TWI635122B - Liquid crystal alignment treatment agent, liquid crystal alignment film and liquid crystal display element - Google Patents

Abstract

A liquid crystal alignment treatment agent containing the following components (A), (B) and (C).

(A) Ingredient: Heteropoly acid.

(B) Ingredient: polymer.

(C) Ingredient: A compound having a nitrogen-containing aromatic heterocyclic ring in the molecule.

Description

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

The present invention relates to a liquid crystal alignment treatment agent used in the manufacture of a liquid crystal display element, a liquid crystal alignment film obtained from the liquid crystal alignment treatment agent, and a liquid crystal display element using the liquid crystal alignment film.

The liquid crystal display device is a display device capable of achieving thinness and weight reduction, and is currently widely used. Generally, in this liquid crystal display element, in order to determine the alignment state of a liquid crystal, a liquid crystal alignment film is often used.

Along with the high definition of liquid crystal display elements, from the viewpoint of suppressing the decrease in the contrast of liquid crystal display elements or reducing the phenomenon of afterimages, even in the liquid crystal alignment film used therein, a high voltage retention rate is sought. In this regard, it is known to use a compound containing one carboxylic acid group in the molecule and a compound containing one carboxylic acid anhydride group in the molecule in addition to a very small amount of polyamic acid or its imidized polymer. And a liquid crystal alignment treatment agent for a compound selected from a compound containing one tertiary amine group in the molecule (for example, refer to Patent Document 1).

In addition, with the high definition of liquid crystal display elements, it is also sought to suppress the decrease in contrast of liquid crystal display elements or the long-term use. Problems such as poor display. In response to these problems, in the liquid crystal alignment film using polyimide, methods for improving the alignment of the liquid crystal and reducing the occurrence of poor display in the peripheral portion of the liquid crystal display screen have been proposed. The use of alkoxysilane compounds Proposal for a liquid crystal alignment film of a liquid crystal alignment treatment agent (for example, refer to Patent Document 2 or Patent Document 3).

[Prior technical literature] [Patent Literature]

[Patent Document 1] Japanese Unexamined Patent Publication No. 8-76128

[Patent Document 2] Japanese Unexamined Patent Publication No. 61-171762

[Patent Document 3] Japanese Unexamined Patent Publication No. 11-119226

With the recent high performance of liquid crystal display elements, liquid crystal display elements are often used in large-screen, high-definition liquid crystal televisions, or in-vehicle applications such as car navigation systems and mileage panels. In these applications, in order to obtain high brightness and the like, there may be a case where a backlight source having a large amount of heat is used. Therefore, in other aspects of the liquid crystal alignment film, high reliability is sought, that is, there is a requirement for high stability of the light generated by the backlight. In particular, if the voltage retention rate, which is one of the electrical characteristics of a liquid crystal display device, is reduced by the light generated by the backlight, an afterimage, which is one of the causes of the display failure of the liquid crystal display device, is likely to occur. Defective (also known as linear afterimage) phenomenon, and a liquid crystal display device having high reliability cannot be obtained. Therefore, in the liquid crystal alignment film, in addition to the initial characteristics being required to be good, for example, after a long time exposure to light irradiation, the effect of not easily reducing the voltage holding ratio is also sought.

Moreover, in portable applications such as smart phones and mobile phones, the use environment has become more severe than in the past. That is, in addition to the room temperature and low humidity environment so far, it may be used under high temperature and high humidity. Such use under high-temperature and high-humidity conditions causes moisture to easily mix between the liquid crystal display element sealant and the liquid crystal alignment film. Therefore, near the front edge of the liquid crystal display element, there may be problems such as display spots. Therefore, there is a need for a situation in which such display failures do not occur even under high temperature and high humidity conditions.

Therefore, the present invention aims to provide a liquid crystal alignment film having the above-mentioned characteristics. That is, the object of the present invention is to provide a liquid crystal alignment film that can suppress a decrease in voltage holding ratio even after long-term exposure to light irradiation. In addition, even under high-temperature and high-humidity conditions, a liquid crystal alignment film that does not cause display spots near the front edge of the liquid crystal display element is intended.

In addition, a liquid crystal display element having the liquid crystal alignment film, a liquid crystal alignment treatment agent capable of providing the liquid crystal alignment film, and a composition using the liquid crystal alignment treatment agent are also provided.

