TW201920362A - Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element using same - Google Patents

Abstract

The present invention contains: a polyimide precursor, which is obtained from a tetracarboxylic acid component and a diamine component including a diamine having a specific side-chain structure and a diamine having the structure represented by formula (1); and/or a polyimide polymer being an imidized product of said polyimide precursor (in formula (1), R1 represents a hydrogen atom, an alkyl or fluoroalkyl group having 1-5 carbon atoms, a tert-butoxycarbonyl group, or a monovalent organic group, "*" represents a site that binds to another group, and any hydrogen atom forming the benzene ring may be substituted by a monovalent organic group).

Description

Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element using the same

The present invention relates to a liquid crystal alignment agent, a liquid crystal alignment film, and a liquid crystal display element using the same. In particular, the present invention relates to a liquid crystal alignment agent, a liquid crystal alignment film, and a liquid crystal display element suitable for a liquid crystal display element of the VA type which is used to form a liquid crystal molecule that is vertically aligned with a substrate and responds via an electric field.

Liquid crystal display elements are widely used as display units for personal computers, mobile phones, smartphones, and televisions. The liquid crystal display element includes, for example, a liquid crystal layer sandwiched between an element substrate and a color filter substrate, a pixel electrode and a common electrode that apply an electric field to the liquid crystal layer, an alignment film that controls the alignment of liquid crystal molecules in the liquid crystal layer, Turn off thin film transistors (TFTs), etc., that supply current signals to the pixel electrodes.

One of the driving methods of these liquid crystal display elements is a method (also referred to as a vertical alignment (VA) method) in which liquid crystal molecules in a vertical alignment with the opposite substrate are responded by using an electric field. It is known that in a liquid crystal display element of a vertical alignment method, a photopolymerizable compound is added to a liquid crystal composition in advance, and then a vertical alignment film such as a polyfluorene imide is used to irradiate ultraviolet rays while applying a voltage to a liquid crystal cell. The technology (PSA (Polymer Sustained Alignment)) method of accelerating the response speed of liquid crystals (for example, Patent Document 1 and Non-Patent Document 1).

On the other hand, in such a liquid crystal display element, when static electricity is accumulated in a liquid crystal cell, or when positive and negative asymmetric voltages generated by driving cause electric charges to accumulate in the liquid crystal cell, the accumulated charges may cause The disorder of the liquid crystal alignment or the afterimage affects the display content, which significantly reduces the display quality of the liquid crystal element. [Prior Art Literature] [Patent Literature]

[Patent Document 1] JP 2003-307720 [Non-Patent Document]

[Non-Patent Document 1] K. Hanaoka, SID 04 DIGEST, P1200-1202

[Problems to be solved by the invention]

The present invention aims to provide a liquid crystal alignment agent, a liquid crystal alignment film, and a liquid crystal display element using the liquid crystal alignment film, which can obtain a liquid crystal alignment film having excellent voltage retention, rapid relaxation of accumulated charges, and excellent afterimage characteristics. [Solution to the problem]

As a result of intensive research, the present inventors found that the above problems can be solved by using a liquid crystal alignment agent containing a diamine having a specific structure in a polymer, and thus the present invention has been completed. The present invention is based on this knowledge, and it is based on the following technologies.

Aspects of the present invention that can solve the above problems are: ， a liquid crystal alignment agent, which is characterized by containing: represented by a diamine having a structure of the following formula (1) and represented by the following formulas [S1] to [S3] The diamine component of at least one type of diamine of the side chain structure selected by the group, and the polyimide precursor obtained from the tetracarboxylic acid component (including the tetracarboxylic acid derivative component) and / or the polyimide Polyimide polymers of the precursor imidates;

(In formula (1), R ₁ represents hydrogen, an alkyl or fluoroalkyl group having 1 to 5 carbon atoms, a tert-butoxycarbonyl group, or a monovalent organic group; * represents a site that can be bonded to other groups; (Any hydrogen atom forming a benzene ring may be replaced by a monovalent organic group)

(In the formula [S1], X ¹ and X ² each independently represent a single bond,-(CH ₂ ) _a- (a is an integer of 1 to 15), -CONH-, -NHCO-, -CON (CH ₃ )- , -NH-, -O-, -COO-, -OCO-, or-((CH ₂ ) _a1 -A ₁ ) _m1- ; wherein each of the plural a1 independently represents an integer from 1 to 15, and each of the plural A ₁ Independently represents an oxygen atom or -COO-; m ₁ is 1 to 2; G ¹ and G ² each independently represent a divalent aromatic group having 6 to 12 carbon atoms or a divalent alicyclic group having 3 to 8 carbon atoms A bivalent cyclic group selected by a radical; any hydrogen atom on the aforementioned cyclic group may be composed of an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, and 1 to 3 carbon atoms. Substituted by at least one selected from the group consisting of a fluoroalkyl group, a fluorine-containing alkoxy group having 1 to 3 carbon atoms or a fluorine atom; m and n each independently represent an integer of 0 to 3, and the total of m and n 1 to 4; R ¹ represents an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or an alkoxyalkyl group having 2 to 20 carbon atoms; any hydrogen that forms R ¹ may be fluorine Replaced).

(In the formula [S2], X ³ represents a single bond, -CONH-, -NHCO-, -CON (CH ₃ )-, -NH-, -O-, -CH ₂ O-, -COO-, or -OCO- ; R ² represents an alkyl group having 1 to 20 carbon atoms or an alkoxyalkyl group having 2 to 20 carbon atoms; any hydrogen that forms R ² may be replaced by fluorine).

(In the formula [S3], X ⁴ represents -CONH-, -NHCO-, -O-, -COO-, or -OCO-; R ³ represents a structure having a cholesterol skeleton).

Among them, the diamine having the structure of the formula (1) is preferably a structure having the following formula (1-1).

(In the formula (1-1), R _{1 is the} same as that in the case of the aforementioned formula (1); * indicates a site which can be bonded to other groups; any hydrogen atom forming a benzene ring can be monovalent Substituted with an organic group).

The diamine having the structure of the formula (1) is preferably a structure having the following formula (1-4).

(In the formula (1-4), R _{1 is the} same as that in the case of the aforementioned formula (1); two Q ₂ each independently represent a single bond or a divalent organic group; any hydrogen atom forming a benzene ring may be Is replaced by a monovalent organic group).

The diamine component preferably contains a diamine having a side chain structure represented by the formula [S1].

The side chain structure represented by the formula [S1] is preferably at least one selected from the group consisting of the following formulas [S1-x1] to [S1-x7].

(In the formulas [S1-x1] to [S1-x7], R ¹ represents an alkyl group having 1 to 20 carbon atoms; X ^p represents-(CH ₂ ) _a- (a is an integer from 1 to 15), -CONH- , -NHCO-, -CON (CH ₃ )-, -NH-, -O-, -CH ₂ O-, -COO-, or -OCO-; A ₁ represents an oxygen atom or -COO- * (but, with "*" Is bonded to (CH ₂ ) _a2 ); A ₂ represents an oxygen atom or * -COO- (but the bond with "*" is bonded to (CH ₂ ) _a2 ) ; A3 is an integer of 0 or 1, and a1 and a2 each independently represent an integer of 2 to 10; Cy represents 1,4-cyclohexyl or 1,4-phenylene).

In the diamine having a side chain structure represented by the formula [S2], X ³ is -CONH-, -NHCO-, -O-, -CH ₂ O-, -COO-, or -OCO-, and R ² An alkyl group having 3 to 20 carbon atoms or an alkoxyalkyl group having 2 to 20 carbon atoms is preferred.

The side chain structure represented by the formula [S3] is preferably one having a structure represented by the following formula [S3-x].

(In formula [S3-x], X represents formula [X1] or formula [X2]; Col represents at least one selected from the group formed by formulas [Col1] to [Col3]; G represents formula [G1] ~ [G4]; in these formulas, * represents the bonding position).

The diamine component having a specific side chain structure preferably contains at least one selected from the diamines represented by the following formulas [1] and [2].

(In the formula [1], X represents a single bond, -O-, -C (CH ₃ ) _2- , -NH-, -CO-,-(CH ₂ ) _m- , -SO ₂ -or any of these A divalent organic group formed by combination; m is an integer from 1 to 8. The two Ys each represent at least one selected from the side chain structure represented by the aforementioned formulas [S1] to [S3]).

Another aspect of the present invention that solves the above-mentioned problems is a liquid crystal alignment film characterized by being formed using any one of the liquid crystal alignment agents described above.

Another aspect of the present invention that solves the above problems is a liquid crystal display element having a liquid crystal alignment film obtained from the liquid crystal alignment film. [Effect of the invention]

When the liquid crystal alignment agent of the present invention is used, it is possible to provide a liquid crystal alignment film having excellent voltage retention, rapid relaxation of accumulated charges, and excellent afterimage characteristics, and a liquid crystal display element having excellent display characteristics. That is, in the liquid crystal alignment film and the liquid crystal display element according to the present invention, it is possible to meet expectations for the characteristics of the liquid crystal alignment film or the liquid crystal display element with the recent high performance. [Form of Implementing Invention]

The liquid crystal alignment agent of the present invention contains: at least one selected from a diamine having a structure of the following formula (1) and a side chain structure selected from the group represented by the following formulas [S1] to [S3] A diamine component of a diamine, a polyimide precursor obtained from a tetracarboxylic acid component, and / or a polyimide polymer of a polyimide of the polyimide precursor.

Hereinafter, a diamine having a structure of formula (1) is sometimes referred to as a "diamine having a specific structure" or a "specific diamine". The diamine having at least one type of side chain structure selected from the group represented by the formulas [S1] to [S3] is sometimes referred to as a "diamine having a specific side chain structure". Moreover, the polymer containing the specific diamine of this invention and the diamine which has a specific side chain structure may be called "specific polymer."

<Specific diamine> Specific diamine has a structure having the following formula (1).

In the above formula (1), R ₁ represents hydrogen, an alkyl or fluoroalkyl group having 1 to 5 carbon atoms, a tert-butoxycarbonyl group, or a monovalent organic group; * represents a site that can be bonded to other groups; Any hydrogen atom that forms a benzene ring may be replaced by a monovalent organic group. Examples of the monovalent organic group herein include alkyl, alkenyl, alkoxy, fluoroalkyl, fluoroalkenyl, or fluoroalkoxy having 1 to 10 carbon atoms, preferably 1 to 3 Base etc. Among them, R _{1 is} preferably a hydrogen atom or a methyl group.

In the above formula (1), from the viewpoint of charge transfer with respect to the bonding position of the pyrrole ring of the benzene ring, the carbon atom adjacent to the nitrogen atom on the pyrrole ring represented by the following formula (1-1) is preferable .

Examples of the specific diamine may be represented by the following formula (1-2), for example, a diamine represented by the following formula (1-3) is preferred, and a diamine represented by the following formula (1-4) is more preferred The indicated diamine is preferred.

In the formulae (1-2) to (1-4), R ₁ is the same as when formula (1) is used. Q ₁ and Q ₂ each independently represent a single bond or a divalent organic group. That is, Q ₁ and Q ₂ may have different structures. In Formula (1-4), two Q ₂ may have different structures from each other. In addition, an arbitrary hydrogen atom forming a benzene ring has the same content as in the case of formula (1), and may be substituted with a monovalent organic group.

Preferred examples of the specific diamine include, for example, a diamine represented by the following formula (2), and more preferably a diamine represented by the following formula (2-1).

In the above formula (2) and formula (2-1), R ₁ is the same as when formula (1) is used. The two R ₂ each independently represent a single bond or a structure of the following formula (3). In addition, it is the same as when formula (1) is used, and an arbitrary hydrogen atom forming a benzene ring may be substituted with a monovalent organic group.

In formula (3), R ₃ represents a single bond, -O-, -COO-, -OCO-,-(CH ₂ ) _p- , -O (CH ₂ ) _m O-, -CONH-, -NHCO- , -CON (CH ₃ )-and -N (CH ₃ ) CO-, -NR ₁ -selected divalent organic groups in the group. Among them, p and m each independently represent an integer of 1 to 14, and R ₁ has the same content as when it is in formula (1). Wherein relaxes view of accumulated charge, R ₃ via a single bond, -O -, - COO -, - OCO -, - CONH -, - NHCO- or -N (CH ₃₎ - is preferred. In addition, * ₁ indicates a site bonded to a benzene ring in Formula (2); * ₂ indicates a site bonded to an amine group in Formula (2). In formula (2) and formula (2-1), n is an integer of 1 to 3, preferably 1 or 2.

Specific examples of the formula (2) include, for example, the following formulae (2-1-1) to (2-1-16) and the like, but are not limited to these contents. Among them, from the viewpoint of easing the accumulated charge, the following equations (2-1-1), (2-1-2), (2-1-3), (2-1-5), and (2- 1-8), formula (2-1-9), formula (2-1-10), formula (2-1-11), formula (2-1-12), formula (2-1-13), Formula (2-1-14), formula (2-1-15) or formula (2-1-16) is preferred, and formula (2-1-1), formula (2-1-2), formula ( 2-1-3), formula (2-1-11), or formula (2-1-12), formula (2-1-13), formula (2-1-14), formula (2-1- 15) or formula (2-1-16) is particularly preferred. In the following formulae (2-1-6) and (2-1-7), n is an integer of 1 to 14.

<Synthesis method of specific diamine> The synthesis method of the specific diamine is not particularly limited. For example, a method in which a dinitro compound represented by the following formula (4) is used, and the nitro group is subjected to a reduction reaction to convert it to an amine group, and the like.

In formula (4), R ₁ is the same as when formula (1) is used.

The catalyst used for the reduction reaction is preferably an activated carbon supporting metal that is commercially available, for example, palladium-activated carbon, platinum-activated carbon, rhodium-activated carbon, and the like. In addition, palladium hydroxide, platinum oxide, Raney nickel, etc. may be used, and it is not necessary to use an activated carbon-supporting metal catalyst. On the other hand, palladium-activated carbon, which is widely used in general, is preferable because it is easy to obtain good results.

In order to make the reduction reaction proceed more effectively, the reaction may be performed in the presence of activated carbon. At this time, the amount of activated carbon used is not particularly limited, and is generally preferably 1 to 30% by mass and more preferably 10 to 20% by mass relative to the dinitro compound of the formula (4). . For the same reason, the reaction may be performed under pressure. At this time, the reduction of the benzene ring and the pyrrole ring is avoided, and it can be performed in a pressure range from atmospheric pressure to 20 atmospheric pressure. The reaction is preferably performed within a range of atmospheric pressure to 10 atmospheric pressure.

