Acetic anhydride (7.20 g) and pyridine (2.25 g) were added as imidation catalysts and reacted at 40 ° C for 1.5 hours . This reaction solution was poured into methanol (460 ml), and the resulting precipitate was separated by filtration. The precipitate was washed with methanol and dried under reduced pressure at 100 ° C to obtain a polyimide powder (8). The imidization ratio of the polyimide was 71%, the number average molecular weight was 17,600, and the weight average molecular weight was 39,900.

&Lt; 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) 16.8 mmol) and NMP (16.6 g) were added and reacted at 40 占 폚 for 6 hours to obtain a polyamic acid solution having a resin solid content concentration of 25 mass%.

NMP was added to the resulting polyamic acid solution (30.0 g) to dilute to 6 mass%, acetic anhydride (3.90 g) and pyridine (2.45 g) were added as imidation catalysts and the mixture was reacted at 70 ° C for 2 hours . This reaction solution was poured into methanol (460 ml), and the resulting precipitate was separated by filtration. The precipitate was washed with methanol and dried under reduced pressure at 100 ° C to obtain a polyimide powder (9). The imidization ratio of the polyimide was 60%, the number average molecular weight was 18,500, and the weight average molecular weight was 56,900.

&Lt; Synthesis Example 10 &

Dl (4.29 g, 16.8 mmol) and NMP (12.8 g) were added to the reaction mixture at 25 ° C, And the reaction was carried out at 40 占 폚 for 6 hours to obtain a polyamic acid solution (10) having a resin solid content concentration of 25 mass%. This polyamic acid had a number average molecular weight of 26,400 and a weight average molecular weight of 80,900.

&Lt; Synthesis Example 11 &

NMP was added to the polyamic acid solution (10) (10) (10) obtained in Synthesis Example 10 to dilute it to 6 mass%, acetic anhydride (3.85 g) and pyridine (2.45 g) The reaction was carried out at 70 DEG C for 2 hours. This reaction solution was poured into methanol (460 ml), and the resulting precipitate was separated by filtration. The precipitate was washed with methanol and dried under reduced pressure at 100 ° C to obtain a polyimide powder (11). The imidization ratio of the polyimide was 60%, the number average molecular weight was 22,100, and the weight average molecular weight was 62,900.

The polyimide polymers obtained in Synthesis Examples 1 to 11 are listed in Table 1 together.

&Quot; Preparation of liquid crystal composition &quot;

(Liquid crystal composition (1))

L1 (11.5 g), R1 (1.73 g) and P1 (0.12 g) were mixed and heated (110 캜) and then cooled to 25 캜 to obtain liquid crystal composition (1).

(Liquid crystal composition (2))

L1 (12.0 g), R1 (2.40 g) and P1 (0.12 g) were mixed and heated (110 캜) and then cooled to 25 캜 to obtain liquid crystal composition (2).

&Quot; Fabrication of liquid crystal display element (glass substrate) &quot;

The liquid crystal alignment treatment agent of the later-described Examples or Comparative Examples was pressure-filtered through a membrane filter having a pore diameter of 1 占 퐉. The obtained solution was applied on an ITO surface of a glass substrate (length: 100 mm, width: 100 mm, thickness: 0.7 mm) having a 100 × 100 mm ITO electrode cleaned with pure water and IPA (isopropyl alcohol) Spin-coated, and heated on a hot plate at 100 占 폚 for 2 minutes and at 210 占 폚 for 10 minutes in a thermocycling type clean oven to obtain an ITO substrate having a liquid crystal alignment film with a thickness of 100 nm. Two ITO substrates on which the obtained liquid crystal alignment film was formed were prepared, and a spacer of 6 占 퐉 was coated on the liquid crystal alignment film surface of one of the substrates. Thereafter, the above liquid crystal composition was dropped by a ODF (One Drop Filling) method on the surface of the liquid crystal alignment film coated with the spacer of the substrate, and then the liquid crystal alignment was performed so that the interface of the liquid crystal alignment film of the other substrate faced, A display device was obtained.