The inventors conducted intensive research and found that The liquid crystal alignment treatment agent of two kinds of compounds and polymers having a specific structure is extremely effective in achieving the above object, and thus the present invention has been completed.

That is, the present invention has the following requirements.

(1) A liquid crystal alignment treatment agent containing the following components (A), (B) and (C).

(A) Ingredient: Heteropoly acid.

(B) Ingredient: polymer.

(C) Ingredient: A compound having a nitrogen-containing aromatic heterocyclic ring in the molecule.

(2) The liquid crystal alignment treatment agent according to the above (1), wherein the heteropoly acid is selected from the group consisting of phosphomolybdic acid, silomolybdic acid, phosphotungstic acid, silototungstic acid, and phosphotungstomolybdic acid At least one.

(3) The liquid crystal alignment treatment agent according to the above (1) or (2), wherein the polymer is an acrylic polymer, a methacrylic polymer, a novolac resin, polyhydroxystyrene, or polyimide At least one selected from the group consisting of a precursor, polyimide, polyimide, polyester, cellulose, and polysiloxane.

(4) The liquid crystal alignment treatment agent according to the above (3), wherein the polymer is a polyimide precursor or a polyimide precursor obtained by reacting a diamine component and a tetracarboxylic acid component. Polyfluorene imine obtained by hydrazone imidization.

(5) The liquid crystal alignment treatment agent according to the above (4), wherein the diamine component is a diamine compound containing a side chain structure represented by the following formula [2-1] or formula [2-2].

(Y ¹ represents a single bond,-(CH ₂ ) _a- (a is an integer from 1 to 15), -O-, -CH ₂ O-, -CONH-, -NHCO-, -CON (CH ₃ )- , -N (CH ₃ ) CO-, -COO-, and -OCO- selected from at least one type of bonding group. Y ² represents a single bond or-(CH ₂ ) _b- (b is 1 ~ An integer of 15). Y ³ represents a group formed by a single bond,-(CH ₂ ) _c- (c is an integer from 1 to 15), -O-, -CH ₂ O-, -COO-, and -OCO- At least one selected. Y ⁴ represents a divalent cyclic group of at least one selected from the group consisting of a benzene ring, a cyclohexane ring, and a heterocyclic ring, or a group having 17 to 51 carbon atoms having a cholesterol skeleton. Divalent organic groups, any of the hydrogen atoms on the aforementioned cyclic group can be substituted by an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, carbon It is substituted by a fluorine-containing alkoxy group or a fluorine atom having a number of 1 to 3. Y ⁵ represents at least one kind of cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring, and a heterocyclic ring, and these cyclic groups Any of the above hydrogen atoms can be substituted by an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, and a fluorine-containing alkoxy group having 1 to 3 carbon atoms. substituted with a fluorine atom or represents an integer of 0 to 4, .n of .Y ⁶ represents an alkyl carbon number of 1 to 18 Selected from the group consisting of alkenyl with 2 to 18 carbons, fluorinated alkyl with 1 to 18 carbons, alkoxy with 1 to 18 carbons and fluorinated alkoxy with 1 to 18 carbons 1).

[化 2] -Y ⁷ -Y ⁸ [2-2]

(Y ⁷ represents a single bond, -O-, -CH ₂ O-, -CONH-, -NHCO-, -CON (CH ₃ )-, -N (CH ₃ ) CO-, -COO-, and -OCO- At least one type of bonding group selected for the formed group. Y ⁸ is an alkyl group having 8 to 18 carbon atoms or a fluorine-containing alkyl group having 6 to 18 carbon atoms.

(6) The liquid crystal alignment treatment agent according to the above (5), wherein the diamine compound is the liquid crystal alignment treatment agent according to the above (5) represented by the following formula [2a].

(Y represents the structure represented by the aforementioned formula [2-1] or [2-2]. N1 represents an integer of 1 to 4).

(7) The liquid crystal alignment treatment agent according to any one of the above (4) to (6), wherein the tetracarboxylic acid component contains a tetracarboxylic dianhydride represented by the following formula [3].

(Z represents a structure represented by the following formula [3a] to [3k] At least one selected structure of the formed group).

(Z ¹ to Z ⁴ each independently represent at least one selected from the group consisting of a hydrogen atom, a methyl group, a chlorine atom, and a benzene ring. Z ⁵ and Z ⁶ each independently represent a hydrogen atom or a methyl group).