The solvent used for the synthesis of a specific diamine can be used without any limitation as long as it does not react with each raw material. For example, aprotic polar organic solvents (dimethylformamide, dimethylsulfoxide, dimethylacetate, N-methyl-2-pyrrolidone, etc.) can be used; ethers (two Diethyl ether, diisopropyl ether, t-butyl methyl ether, cyclopentyl methyl ether, tetrahydrofuran, dioxane, etc.); aliphatic hydrocarbons (pentane, hexane, heptane, petroleum ether, etc.); aromatic hydrocarbons ( Benzene, toluene, xylene, xylene, chlorobenzene, dichlorobenzene, nitrobenzene, tetrahydronaphthalene, etc.); halogen-based hydrocarbons (chloroform, dichloromethane, carbon tetrachloride, dichloroethane, etc.); Lower fatty acid esters (methyl acetate, ethyl acetate, butyl acetate, methyl propionate, etc.); nitriles (acetonitrile, propionitrile, butyronitrile, etc.); etc. These solvents can be used alone or in combination of two or more. The solvent may be dried using a suitable dehydrating agent or desiccant, or may be used as a non-aqueous solvent.

The use amount (reaction concentration) of the solvent is not particularly limited, and is generally 0.1 to 100 times the mass of the dinitro compound of the formula (4). It is preferably 0.5 to 30 mass times, and particularly preferably 1 to 10 mass times. The reaction temperature is not particularly limited, but generally ranges from -100 ° C to the boiling point of the solvent used, and is preferably -50 to 150 ° C. The reaction time is usually 0.05 to 350 hours, preferably 0.5 to 100 hours.

[Production method of dinitro compound of formula (4)] The method for synthesizing the dinitro compound of formula (4) is not particularly limited. For example, the compound (II) represented by the following formula (5) can be synthesized first. A nitro group), and a method for introducing a protective group R _{4 to} the NH group of the dinitro group.

When R ₄ is introduced, any compound may be used as long as it can react with the NH site of the pyrrole ring of formula (5). For example, acid halides, acid anhydrides, isocyanates, epoxy compounds, oxycyclobutanes, halogenated aryls, halogenated alkyls, and the like. In addition, alcohols in which the hydroxyl group of the alcohol is replaced with a dissociating group such as OMs (methanesulfonyl), OTf (trifluoromethanesulfonate), OTs (tosylsulfonyl) and the like can also be used.

When R ₄ is introduced by reaction with an acid halide, it is preferably carried out in the presence of a base. Examples of acid halides include acetamidine chloride, propionic acid chloride, methyl chloroformate, ethyl chloroformate, n-propyl chloroformate, i-propyl chloroformate, n-butyl chloroformate, i-chloroformate -Butyl, t-butyl chloroformate, benzyl chloroformate, 9-fluorenyl chloroformate, and the like. The base is not particularly limited as long as it can be synthesized, and inorganic substances such as potassium carbonate, sodium carbonate, cesium carbonate, sodium alkoxide, potassium alkoxide, sodium hydroxide, potassium hydroxide, and sodium hydride can be used. Organic bases such as bases, pyridine, dimethylaminopyridine, trimethylamine, triethylamine, tributylamine, and the like. The reaction solvent or reaction temperature is the same as that in the case of the reduction reaction in the synthesis of the dinitro compound of the formula (4).

When reacting with an acid anhydride to introduce R ₄ , the acid anhydride is, for example, acetic anhydride, propionic anhydride, dimethyl dicarbonate, diethyl dicarbonate, di-di-tert-butyl dicarbonate, dibenzyl dicarbonate, or the like. As a catalyst for promoting the reaction, pyridine, collin base, N, N-dimethyl-4-aminopyridine, and the like can be used. The catalyst amount is 0.0001 mol to 1 mol relative to the compound of the formula (5). The reaction solvent or the reaction temperature is the same as when the acid halide is used.

When reacting with isocyanates to introduce R ₄ , the isocyanates are, for example, methyl isocyanate, ethyl isocyanate, n-propyl isocyanate, phenyl isocyanate, and the like. The reaction solvent or reaction temperature is the same as that in the case of the acid halide.

When reacting with epoxy compounds or oxetane compounds to introduce R ₄ , the epoxy compounds or oxetane compounds such as ethylene oxide, propylene oxide, 1,2-butene oxide, Trimethyl oxide etc. The reaction solvent or reaction temperature is the same as that in the case of the acid halide.

In the case of reacting with an alcohol having a hydroxyl group of the alcohol substituted by a dissociating group such as OMs, OTf, OTs, etc. to introduce R ₄ , it is preferably carried out in the presence of a base. Examples of alcohols include methanol, ethanol, and 1-propanol. These alcohols react with methanesulfonyl chloride, trifluoromethanesulfonyl chloride, p-toluenesulfonic acid chloride, and the like. An alcohol substituted with a dissociation group such as OMs, OTf, OTs, etc. is obtained. Examples of the base, the reaction solvent, and the reaction temperature are the same as those in the case of the acid halide.

When reacting with a halogenated alkyl group to introduce R ₄ , it is preferably carried out in the presence of a base. Examples of the halogenated alkyl group include methyl iodide, ethyl iodide, n-propyl iodide, methyl bromide, ethyl bromide, and n-propyl bromide. Examples of the base include metal alkoxides such as potassium-tert-butoxide and sodium-tert-butoxide in addition to the aforementioned bases. The reaction solvent or reaction temperature is the same as that in the case of the acid halide.

[Production method of compound of formula (5)] The method of synthesizing the compound of formula (5) is not particularly limited. When the substitution positions on the pyrrole ring of the compound of formula (5) are in the 2- and 4-positions For example, as shown in the following reaction formula 1, an α-halogenated ketone having a nitro group and a ketone having a nitro group are preferably reacted in the presence of a base to obtain the ketone. In Reaction Formula 1, X represents Br, I, or OTf.

Examples of the base used in the above reaction formula 1 include, for example, the bases exemplified for the aforementioned acid halide. The reaction solvent or reaction temperature is the same as that in the case of the acid halide. For the purpose of promoting the reaction rate of Reaction Formula 1, zinc chloride, sodium iodide, potassium iodide, tetrabutylammonium iodide, and the like can be used as the accelerator.

On the other hand, in the pyrrole ring of the compound of the formula (5), when the substituted positions are other than the 2 and 4 positions, the corresponding halogenated pyrrole and the organometallic reagent can be cross-coupled with each other, preferably using a metal catalyst. It can be obtained by reaction formula 2.

(In Reaction Scheme 2, X represents Br, I, or OTf. M represents B (OH) ₂ or 4,4,5,5-tetramethyl-1,3,2-dioxocyclopentane-2- base).

The cross-coupling reaction (also referred to as "Suzuki-Miyaura reaction") in the above reaction formula 2 is preferably using a metal complex and a ligand as a catalyst, but the reaction can also be performed without a catalyst. Examples of metal complexes include palladium acetate, palladium chloride, palladium chloride-acetonitrile complex, palladium-activated carbon, bis (dibenzylideneacetone) palladium, ginseng (dibenzylideneacetone) dipalladium, bis (Acetonitrile) dichloropalladium, bis (benzonitrile) dichloropalladium, CuCl, CuBr, CuI, CuCN, and the like. Examples of ligands include triphenylphosphine, tri-o-tolylphosphine, diphenylmethylphosphine, phenyldimethylphosphine, 1,2-bis (diphenylphosphine) ) Ethane, 1,3-bis (diphenylphosphino) propane, 1,4-bis (diphenylphosphino) butane, 1,1'-bis (diphenylphosphino) ferrocene, Trimethyl phosphite, triethyl phosphite, triphenyl phosphite, tri-tert-butylphosphine and the like. The use amount of the above metal complex, that is, the so-called catalyst amount, is sufficient, and it is sufficient to use 20 mol% or less with respect to the substrate, and preferably 10 mol% or less.

<Diamine having a specific side chain structure> In this embodiment, the diamine having a specific side chain structure is, for example, those represented by the following formulas [1] and [2].

In the above formula [2], X represents a single bond, -O-, -C (CH ₃ ) _2- , -NH-, -CO-, -NHCO-, -COO-,-(CH ₂ ) _m -,- SO ₂ -or a divalent organic group formed by any of these combinations; X is preferably a single bond, -O-, -NH-, -O- (CH ₂ ) _m -O-. "These arbitrary combinations" include, for example, -O- (CH ₂ ) _m -O-, -OC (CH ₃ ) _2- , -CO- (CH ₂ ) _m- , -NH- (CH ₂ ) _m -, -SO _2- (CH ₂ ) _m- , -CONH- (CH ₂ ) _m- , -CONH- (CH ₂ ) _m -NHCO-, -COO- (CH ₂ ) _m -OCO-, etc., but not only Limited to these contents. m is an integer from 1 to 8.

In the above formulas [1] and [2], Y independently represents at least one selected from the side chain structure represented by the formulas [S1] to [S3]. The details of the side chain structure represented by the formulas [S1] to [S3] will be described later.

Further, in the above formula [2], the position of Y with respect to X may be meta or adjacent, and is preferably adjacent. That is, in the above formula [2], the following formula [2 '] is more preferable.

The position of the two amine groups (-NH ₂ ) in the above formula [2] may be any position on the benzene ring, but it is represented by the following formulas [2] -a1 to [2] -a3 The position is preferable, and the following formula [2] -a1 is more preferable. In the following formula, X is the same as when the formula [2] is used. In addition, the following formulas [2] -a1 to [2] -a3 are for explaining the positions of two amine groups, and are those in which Y described in the above formula [2] is omitted.

Therefore, based on the above formulas [2 '] and [2] -a1 ~ [1] -a3, the above formula [2] is represented by the following formulas [2] -a1-1 ~ [2] -a3-2 Any one of the selected structures is preferable, and a structure represented by the following formula [2] -a1-1 is more preferable. In the following formulae, X and Y have the same contents as those in the case of formula [2].

These two side chain diamines represented by the formula [2] may be used singly or in combination of two or more kinds. According to the characteristics required for a liquid crystal alignment film or a liquid crystal display element, one type may be used alone, or two or more types may be used in combination, and when two or more types are used in combination, the ratio thereof may be appropriately adjusted.

In the above formulas [1] and [2], Y represents a specific side chain structure selected from the group represented by the following formulas [S1] to [S3]. Hereinafter, the specific side chain structure will be described in the order of the formulas [S1] to [S3].

Examples of the specific side chain structure include a diamine having a specific side chain structure represented by the following formula [S1].

In the above formula [S1], X ¹ and X ² each independently represent a single bond,-(CH ₂ ) _a- (a is an integer from 1 to 15), -CONH-, -NHCO-, -CON (CH ₃ )- , -NH-, -O-, -COO-, -OCO-, or-((CH ₂ ) _a1 -A ₁ ) _m1- ; wherein each of the plural a1 independently represents an integer from 1 to 15, and each of the plural A ₁ Independently represents an oxygen atom or -COO-; m ₁ is 1 to 2.

Among them, X ¹ and X ² each independently represent a single bond,-(CH ₂ ) _a- (a is an integer of 1 to 15), -O-, -CH from the viewpoint of availability of raw materials or ease of synthesis. ₂ O- or -COO- is preferred. More preferably, X ¹ and X ² each independently represent a single bond,-(CH ₂ ) _a- (a is an integer from 1 to 10), -O-, -CH ₂ O-, or -COO-.

In the above formula [S1], G ¹ and G ² each independently represent a divalent number selected from a divalent aromatic group having 6 to 12 carbon atoms or a divalent alicyclic group having 3 to 8 carbon numbers. Cyclic group; any hydrogen atom on the cyclic group can be an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a fluoroalkyl group having 1 to 3 carbon atoms, and 1 to 3 carbon atoms Substituted by a fluorine-containing alkoxy group or a fluorine atom of 3. m and n each independently represent an integer of 0 to 3; the total of m and n is 1 to 4.

Furthermore, in the above formula [S1], R ¹ represents an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms or an alkoxyalkyl group having 2 to 20 carbon atoms; any hydrogen that forms R ¹ , Can be replaced by fluorine. Among them, examples of the divalent aromatic group having 6 to 12 carbon atoms include phenylene, phenylene, and naphthalene. Examples of the divalent alicyclic group having 3 to 8 carbon atoms include cyclopropyl and cyclohexyl.

Therefore, preferable specific examples of the above formula [S1] include, for example, the following formulas [S1-x1] to [S1-x7] and the like, but are not limited to these contents.

In the formulas [S1-x1] to [S1-x7], R ¹ has the same content as when the formula [S1] is. X ^p represents-(CH ₂ ) _a- (a is an integer from 1 to 15), -CONH-, -NHCO-, -CON (CH ₃ )-, -NH-, -O-, -CH ₂ O-, -COO- or -OCO-; A ₁ represents an oxygen atom or -COO- * (bonding with "*" is bonding with (CH ₂ ) _a2 ). A ₂ represents an oxygen atom or * -COO- (a bond with "*" is a bond with (CH ₂ ) _a2 ). a ₁ is an integer of 0 or 1, and a ₂ is an integer of 2-10. Cy, a group described as "Cy" in a cyclohexyl ring, represents 1,4-cyclohexyl or 1,4-phenylene.

The specific side chain structure is, for example, a specific side chain structure represented by the following formula [S2].

In the above formula [S2], X ³ represents a single bond, -CONH-, -NHCO-, -CON (CH ₃ )-, -NH-, -O-, -CH ₂ O-, -COO-, or -OCO- Among them, from the viewpoint of liquid crystal alignment, X ^{3 is} preferably -CONH-, -NHCO-, -O-, -CH ₂ O-, -COO-, or -OCO-. R ² represents an alkyl group having 1 to 20 carbon atoms or an alkoxyalkyl group having 2 to 20 carbon atoms; any hydrogen that forms R ² may be substituted by fluorine. Among them, from the viewpoint of liquid crystal alignment, R ^{2 is} preferably an alkyl group having 3 to 20 carbon atoms or an alkoxyalkyl group having 2 to 20 carbon atoms.

Examples of the specific side chain structure include a specific side chain structure represented by the following formula [S3].

In the formula [S3], X ⁴ represents -CONH-, -NHCO-, -O-, -COO-, or -OCO-; and R ³ represents a structure having a cholesterol skeleton. The cholesterol skeleton here is a skeleton represented by the following formula (st) having three six-membered rings and one five-membered ring bonded.

Examples of the above formula [S3] are, for example, the following formula [S3-x] and the like, but they are not limited to this content.