A wavelength of 350 nm or less was cut into a liquid crystal display element before this treatment using a metal halide lamp having an illuminance of 60 mW and irradiated with ultraviolet light of 7 J / cm 2 in terms of 365 nm. At this time, the temperature in the irradiation apparatus when the element was irradiated with ultraviolet light was controlled at 25 占 폚. Thus, a liquid crystal display element (reverse type element) was obtained.

"Fabrication of Liquid Crystal Display Device (Plastic Substrate)"

The liquid crystal alignment treatment agent of the later examples was pressure-filtered through a membrane filter having a pore diameter of 1 占 퐉. The obtained solution was applied on a ITO surface of a PET (polyethylene terephthalate) substrate (length: 150 mm, width: 150 mm, thickness: 0.2 mm) having a 150 mm x 150 mm ITO electrode cleaned with pure water by a bar coater , And then heat-treated on a hot plate at 100 占 폚 for 2 minutes and at 150 占 폚 for 1 minute in a thermocycling type clean oven to obtain an ITO substrate on which a liquid crystal alignment film having a thickness of 100 nm was formed. Two ITO substrates on which the obtained liquid crystal alignment film was formed were prepared, and a spacer of 6 占 퐉 was coated on the liquid crystal alignment film surface of one of the substrates. Thereafter, the liquid crystal composition was dropped on the surface of the liquid crystal alignment film coated with the spacer of the substrate by the ODF method, and then the liquid crystal display element before the treatment was obtained by bonding the liquid crystal alignment film so that the interface of the liquid crystal alignment film of the other substrate faced each other.

A wavelength of 350 nm or less was cut into a liquid crystal display element before this treatment using a metal halide lamp having an illuminance of 60 mW and irradiated with ultraviolet light of 7 J / cm 2 in terms of 365 nm. At this time, the temperature in the irradiation apparatus when the element was irradiated with ultraviolet light was controlled at 25 占 폚. Thus, a liquid crystal display element (reverse type element) was obtained.

&Quot; Evaluation of liquid crystal display element &

(Liquid crystal alignment property)

The liquid crystal alignability of the liquid crystal display element (reverse type element) of the glass substrate and the plastic substrate was observed with a polarizing microscope (ECLIPSE E600WPOL) (Nikon Corporation), and it was confirmed whether or not the liquid crystal was aligned vertically. Specifically, it is said that the liquid crystal is oriented vertically, which is excellent in this evaluation.

Subsequently, the device in which the evaluation of the liquid crystal alignability was completed was stored for 336 hours in a high-temperature bath at a temperature of 100 占 폚. Thereafter, the liquid crystal alignability was evaluated under the same conditions as described above. Specifically, it is said that the liquid crystal alignability is not disturbed and the liquid crystal is uniformly aligned, which is excellent in the present evaluation.

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

(Optical properties (transparency and scattering properties))

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 evaluated as follows.

Transparency at the time of voltage unapplication was measured by measuring the transmittance of the device in a voltage unapplied state. Specifically, a UV-3600 (manufactured by Shimadzu Corporation), a temperature of 25 캜, a glass substrate on which the ITO electrode was formed (PET substrate in the case of evaluation of a plastic substrate), a scan wavelength of 300 to 800 nm The transmittance was measured under the conditions. The evaluation was carried out with a transmittance at a wavelength of 450 nm, and the higher the transmittance, the better the evaluation.

The scattering characteristics at the time of voltage application were obtained by applying an AC voltage of 40 V to the device and visually observing the alignment state of the liquid crystal. Specifically, it was found that the element was cloudy, that is, the scattering characteristic was obtained, which was excellent in this evaluation.

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 are summarized in Tables 8 to 10.

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

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

Specifically, the device was kept in a high-temperature and high-humidity bath having a temperature of 80 캜 and a humidity of 90 RH% for 96 hours, and the presence of bubbles in the device and the peeling of the device were confirmed. At that time, it was said that the bubbles were not seen in the device and the peeling of the device (the state in which the liquid crystal layer and the liquid crystal alignment film were peeled off) did not occur.

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

&Lt; Example 1 &gt;

NEP (22.7 g), BCS (20.8 g) and CE-2 (1.00 g) were added to polyamic acid solution (1) (1) (7.43 g) having a resin solid content concentration of 25% by mass obtained in Synthesis Example 1, Lt; / RTI &gt; for 5 hours. M2 (0.286 g) and K1 (0.286 g) were then added to this solution and stirred at 25 占 폚 for 2 hours to obtain a liquid crystal alignment treatment agent (1). No abnormality such as turbidity or precipitation was observed in this liquid crystal alignment treatment agent, and it was confirmed that the solution was a homogeneous solution.