(8) The liquid crystal alignment treatment agent according to any one of (1) to (7) above, wherein the compound of the component (C) has a primary amine group and a nitrogen-containing aromatic heterocyclic compound in the molecule Ring, and the aforementioned primary amine group is an amine compound obtained by bonding to an aliphatic hydrocarbon group or a non-aromatic cyclic hydrocarbon group.

(9) The liquid crystal alignment treatment agent according to the above (8), wherein the amine compound is represented by the following formula [4a-1].

[Chem. 6] H ₂ NS ¹ -S ² [4a-1]

(S ¹ represents a divalent organic group having an aliphatic monovalent hydrogen group or a non-aromatic cyclic hydrocarbon group. S ² represents a nitrogen-containing heterocyclic ring).

(10) The liquid crystal alignment treatment agent according to the above (8), wherein the amine compound is represented by the following formula [4a-2].

[Chem. 7] H ₂ NS ³ -S ⁴ -S ⁵ [4a-2]

(S ³ represents an aliphatic hydrocarbon group or a non-aromatic cyclic hydrocarbon group having 1 to 10 carbon atoms. S ⁴ represents a single bond, -O-, -NH-, -S-, -SO _2- , and carbon number 1 to 19 At least one selected from the group consisting of a divalent organic group, the total of the carbon atoms of S ³ and S ⁴ is 1 to 20. S ⁵ represents a nitrogen-containing heterocyclic ring).

(11) The liquid crystal alignment treatment agent according to the above (10), wherein S ³ , S ⁴ and S ⁵ in the amine compound represented by the formula [4a-2] are selected by a base or a ring described below, respectively. Formed by the combination.

Among them, S ³ is a straight or branched alkyl group having 1 to 10 carbon atoms, an unsaturated alkyl group having 1 to 10 carbon atoms, a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, Cycloheptane ring, cyclooctane ring, cyclononane ring, cyclodecane ring, cycloundecane ring, cyclododecane ring, cyclotridecane ring, cyclotetradecane ring, cyclopentadecane ring, ring Hexadecane ring, cycloheptadecane ring, cyclooctadecane ring, cyclononadecane ring, icosene ring, eicosene ring, docosane ) Ring, dicycloheptane ring, decalin ring, norbornene ring and adamantane ring; S ⁴ is a single bond, -O-, -NH-, -S -, -SO _2- , hydrocarbon group with 1 to 19 carbon atoms, -CO-O-, -O-CO-, -CO-NH-, -NH-CO-, -CO-, -CF _2- , -C (CF ₃ ) _2- , -CH (OH)-, -C (CH ₃ ) _2- , -Si (CH ₃ ) _2- , -O-Si (CH ₃ ) _2- , -Si (CH ₃ ) ₂ -O-, -O-Si (CH ₃ ) ₂ -O-, cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, cyclononane ring, Cyclodecane ring, cycloundecane ring, cyclododecane ring, cyclotridecane ring, cyclotetradecane ring, cyclopentadecane , Cyclohexadecane ring, cycloheptadecane ring, cyclooctadecane ring, cyclononadecane ring, cycloicosene ring, icocosene ring, eicosene ring, tricyclic behenane (docosane) ring, dicycloheptane ring, decalin ring, norbornene ring, adamantane ring, benzene ring, naphthalene ring, tetrahydronaphthalene ring, fluorene ring, indene ring, fluorene ring, anthracene ring, phenanthrene ring , Pyrene ring, pyrrole ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, pyridine ring, pyrimidine ring, quinoline ring, pyrazoline ring, isoquinoline ring, carbazole ring, purine ring, thiadi Azole ring, da Ring, three Ring, pyrazidine ring, triazole ring, pyr Ring, benzimidazole ring, benzoimidazole ring, cinnoline ring, phenanthroline ring, indole ring, quinoxaline ring, benzothiazole ring, brown Thi (phenothiazine) ring, oxazole ring, acridine ring, oxazole ring, piperazine ring, piperidine ring, dioxane ring and morpholine ring; one selected from the group; S ⁵ is By pyrrole ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, pyridine ring, pyrimidine ring, quinoline ring, pyrazoline ring, isoquinoline ring, carbazole ring, purine ring, thiadiazole ring ,despair Ring, pyrazoline ring, tris Ring, pyrazidine ring, triazole ring, pyr Ring, benzimidazole ring, benzimidazole ring, octyline ring, phenanthroline ring, indole ring, quinoxaline ring, benzothiazole ring, phenothialine (phenothiazine) ring, oxazole ring and acridine ring group selected from the group.