In the formula [S3-x], X represents the formula [X1] or [X2]. In addition, Col represents at least one selected from the group formed by the formulas [Col1] ~ [Col3], and G represents at least one selected from the group formed by the formulas [G1] ~ [G4]; * Indicates a part which can be bonded to other bases.

Examples of preferred combinations of X, Col, and G in the above formula [S3-x], for example, a combination of formula [X1] and formulas [Col1] and [G2], formula [X1] and formulas [Col2], and [G2 ], Combination of formula [X2] and formulas [Col1] and [G2], combination of formula [X2] and formulas [Col2] and [G2], formula [X1] and formulas [Col3] and [G1] Combination, etc.

Specific examples of the formula [S3] include the structure of removing a hydroxyl group from a cholesterol compound described in paragraph [0024] of Japanese Patent Application Laid-Open No. 4-281427, as described in paragraph [0030] of the same publication. Structure for removing chlorinated acid groups from cholesterol compounds, structure for removing amine groups from cholesterol compounds described in paragraph [0038] of the same publication, structure for removing halogen groups from cholesterol compounds in paragraph [0042] of the same publication, and Japanese special The structures described in paragraphs [0018] to [0022] of Kaiping 8-146421.

These diamines having specific side chain structures represented by the above formulae [S1] to [S3] may be used alone or in combination of two or more. According to the characteristics required for a liquid crystal alignment film or a liquid crystal display element, one type may be used alone, or two or more types may be used in combination, and when two or more types are used in combination, the ratio thereof may be appropriately adjusted.

As described above, the diamine component of the present invention is a diamine having a structure represented by the formula (1) and a specific side chain structure selected from the group having the formulas [S1] to [S3]. Diamine formed by at least one of the diamines.

Among these, a diamine having a side chain structure selected from the group represented by the formulas [S1] to [S3], for example, has the following formulas [1-S1] to [1-S3], [ 2-S1] ~ [2-S3] structured diamine, etc.

In the above-mentioned formulas [1-S1] and [2-S1], X ¹ , X ² , G ¹ , G ² , R ¹ , m, and n have the same contents as in the case of the above formula [S1]. In the above formulas [1-S2] and [2-S2], X ³ and R ^{2 have the} same contents as in the case of the above formula [S2]. In the above-mentioned formulas [1-S3] and [2-S3], X ⁴ and R ^{3 have the} same contents as in the case of the above-mentioned formula [S3].

The diamines represented by the above formulas [1-S1] to [1-S3] have, for example, specific structures shown below, but they are not limited to this content.

The diamines represented by the above formulas [2-S1] to [2-S3] have, for example, specific structures shown below, but they are not limited to this content.

<Other diamines: diamines having photoreactive side chains> 中 Among the diamine components of this embodiment, other diamines may include diamines having photoreactive side chains. When the diamine component contains a diamine having a photoreactive side chain, a photoreactive side chain can be introduced into a specific polymer or a polymer other than the polymer.

The diamine having a photoreactive side chain is, for example, one represented by the following formula [VIII] or [IX], but it is not limited to these contents.

In the above formulas [VIII] and [IX], the position of the two amine groups (-NH ₂ ) may be any position on the benzene ring. For example, the position of the bond group on the side chain is 2 on the benzene ring. Position of 3, position of 2,4, position of 2,5, position of 2,6, position of 3,4 or position of 3,5, etc. From the viewpoint of reactivity when synthesizing polyamic acid, the position of 2,4, the position of 2,5, or the position of 3,5 is preferred. If the viewpoint of easy synthesis of the diamine is added, the position of 2,4 or the position of 3,5 is more preferable.

In the above formula [VIII], R ⁸ represents a single bond, -CH _2- , -O-, -COO-, -OCO-, -NHCO-, -CONH-, -NH-, -CH ₂ O-, -N (CH ₃ )-, -CON (CH ₃ )-, or -N (CH ₃ ) CO-. In particular, R ^{8 is} preferably a single bond, -O-, -COO-, -NHCO-, or -CONH-.

In the formula [VIII], R ⁹ represents a single bond or an alkylene group having 1 to 20 carbon atoms which may be substituted with a fluorine atom. The -CH ₂ -of the alkylene group herein may be arbitrarily substituted by -CF ₂ -or -CH = CH-. When any of the following groups is not adjacent to each other, it may be substituted by these groups;- O-, -COO-, -OCO-, -NHCO-, -CONH-, -NH-, a divalent carbocyclic or heterocyclic ring. The divalent carbocyclic ring or heterocyclic ring is specifically exemplified by the following formula (1a), but is not limited to these contents.

In the above formula [VIII], R ⁹ can be formed by a general organic synthesis method. However, from the viewpoint of ease of synthesis, a single bond or an alkylene group having 1 to 12 carbon atoms is preferred.

In the formula [VIII], R ¹⁰ represents a photoreactive group selected from the group consisting of the following formula (1b). Among them, R ¹⁰ is preferably a methacrylic group, an acrylic group, or a vinyl group from the viewpoint of photoreactivity.

In the formula [IX], Y ₁ represents -CH _2- , -O-, -CONH-, -NHCO-, -COO-, -OCO-, -NH-, or -CO-. Y ₂ represents an alkylene group having 1 to 30 carbon atoms, a divalent carbocyclic ring or a heterocyclic ring. Among the alkylene, divalent carbocyclic or heterocyclic ring, one or a plurality of hydrogen atoms may be substituted by a fluorine atom or an organic group. In Y ₂ , when the following groups are not adjacent to each other, -CH ₂ -may be substituted by these groups; -O-, -NHCO-, -CONH-, -COO-, -OCO-, -NH- , -NHCONH-, -CO-.

In the formula [IX], Y ₃ represents -CH _2- , -O-, -CONH-, -NHCO-, -COO-, -OCO-, -NH-, -CO-, or a single bond. Y ₄ represents a cinnamoyl group. Y ₅ represents a single bond, an alkylene group having 1 to 30 carbon atoms, a divalent carbocyclic ring or a heterocyclic ring. Herein, in the alkylene, divalent carbocyclic or heterocyclic ring, one or a plurality of hydrogen atoms may be substituted by a fluorine atom or an organic group. When the following groups of Y ₅ are not adjacent to each other, -CH ₂ -may be replaced by these groups; -O-, -NHCO-, -CONH-, -COO-, -OCO-, -NH-,- NHCONH-, -CO-. Y ₆ represents a photopolymerizable group such as an acrylic group or a methacrylic group.

Specific examples of the diamine having a photoreactive side chain represented by the above formula [VIII] or [IX] include, for example, the following formula (1c) and the like, but they are not limited to these contents.

In the formula (1c), X ⁹ and X ¹⁰ each independently represent a single bond, -O-, -COO-, -NHCO-, or -NH- bonding group. Y represents an alkylene group having 1 to 20 carbon atoms which may be substituted by a fluorine atom.

The diamine having a photoreactive side chain is, for example, a diamine of the following formula [VII]. The diamine of the formula [VII] has a site having a radical generating structure in a side chain. The free radical generating structure can be decomposed by the irradiation of ultraviolet rays to generate free radicals.

In the above formula [VII], Ar represents at least one type of aromatic hydrocarbon group selected from the group consisting of phenylene, naphthalene and phenylene. The hydrogen atoms in the rings may be replaced by halogen atoms. . Ar, which is bonded to a carbonyl group, is related to the absorption wavelength of ultraviolet rays. Therefore, when a long wavelength is desired, a long structure having a conjugate length such as a naphthyl group or a biphenyl group is preferred. On the other hand, when Ar is a structure such as a naphthyl group or a biphenylene group, the solubility may be reduced. In this case, the ease of synthesis will be increased. In addition, as long as the ultraviolet wavelength is in a range of 250 nm to 380 nm, sufficient characteristics can also be obtained with phenyl, and Ar is preferably phenyl.

In the Ar, the aromatic hydrocarbon group may be provided with a substituent. Examples of the substituent here include an alkyl group, a hydroxyl group, an alkoxy group, an amine group, and the like, and an electron-donating organic group is preferred.

In the formula [VII], R ₁ and R ₂ each independently represent an alkyl group, alkoxy group, benzyl group, or phenethyl group having 1 to 10 carbon atoms. When it is an alkyl group or an alkoxy group, R ₁ and R ₂ may form a ring together.

In the above formula [VII], T ₁ and T ₂ each independently represent a single bond, -O-, -COO-, -OCO-, -NHCO-, -CONH-, -NH-, -CH ₂ O- , -N (CH ₃ )-, -CON (CH ₃ )-, or -N (CH ₃ ) CO-.

In Formula [VII], S represents a single bond, unsubstituted or substituted alkyl group having 1 to 20 carbon atoms. The -CH ₂ -or -CF ₂ -of the alkylene group herein may be arbitrarily substituted by -CH = CH-. When any of the enumerated below is not adjacent to each other, it may be substituted by these groups. ; -O-, -COO-, -OCO-, -NHCO-, -CONH-, -NH-, a divalent carbocyclic ring, a divalent heterocyclic ring.

In formula [VII], Q represents a structure selected by the following formula (1d).

In the formula (1d), R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. R ₃ represents -CH _2- , -NR-, -O-, or -S-.

In the above formula [VII], Q is preferably an electron-donating organic group, and is more preferably an alkyl group, a hydroxyl group, an alkoxy group, an amine group, or the like exemplified by Ar. When Q is an amine derivative, when polymerizing polyamic acid, which is a precursor of polyimide, from the viewpoint that the resulting carboxylic acid group will form a salt with the amine group and cause polymerization obstacles. Alkoxy is preferred.

In addition, in the formula [VII], the position of the two amine groups (-NH ₂ ) may be any of o-phenylenediamine, m-phenylenediamine, or p-phenylenediamine, and From the viewpoint of the reactivity of the acid dianhydride, m-phenylenediamine or p-phenylenediamine is preferred.

Therefore, as a preferable specific example of the said formula [VII], the following formula etc. are mentioned from a viewpoint of the ease of synthesis | combination, the height of the versatility, and a characteristic. In the following formula, n is an integer of 2 to 8.

These diamines having a photoreactive side chain represented by the formula [VII], [VIII], or [IX] may be used alone or in combination of two or more. It can be used alone or as a mixture of two or more liquid crystal alignment characteristics, pretilt angles, voltage holding characteristics, and charge accumulation characteristics when used as a liquid crystal alignment film, and liquid crystal response speed when used as a liquid crystal display element. When two or more kinds are mixed and used, the ratio and the like can be appropriately adjusted.

In this embodiment, when the diamine component contains a photoreactive side chain diamine, the photoreactive side chain diamine preferably contains 10 to 70 mole% and 10 to 60 mole% of the total diamine component. Is better.

<Other diamines: Diamines other than the above> Other diamines included in the diamine component used in the production of a specific polymer are not limited to the above-mentioned diamines having a photoreactive side chain and the like. Examples of the diamine other than the diamine having a photoreactive side chain are, for example, those represented by the following formula [2].

In the above formula [2], A ₁ and A ₂ each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms or an alkynyl group having 2 to 5 carbon atoms. Among these, A ₁ and A ₂ are preferably a hydrogen atom or a methyl group from the viewpoint of the reactivity of the monomer. In addition, when exemplifying the Y ₁ structure, the following formulae (Y-1) to (Y-160), (Y162) to (Y-168), and (Y-170) to (Y-174) are listed. Wait.

In the above formulas, in the structural formula in which the range of n is not specifically described, n is an integer of 1 to 6. In the above formula, Me represents a methyl group.

In the above formula, Boc represents a tert-butoxycarbonyl group.

The other diamines including the diamine having a photoreactive side chain described above may be used singly or in combination of two or more kinds. When the diamine component contains other diamines, in the specific polymer, the specific diamine is 5 mol% to 80 mol%, and preferably 10 mol% to 70 mol% relative to the specific diamine of other diamines. The amount is preferably 20 mol% to 70 mol%.

<Tetracarboxylic acid component> The tetracarboxylic acid component of a specific polymer can be prepared, for example, tetracarboxylic acid, tetracarboxylic dianhydride, tetracarboxylic dihalide, tetracarboxylic acid dialkyl ester, or tetracarboxylic acid dialkyl ester. Dihalides and the like are collectively referred to as tetracarboxylic acid components in the present invention.

A tetracarboxylic acid component, for example, a tetracarboxylic dianhydride, or a derivative thereof, a tetracarboxylic acid, a tetracarboxylic acid dihalide, a tetracarboxylic acid dialkyl ester, or a tetracarboxylic acid dialkyl dihalide ( These are collectively referred to as the first group of tetracarboxylic acid components).

Examples of the tetracarboxylic dianhydride include aliphatic tetracarboxylic dianhydride, alicyclic tetracarboxylic dianhydride, and aromatic tetracarboxylic dianhydride. Specific examples of these include the contents of the following groups [1] to [5].

[1] aliphatic tetracarboxylic dianhydride, for example, 1,2,3,4-butanetetracarboxylic dianhydride, etc .;

[2] Alicyclic tetracarboxylic dianhydrides, for example, acid dianhydrides such as the following formulae (X1-1) to (X1-13),

In the above formulae (X1-1) to (X1-4), R ₃ to R ₂₃ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, and a carbon number 2 An alkynyl group of ~ 6, a monovalent organic group of 1 to 6 carbon atoms containing a fluorine atom, or a phenyl group. R _M represents a hydrogen atom or a methyl group. In the formula (X1-13), Xa represents a tetravalent organic group represented by the following formulae (Xa-1) to (Xa-7).

[3] 3-oxabicyclo [3.2.1] octane-2,4-dione-6-spiro-3 '-(tetrahydrofuran-2', 5'-dione), 3,5,6- Tricarboxy-2-carboxymethyl norbornane-2: 3,5: 6-dianhydride, 4,9-dioxatricyclo [5.3.1.02,6] undecane-3,5,8,10 -Tetraketone, etc .;

[4] Aromatic tetracarboxylic dianhydrides, such as pyromellitic anhydride, 4,4 '-(hexafluoroisopropylidene) diphthalic anhydride, 3,3', 4,4'-diphenyl碸 tetracarboxylic dianhydride, acid dianhydride represented by the following formulae (Xb-1) to (Xb-10), and

[5] Acid dianhydrides represented by formulae (X1-44) to (X1-52), tetracarboxylic dianhydride described in Japanese Patent Application Laid-Open No. 2010-97188, and the like.

The tetracarboxylic acid components described above can be used singly or in combination of two or more. According to the characteristics required for a liquid crystal alignment film or a liquid crystal display element, one type may be used alone, or two or more types may be used in combination, and when two or more types are used in combination, the ratio thereof may be appropriately adjusted.