Using the obtained liquid crystal alignment treatment agent (1) and liquid crystal composition (1), a liquid crystal display element (glass substrate) was produced and various evaluations were carried out.

&Lt; Example 2 &gt;

NMP (27.3 g), BCS (25.5 g) and CE-2 (1.05 g) were added to polyamic acid solution (2) (9.80 g) having a resin solid content concentration of 25% by mass obtained in Synthesis Example 2, At room temperature for 5 hours to obtain a liquid crystal alignment treatment agent (2). No abnormality such as turbidity or precipitation was observed in this liquid crystal alignment treatment agent, and it was confirmed that the solution was a homogeneous solution.

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

&Lt; Example 3 &gt;

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 conducted.

<Example 4>

NMP (35.4 g) and BCS (24.2 g) were added to the polyimide powder (3) (2.33 g) obtained in Synthesis Example 3 and dissolved by stirring at 70 占 폚 for 24 hours. CE-2 (1.00 g) was then added to this solution and stirred at 50 占 폚 for 5 hours to obtain a liquid crystal alignment treating agent (3). No abnormality such as turbidity or precipitation was observed in this liquid crystal alignment treatment agent, and it was confirmed that the solution was a homogeneous solution.

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

&Lt; Example 5 &gt;

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 conducted.

&Lt; Example 6 &gt;

NEP (32.8 g) and PB (18.2 g) were added to the polyimide powder (3) (1.86 g) obtained in Synthesis Example 3 and dissolved by stirring at 70 占 폚 for 24 hours. Then CE-2 (1.10 g) was added to this solution, and the mixture was stirred at 50 占 폚 for 5 hours. To this solution, S2 (0.143 g), M2 (0.429 g) and K1 (0.286 g) were added and stirred at 25 占 폚 for 2 hours to obtain a liquid crystal alignment treating agent (4). No abnormality such as turbidity or precipitation was observed in this liquid crystal alignment treatment agent, and it was confirmed that the solution was a homogeneous solution.

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

&Lt; Example 7 &gt;

? -BL (6.40 g) and PGME (42.5 g) were added to the polyimide powder (3) (1.65 g) obtained in Synthesis Example 3 and dissolved by stirring at 70 占 폚 for 24 hours. Then CE-2 (1.10 g) was added to this solution, and the mixture was stirred at 50 占 폚 for 5 hours. S2 (0.138 g) and M1 (0.550 g) were added to this solution and stirred at 25 占 폚 for 2 hours to obtain a liquid crystal alignment treatment agent (5). No abnormality such as turbidity or precipitation was observed in this liquid crystal alignment treatment agent, and it was confirmed that the solution was a homogeneous solution.

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

&Lt; Example 8 &gt;

NEP (34.0 g), BCS (12.4 g) and PB (14.6 g) were added to the polyimide powder (4) (2.55 g) obtained in Synthesis Example 4 and dissolved by stirring at 70 占 폚 for 24 hours. Thereafter, CE-1 (0.85 g) was added to this solution, and the mixture was stirred at 50 占 폚 for 5 hours. S1 (0.170 g) and M2 (0.170 g) were added to this solution and stirred at 25 占 폚 for 2 hours to obtain a liquid crystal alignment treatment agent (6). No abnormality such as turbidity or precipitation was observed in this liquid crystal alignment treatment agent, and it was confirmed that the solution was a homogeneous solution.

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

&Lt; Example 9 &gt;

? -BL (12.8 g) and PGME (43.2 g) were added to the polyimide powder (4) (2.04 g) obtained in Synthesis Example 4 and dissolved by stirring at 70 占 폚 for 24 hours. Then CE-2 (1.10 g) was added to this solution, and the mixture was stirred at 50 占 폚 for 5 hours. Further, S1 (0.314 g) and M2 (0.314 g) were added to this solution and stirred at 25 占 폚 for 2 hours to obtain a liquid crystal alignment treatment agent (7). No abnormality such as turbidity or precipitation was observed in this liquid crystal alignment treatment agent, and it was confirmed that the solution was a homogeneous solution.