(12) The liquid crystal alignment treatment agent according to any one of (1) to (11) above, which is obtained by mixing a solvent containing the component (B) and the component (C) under heating.

(13) The liquid crystal alignment treatment agent according to any one of the above (1) to (12), wherein the liquid crystal alignment treatment agent contains N-methyl-2-pyrrolidone, N-ethyl At least one selected from the group consisting of 2--2-pyrrolidone and γ-butyrolactone.

(14) The liquid crystal alignment treatment agent according to any one of the above (1) to (13), wherein the liquid crystal alignment treatment agent contains 1-hexanol, cyclohexanol, 1,2-ethyl A group consisting of alkanediol, 1,2-propanediol, propylene glycol monobutyl ether, ethylene glycol monobutyl ether, dipropylene glycol dimethyl ether, and a solvent represented by the following formulae [D1] to [D3] At least 1 kind of solvent.

(D ¹ represents an alkyl group having 1 to 3 carbon atoms. D ² represents an alkyl group having 1 to 3 carbon atoms. D ³ represents an alkyl group having 1 to 4 carbon atoms).

(15) The liquid crystal alignment treatment agent according to any one of the above (1) to (14), wherein the liquid crystal alignment treatment agent contains Yes, cross-linking compounds selected from the group consisting of epoxy groups, isocyanate groups, propylene oxide groups, and cyclic carbonate groups, and hydroxyl groups, hydroxyalkyl groups, and alkoxyalkyl groups having 1 to 3 carbon atoms The cross-linking compound selected by the group, or the cross-linking compound having a polymerizable unsaturated bond group.

(16) A liquid crystal alignment film, which is obtained from the liquid crystal alignment treatment agent according to any one of (1) to (15) above.

(17) A liquid crystal alignment film, which is obtained by applying the liquid crystal alignment treatment agent according to any one of (1) to (15) above by an inkjet method.

(18) A liquid crystal display element having the liquid crystal alignment film according to the above (16) or (17).

(19) The liquid crystal alignment film according to the above (16) or (17), wherein the liquid crystal alignment film is used between a pair of substrates having electrodes, and a liquid crystal layer is arranged between the pair of substrates. A liquid crystal composition of a polymerizable compound polymerized by at least one of the heat is a liquid crystal display element obtained by applying a voltage between the electrodes to polymerize the polymerizable compound.

(20) A liquid crystal display element comprising the liquid crystal alignment film according to the above (19).

(21) The liquid crystal alignment film according to the above (16) or (17), wherein the liquid crystal alignment film is used between a pair of substrates having electrodes, and a liquid crystal layer is arranged between the pair of substrates. Polymerizable group liquid crystal alignment film polymerized by at least one of the heat, and A liquid crystal display element obtained by applying a voltage between the electrodes to polymerize the polymerizable group.

(22) A liquid crystal display element comprising the liquid crystal alignment film according to the above (21).

The liquid crystal alignment treatment agent containing two kinds of specific compounds and polymers of the present invention can produce a liquid crystal alignment film that can suppress a decrease in voltage holding rate even after long-term exposure to light irradiation. In addition, even under conditions of high temperature and high humidity, a liquid crystal alignment film with no display spots is generated near the front edge of the liquid crystal display element.

Although the action mechanism for obtaining a liquid crystal display element having the above-mentioned excellent characteristics in the present invention is not fully understood, it is supposed to be as follows.

The present invention relates to a liquid crystal alignment treatment agent containing the following components (A), (B) and (C), a liquid crystal alignment film obtained by using the liquid crystal alignment treatment agent, and a liquid crystal having the liquid crystal alignment film. Display element.

(A) Ingredient: Heteropoly acid (also known as a specific compound).

(B) Ingredient: polymer.

(C) Ingredient: A compound having a nitrogen-containing aromatic heterocyclic ring in the molecule.

The effects of specific compounds are as follows. One of the main causes of the decrease in the voltage holding ratio is the presence of most ionic impurity components in the liquid crystal. In this regard, it is presumed that the liquid crystal display element is exposed to a long time. In the case where the liquid crystal is decomposed by light irradiation, the ionic impurity component generated at this time will be adsorbed by a specific compound, and the reduction of the voltage holding ratio can be suppressed. Moreover, it is estimated that the compound which has a nitrogen-containing aromatic heterocyclic ring in a molecule can improve the said effect further based on the nitrogen-containing aromatic heterocyclic ring contained in the structure.