<Manufacturing method of a specific polymer> A specific polymer can be produced by a method in which the diamine component (diamine component formed by a plurality of types of diamines) of the present embodiment described above is reacted with a tetracarboxylic acid component. In this method, for example, a diamine component formed by one or more types of diamines and at least one type of tetracarboxylic acid selected from the group consisting of tetracarboxylic dianhydride and its tetracarboxylic acid derivative are used. Ingredients, and a method for preparing polyamic acid by reacting. Specifically, for example, a method in which a primary or secondary diamine is polycondensed with a tetracarboxylic dianhydride to obtain a polyamic acid can be used.

In the production of polyalkylamino alkyl esters, for example, a method of polycondensing a tetracarboxylic acid obtained by dialkylating a carboxylic acid group with a primary or secondary diamine and halogenating the carboxylic acid group can be used. A method of polycondensation of a tetracarboxylic acid dihalide with a primary or secondary diamine, or a method of converting a carboxyl group of a polyamic acid into an ester. In the production of polyimide, a method of forming a polyimide by ring-closing the polyamic acid or an alkyl polyamic acid may be used.

The reaction of the diamine component and the tetracarboxylic acid component is usually performed in a solvent. The solvent used in this case is not particularly limited as long as it can dissolve the produced polyimide precursor. Examples of the solvent here are, for example, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone or γ-butyrolactone, N, N-dimethylformamide, N, N -Dimethylacetamide, dimethyl sulfenimide, 1,3-dimethyl-imidazolinone, and the like. In addition, when the solvent solubility of the polyimide precursor is high, methyl ethyl ketone, cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone, or the following formula [D -1] ~ [D-3], etc.

In the formula [D-1], D ¹ represents an alkyl group having 1 to 3 carbon atoms. In the formula [D-2], D ² represents an alkyl group having 1 to 3 carbon atoms. In the formula [D-3], D ³ represents an alkyl group having 1 to 4 carbon atoms.

These solvents may be used alone or in combination of two or more. Even if the solvent does not dissolve the polyfluorene imide precursor, as long as it is within a range that does not precipitate the generated polyfluorene imide precursor, it can be mixed and used in the above-mentioned solvent. In addition, the water in the solvent is to prevent the polymerization reaction, and also to cause hydrolysis of the produced polyimide precursor. Therefore, the solvent is preferably dehydrated and dried.

When the diamine component and the tetracarboxylic acid component are reacted in a solvent, for example, the diamine component is dispersed in a solvent, or the dissolved solution is stirred, the tetracarboxylic acid component itself, or dispersed or dissolved in A method of adding after the solvent. Conversely, a method of dispersing a tetracarboxylic acid component in a solvent or a solution after dissolution and adding a diamine component, a method of adding a diamine component and a tetracarboxylic acid component alternately, etc. , You can also use any of these methods. In addition, when the diamine component or the tetracarboxylic acid component is reacted by using a plurality of types, the reaction may be carried out in a state of being mixed in advance, or the reactions may be performed in sequence, or the The low-molecular weight body may be mixed to form a polymer.

The temperature for the polycondensation reaction between the diamine component and the tetracarboxylic acid component can be selected from any temperature of -20 to 150 ° C, preferably in the range of -5 to 100 ° C. The reaction can be carried out at an arbitrary concentration, but when the concentration is too low, it is difficult to obtain a polymer with a high molecular weight, and when the concentration is too high, it is difficult to stir uniformly because the viscosity of the reaction solution is too high. Therefore, it is preferably 1 to 50% by mass, and more preferably 5 to 30% by mass. It is also possible to use a method in which the reaction is carried out at a high concentration at the beginning of the reaction, and thereafter, a solvent is added.

In the polymerization reaction of the polyfluorene imide 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. This is the same as a normal polycondensation reaction, and the closer the mole ratio is to 1.0, the larger the molecular weight of the polyfluorene imide precursor produced.

Polyimide is a polyimide obtained from the aforementioned polyimide precursor through ring closure. In this polyimide, the ring closure rate (also known as the amidation rate) of the amido acid group is not Must be 100%, which can be adjusted arbitrarily according to the purpose or purpose. Method for polyimide precursor imidization, for example, heating the polyimide precursor solution without processing to thermally imidize it, or adding a catalyst to the polyimide precursor solution Make it catalyst 醯 imidization and other methods.

The temperature when the polyfluorene imine precursor is thermally fluorinated in the solution is 100-400 ° C, preferably 120-250 ° C, in order to discharge the water generated from the fluorimide reaction to the outside of the reaction system. The reaction is preferably carried out. The catalyst of polyimide precursor can be imidized, and alkaline catalyst and acid anhydride can be added to the solution of polyimide precursor, and then the temperature is -20 ~ 250 ℃, preferably 0 ~ 180 ℃. Performed by stirring.

The amount of the alkaline catalyst is 0.5 to 30 mol times of the amino acid group, preferably 2 to 20 mol times, and the amount of the acid anhydride is 1 to 50 mol times of the amino acid group, preferably 3 ~ 30 mol times. Basic catalysts, for example, pyridine, triethylamine, trimethylamine, tributylamine, trioctylamine and the like. Among them, pyridine is preferably used in the reaction to maintain proper basicity. The acid anhydride is, for example, acetic anhydride, trimellitic anhydride, pyromellitic anhydride, and the like. In particular, when acetic anhydride is used, it is preferable to facilitate purification after completion of the reaction. The rate of catalyst imidization obtained by imidization of catalyst can be controlled by adjusting the amount of catalyst and the reaction temperature and reaction time.

When recovering a polyfluorene imide precursor or a polyfluorene imide generated from a polyfluorene imide precursor or a polyimide reaction solution, the reaction solution can be put into a solvent to precipitate. The solvent used for the precipitation is, for example, methanol, ethanol, isopropanol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, toluene, benzene, water, and the like. The polymer precipitated by adding a solvent is filtered and recovered, and then it can be dried under normal pressure or reduced pressure, or under normal temperature or heating. In addition, when the polymer after precipitation recovery is repeated 2 to 10 times to re-dissolve in a solvent and re-precipitation recovery operation, impurities in the polymer can be reduced. The solvents used at this time include, for example, alcohols, ketones, and hydrocarbons. When three or more solvents selected from these are used, it is more preferable to improve the efficiency of purification.

In the method for producing the polyalkylaminophosphonate of the present invention, more specific method examples are shown in the following (1) to (3), for example.

(1) Production method based on esterification reaction of polyamidic acid This method, for example, manufactures polyamidic acid from a diamine component and a tetracarboxylic acid component, and chemically reacts the carboxyl group (COOH group) to perform esterification. Chemical reaction to produce polyalkylammonium alkylate. The esterification reaction is carried out at a temperature of -20 to 150 ° C (preferably 0 to 50 ° C) for 30 minutes to 24 hours (preferably 1 to 4) in order to make the polyamic acid and the esterifying agent in the presence of a solvent. Hours) method of reaction.

The esterifying agent is preferably one which can be easily removed after the esterification reaction, and examples thereof include N, N-dimethylformamide dimethyl acetal, and N, N-dimethylformamide diethyl Acetal, N, N-dimethylformamide dipropyl acetal, N, N-dimethylformamide dineopentylbutyl acetal, N, N-dimethylformamide diacetal -t-butylacetal, 1-methyl-3-p-tolyltriazene, 1-ethyl-3-p-tolyltriazene, 1-propyl-3-p-tolyltriazene Azene, 4- (4,6-dimethoxy-1,3,5-tri 2-yl) -4-methylmorpholinium chloride and the like. The amount of the esterifying agent is preferably 2 to 6 mol equivalents relative to 1 mol of the repeating unit of polyamic acid. Among them, 2 to 4 mole equivalents are preferred.

The solvent used for the esterification reaction is, for example, a solvent used when the diamine component reacts with a tetracarboxylic acid component from the viewpoint of solubility in a polyamic acid solvent. Among them, N, N-dimethylformamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone or γ-butyrolactone is more preferable. These solvents may be used singly or in combination of two or more kinds. In the above-mentioned esterification reaction, the concentration of the polyamic acid in the solvent is preferably 1 to 30% by mass from the viewpoint that the polyamic acid is unlikely to cause precipitation. Among them, 5 to 20% by mass is preferred.

(2) A method for producing by reacting a diamine component with a tetracarboxylic acid diester dichloride. This method, for example, makes a diamine component and a tetracarboxylic acid diester dichloride in the presence of a base and a solvent. A method of performing a reaction at -20 to 150 ° C (preferably 0 to 50 ° C) for 30 minutes to 24 hours (preferably 1 to 4 hours). As the base, pyridine, triethylamine, 4-dimethylaminopyridine and the like can be used. Among them, it is preferable to use pyridine for the reaction to proceed stably. The amount of base used is preferably an amount that can be easily removed after the reaction. Generally, 2 to 4 mol times is preferred, and 2 to 3 mol times is more preferred to tetracarboxylic diester dichloride.

The solvent is, from the viewpoint of the solubility of the obtained polymer, that is, the alkyl polyamidoate to the solvent, for example, a solvent used for the reaction between the diamine component and the tetracarboxylic acid component. Among them, N, N-dimethylformamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone or γ-butyrolactone is more preferable. Among these solvents, one kind may be used alone or two or more kinds may be used in combination.

From the viewpoint that the concentration of the polyalkylene alkylate in the solvent during the reaction is not likely to cause the precipitation of the polyalkylamino alkyl ester, the concentration is preferably 1 to 30% by mass. Among them, 5 to 20% by mass is preferred. From the viewpoint of preventing hydrolysis of the tetracarboxylic acid diester dichloride, it is preferable to use as much as possible a solvent for the production of the polyalkylamino alkyl ester. In addition, the reaction is performed in a nitrogen atmosphere, and it is preferable to prevent outside air from being mixed.

(3) Method for producing by reacting a diamine component with a tetracarboxylic acid diester This method, for example, makes a diamine component and a tetracarboxylic acid diester in the presence of a condensing agent, a base, and a solvent at 0 to 150 A method of carrying out a polycondensation reaction at a temperature of 30 ° C (preferably 0 to 100 ° C) for 30 minutes to 24 hours (preferably 3 to 15 hours).

As the condensing agent, for example, triphenylphosphite, dicyclohexylcarbodiimide, 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride, N, N'-carbonyldiimidazole, dimethoxy-1,3,5-tri Methylmorpholinium, O- (benzotriazol-1-yl) -N, N, N ', N'-tetramethylurea tetrafluoroborate, O- (benzotriazol-1-yl ) -N, N, N ', N'-tetramethylurea hexafluorophosphate, (2,3-dihydro-2-thio-3-benzoxazolyl) phosphonic acid diphenyl Base etc. The amount of the condensing agent is preferably 2 to 3 mol times, especially 2 to 2.5 mol times relative to the tetracarboxylic acid diester.

As the base, tertiary amines such as pyridine and triethylamine can be used. The amount of alkali used is preferably an amount that can be easily removed after the polycondensation reaction. Generally, it is preferably 2 to 4 mol times, and more preferably 2 to 3 mol times relative to the diamine component. For the solvent used in the polycondensation reaction, from the viewpoint of the solubility of the obtained polymer, that is, the alkyl alkyl polyamine, to the solvent, for example, the solvent used for the reaction between the diamine component and the tetracarboxylic acid component described above can be used. . Among them, N, N-dimethylformamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone or γ-butyrolactone is more preferable. These solvents may be used singly or in combination of two or more kinds.

In addition, when a Lewis acid is added as an additive in the polycondensation reaction, the reaction can be efficiently performed. The Lewis acid is preferably a lithium halide such as lithium chloride or lithium bromide. The amount of Lewis acid used is preferably 0.1 to 10 mole times relative to the diamine component. Among them, 2.0 ~ 3.0 Molar times is better.

When recovering the polyalkylamine solution from the solution of the polyalkylamino acid ester obtained by the methods (1) to (3) above, the reaction solution may be added to the solvent to precipitate it. The solvent used for the precipitation is, for example, water, methanol, ethanol, 2-propanol, hexane, cellosolve, acetone, toluene, and the like. When the polymer which is precipitated by adding a solvent is used for the purpose of removing the additives, catalysts and the like used above, it is preferable to perform the washing operation several times using the above-mentioned solvent. After washing, filtering, and recovering, the polymer can be dried under normal pressure or reduced pressure, or under normal temperature or heating. In addition, by repeating the operation of re-dissolving the polymer recovered by precipitation 2 to 10 times in a solvent and re-precipitating and recovering, the impurities in the polymer can be reduced. The polyalkylene alkanoate is preferably produced by the method (2) or (3).

<Liquid crystal alignment agent> The liquid crystal alignment agent of the present invention contains the specific polymer described above, but may also contain two or more specific polymers having different structures. In addition to the specific polymer, other polymers may be contained, that is, a polymer obtained without a divalent group represented by the formula (1) (does not contain the specific diamine represented by the formula (1) And obtained polymer). Forms of polymers, for example, polyamic acid, polyimide, polyamidate, polyester, polyamine, polyurea, polyorganosiloxane, cellulose derivative, polyacetal, polyphenylene Ethylene or its derivatives, poly (styrene-phenylmaleimide) derivatives, poly (meth) acrylates, and the like. When the liquid crystal alignment agent of the present invention contains other polymers, the proportion of the specific polymer is preferably 5% by mass or more, for example, 5 to 95% by mass, relative to the total polymer component.

From the viewpoint that a liquid crystal alignment agent can form a uniform film, it is generally in the form of a coating liquid. The liquid crystal alignment agent of the present invention is also preferably a coating liquid containing the above polymer component and an organic solvent in which the polymer component is dissolved. At this time, the concentration of the polymer in the liquid crystal alignment agent can be appropriately changed according to the thickness of the coating film to be formed. From a viewpoint of forming a uniform and defect-free coating film, 1 mass% or more is preferable, and from a viewpoint of storage stability of a solution, 10 mass% or less is preferable. The concentration of the particularly good polymer is 2 to 8% by mass.

The organic solvent contained in the liquid crystal alignment agent is not particularly limited as long as the polymer component can be uniformly dissolved. When specific examples are given, for example, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone , Dimethyl sulfene, γ-butyrolactone, 1,3-dimethyl-imidazolinone, methyl ethyl ketone, cyclohexanone, cyclopentanone, and the like. Among them, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, or γ-butyrolactone is more preferable.

In addition, the organic solvent contained in the liquid crystal alignment agent of the present invention can be used in addition to the solvents described above, and when the liquid crystal alignment agent is applied, a solvent that can improve the coatability or the surface smoothness of the coating film. Specific examples of the organic solvent include those listed below, but they are not limited to these.