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

&Lt; Example 10 &gt;

? -BL (12.7 g), PGME (36.1 g) and ECS (5.50 g) were added to the polyimide powder (4) (2.70 g) obtained in Synthesis Example 4 and dissolved by stirring at 70 占 폚 for 24 hours. Then CE-1 (0.30 g) was added to this solution, and the mixture was stirred at 50 占 폚 for 5 hours. To this solution, S2 (0.210 g), M3 (0.450 g) and K1 (0.450 g) were added and stirred at 25 占 폚 for 2 hours to obtain a liquid crystal alignment treatment agent (8). No abnormality such as turbidity or precipitation was observed in this liquid crystal alignment treatment agent, and it was confirmed that the solution was a homogeneous solution.

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

&Lt; Example 11 &gt;

? -BL (7.20 g), PGME (44.7 g) and EC (5.90 g) were added to the polyimide powder (5) (1.95 g) obtained in Synthesis Example 5 and dissolved by stirring at 70 占 폚 for 24 hours. Then CE-2 (1.30 g) was added to this solution, and the mixture was stirred at 50 占 폚 for 5 hours. To this solution, M2 (0.325 g) and K1 (0.488 g) were added and stirred at 25 占 폚 for 2 hours to obtain a liquid crystal alignment treatment agent (9). No abnormality such as turbidity or precipitation was observed in this liquid crystal alignment treatment agent, and it was confirmed that the solution was a homogeneous solution.

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

&Lt; Example 12 &gt;

To the polyimide powder (5) (1.83 g) obtained in Synthesis Example 5, γ-BL (16.2 g) and PGME (43.0 g) were added and dissolved by stirring at 70 ° C for 24 hours. CE-2 (1.50 g) was then added to this solution, and the mixture was stirred at 50 占 폚 for 5 hours. To this solution, S2 (0.500 g) and M3 (0.167 g) were added and stirred at 25 占 폚 for 2 hours to obtain a liquid crystal alignment treating agent (10). No abnormality such as turbidity or precipitation was observed in this liquid crystal alignment treatment agent, and it was confirmed that the solution was a homogeneous solution.

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

&Lt; Example 13 &gt;

NEP (38.9 g) and PB (19.5 g) were added to the polyimide powder (5) (2.60 g) obtained in Synthesis Example 5 and dissolved by stirring at 70 占 폚 for 24 hours. CE-1 (0.65 g) was then added to this solution, and the mixture was stirred at 50 占 폚 for 5 hours. S2 (0.033 g), M2 (0.975 g) and K1 (0.163 g) were added to this solution and stirred at 25 占 폚 for 2 hours to obtain a liquid crystal alignment treatment agent 11. No abnormality such as turbidity or precipitation was observed in this liquid crystal alignment treatment agent, and it was confirmed that the solution was a homogeneous solution.

Using the obtained liquid crystal alignment treatment agent 11 and the liquid crystal composition 1, a liquid crystal display element (glass substrate) was produced and various evaluations were carried out.

&Lt; Example 14 &gt;

To the polyimide powder (6) (1.55 g) obtained in Synthesis Example 6, γ-BL (14.9 g) and PGME (39.9 g) were added and dissolved by stirring at 70 ° C. for 24 hours. Then, CE-2 (1.55 g) was added to this solution, and the mixture was stirred at 50 占 폚 for 5 hours. M2 (0.620 g) and K1 (0.155 g) were further added to this solution and stirred at 25 占 폚 for 2 hours to obtain a liquid crystal alignment treatment agent 12. No abnormality such as turbidity or precipitation was observed in this liquid crystal alignment treatment agent, and it was confirmed that the solution was a homogeneous solution.

Using the obtained liquid crystal alignment treatment agent 12 and the liquid crystal composition 1, a liquid crystal display element (glass substrate, plastic substrate) was produced and various evaluations were conducted.