In the polymer, a polyimide precursor obtained by reacting a diamine component and a tetracarboxylic acid component or a polyimide obtained by polyimide imidization of the polyimide precursor is used. Among the diamine components, a diamine compound having a structure represented by the above formula [2-1] or formula [2-2] is used, and it is used in a vertical (VA: Vertical Alignment) mode and a PSA (Polymer Sustained Alignment) When the liquid crystal display element in the mode and SC-PVA mode is used, the structure shown in formula [2-1] is a display rigidity structure. Therefore, the liquid crystal display element using the liquid crystal alignment film having the structure is stable to ultraviolet rays and the like. It can suppress the decrease of voltage holding ratio and the generation of ionic impurities.

In addition, the liquid crystal display element provided with the liquid crystal alignment film obtained by the liquid crystal alignment treatment agent of the present invention has excellent reliability, and can be applied to large-screen and high-definition liquid crystal televisions and the like. In particular, when producing a liquid crystal display element, it is useful to use a PSA mode or SC-PVA mode liquid crystal display element that irradiates high-energy ultraviolet rays.

[Form of Implementing Invention] <Specific compound>

A specific compound in the present invention is a heteropolyacid.

Heteropoly acids are typically represented by the chemical structure of the Keggin type or the Dawson type shown in the formula [1-1], which has a structure in which the heteroatom is located at the center of the molecule. Polyacids obtained from the condensation of oxo acids such as vanadium (V), molybdenum (Mo), and tungsten (W) with oxo acids of dissimilar elements. The oxyacids of these dissimilar elements include, for example, oxyacids of silicon (Si), phosphorus (P), and arsenic (As).

Specific examples of the heteropoly acid compound include, for example, phosphomolybdic acid, silomomolybdic acid, phosphotungstic acid, silototungstic acid, or phosphotungstomolybdic acid. In the present invention, those components are preferably used. These may be used alone or in combination of two or more kinds. The heteropolyacid compound in the present invention can be obtained in the form of a commercially available article, and can also be synthesized by a known method.

Heteropoly acids, in quantitative analysis such as elemental analysis, whether the number of elements known from the structure shown by the general formula is larger or smaller, can be obtained in the form of commercially available items, or when appropriately synthesized by a known synthesis method Can be used in the present invention.

That is, for example, in general, phosphotungstic acid has the following formula [ 1a], and phosphomolybdic acid is a structure represented by formula [1b].

[Chem. 10] H ₃ (PW ₁₂ O ₄₀ ). nH ₂ O [1a] H ₃ (PMo ₁₂ O ₄₀ ). nH ₂ O [1b]

For these contents, in the quantitative analysis, whether the number of P (phosphorus), O (oxygen), or W (tungsten) or Mo (molybdenum) in the formulas is larger or smaller, it is commercially available Those who have obtained the item method or those who have appropriately synthesized by a known synthesis method can be used in the present invention. In this case, the quality of the heteropolyacid specified in the present invention means not only the mass of pure phosphotungstic acid (phosphotungstic acid content) in the composition or the commercially available product, but also the form obtained from commercially available items In the form that can be isolated by a known synthetic method, it means full mass in a state including hydrated water or other impurities.

<Polymer>

The polymers in the present invention include acrylic polymer, methacrylic polymer, novolac resin, polyhydroxystyrene, polyimide precursor, polyimide, polyimide, polyester, cellulose and polyimide. At least one polymer selected from the group of siloxanes is preferred. Preferred are polyimide precursors, polyimide or polysiloxane. Particularly preferred is a polyimide precursor or polyimide (also collectively referred to as a specific polyimide-based polymer).

<Specific polyimide-based polymer>

In the case of using a specific polyfluorene imine polymer in the polymer of the present invention, the polyfluorene obtained by reacting a diamine component with a tetracarboxylic acid component An imine precursor or polyimide is preferred.