For example, ethanol, isopropanol, 1-butanol, 2-butanol, isobutanol, tert-butanol, 1-pentanol, 2-pentanol, 3-pentanol, 2-methyl-1-butanol Alcohol, isoamyl alcohol, tert-pentanol, 3-methyl-2-butanol, neopentyl alcohol, 1-hexanol, 2-methyl-1-pentanol, 2-methyl-2-pentanol, 2-ethyl-1-butanol, 1-heptanol, 2-heptanol, 3-heptanol, 1-octanol, 2-octanol, 2-ethyl-1-hexanol, cyclohexanol, 1 -Methylcyclohexanol, 2-methylcyclohexanol, 3-methylcyclohexanol, 2,6-dimethyl-4-heptanol, 1,2-ethanediol, 1,2-propane Glycol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,5 -Pentanediol, 2-methyl-2,4-pentanediol, 2-ethyl-1,3-hexanediol, diisopropyl ether, dipropyl ether, dibutyl ether, dihexyl ether, Dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, 1,2-butoxyethane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, 4 -Hydroxy-4-methyl-2-pentanone, diethylene glycol methyl ether, diethylene glycol dibutyl ether, 2-pentanone, 3-pentanone, 2-hexanone, 2-heptanone, 4 -Heptanone, 2,6-dimethyl-4-heptanone, 4,6-di Methyl-2-heptanone, 3-ethoxybutyl acetate, 1-methylpentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, ethylenedi Alcohol monoacetate, ethylene glycol diacetate, propylene carbonate, ethylene carbonate, 2- (methoxymethoxy) ethanol, ethylene glycol monobutyl ether, ethylene glycol monoisoamyl ether, ethylene glycol Alcohol monohexyl ether, 2- (hexyloxy) ethanol, furfuryl alcohol, diethylene glycol, propylene glycol, propylene glycol monobutyl ether, 1- (butoxyethoxy) propanol, propylene glycol monomethyl ether acetate, two Propylene glycol, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol dimethyl ether, tripropylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, Ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monoacetate, ethylene glycol diacetate, diethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether Butyl ether acetate, 2- (2-ethoxyethoxy) ethyl acetate, diethylene glycol acetate, triethylene glycol, triethylene glycol monomethyl ether, triethylene glycol mono Diethyl ether, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, ethyl acetate n-butyl ester, propylene glycol monoethyl ether, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, ethyl methyl 3-ethoxypropionate , Ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, propyl 3-methoxypropionate, butyl 3-methoxypropionate, methyl lactate , Ethyl lactate, n-propyl lactate, n-butyl lactate, isoamyl lactate, solvents represented by the above formulas [D-1] to [D-3], and the like.

Among these, 1-hexanol, cyclohexanol, 1,2-ethanediol, 1,2-propanediol, propylene glycol monobutyl ether, diethylene glycol diethyl ether, and 4-hydroxy-4 are used as the organic solvent. -Methyl-2-pentanone, ethylene glycol monobutyl ether or dipropylene glycol dimethyl ether is preferred. The types and contents of these solvents can be appropriately selected according to the coating device, coating conditions, and coating environment of the liquid crystal alignment agent.

The liquid crystal alignment agent of the present invention may further contain components other than the polymer component and the organic solvent. These additional components, for example, improve the adhesion between the liquid crystal alignment film and the substrate, or improve the adhesion between the liquid crystal alignment film and the film material, a cross-linking agent that enhances the strength of the liquid crystal alignment film, and adjust the liquid crystal. The dielectric constant of the alignment film or the dielectric or conductive material used for the resistance. Specific examples of these additional components include, for example, the poor solvents or crosslinkable compounds disclosed in paragraphs [0104] to 60 of paragraphs [0116] on page 53 of International Publication No. 2015/060357.

The liquid crystal alignment agent of the present invention may contain, in addition to the above, a polymer other than the specific polymer described in the present invention, for example, a dielectric for the purpose of changing electrical properties such as the dielectric constant or conductivity of the liquid crystal alignment film. Body, a silane coupling agent for the purpose of improving the adhesion between the liquid crystal alignment film and the substrate, a crosslinkable compound for the purpose of improving the hardness or density of the film when used as the liquid crystal alignment film, and when the coating film is sintered, A polyimide imidization accelerator, etc., for the purpose of efficiently performing polyimidization when heating a polyimide precursor.

Examples of the compound for improving the adhesion between the liquid crystal alignment film and the substrate include a functional silane-containing compound or an epoxy-containing compound, for example, 3-aminopropyltrimethoxysilane and 3-aminopropyltriamine. Ethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 2- Aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3 -Aminopropylmethyldimethoxysilane, 3-ureidepropyltrimethoxysilane, 3-ureaylpropyltriethoxysilane, N-ethoxycarbonyl-3-aminopropyltrimethylsilane Oxysilane, N-ethoxycarbonyl-3-aminopropyltriethoxysilane, N-triethoxysilylpropyltriethylenetriamine, N-trimethoxysilylpropyltriethylene Ethyltriamine, 10-trimethoxysilyl-1,4,7-triazadecane, 10-triethoxysilyl-1,4,7-triazadecane, 9-trimethoxy Silyl-3,6-diazanonyl acetate, 9-triethoxysilyl-3,6-diazanonyl acetate, N-benzyl-3- Aminopropyltrimethoxysilane, N-benzyl-3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriamine Ethoxysilane, N-bis (oxyvinyl) -3-aminopropyltrimethoxysilane, N-bis (oxyethylene) -3-aminopropyltriethoxysilane, ethylene glycol diglycidyl Ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether Ether, glycerol diglycidyl ether, 2,2-dibromo neopentyl glycol diglycidyl ether, 1,3,5,6-tetraglycidyl-2,4-hexanediol, N, N, N ', N',-tetraglycidyl-m-xylylenediamine, 1,3-bis (N, N-diglycidylamine methyl) cyclohexane or N, N, N ', N',-tetra Glycidol-4, 4'-diaminodiphenylmethane and the like.

In addition, to the liquid crystal alignment agent of the present invention, from the viewpoint of improving the mechanical strength of the liquid crystal alignment film, the following additives may be added.

The additive is preferably 0.1 to 30 parts by mass based on 100 parts by mass of the polymer component contained in the liquid crystal alignment agent. If it is less than 0.1 parts by mass, the effect cannot be expected, and if it exceeds 30 parts by mass, the alignment of the liquid crystal is reduced, so it is more preferably 0.5 to 20 parts by mass.

<Liquid crystal alignment film> The liquid crystal alignment film of the present invention is prepared from the above-mentioned liquid crystal alignment agent. The use of the liquid crystal alignment agent according to the present invention is a VA method suitable for liquid crystal molecules that form a vertical alignment with a substrate to respond to changes in an electric field, and is particularly suitable for use in a PSA mode. It can provide an excellent voltage retention rate, A liquid crystal alignment film or a liquid crystal display element that rapidly alleviates the accumulated charge and has excellent afterimage characteristics. For example, a method for manufacturing a liquid crystal alignment film is described. For example, the liquid crystal alignment agent of the present invention can be applied to a substrate, and a hardened film obtained by drying and sintering can be used as a liquid crystal alignment film without processing. . In addition, the cured film may be subjected to rubbing treatment, irradiation with polarized light or light of a specific wavelength, and ion beam treatment to form an alignment film for PSA and apply a voltage to a liquid crystal display element filled with liquid crystal. Irradiate UV. It is particularly suitable for use as an alignment film for PSA.

The substrate to which the liquid crystal alignment agent is applied is not particularly limited as long as it is a substrate having high transparency. In addition to a glass substrate and a silicon nitride substrate, a plastic substrate such as an acrylic substrate or a polycarbonate substrate may be used. In this case, when a substrate having an ITO electrode for driving the liquid crystal is used, it is preferable from the viewpoint of simplifying the manufacturing process. In the case of a reflective liquid crystal display device, if the substrate is a single-sided substrate, an opaque body such as a silicon wafer can also be used, and an electrode such as aluminum that can reflect light can also be used.

The coating method of the liquid crystal alignment agent is not particularly limited. In industry, generally, screen printing, lithography, flexo printing, inkjet method, and the like are used. Other coating methods include, for example, a dipping method, a roll coating method, a slit coating method, a spin coater method, and a spray method. These methods can be used in accordance with the purpose. After the liquid crystal alignment agent is coated on the substrate, the solvent is evaporated and sintered through heating means such as a hot plate, a thermal cycle type oven, and an IR (infrared) type oven. In the drying and sintering steps after applying the liquid crystal alignment agent, an arbitrary temperature and time can be selected. The drying step is not absolutely necessary, but when the time from coating to sintering cannot be specified depending on each substrate, or when sintering is not performed immediately after coating, the drying step is preferably performed. This drying means is only required to remove the solvent to such an extent that the shape of the coating film is not deformed when the substrate or the like is transported, and the drying means is not particularly limited. For example, drying on a hot plate at a temperature of 40 ° C to 150 ° C, preferably 60 ° C to 100 ° C, for 0.5 minutes to 30 minutes, preferably 1 minute to 5 minutes.

The sintering temperature for forming a coating film by applying the liquid crystal alignment agent is not particularly limited, and may be, for example, 100 to 350 ° C, preferably 120 to 300 ° C, and more preferably 150 to 250 ° C. The sintering time is 5 minutes to 240 minutes, preferably 10 minutes to 90 minutes, and more preferably 20 minutes to 90 minutes. Heating can be performed by a generally known method, for example, a hot plate, a hot-air circulation furnace, an infrared furnace, or the like.

The thickness of the sintered liquid crystal alignment film may reduce the reliability of the liquid crystal display element when it is too thin. Therefore, the thickness is preferably 5 to 300 nm, and more preferably 10 to 200 nm. The liquid crystal alignment film of the present invention is useful as a liquid crystal alignment film of a liquid crystal display element of a VA system, particularly a PSA mode.

<Liquid crystal display element and its manufacturing method> (1) A liquid crystal display element can be made into a liquid crystal cell by a known method after forming a liquid crystal alignment film on a substrate according to the method described above. Specific examples of the liquid crystal display element include, for example, a liquid crystal alignment film including two substrates disposed opposite to each other, a liquid crystal layer provided between the substrates, and a liquid crystal alignment agent provided between the substrate and the liquid crystal layer. A liquid crystal display element of a vertical alignment method obtained from a liquid crystal cell. Specifically, a liquid crystal alignment agent is coated on two substrates, and a liquid crystal alignment film is formed by sintering. The two substrates are arranged with the liquid crystal alignment film facing each other, and sandwiched between the two substrates. A liquid crystal layer made of liquid crystal, that is, a liquid crystal layer is provided by contacting the liquid crystal alignment film, and a voltage is applied to the liquid crystal alignment film and the liquid crystal layer while irradiating ultraviolet rays to produce a liquid crystal display with a vertical alignment method including a liquid crystal cell. element.

The substrate of the liquid crystal display element is not particularly limited as long as it is a substrate having high transparency, and is generally a substrate having a transparent electrode for driving liquid crystals formed on the substrate. Specifically, for example, the substrate is the same as the substrate described in the liquid crystal alignment film. A conventional substrate provided with an electrode pattern or a projection pattern can also be used. In a liquid crystal display element, a liquid crystal alignment agent containing the polyfluorene-imide polymer of the present invention is used, and for example, 1 μm to 10 μm is formed on a single-sided substrate. In the case of a line / space electrode pattern, operation can be performed even when a structure having no space pattern or protrusion pattern is formed on the opposing substrate. A liquid crystal display element having this structure can simplify the manufacturing process at the time of manufacture, and Higher penetration can be obtained.

In addition, in a high-performance device such as a TFT type device, an element such as a transistor can be formed between an electrode for driving liquid crystal and a substrate.

In the case of a transmissive liquid crystal display element, the above-mentioned substrate is generally used. In the case of a reflective liquid crystal display element, an opaque substrate such as a silicon wafer can be used for only one substrate. In this case, the electrode formed on the substrate may be made of a material such as aluminum that reflects light.

The liquid crystal material constituting the liquid crystal layer of the liquid crystal display element is not particularly limited. The liquid crystal material used in the conventional vertical alignment method can be used. For example, MLC-6608, MLC-6609, MLC- 3023 and other negative liquid crystals. In the PSA mode, for example, a liquid crystal containing a polymerizable compound represented by the following formula can be used.

As a method of sandwiching the liquid crystal layer between two substrates, for example, a known method can be used. For example, a pair of substrates on which a liquid crystal alignment film is formed is prepared, and spacers such as particles are dispersed on the liquid crystal alignment film of one of the substrates, and then the side on which the liquid crystal alignment film is formed is inwardly bonded to the other sheet. The method of injecting liquid crystal under reduced pressure and sealing the substrate. In addition, a pair of substrates on which a liquid crystal alignment film is formed is prepared, and spacers such as particles are dispersed on the liquid crystal alignment film of one of the substrates, and then the liquid crystal is dropped, and then the side on which the liquid crystal alignment film is formed is inward. A liquid crystal cell can also be prepared by bonding it to another substrate and then sealing it. The thickness of the spacer is preferably 1 to 30 μm, and more preferably 2 to 10 μm.

In applying a voltage to the liquid crystal alignment film and the liquid crystal layer, a step of manufacturing a liquid crystal cell is performed by irradiating ultraviolet rays, for example, applying a voltage between electrodes provided on a substrate to apply an electric field to the liquid crystal alignment film and the liquid crystal layer, and A method of irradiating ultraviolet rays while maintaining the electric field. The voltage applied between the electrodes is, for example, 5 to 30 Vp-p, and preferably 5 to 20 Vp-p. The amount of ultraviolet radiation is, for example, 1 to 60 J, preferably 40 J or less. When the amount of ultraviolet radiation is low, it is possible to suppress a decrease in reliability caused by damage to a member constituting the liquid crystal display element, and to reduce the time of ultraviolet radiation. It is better to improve manufacturing efficiency.

As described above, when a voltage is applied to the liquid crystal alignment film and the liquid crystal layer, a polymerizable compound can be reacted to form a polymer when irradiated with ultraviolet rays, and the oblique direction of the liquid crystal molecules can be memorized through the polymer, thereby accelerating the obtained liquid crystal display Response speed of components. In addition, when a voltage is applied to the liquid crystal alignment film and the liquid crystal layer, when ultraviolet rays are irradiated, a polyimide precursor having a side chain in which the liquid crystal is vertically aligned and a side chain reactive with light can be made, and the polyimide Polyamines obtained by fluorination of amine precursors with at least one polymer selected from the photoreactive side chains of the polymer, or the photoreactive side chains of the polymer and the polymerization The compound reacts to accelerate the response speed of the obtained liquid crystal display element.