&Lt; Example 15 &gt;

NEP (33.5 g), PB (20.0 g) and EC (6.10 g) were added to the polyimide powder (6) (2.33 g) obtained in Synthesis Example 6 and dissolved by stirring at 70 占 폚 for 24 hours. Then CE-2 (1.00 g) was added to this solution, and the mixture was stirred at 50 占 폚 for 5 hours. To this solution, S1 (0.233 g) and K1 (0.333 g) were added and stirred at 25 占 폚 for 2 hours to obtain a liquid crystal alignment treatment agent (13). No abnormality such as turbidity or precipitation was observed in this liquid crystal alignment treatment agent, and it was confirmed that the solution was a homogeneous solution.

Using the obtained liquid crystal alignment treatment agent 13 and the liquid crystal composition 2, a liquid crystal display element (glass substrate) was produced and various evaluations were carried out.

&Lt; Example 16 &gt;

? -BL (20.1 g), PGME (36.1 g) and ECS (6.40 g) were added to the polyimide powder (7) (2.45 g) obtained in Synthesis Example 7 and dissolved by stirring at 70 占 폚 for 24 hours. Then CE-2 (1.05 g) was added to this solution, and the mixture was stirred at 50 占 폚 for 5 hours. M2 (0.875 g) and K1 (0.350 g) were further added to this solution and stirred at 25 占 폚 for 2 hours to obtain a liquid crystal alignment treatment agent 14. [ No abnormality such as turbidity or precipitation was observed in this liquid crystal alignment treatment agent, and it was confirmed that the solution was a homogeneous solution.

Using the obtained liquid crystal alignment treatment agent 14 and the liquid crystal composition 2, a liquid crystal display element (glass substrate, plastic substrate) was produced and various evaluations were conducted.

&Lt; Example 17 &gt;

NEP (26.8 g), BCS (24.7 g) and EC (5.80 g) were added to the polyimide powder (7) (2.40 g) obtained in Synthesis Example 7 and dissolved by stirring at 70 占 폚 for 24 hours. Then CE-1 (0.80 g) was added to this solution, and the mixture was stirred at 50 占 폚 for 5 hours. To this solution, S2 (0.032 g), M3 (0.320 g) and K1 (0.160 g) were added and stirred at 25 占 폚 for 2 hours to obtain a liquid crystal alignment treatment agent 15. No abnormality such as turbidity or precipitation was observed in this liquid crystal alignment treatment agent, and it was confirmed that the solution was a homogeneous solution.

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

&Lt; Example 18 &gt;

NMP (32.7 g) and BCS (25.1 g) were added to the polyimide powder (8) (1.95 g) obtained in Synthesis Example 8 and dissolved by stirring at 70 占 폚 for 24 hours. CE-2 (1.30 g) was then added to this solution and stirred at 50 占 폚 for 5 hours to obtain a liquid crystal alignment treatment agent 16. No abnormality such as turbidity or precipitation was observed in this liquid crystal alignment treatment agent, and it was confirmed that the solution was a homogeneous solution.

Using the obtained liquid crystal alignment treatment agent 16 and the liquid crystal composition 1, a liquid crystal display element (glass substrate) was produced and various evaluations were carried out.

&Lt; Example 19 &gt;

? -BL (10.1 g) and PGME (45.9 g) were added to the polyimide powder (8) (2.04 g) obtained in Synthesis Example 8 and dissolved by stirring at 70 占 폚 for 24 hours. Then CE-2 (1.10 g) was added to this solution, and the mixture was stirred at 50 占 폚 for 5 hours. S2 (0.094 g), M2 (0.628 g) and K1 (0.314 g) were added to this solution and stirred at 25 占 폚 for 2 hours to obtain a liquid crystal alignment treatment agent 17. No abnormality such as turbidity or precipitation was observed in this liquid crystal alignment treatment agent, and it was confirmed that the solution was a homogeneous solution.

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

&Lt; Example 20 &gt;

NEP (38.2 g) and PB (19.5 g) were added to the polyimide powder (9) (1.95 g) obtained in Synthesis Example 9 and dissolved by stirring at 70 ° C for 24 hours. Then CE-2 (1.30 g) was added to this solution, and the mixture was stirred at 50 占 폚 for 5 hours. S1 (0.098 g), M1 (0.488 g) and K1 (0.325 g) were added to this solution, and the mixture was stirred at 25 占 폚 for 2 hours to obtain a liquid crystal alignment treatment agent 18. No abnormality such as turbidity or precipitation was observed in this liquid crystal alignment treatment agent, and it was confirmed that the solution was a homogeneous solution.