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

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

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

The specific polyfluorene-imide-based polymer can be produced in a relatively simple manner by using a tetracarboxylic dianhydride represented by the following formula [B] and a diamine represented by the following formula [C] as raw materials, It is preferable to use a polyamidic acid composed of a structural formula of a repeating unit represented by the following formula [D], or a polyimide obtained by subjecting the polyamidic acid to amidation. Among them, in the present invention, from the viewpoints of physical and chemical stability of the liquid crystal alignment film, polyfluorene imide in which the polyfluorene imide precursor is fluorinated is preferred.

(R ¹ and R ² have the same contents as those defined by the formula [A]).

(R ¹ , R ² and nA have the same contents as those defined by formula [A]).

In addition, a general synthetic method can be used to introduce into the polymer of the formula [D] obtained above the alkyl groups having 1 to 8 carbon atoms of A ¹ and A ² represented by the formula [A], and the compound of the formula [A]. Shows A ³ and A ⁴ carbon or alkyl groups with 1 to 5 carbon atoms.

As the diamine component in the present invention, known components can be used.

Among them, in the case where the liquid crystal alignment treatment agent of the present invention is used in a liquid crystal display element of VA mode, PSA mode, or SC-PVA mode, the diamine component has the following formula [2-1] or formula [2-2] A diamine compound having a side chain structure (also referred to as a specific side chain structure) is preferred.

In the formula [2-1], Y ¹ , Y ² , Y ³ , Y ⁴ , Y ⁵ , Y ^6, and n are as defined above, and among them, the following contents are preferred.

Y ¹ , from the viewpoint of availability of raw materials or easy synthesis, preferably a single bond,-(CH ₂ ) _a- (a is an integer from 1 to 15), -O-, -CH ₂ O-, or -COO- . Preferred are a single bond,-(CH ₂ ) _a- (a is an integer from 1 to 10), -O-, -CH ₂ O-, or -COO-.

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

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

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

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

Y ^{6 is} composed of an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 18 carbon atoms or 1 to 10 carbon atoms Fluoroalkoxy is preferred. More preferably, it is an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms. Particularly preferred are alkyl groups having 1 to 9 carbon atoms, alkenyl groups having 2 to 12 carbon atoms or alkoxy groups having 1 to 9 carbon atoms.

n, from the viewpoint of availability of raw materials or easy synthesis, 0 to 3 is preferred, and 0 to 2 is more preferred.

The preferred combination of Y ¹ , Y ² , Y ³ , Y ⁴ , Y ⁵ , Y ⁶ and n can be exemplified by Table 6 on pages 13 to 34 of International Publication WO2011 / 132751 (published on 2011.10.27). (2-1) to (2-629) disclosed in Table 47 are the same combination. In the tables of the International Publication, Y ¹ to Y ⁶ in the present invention are labeled as Y ¹ to Y ^6. Therefore, Y ¹ to Y ^{6 are} interpreted as Y ¹ to Y ⁶ . In addition, in (2-605) to (2-629) disclosed in the tables of the International Publication, the organic group having a carbon number of 17 to 51 in the present invention is the carbon number indicated as having a cholesterol frame. Organic groups of 12 to 25, so organic groups having 12 to 25 carbons with a cholesterol skeleton should be interpreted as organic groups having 17 to 51 carbons with a cholesterol skeleton.

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

[化 15] -Y ⁷ -Y ⁸ [2-2]

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

Y ^{7 is} preferably a single bond, -O-, -CH ₂ O-, -CONH-, -CON (CH ₃ )-, or -COO-. More preferably, it is a single bond, -O-, -CONH-, or -COO-.

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

In the present invention, from the viewpoint that a vertical alignment of a liquid crystal having high stability can be obtained by specifying a side chain structure, it is preferable to use a structure represented by formula [2-1].

As the diamine compound having a specific side chain structure, it is preferable to use a diamine compound (also referred to as a specific side chain type diamine compound) represented by the following formula [2a].

In the formula [2a], Y represents a structure represented by the aforementioned formula [2-1] or formula [2-2].

In addition, the detailed contents and preferred combinations of Y ¹ , Y ² , Y ³ , Y ⁴ , Y ⁵ , Y ^6, and n in Formula [2-1] can be listed as shown in the aforementioned Formula [2-1] For details, the details and preferred combinations of Y ⁷ and Y ^{8 in} the formula [2-2], for example, the contents shown in the foregoing formula [2-2].

n1, from the viewpoint of easy synthesis, 1 is preferred.

The specific side chain type diamine compound having a specific side chain structure represented by the formula [2-1] is specifically, for example, a diamine compound represented by the following formula [2a-1] to [2a-31].