Then, the polarizing plate is set. Specifically, for example, a pair of polarizing plates is preferably attached to the surfaces of the two substrates on the opposite sides to the liquid crystal layer.

The liquid crystal alignment film and the liquid crystal display element of the present invention are not limited to the above-mentioned constitution or manufacturing method as long as the liquid crystal alignment agent of the present invention is used, and they can be produced by other known methods. The steps from the liquid crystal alignment agent to the production of a liquid crystal display element are disclosed in, for example, paragraph [0074] on page 17 of Japanese Patent Application Publication No. 2015-135393 to paragraph [0082] on page 19.

When the polymer has a photoreactive side chain, the polymerizable compound is polymerized, and the photoreactive side chain and the polymerizable compound are reacted with each other via the photoreactive side chain or the polymer. The liquid crystal alignment is more efficiently fixed, and a liquid crystal display element having an excellent response speed is obtained.

[Example]

Examples will be listed below to describe the present invention in more detail, but the present invention is not limited or interpreted by these contents. The compounds used are as follows.

(Liquid crystal) MLC-3023 (Mico Corporation, a liquid crystal containing a negative polymerizable compound)

(Specific diamine) Compound A1 represented by the following formulas [A1] to [A6]: Compound A2 represented by formula [A1]: Compound A3 represented by formula [A2]: Compound A4 represented by formula [A3] : Compound A5 represented by Formula [A4]: Compound A6 represented by Formula [A5]: Compound A7 represented by Formula [A6]: A7: Compound represented by Formula [A7]

(Diamine having a specific side chain structure) Compound B1 represented by the following formulas [B1] to [B3]: Compound B2 represented by formula [B1]: Compound B3 represented by formula [B2]: Formula [B3] Represented compound

(Other diamines) Compounds C1 represented by the following formulas [C1] to [C5]: Compounds represented by the formula [C1] C2: Compounds represented by the formula [C2] C3: Compounds represented by the formula [C3] C4: compound represented by formula [C4] C5: compound represented by formula [C5]

(Tetracarboxylic acid component) Compounds D1 represented by the following formulas [D1] to [D3]: 1, 2, 3, 4-cyclobutane tetracarboxylic dianhydride D2: bicyclo [3,3,0] octyl Alkane-2,4,6,8-tetracarboxylic dianhydride D3: 3,3 ', 4,4'-benzophenone tetracarboxylic dianhydride D4: Compound represented by formula [D4]

(Solvent) NMP: N-methyl-2-pyrrolidone BCS: ethylene glycol monobutyl ether γBL: γ-butyrolactone

<Synthesis of A2, A4, and A5> A2, A4, and A5 are novel compounds not disclosed in the literature and the like, and their synthesis methods will be described in detail below.

The products described in the following [Synthesis Example A-1] to [Synthesis Example A-3] were identified by ¹ H-NMR analysis (the analysis conditions are shown below). Device: Varian NMR System 400 NB (400 MHz) Measurement solvent: CDCl _{3 ,} DMSO-d ₆ Reference substance: Tetramethylsilane (TMS) (δ 0.0 ppm for ¹ H)

[Synthesis Example A-1]: Synthesis of A4

<Synthesis of compound [1] in the reaction formula> (1) Zinc chloride (295.6g) was vacuum-dried at 100 ° C for 1 hour, and after removing water, toluene (742.0g), diethylamine (111.4g), and tert-butanol (120.2 g), 3'-nitroacetophenone (251.8 g), and the internal temperature was set to 42 ° C. Subsequently, tetrahydrofuran (494.6 g) in which 2-bromo-3'-nitroacetophenone (247.3 g, 1.01 mol) was dissolved was added dropwise over 90 minutes, and a reaction was performed at an internal temperature of 45 ° C for 16 hours. After the reaction was completed, sulfuric acid (49.7 g) and pure water (939.7 g) were poured into the reaction solution to precipitate crystals. After filtering the crystals, the filtered substance was washed with a mixed solvent of tetrahydrofuran (247.3 g) and pure water (247.3 g). After drying 3 times, 275.7 g of a compound [1] was obtained (yield: 83%, property: pale yellow crystals).

<Synthesis of compound [2] in the reaction formula> In tetrahydrofuran (110.7g) and ethanol (84.6g), add compound [1] (27.6g, 84.1mmol) and methylamine (about 7% tetrahydrofuran solution, about 2mol) / L, 100 mL), and under ice-cooled conditions in a nitrogen atmosphere, acetic acid (25.5 g) was added. After the addition of acetic acid, the reaction was carried out for 24 hours under reflux conditions in a nitrogen atmosphere. After the reaction was completed, pure water (276.0 g) was added to precipitate crystals, which was then filtered, and the filtrate was washed three times with methanol (55.2 g) and dried to obtain 26.0 g of compound [2] (yield: 96%, traits: pale orange crystals).

〈Synthesis of A4〉 To tetrahydrofuran (216.2g), compound [2] (26.0g, 80.5mmol) and 5% palladium carbon (2.1g) were added, and the reaction was carried out in a hydrogen atmosphere at 40 ° C for about 3 days. reaction. After completion of the reaction, filtration and concentration under reduced pressure were performed to obtain a total internal weight of 42.3 g. Subsequently, methanol (104.0 g) was added to precipitate crystals, and after filtration and drying, 17.4 g of A4 was obtained (yield: 82%, properties: white crystals). ¹ H-NMR (400MHz) in DMSO-d ₆ : 3.53ppm (s, 3H), 5.13 ppm (s, 4H), 6.12ppm (s, 2H), 6.50-6.53ppm (m, 2H), 6.60-6.62 ppm (m, 2H), 6.67ppm (t, J = 1.8Hz, 2H), 7.07ppm (t, J = 7.8 Hz, 2H)

[Synthesis example A-2]: Synthesis of A5

<Synthesis of compound [3] in the reaction formula> In tetrahydrofuran (1702 g), add compound [1] (243.2 g, 741 mmol) and ammonium acetate (286.0 g), and perform a reaction for 22 hours under a nitrogen atmosphere and reflux conditions. . After the reaction was completed, pure water (1702 g) was added to precipitate crystals. After filtration, the filtrate was washed twice with a mixed solution of tetrahydrofuran (243 g) and pure water (243 g), and then washed twice with methanol (365 g). Then, a drying treatment was performed to obtain 194.5 g of a compound [3] (yield: 85%, property: orange crystal).

<Synthesis of compound [4] in the reaction formula> In tetrahydrofuran (159.3g), add compound [3] (22.7g, 73.3 mmol) and 4-dimethylaminopyridine (0.44g), in a nitrogen atmosphere, room Tetrahydrofuran (11.3 g) in which di-tert-butyl dicarbonate (18.4 g) was dissolved was added dropwise under warm conditions, and the reaction was carried out at the same temperature for 5 hours. After the reaction was completed, methanol (90.8 g) was added, and the mixture was stirred, filtered, and washed with methanol under ice-cooling conditions to obtain 28.6 g of a compound [4] (yield: 95%, properties: pale yellow crystals).

<Synthesis of A5> To tetrahydrofuran (257.4 g), compound [4] (28.6 g, 69.9 mmol) and 5% palladium carbon (2.20 g) were added, and the reaction was performed in a hydrogen atmosphere at 40 ° C for about 3 days. reaction. After completion of the reaction, filtration, concentration under reduced pressure, and other treatments were performed to obtain a total internal weight of 41.6 g. Subsequently, 2-propanol (114.4 g) was added to precipitate crystals, and after filtering and drying treatment, 12.8 g of A5 was obtained (yield: 52%, properties: white crystals). ¹ H-NMR (400MHz) in DMSO-d ₆ : 1.23ppm (s, 9H), 5.12 ppm (s, 4H), 6.14ppm (s, 2H), 6.44-6.46ppm (m, 2H), 6.51-6.53 ppm (m, 4H), 6.99-7.03ppm (m, 2H).

[Synthesis Example A-3]: Synthesis of A2

<Synthesis of compound [5] in the reaction formula> Elimination of changing 3'-nitroacetophenone to 4'-nitroacetophenone and 2-bromo-3'-nitroacetophenone to 2 Except for -bromo-4'-nitroacetophenone, the others were synthesized in the same manner as in the synthesis of compound [1].

<Synthesis of compound [6] in the reaction formula> The compound [1] was synthesized in the same manner as the compound [3] except that the compound [1] was changed to the compound [5].

<Synthesis of compound [7]> Except that the compound [3] was changed to the compound [6], the rest were synthesized by the same method as the synthesis of the compound [4].

<Synthesis of A2> Except that the compound [4] was changed to the compound [7], everything was synthesized by the same method as the synthesis of A5. ¹ H-NMR (400MHz) in CDCl ₃ : 1.21ppm (s, 9H), 3.69ppm (s, 4H), 6.12ppm (s, 2H), 6.67-6.69ppm (m, 4H), 7.17-7.26 ppm ( m, 4H).

(Measurement of Polyimide Imidization Rate) 20 mg of polyimide powder was added to an NMR (nuclear magnetic resonance) sample tube (NMR standard sample tube, f5 (made by Kusano Science Co., Ltd.)), and deuterated dimethyl Glycoarene (DMSO-d6, 0.05% by mass TMS (tetramethylsilane) mixed product) (0.53 ml), completely dissolved by applying ultrasonic waves. This solution was used to measure a proton NMR at 500 MHz using an NMR measuring machine (JNW-ECA500) (manufactured by Japan Electronics Standard Corporation). The hydrazone imidization rate is the proton generated from a structure that has not changed before and after hydrazone imidization. It is used as the reference proton, and the peak value of the proton is used to calculate the ratio of the sulfamic acid that occurs around 9.5 to 10.0 ppm The integral value of the proton peak generated by the NH group can be obtained by the following calculation formula.醯 Imination ratio (%) = (1-α ･ x / y) × 100

In the above calculation formula, x is the integrated value of the proton peak generated by the NH group of the amino acid, y is the integrated value of the peak value of the reference proton, and α is the ratio with respect to one polyamidic acid (the imidization rate of the fluorene is 0% The ratio of the number of reference protons of the NH matrix proton of ammonium acid.

(Viscosity measurement) The viscosity of the polyimide-based polymer in the synthesis examples or comparative synthesis examples is an E-type viscosity meter TVE-22H (manufactured by Toki Sangyo Co., Ltd.). Rotor TE-1 (1 ° 34 ', R24), measured at 25 ° C.

<Synthesis of polyfluorene-imide-based polymer> [Synthesis Example 1] D2 (2.50 g, 10.0 mmol), A1 (3.49 g, 14.0 mmol), B1 (2.28 g, 6.00 mmol) in NMP (31.9 g) and γBL (8.0 g) was mixed and reacted at 50 ° C for 3 hours. D1 (1.70 g, 8.66 mmol) was added. After reacted at 40 ° C for 3 hours, polyfluorene having a resin solid content concentration of 20% by mass was obtained. Amino acid solution. The viscosity of the polyamidic acid solution was determined to be 759 mPa759s.

NMP was added to the obtained polyamic acid solution (20.0 g), diluted to 6.5% by mass, and then acetic anhydride (3.99 g) and pyridine (1.24 g) were added as the fluorinated imidization catalyst, and the temperature was adjusted to 50 ° C The reaction was carried out for 3 hours. The reaction solution was poured into methanol (234 ml), and the obtained precipitate was filtered off. The precipitate was washed with methanol and dried under reduced pressure at 60 ° C to obtain a polyfluorene imine powder (1). The polyimide imidization ratio was 54.1%.

[Synthesis Example 2] D2 (2.50 g, 10.0 mmol), A1 (3.99 g, 16.0 mmol), and B2 (1.74 g, 4.00 mmol) were mixed in NMP (31.8 g) and γBL (7.9 g), and the temperature was 50 ° C. After the reaction was carried out for 3 hours, D1 (1.69 g, 8.60 mmol) was added, and the reaction was performed at 40 ° C for 3 hours to obtain a polyamic acid solution having a resin solid content concentration of 20% by mass. The viscosity of the polyamidic acid solution was measured to be 1122 mPa1s.

NMP was added to the obtained polyamidic acid solution (20.0g), diluted to 6.5% by mass, and then acetic anhydride (4.01g) and pyridine (1.24g) were added as the imidization catalyst, and the mixture was allowed to stand at 50 ° C The reaction was carried out for 3 hours. The reaction solution was poured into methanol (234 ml), and the obtained precipitate was filtered off. The precipitate was washed with methanol, and dried under reduced pressure at 60 ° C to obtain a polyfluorene imine powder (2). The polyimide has a fluorinated imidization rate of 54.6%.

[Synthesis Example 3] (1) D2 (2.50 g, 10.0 mmol), A2 (4.89 g, 14.0 mmol), and B1 (2.28 g, 6.00 mmol) were mixed in NMP (45.8 g), and the reaction was performed at 50 ° C for 3 hours. After adding D1 (1.76 g, 8.98 mmol) and reacting at 40 ° C. for 3 hours, a polyamic acid solution having a resin solid content concentration of 20% by mass was obtained. The viscosity of the polyamidic acid solution was determined to be 728 mPa728s.

NMP was added to the obtained polyamic acid solution (20.0 g), diluted to 6.5% by mass, and then acetic anhydride (3.51 g) and pyridine (1.09 g) were added as the imidization catalyst, and the mixture was allowed to stand at 50 ° C. The reaction was carried out for 3 hours. This reaction solution was poured into methanol (232 ml), and the obtained precipitate was filtered off. The precipitate was washed with methanol and dried under reduced pressure at 60 ° C to obtain a polyfluorene imine powder (3). The polyimide has an imidization ratio of 46.9%.

[Synthesis Example 4] (1) D2 (2.50 g, 10.0 mmol), A3 (3.49 g, 14.0 mmol), and B1 (2.28 g, 6.00 mmol) were mixed in NMP (40.2 g), and the reaction was performed at 50 ° C for 3 hours. After adding D1 (1.76 g, 9.00 mmol) and reacting at 40 ° C for 3 hours, a polyamic acid solution having a resin solid content concentration of 20% by mass was obtained. The viscosity of the polyamidic acid solution was determined to be 758 mPa758s.

NMP was added to the obtained polyamic acid solution (20.0 g), diluted to 6.5% by mass, and then acetic anhydride (3.99 g) and pyridine (1.24 g) were added as the fluorinated imidization catalyst, and the mixture was allowed to stand at 50 ° C. The reaction was carried out for 3 hours. The reaction solution was poured into methanol (234 ml), and the obtained precipitate was filtered off. This precipitate was washed with methanol, and dried under reduced pressure at 60 ° C to obtain a polyfluorene imine powder (4). The polyimide has an imidization ratio of 46.1%.