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

&Lt; Comparative Example 1 &

NMP (16.8 g) and BCS (16.5 g) were added to the polyamide acid solution 10 (10.5 g) having a resin solid content concentration of 25 mass% obtained in Synthesis Example 10 and stirred at 25 캜 for 5 hours, A treating agent 19 was obtained. No abnormality such as turbidity or precipitation was observed in this liquid crystal alignment treatment agent, and it was confirmed that the solution was a homogeneous solution.

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

&Lt; Comparative Example 2 &

NMP (23.5 g) and BCS (15.7 g) were added to the polyimide powder (11) (2.50 g) obtained in Synthesis Example 11 and stirred at 70 占 폚 for 24 hours to obtain a liquid crystal alignment treating agent (20). No abnormality such as turbidity or precipitation was observed in this liquid crystal alignment treatment agent, and it was confirmed that the solution was a homogeneous solution.

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

&Lt; Comparative Example 3 &

NMP (16.0 g) and BCS (15.7 g) were added to polyamic acid solution (2) (10.0 g) having a resin solid content concentration of 25 mass% obtained in Synthesis Example 2 and stirred at 25 占 폚 for 5 hours, A treating agent 21 was obtained. No abnormality such as turbidity or precipitation was observed in this liquid crystal alignment treatment agent, and it was confirmed that the solution was a homogeneous solution.

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

&Lt; Comparative Example 4 &

A liquid crystal display element (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 conducted.

&Lt; Comparative Example 5 &

NMP (24.0 g) and BCS (16.0 g) were added to the polyimide powder (3) (2.55 g) obtained in Synthesis Example 3 and stirred at 70 占 폚 for 24 hours to obtain a liquid crystal alignment treatment agent (22). No abnormality such as turbidity or precipitation was observed in this liquid crystal alignment treatment agent, and it was confirmed that the solution was a homogeneous solution.

Using the obtained liquid crystal alignment treatment agent 22 and the liquid crystal composition 1, a liquid crystal display element (glass substrate) was produced and various evaluations were carried out.

&Lt; Comparative Example 6 &gt;

A liquid crystal display element (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 conducted.

&Lt; Comparative Example 7 &

NMP (22.8 g) and BCS (15.2 g) were added to CE-2 (2.00 g) and stirred at 50 占 폚 for 5 hours to obtain a liquid crystal alignment treatment agent (23). No abnormality such as turbidity or precipitation was observed in this liquid crystal alignment treatment agent, and it was confirmed that the solution was a homogeneous solution.

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

&Lt; Examples 1 to 20 and Comparative Examples 1 to 7 &gt;

Tables 2 to 4 below show the liquid crystal alignment treatment agents obtained in the above Examples and Comparative Examples, respectively.

As shown in Tables 5 to 10 below, the liquid crystal alignment treatment agents (1) to (23) obtained in each of the above Examples and Comparative Examples and the liquid crystal composition (1) or (2) (Liquid crystal alignability, optical properties (transparency and scattering properties), adhesion between the liquid crystal layer and the liquid crystal alignment film) of a liquid crystal display device (glass substrate, plastic substrate) and evaluation of a liquid crystal display device.

In addition, in the evaluation of the liquid crystal display element (adhesion between the liquid crystal layer and the vertical liquid crystal alignment film) in Examples 4, 6, 18 and 19, the temperature and the humidity of 90 RH / (The other conditions were the same as the above conditions). As a result, bubbles were not observed in the devices in Examples 6 and 19, but in Examples 4 and 18, a small amount of bubbles were found in the device.

As can be seen from the above results, in the liquid crystal display element of the example, the adhesion between the liquid crystal layer and the liquid crystal alignment film is higher than that of the liquid crystal display device of the comparative example, and the vertical alignment property of the liquid crystal is high, , Transparency at the time of no voltage application and scattering characteristics at the time of voltage application were good.

On the other hand, in the liquid crystal display element of the comparative example, the adhesion between the liquid crystal layer and the liquid crystal alignment film was poor, and after storing in a high-temperature and high-humidity vessel, bubbles were seen in the device or peeling occurred between the liquid crystal layer and the liquid crystal alignment film. Further, after storage in a high-temperature bath, disturbance of liquid crystal alignability due to lack of vertical orientation of the liquid crystal was observed.