(R ¹ represents at least one type of bonding group selected from the group consisting of -O-, -OCH _2- , -CH ₂ O-, -COOCH _2- , and -CH ₂ OCO-. R ² represents each Linear or branched alkyl group with 1 to 18 carbons, linear or branched alkoxy group with 1 to 18 carbons, linear or branched fluoroalkyl group with 1 to 18 carbons, or carbon Straight-chain or branched fluorine-containing alkoxy groups of 1 to 18).

(R ³ represents -COO-, -OCO-, -CONH-, -NHCO-, -COOCH _2- , -CH ₂ OCO-, -CH ₂ O-, -OCH ₂ -and -CH _2- At least one type of bonding group selected by the group. R ⁴ represents a linear or branched alkyl group having 1 to 18 carbon atoms, a linear or branched alkoxy group having 1 to 18 carbon atoms, and carbon number, respectively. 1 to 18 linear or branched fluorine-containing alkyl group, or 1 to 18 carbon linear or branched fluorine-containing alkoxy group).

(R ⁵ represents -COO-, -OCO-, -CONH-, -NHCO-, -COOCH _2- , -CH ₂ OCO-, -CH ₂ O-, -OCH _2- , -CH ₂ -,- At least one type of bonding group selected from the group consisting of O- and -NH-. R ⁶ represents a fluoro group, a cyano group, a trifluoromethylalkyl group, a nitro group, an azo group, a formamyl group, and an acetamyl group, respectively. At least one selected from the group consisting of acetoxy, hydroxy and ethoxy).

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

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

(A ₄ represents a linear or branched alkyl group having 3 to 18 carbon atoms which may be substituted by a fluorine atom. A ₃ represents 1,4-cyclohexyl or 1,4-phenylene. A ₂ represents an oxygen atom Or -COO- * (where the bond with "*" is bonded to A ₃ ). A ₁ represents an oxygen atom or -COO- * (where the bond with "*" is and ( CH ₂ ) a ₂ ) bond). In addition, a ₁ represents an integer of 0 or 1. a ₂ represents an integer from 2 to 10. a ₃ represents an integer of 0 or 1).

Among the above formulae [2a-1] to [2a-31], preferred diamine compounds are formulae [2a-1] to [2a-6], formulas [2a-9] to [2a-13], or formulae [2a-22] ~ Formulas [2a-31].

The specific side chain type diamine compound having the specific side chain structure represented by the aforementioned formula [2-2], specifically, for example, diamine compounds represented by the following formulas [2a-32] to [2a-35] and the like.

(A ¹ represents an alkyl group or a fluorine-containing alkyl group having 8 to 18 carbon atoms, respectively).

The use ratio of the specific diamine compound (2), particularly in the case of a liquid crystal display element in the VA mode, the PSA mode, or the SC-PVA mode, is preferably 10 to 70 mol% relative to the entire diamine component. It is more preferably 20 to 70 mole%, and particularly preferably 20 to 60 mole%.

In addition, the specific side chain type diamine compound can be combined with the solubility of a specific polyimide-based polymer in a solvent, the liquid crystal alignment property when used as a liquid crystal alignment film, or the electrical characteristics of a liquid crystal display element. One type or two or more types can be used in combination.

In addition, the specific side chain type diamine compound can be appropriately selected and used in accordance with the display mode of the liquid crystal display element, that is, TN (TwistedNematic) mode, IPS (In-planeSwitching) mode, VA mode, PSA mode, and SC-PVA mode .

The diamine component of a specific polyfluorene-imide-based polymer may be, for example, the following diamine compounds (also referred to as other diamine compounds) can be used.