[Synthesis Example 5] (1) D2 (2.50 g, 10.0 mmol), A4 (3.69 g, 14.0 mmol), and B1 (2.28 g, 6.00 mmol) were mixed in NMP (41.7 g), and the reaction was performed at 50 ° C for 3 hours. After adding D1 (1.95 g, 9.94 mmol) and reacting at 40 ° C. for 3 hours, a polyamic acid solution having a resin solid content concentration of 20% by mass was obtained. The viscosity of the polyamidic acid solution was determined to be 805 mPa805s.

NMP was added to the obtained polyamidic acid solution (20.0g), diluted to 6.5% by mass, and then acetic anhydride (3.91g) and pyridine (1.21g) were added as the imidization catalyst, and the mixture was allowed to stand at 50 ° C. The reaction was carried out for 3 hours. The reaction solution was poured into methanol (233 ml), and the obtained precipitate was filtered off. This precipitate was washed with methanol, and dried under reduced pressure at 60 ° C to obtain a polyfluorene imine powder (5). The polyimide has a fluorinated imidization rate of 56.4%.

[Synthesis Example 6] (1) D2 (2.50 g, 10.0 mmol), A5 (4.89 g, 14.0 mmol), and B1 (2.28 g, 6.00 mmol) were mixed in NMP (46.5 g) and reacted at 50 ° C for 3 hours. After adding D1 (1.95 g, 9.94 mmol) and reacting at 40 ° C. for 3 hours, a polyamic acid solution having a resin solid content concentration of 20% by mass was obtained. The viscosity of the polyamidic acid solution was determined to be 461 mPa461s.

NMP was added to the obtained polyamic acid solution (20.0 g), diluted to 6.5% by mass, and then acetic anhydride (3.51 g) and pyridine (1.09 g) were added as the imidization catalyst, and the mixture was allowed to stand at 50 ° C. The reaction was carried out for 3 hours. This reaction solution was poured into methanol (232 ml), and the obtained precipitate was filtered off. The precipitate was washed with methanol and dried under reduced pressure at 60 ° C to obtain a polyfluorene imine powder (6). The polyimide has a fluorinated imidization rate of 53.6%.

[Synthesis Example 7] (1) D2 (2.50 g, 10.0 mmol), A1 (2.49 g, 10.0 mmol), B2 (3.48 g, 8.00 mmol), and C1 (0.66 g, 2.00 mmol) were mixed in NMP (43.6 g). After reacting at 50 ° C for 3 hours, D1 (1.78 g, 9.06 mmol) was added, and after reacting at 40 ° C for 3 hours, a polyamic acid solution having a resin solid content concentration of 20% by mass was obtained. The viscosity of the polyamidic acid solution was determined to be 693 mPa693s.

NMP was added to the obtained polyamic acid solution (20.0 g), diluted to 6.5% by mass, and then acetic anhydride (3.68 g) and pyridine (1.14 g) were added as the imidization catalyst, and the mixture was allowed to stand at 50C The reaction was carried out for 3 hours. This reaction solution was poured into methanol (232 ml), and the obtained precipitate was filtered off. The precipitate was washed with methanol, and dried under reduced pressure at 60 ° C to obtain a polyfluorene imine powder (7). The polyimide has a fluorinated imidization rate of 55.9%.

[Synthesis Example 8] (1) D2 (2.50 g, 10.0 mmol), A6 (3.79 g, 8.00 mmol), B1 (2.28 g, 6.00 mmol), and C2 (0.91 g, 6.00 mmol) were mixed in NMP (45.1 g). After reacting at 50 ° C for 3 hours, D1 (1.79 g, 9.12 mmol) was added, and after reacting at 40 ° C for 3 hours, a polyamic acid solution having a resin solid content concentration of 20% by mass was obtained. As a result of measuring the viscosity of the polyamidic acid solution, it was 740 mPa ･ s.

NMP was added to the obtained polyamic acid solution (20.0 g), diluted to 6.5% by mass, and then acetic anhydride (3.57 g) and pyridine (1.11 g) were added as the imidization catalyst, and the mixture was allowed to stand at 50 ° C. The reaction was carried out for 3 hours. This reaction solution was poured into methanol (232 ml), and the obtained precipitate was filtered off. This precipitate was washed with methanol, and dried under reduced pressure at 60 ° C to obtain a polyfluorene imine powder (8). The polyimide has a fluorinated imidization rate of 50.5%.

[Synthesis Example 9] D2 (2.50 g, 10.0 mmol), A3 (1.75 g, 7.00 mmol), B3 (3.79 g, 5.00 mmol), C1 (0.66 g, 2.00 mmol), C4 (2.05 g, 6.00 mmol) After mixing in NMP (50.3 g) and reacting at 50 ° C for 3 hours, D1 (1.82 g, 9.4 mmol) was added. After reacting at 40 ° C for 3 hours, a resin having a solid content concentration of 20% by mass was obtained. Amino acid solution. The viscosity of the polyamidic acid solution was determined to be 755 mPa755s.

NMP was added to the obtained polyamic acid solution (20.0 g), diluted to 6.5% by mass, and then acetic anhydride (3.21 g) and pyridine (1.00 g) were added as the imidization catalyst, and the reaction was performed at 80 ° C. 3 hours response. This reaction solution was poured into methanol (230 ml), and the obtained precipitate was filtered off. This precipitate was washed with methanol, and dried under reduced pressure at 60 ° C to obtain a polyfluorene imine powder (9). The polyimide imidization ratio was 71.0%.

[Synthesis Example 10] D2 (2.50 g, 10.0 mmol), A1 (1.99 g, 8.00 mmol), B3 (1.51 g, 2.00 mmol), C4 (3.41 g, 10.0 mmol) in NMP (35.8 g) and γBL ( 9.0g), after reacting at 50 ° C for 3 hours, D1 (1.76g, 9.00mmol) was added, and after reacting at 40 ° C for 3 hours, a polyamic acid solution having a resin solid content concentration of 20% by mass was obtained. (10A). As a result of measuring the viscosity of the polyamic acid solution, it was 797 mPa ･ s.

Furthermore, NMP was added to the obtained polyamidic acid solution (20.0g), diluted to 6.5% by mass, and then acetic anhydride (3.59g) and pyridine (1.11g) were added as the imidization catalyst, and the temperature was 80 ° C. The reaction was carried out for 3 hours. This reaction solution was poured into methanol (232 ml), and the obtained precipitate was filtered off. This precipitate was washed with methanol, and dried under reduced pressure at 60 ° C to obtain a polyfluorene imine powder (10). The polyimide has a fluorinated imidization rate of 75.2%.

[Synthesis Example 11] (1) D1 (2.47 g, 12.6 mmol), A1 (1.00 g, 4.00 mmol), B3 (1.51 g, 2.00 mmol), and C5 (2.78 g, 14.0 mmol) in NMP (31.0 g) and γBL ( 7.7g), and after reacting for 1 hour at room temperature, D3 (1.92g, 6.00mmol) was added, and the reaction was performed at room temperature for 5 hours to obtain a polyamic acid having a resin solid content concentration of 20% by mass. Solution. As a result of measuring the viscosity of the polyamidic acid solution, it was 1129 mPa ･ s.

[Synthesis Example 12] (1) D2 (2.50 g, 10.0 mmol), A7 (3.49 g, 14.0 mmol), and B1 (2.28 g, 6.00 mmol) were mixed in NMP (39.8 g), and the reaction was performed at 50 ° C for 3 hours. After adding D1 (1.69 g, 8.60 mmol) and reacting at 40 ° C. for 3 hours, a polyamic acid solution having a resin solid content concentration of 20% by mass was obtained. The viscosity of the polyamidic acid solution was measured to be 1023 mPa10s. NMP was added to the obtained polyamic acid solution (20.0 g) to dilute to 6.5% by mass, and then acetic anhydride (3.99 g) and pyridine (1.24 g) were added as the imidization catalyst, and the mixture was allowed to stand at 50 ° C. The reaction was carried out for 3 hours. The reaction solution was poured into methanol (234 ml), and the obtained precipitate was filtered off. The precipitate was washed with methanol, and dried under reduced pressure at 60 ° C to obtain a polyfluorene imine powder (12). The polyimide imidization ratio was 54.3%.

[Synthesis Example 13] (1) A3 (3.49 g, 14.0 mmol), B1 (2.28 g, 6.00 mmol), and D4 (4.47 g, 19.94 mmol) were mixed in NMP (41.0 g), and the reaction was performed at 60 ° C for 6 hours. A polyamic acid solution having a resin solid content concentration of 20% by mass was obtained. The viscosity of the polyamidic acid solution was determined to be 410 mPa ･ s. NMP was added to the obtained polyamic acid solution (20.0 g) to dilute to 6.5% by mass, and then acetic anhydride (3.98) and pyridine (1.23 g) were added as the imidization catalyst, and the temperature was measured at 80 ° C for 3 hours. Hours of response. This reaction solution was poured into methanol (334 ml), and the obtained precipitate was filtered off. The precipitate was washed with methanol and dried under reduced pressure at 60 ° C to obtain a polyfluorene imine powder (13). The polyimide has a fluorene imidization rate of 60.0%.

[Comparative Synthesis Example 1] D2 (2.50 g, 10.0 mmol), B1 (2.28 g, 6.00 mmol), and C2 (2.13 g, 14.0 mmol) were mixed in NMP (35.5 g), and reacted at 50 ° C for 3 hours. Then, D1 (1.95 g, 9.96 mmol) was added, and reaction was performed at 40 ° C for 3 hours to obtain a polyamic acid solution having a resin solid content concentration of 20% by mass. The viscosity of the polyamidic acid solution was determined to be 768 mPams.

NMP was added to the obtained polyamic acid solution (20.0 g), diluted to 6.5% by mass, and then acetic anhydride (4.60 g) and pyridine (1.43 g) were added as the imidization catalyst, and the mixture was allowed to stand at 50 ° C. The reaction was carried out for 3 hours. The reaction solution was poured into methanol (237 ml), and the obtained precipitate was filtered off. The precipitate was washed with methanol and dried under reduced pressure at 60 ° C to obtain a polyfluorene imine powder (R1). The polyimide imidization ratio was 53.1%.

[Comparative Synthesis Example 2] (1) D2 (2.50 g, 10.0 mmol), B3 (3.79 g, 5.00 mmol), C1 (0.66 g, 2.00 mmol), and C4 (4.44 g, 13.0 mmol) were mixed in NMP (53.0 g). After reacting at 50 ° C. for 3 hours, D1 (1.87 g, 9.52 mmol) was added, and after reacting at 40 ° C. for 3 hours, a polyamic acid solution having a resin solid content concentration of 20% by mass was obtained. As a result of measuring the viscosity of the polyamidic acid solution, it was 710 mPa ･ s.

NMP was added to the obtained polyamic acid solution (20.0 g), diluted to 6.5% by mass, and then acetic anhydride (3.06 g) and pyridine (0.95 g) were added as the imidization catalyst, and the reaction was performed at 80 ° C. 3 hours response. The reaction solution was poured into methanol (237 ml), and the obtained precipitate was filtered off. This precipitate was washed with methanol, and dried under reduced pressure at 60 ° C to obtain a polyfluorene imine powder (R2). The polyimide has a hydrazone imidization rate of 75.6%.

[Comparative Synthesis Example 3] D2 (2.50 g, 10.0 mmol), B3 (3.03 g, 4.00 mmol), C1 (0.66 g, 2.00 mmol), C3 (2.39 g, 6.00 mmol), C5 (1.59 g, 8.00 mmol) ) After mixing in NMP (48.1g) and reacting at 50 ° C for 3 hours, D1 (1.86g, 9.50mmol) was added and reacting at 40 ° C for 3 hours to obtain a polymer having a solid content concentration of 20% by mass. Phenylamine solution. The viscosity of the polyamidic acid solution was determined to be 651 mPams.

NMP was added to the obtained polyamic acid solution (20.0 g), diluted to 6.5% by mass, and then acetic anhydride (3.37 g) and pyridine (1.04 g) were added as the imidization catalyst, and the mixture was allowed to stand at 50 ° C. The reaction was carried out for 3 hours. This reaction solution was poured into methanol (231 ml), and the obtained precipitate was filtered off. This precipitate was washed with methanol, and dried under reduced pressure at 60 ° C to obtain a polyfluorene imine powder (R3). The polyimide has an imidization ratio of 50.0%.

[Table 1]

<Production of liquid crystal alignment agent> In Examples and Comparative Examples, production examples of the liquid crystal alignment agent are described. In the following, the liquid crystal alignment agents obtained in the examples and comparative examples will be used for the production of liquid crystal display elements and various evaluations.

[Example 1] NMP (27.0 g) was added to the polyfluorene imine powder (1) (3.00 g) obtained in Synthesis Example 1, and stirred at 70 ° C for 24 hours to dissolve. After adding BCS (20.0 g) to this solution, the liquid crystal alignment agent (V-1) of Example 1 was prepared.

[Example 2] ~ [Example 9] The polyimide powder (1) was replaced with the polyimide powder (2) to (9), and the rest were prepared in the same manner as in Example 1. The liquid crystal alignment agents (V-2) to (V-9) of Examples 2-9.

[Example 10] NMP (27.0 g) was added to the polyfluorene imine powder (10) (3.00 g) obtained in Synthesis Example 10, and the mixture was stirred at 70 ° C for 24 hours to be dissolved. To this solution, BCS (20.0 g) was added to prepare a liquid crystal alignment agent (V-10). This liquid crystal alignment agent (V-10) (5.00 g) was mixed with the liquid crystal alignment agent (R-V2) (5.00 g) obtained in Comparative Example 2 to obtain a liquid crystal alignment agent (B-10) of Example 10.

[Example 11] Into the polyamidic acid solution (10A) (15.0 g) obtained in Synthesis Example 10, NMP (15.0 g) and BCS (20.0 g) were added to prepare a liquid crystal alignment agent (V-10A). 5.00 g of the liquid crystal alignment agent (V-10A) and 5.00 g of the liquid crystal alignment agent (R-V2) obtained in Comparative Example 2 were mixed to prepare a liquid crystal alignment agent (B-11) of Example 11.