Specifically, the examples containing the specific cellulose polymer as the component (A) and the comparative examples not containing the same, that is, Examples 2 and 3, Example 3 and Comparative Example 4, Example 4 and Comparative Example 5 , And a comparison between Example 5 and Comparative Example 6, a clear difference was recognized.

In Comparative Example 1 and Comparative Example 2 using the polyimide polymer not including the specific side chain structure and Comparative Example 7 containing only the specific cellulose polymer, the liquid crystal was not vertically aligned.

In addition, when a generator, an adhesive compound and a crosslinkable compound are introduced into a liquid crystal alignment treatment agent, the adhesion between the liquid crystal layer and the vertical liquid crystal alignment film becomes a more excellent liquid crystal display element. Specifically, a clear difference was recognized in the comparison between Example 4 and Example 6 and the comparison between Example 18 and Example 19. [

Industrial availability

The liquid crystal display element of the present invention can be suitably used for a reverse type element which is in a transmissive state when no voltage is applied and which is in a scattering state when a voltage is applied thereto and can be preferably used for a liquid crystal display for display purposes, It is useful for a flashlight or an optical shutter device that controls transmission and blocking. When the liquid crystal display element of the present invention is made of a plastic substrate such as a film substrate, it can be used by attaching it to a glass substrate or a window glass used as a support.

The entire contents of the specification, claims, and abstract of Japanese Patent Application No. 2013-154864 filed on July 25, 2013 are incorporated herein by reference, and are hereby incorporated by reference.

Claims (16)

A liquid crystal composition comprising a liquid crystal and a polymerizable compound polymerized by an active energy ray or heat is disposed between two substrates provided with electrodes and has a liquid crystal alignment film on at least one of the substrates, Wherein the liquid crystal alignment layer is a liquid crystal alignment layer comprising a liquid crystal alignment layer containing the following components (A) and (B) Wherein the liquid crystal display element is formed of a treatment agent.
Component (A): A cellulosic polymer having a structure represented by the following formula [1].
[Chemical Formula 1]

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

(3)

(X ⁷ and X ⁸ each independently represent a benzene ring or an alkyl group having 1 to 4 carbon atoms), X ⁹ , X ¹⁰ , X ¹¹ , X ¹² , X ¹³ and X ¹⁴ each independently represent a benzene ring or An alkylene group having 1 to 4 carbon atoms, and m and n represent an integer of 0 to 3.)
Component (B): At least one compound selected from the group consisting of a polyimide precursor and a polyimide having at least one structure selected from the group consisting of structures represented by the following formulas [2-1] and [2-2] One kind of polyimide-based polymer.
[Chemical Formula 4]

(Y ¹ is at least one 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- denotes a species Y ² represents a single bond or - in (c is 1 ~ 15 - (CH _{2) b} - represents a (b is an integer of 1 ~ 15) Y ³ represents a single bond, - (CH _{2) c} Y ⁴ is at least one member selected from the group consisting of a benzene ring, a cyclohexane ring, and a heterocyclic ring, and Y ⁴ is at least one selected from the group consisting of -O-, -CH ₂ O-, -COO- and -OCO- Or a divalent organic group having 17 to 51 carbon atoms and having a steroid skeleton, and any hydrogen atom on the cyclic group may be substituted with an alkyl group having 1 to 3 carbon atoms, an alkoxyl group having 1 to 3 carbon atoms , A fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxyl group having 1 to 3 carbon atoms, or a fluorine atom, Y ⁵ is a benzene ring, cyclohexane And any hydrogen atom on the cyclic group may be an alkyl group having 1 to 3 carbon atoms, an alkoxyl group having 1 to 3 carbon atoms, an alkoxyl group having 1 to 3 carbon atoms N is an integer of 0 to 4. Y ⁶ represents an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkoxy group having 1 to 3 carbon atoms, An alkoxyl group having 1 to 18 carbon atoms, and a fluorinated alkoxyl group having 1 to 18 carbon atoms, and n represents an integer of 0 to 4.)
[Chemical Formula 5]