[Example 12] (1) A polyamic acid solution (11A) (15.0 g) obtained in Synthesis Example 11 was added with NMP (15.0 g) and BCS (20.0 g) to prepare a liquid crystal alignment agent (V-11A). 5.00 g of the liquid crystal alignment agent (V-11A) and 5.00 g of the liquid crystal alignment agent (R-V3) obtained in Comparative Example 3 were mixed to prepare a liquid crystal alignment agent (B-12) of Example 12.

In the liquid crystal alignment agents (V-1) to (V-9) and (B-10) to (B-12) prepared in the above manner, no abnormalities such as turbidity or precipitation were found, and they were confirmed to be uniform. Solution.

Using the obtained liquid crystal alignment agents (V-1) to (V-9), (B-10) to (B-12) and (V-13) to (V-14) described later, a liquid crystal display element was produced, and Evaluation of vertical alignment, evaluation of pretilt angle, evaluation of voltage retention, evaluation of afterimage characteristics.

[Example 13] ~ [Example 14] The polyimide powder (1) was replaced by the polyimide powder (12) to (13), and the rest were prepared in the same manner as in Example 1. Liquid crystal alignment treatment agents (V-13) to (V-14). No abnormalities such as turbidity or precipitation were found in this liquid crystal alignment treatment agent, and it was confirmed that the solution was a uniform solution.

[Comparative Example 1] NMP (27.0g) and BCS (20.0g) were added to polyimide powder (R1) (3.00g) obtained in Comparative Synthesis Example 1, and stirred at 70 ° C for 24 hours to obtain a liquid crystal. Alignment agent (R-V1).

[Comparative Example 2] 液晶 Except that the polyfluorene imine powder (R1) obtained in Comparative Synthesis Example 1 was replaced by the polyfluorene imine powder (R2), the other methods were the same as those of Comparative Example 1 to obtain a liquid crystal alignment. Agent (R-V2).

[Comparative Example 3] Except that the polyfluorene imine powder (R1) obtained in Comparative Synthesis Example 1 was replaced by the polyfluorene imine powder (R3), the other methods were the same as those of Comparative Example 1 to obtain a liquid crystal alignment. Agent (R-V3).

In the liquid crystal alignment agents (R-V1) to (R-V3) prepared as described above, no abnormal phenomenon such as turbidity or precipitation was found, and it was confirmed that the solution was a uniform solution. Using the obtained liquid crystal alignment agents (R-V1) to (R-V2), production of a liquid crystal display element, evaluation of vertical alignment, evaluation of a pretilt angle, evaluation of a voltage holding ratio, and evaluation of an afterimage characteristic were performed.

<Production of liquid crystal display elements for measuring voltage holding ratio and residual DC voltage> The liquid crystal alignment agents (V-1) to (V-9), (B-10) to (B-12), (V -13) ~ (V-14) and the liquid crystal alignment agents (R-V1) ~ (R-V2) obtained in the comparative examples were subjected to pressure filtration using a membrane filter having a pore size of 1 μm. The obtained solution was washed with pure water and IPA (isopropanol), and then spin-coated on the ITO surface of a glass substrate (length: 40 mm, width: 30 mm, thickness: 1.1 mm) with an ITO electrode of 40 mm × 30 mm. The heating plate was subjected to a heating treatment at 70 ° C, 90 seconds, and 230 ° C for 30 minutes in a thermal cycle type dust-free oven to obtain an ITO substrate with a liquid crystal alignment film with a thickness of 100 nm. Two pieces of the obtained ITO substrate with a liquid crystal alignment film were prepared, and a particle spacer with a diameter of 4 μm was applied to the liquid crystal alignment film surface of one of the substrates (Silk Ball, SW-D1, manufactured by Nippon Kasei Kasei Co., Ltd.).

Subsequently, a sealing material (XN-1500T manufactured by Mitsui Chemicals) was applied to the surroundings. Next, the surface of the other substrate on which the liquid crystal alignment film is formed is used as the inner side, and the sealing material is hardened after being bonded to the previous substrate to obtain an empty cell. Liquid crystal MLC-3023 (trade name, manufactured by Meike Corporation) was injected into the empty cell by a reduced pressure injection method to prepare a liquid crystal cell. In a state where a DC voltage of 15 V is applied to the liquid crystal cell, the UV of the high-pressure mercury lamp is irradiated from the outside of the liquid crystal cell through a CUT filter of 325 nm or less (1st-UV) under the condition of 10 J / cm ² .

Thereafter, the liquid crystal cell was irradiated with a fluorescent UV lamp (FLR40SUV32 / A-1) for 30 minutes (2nd-UV) in a state where no voltage was applied to passivate the unreacted polymerizable compound existing in the liquid crystal cell. In addition, the measurement of the amount of ultraviolet irradiation was performed using a UV-M03A photoreceptor connected to UV-35 by ORC.

<Preparation of liquid crystal display elements for pretilt angle and afterimage evaluation> The liquid crystal alignment agents (V-1) to (V-9), (B-10) to (B-12), (V-13) ) ~ (V-14) and the liquid crystal alignment agents (R-V1) ~ (R-V2) obtained in the comparative example were subjected to pressure filtration using a membrane filter having a pore size of 1 μm. The obtained solution was washed with pure water and IPA (isopropanol), and each was spin-coated on an ITO electrode substrate (vertical: 35 mm) with an ITO electrode pattern having a pixel size of 200 μm × 600 μm and a line / space of 3 μm. , Horizontal: 30mm, thickness: 0.7mm), glass substrate with ITO electrodes (vertical: 35mm, horizontal: 30mm, thickness: 0.7mm) patterned with an optical spacer with a height of 3.2μm On the ITO surface, heat treatment was performed on a hot plate at 70 ° C, 90 seconds, and 230 ° C for 30 minutes in a thermal cycle type dust-free oven to obtain an ITO substrate with a liquid crystal alignment film with a thickness of 100 nm. In addition, the ITO electrode substrate forming the ITO electrode pattern is divided into four parts to form a crosscheck, and the four blocks can be driven separately.

Subsequently, a sealing material (XN-1500T manufactured by Mitsui Chemicals) was applied to the surroundings. Next, the other side of the substrate is bonded to the previous substrate with the side on which the liquid crystal alignment film is formed as an inner side, and the sealing material is hardened to obtain an empty cell. Liquid crystal MLC-3023 (trade name, manufactured by Meike Corporation) was injected into the empty cell using a reduced pressure injection method to prepare a liquid crystal cell. The liquid crystal cell was irradiated with a DC voltage of 15 V, and the UV of the high-pressure mercury lamp was irradiated from the outside of the liquid crystal cell at a condition of 10 J / cm ² through a CUT filter of 325 nm or less (1st-UV).

Thereafter, the liquid crystal cell was irradiated with a fluorescent UV lamp (FLR40SUV32 / A-1) for 30 minutes (2nd-UV) in a state where no voltage was applied to passivate the unreacted polymerizable compound existing in the liquid crystal cell. In addition, the measurement of the amount of ultraviolet irradiation was performed using a UV-M03A photoreceptor connected to UV-35 by ORC.

<Evaluation> (Vertical Alignment) The liquid crystal alignment of a liquid crystal display device was observed using a polarizing microscope (ECLIPSE E600WPOL) (manufactured by Nikon Corporation) to confirm whether the liquid crystals formed a vertical alignment. Specifically, for example, if no defect due to liquid crystal flow or bright spots due to alignment defects is found, the mark is good. The evaluation results are shown in Table 2.

(Voltage holding rate) On the liquid crystal display element for voltage holding rate evaluation obtained in the above manner, a voltage of 1 V was applied for a period of 60 microseconds, and the voltage was applied at intervals of 1667 milliseconds. Voltage retention (%) at 60 ° C after 1667 ms. As the measuring device, VHR-1 manufactured by Dongyang Technology was used. The evaluation results are shown in Table 2.

(Pre-tilt angle) Using an LCD analyzer (LCA-LUV42A, manufactured by Mingling Technology Co., Ltd.), among the liquid crystal display elements used for the evaluation of the pre-tilt angle manufactured in the above manner, no liquid crystal display element was found to have an adverse result due to the liquid crystal flow relationship. Determination. The evaluation results are shown in Table 2.

(After-image characteristics)) Using the liquid crystal display element for after-image evaluation obtained above, an AC voltage of 60 Hz and 20 Vp-p was applied to 4 pixel regions at a temperature of 23 ° C and a driving time of 168 hours. In 2 areas forming a diagonal line. After that, all 4 pixel regions were driven with an AC voltage of 5Vp-p, and the brightness difference of the pixels was observed visually. In a state where the difference in brightness was hardly confirmed, the evaluation was good. In the table, those that are good are marked as ○, and those that are particularly good are marked as ◎. The evaluation results are shown in Table 2.

(Residual DC voltage) 矩形 A rectangular wave of 30 Hz and 7.8 Vpp after overlapping 2 V DC at 23 ° C. for 100 hours was applied to the liquid crystal display element used for the evaluation of the voltage retention ratio manufactured as described above, and the flicker elimination method was used. of eliminating flicker) to obtain the voltage (residual DC voltage) remaining in the liquid crystal cell after removing the DC voltage for 1 hour. This value is an indicator that an afterimage occurs due to DC accumulation. When the value is about 50 mV or less, it is judged that it has excellent afterimage characteristics.

[Table 2]

Claims (10)

A liquid crystal alignment agent comprising: at least one selected from a diamine having a structure of the following formula (1) and a side chain structure selected from the group represented by the following formulas [S1] to [S3] A diamine component of a diamine, a polyimide precursor obtained from a tetracarboxylic acid component, and / or a polyimide polymer of a polyimide precursor of the polyimide precursor; (In formula (1), R ₁ represents hydrogen, an alkyl or fluoroalkyl group having 1 to 5 carbon atoms, a tert-butoxycarbonyl group, or a monovalent organic group; * represents a site that can be bonded to other groups; (Any hydrogen atom forming a benzene ring may be replaced by a monovalent organic group) (In the formula [S1], X ¹ and X ² each independently represent a single bond,-(CH ₂ ) _a- (a is an integer of 1 to 15), -CONH-, -NHCO-, -CON (CH ₃ )- , -O-, -COO-, -OCO-, or-((CH ₂ ) _a1 -A ₁ ) _m1- ; wherein each of the plural a1 independently represents an integer from 1 to 15, and each of the plural A1 independently represents an oxygen atom or -COO-; m ₁ is 1 to 2; G ¹ and G ² each independently represent 2 selected from a divalent aromatic group having 6 to 12 carbon atoms or a divalent alicyclic group having 3 to 8 carbon atoms Valent cyclic group; any hydrogen atom on the aforementioned cyclic group may be composed of an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, carbon At least one selected from the group consisting of fluorine-containing alkoxy groups or fluorine atoms of 1 to 3; m and n each independently represent an integer of 0 to 3, and the total of m and n is 1 to 4; R ¹ represents an alkyl group having 1 to 20 carbons, an alkoxy group having 1 to 20 carbons, or an alkoxyalkyl group having 2 to 20 carbons; any hydrogen forming R ¹ may be substituted by fluorine) (In the formula [S2], X ³ represents a single bond, -CONH-, -NHCO-, -CON (CH ₃ )-, -NH-, -O-, -CH ₂ O-, -COO-, or -OCO- ; R ² represents an alkyl group having 1 to 20 carbon atoms or an alkoxyalkyl group having 2 to 20 carbon atoms; any hydrogen that forms R ² may be replaced by fluorine) (In the formula [S3], X ⁴ represents -CONH-, -NHCO-, -O-, -COO-, or -OCO-; R ³ represents a structure having a cholesterol skeleton). The liquid crystal alignment agent according to claim 1, wherein the diamine having the structure of the aforementioned formula (1) has a structure of the following formula (1-1); (In the formula (1-1), R _{1 is the} same as that in the case of the aforementioned formula (1); * indicates a site which can be bonded to other groups; any hydrogen atom forming a benzene ring can be monovalent Substituted with an organic group). The liquid crystal alignment agent according to claim 1, wherein the diamine having the structure of the aforementioned formula (1) is a structure having the following formula (1-4); (In the formula (1-4), R _{1 is the} same as that in the case of the aforementioned formula (1); two Q ₂ each independently represent a single bond or a divalent organic group; any hydrogen atom forming a benzene ring may be Is replaced by a monovalent organic group). The liquid crystal alignment agent according to claim 1, wherein the diamine component is a diamine having a side chain structure represented by the formula [S1]. The liquid crystal alignment agent according to claim 1, wherein the side chain structure represented by the aforementioned formula [S1] is at least one selected from the group consisting of the following formulas [S1-x1] to [S1-x7]; (In the formulas [S1-x1] to [S1-x7], R ¹ represents an alkyl group having 1 to 20 carbon atoms; X ^p represents-(CH ₂ ) _a- (a is an integer from 1 to 15), -CONH- , -NHCO-, -CON (CH ₃ )-, -NH-, -O-, -CH ₂ O-, -COO-, or -OCO-; A ₁ represents an oxygen atom or -COO- * (but, with "*" Is bonded to (CH ₂ ) _a2 ); A ₂ represents an oxygen atom or * -COO- (but the bond with "*" is bonded to (CH ₂ ) _a2 ) ; A3 is an integer of 0 or 1, and a1 and a2 each independently represent an integer of 2 to 10; Cy represents 1,4-cyclohexyl or 1,4-phenylene). The liquid crystal alignment agent according to claim 1, wherein in the diamine having a side chain structure represented by the formula [S2], X ³ is -CONH-, -NHCO-, -O-, -CH ₂ O-,- COO- or -OCO-, and R ² is an alkyl group having 3 to 20 carbon atoms or an alkoxyalkyl group having 2 to 20 carbon atoms. The liquid crystal alignment agent according to claim 1, wherein the side chain structure represented by the aforementioned formula [S3] has a structure represented by the following formula [S3-x]; (In formula [S3-x], X represents formula [X1] or formula [X2]; Col represents at least one selected from the group formed by formulas [Col1] to [Col3]; G represents formula [G1] ~ [G4]; in these formulas, * represents the bonding position). The liquid crystal alignment agent according to claim 1, wherein the diamine component is at least one selected from the group consisting of diamines represented by the following formulas [1] and [2]; (In the formula [1], X represents a single bond, -O-, -C (CH ₃ ) _2- , -NH-, -CO-,-(CH ₂ ) _m- , -SO ₂ -or any of these A divalent organic group formed by combination; m is an integer from 1 to 8; and two Y's each independently represent at least one selected from the side chain structure represented by the aforementioned formulas [S1] to [S3]). A liquid crystal alignment film, which is formed by using the liquid crystal alignment agent according to any one of claims 1 to 8. A liquid crystal display element comprising a liquid crystal alignment film obtained from the liquid crystal alignment film of claim 9.