(Y ⁷ represents a single bond, -O-, -CH ₂ O-, -CONH-, -NHCO-, -CON (CH ₃ ) -, -N (CH ₃ ) CO-, -COO- and -OCO- And Y ⁸ represents an alkyl group having 8 to 22 carbon atoms or a fluorine-containing alkyl group having 6 to 18 carbon atoms. The method according to claim 1,
Wherein the ratio of the component (A) to the component (B) is 0.1 to 9 parts by mass relative to 1 part by mass of the component (B). 3. The method according to claim 1 or 2,
Wherein the polyimide polymer of the component (B) is a polyimide precursor obtained by using a diamine compound having a structure represented by the formula [2-1] or [2-2] Lt; RTI ID = 0.0 &gt; 1, &lt; / RTI &gt; The method of claim 3,
Wherein the diamine compound is a diamine compound represented by the following formula [2a].
[Chemical Formula 6]

(Y represents at least one structure selected from the group consisting of structures represented by the formulas [2-1] and [2-2], and n represents an integer of 1 to 4.) 5. The method according to any one of claims 1 to 4,
Wherein the polyimide polymer of the component (B) is at least one selected from the group consisting of a polyimide precursor and a polyimide obtained by using a tetracarboxylic acid component represented by the following formula [3] Display element.
(7)

(Z &lt; ¹ &gt; represents at least one structure selected from the group consisting of the structures represented by the following formulas [3a] to [3j]
[Chemical Formula 8]

(Z ² to Z ⁵ each independently represent a hydrogen atom, a methyl group, a chlorine atom or a benzene ring, and Z ⁶ and Z ⁷ each independently represent a hydrogen atom or a methyl group. 6. The method according to any one of claims 1 to 5,
Wherein the liquid crystal alignment treatment agent further contains a solvent. The method according to claim 6,
Wherein the solvent contains a solvent having a boiling point of less than 180 占 폚 in an amount of 50 mass% or more of the entire solvent. 8. The method according to claim 6 or 7,
Wherein the solvent further contains at least one solvent selected from the group consisting of cyclopentanone, cyclohexanone, and solvents represented by the following formulas [A1] and [A2].
[Chemical Formula 9]

(A ¹ represents an alkyl group having 1 to 3 carbon atoms, and A ² represents an alkyl group having 1 to 3 carbon atoms.) 9. The method according to any one of claims 6 to 8,
Wherein the solvent is 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 And further contains at least one solvent. 10. The method according to any one of claims 6 to 9,
Wherein the solvent is at least one solvent selected from the group consisting of N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone,? -Butyrolactone and a solvent represented by the following formula [A3] , Wherein the liquid crystal display element further comprises:
[Chemical formula 10]

(A &lt; ³ &gt; represents an alkyl group having 1 to 4 carbon atoms) 11. The method according to any one of claims 1 to 10,
Further, the liquid crystal alignment treatment agent contains a compound having at least one group selected from the group consisting of groups represented by the following formulas [B1] to [B8].
(11)

(Wherein B ¹ represents a hydrogen atom or a benzene ring, B ² represents at least one cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring and a heterocyclic ring, B ³ represents an alkyl group having 1 to 18 carbon atoms, At least one member selected from the group consisting of a fluorine-containing alkyl group of 1 to 18 carbon atoms, an alkoxyl group of 1 to 18 carbon atoms, and a fluoro-containing alkoxyl group of 1 to 18 carbon atoms. 12. The method according to any one of claims 1 to 11,
Further, the liquid crystal display element contains at least one generator selected from the group consisting of the liquid crystal alignment treatment agent, photo-radical generator, photo-acid generator and photo-base generator. 13. The method according to any one of claims 1 to 12,
Wherein the substrate is a glass substrate or a plastic substrate. A liquid crystal alignment film to be used in the liquid crystal display element according to any one of claims 1 to 13, wherein the liquid crystal alignment film is formed from a liquid crystal alignment treatment agent containing the component (A) and the component (B). 15. The method of claim 14,
A liquid crystal alignment film having a film thickness of 5 to 500 nm. The liquid crystal alignment treatment agent for forming the liquid crystal alignment film according to claim 14 or 15, which contains the above-mentioned component (A) and the component (B).