Specifically, for example, 2,4-dimethyl-m-phenylenediamine, 2,6-diaminotoluene, m-phenylenediamine, p-phenylenediamine, 2,4 -Diaminophenol, 3,5-diaminophenol, 3,5-diaminobenzyl alcohol, 2,4-diaminobenzyl alcohol, 4,6-diaminoresorcinol, 2,4 -Diaminobenzoic acid, 2,5-diaminobenzoic acid or 3,5-diaminobenzoic acid, 4,4'-diamine Benzene, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 3,3'-dihydroxy -4,4'-diaminobiphenyl, 3,3'-dicarboxy-4,4'-diaminobiphenyl, 3,3'-difluoro-4,4'-biphenyl, 3,3 '-Trifluoromethyl-4,4'-diaminobiphenyl, 3,4'-diaminobiphenyl, 3,3'-diaminobiphenyl, 2,2'-diaminobiphenyl , 2,3'-diaminodiphenyl, 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane , 2,2'-diaminodiphenylmethane, 2,3'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether , 3,4'-diaminodiphenyl ether, 2,2'-diaminodiphenyl ether, 2,3'-diaminodiphenyl ether, 4,4'-sulfobiphenylaniline, 3, 3'-sulfobiphenylaniline, bis (4-aminophenyl) silane, bis (3-aminophenyl) silane, dimethyl-bis (4-aminophenyl) silane, dimethyl- Bis (3-aminophenyl) silane, 4,4'-thiodiphenylamine, 3,3'-thiodiphenylamine, 4,4'-diaminodiphenylamine, 3,3'-diaminodiphenylamine , 3,4'-diaminodiphenylamine, 2,2'-diaminodiphenylamine Amine, 2,3'-diaminodiphenylamine, N-methyl (4,4'-diaminodiphenyl) amine, N-methyl (3,3'-diaminodiphenyl) amine , N-methyl (3,4'-diaminodiphenyl) amine, N-methyl (2,2'-diaminodiphenyl) amine, N-methyl (2,3'-di Aminodiphenyl) amine, 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 3,4'-diaminobenzophenone, 1,4 -Diaminonaphthalene, 2,2'-diaminobenzophenone, 2,3'-diaminobenzophenone, 1,5-diaminonaphthalene, 1,6-diaminonaphthalene, 1,7-Diaminonaphthalene, 1,8-Diaminonaphthalene, 2,5-Diaminonaphthalene, 2,6-Diaminonaphthalene, 2,7-Diaminonaphthalene, 2,8-Di Aminonaphthalene, 1,2-bis (4-aminophenyl) ethane, 1,2-bis (3-aminophenyl) ethane, 1,3-bis (4-aminophenyl) propane , 1,3-bis (3-aminophenyl) propane, 1,4-bis (4-aminophenyl) butane, 1,4-bis (3-aminophenyl) butane, bis (3,5-diethyl-4-aminophenyl) methane, 1,4-bis (4-aminophenoxy) benzene, 1,3- Bis (4-aminophenoxy) benzene, 1,4-bis (4-aminophenyl) benzene, 1,3-bis (4-aminophenyl) benzene, 1,4-bis (4- Aminobenzyl) benzene, 1,3-bis (4-aminophenoxy) benzene, 4,4 '-[1,4-phenylenebis (methylidene)] diphenylamine, 4,4' -[1,3-phenylenebis (methylene)] diphenylamine, 3,4 '-[1,4-phenylenebis (methylene)] diphenylamine, 3,4'-[1, 3-phenylenebis (methylene)] diphenylamine, 3,3 '-[1,4-phenylenebis (methylene)] diphenylamine, 3,3'-[1,3-phenylene Bis (methylene)] diphenylamine, 1,4-phenylenebis [(4-aminophenyl) methanone], 1,4-phenylenebis [(3-aminophenyl) methyl Ketone], 1,3-phenylenebis [(4-aminophenyl) methanone], 1,3-phenylenebis [(3-aminophenyl) methanone], 1,4-phenylene Phenylbis (4-aminobenzoate), 1,4-phenylenebis (3-aminobenzoate), 1,3-phenylenebis (4-aminobenzoate) ), 1,3-phenylenebis (3-aminobenzoate), bis (4-aminophenyl) terephthalate, bis (3-aminophenyl) terephthalate Ester, bis (4- Aminophenyl) isophthalate, bis (3-aminophenyl) isophthalate, N, N '-(1,4-phenylene) bis (4-aminobenzyl) Fluorene), N, N '-(1,3-phenylene) bis (4-aminobenzylamine), N, N'-(1,4-phenylene) bis (3-amine Benzamidine), N, N '-(1,3-phenylene) bis (3-aminobenzamide), N, N'-bis (4-aminophenyl) p-xylylenediamine Amine, N, N'-bis (3-aminophenyl) p-xylylenediamine, N, N'-bis (4-aminophenyl) m-xylylenediamine, N, N'-bis (3 -Aminophenyl) m-phenylenediamine, 9,10-bis (4-aminophenyl) anthracene, 4,4'-bis (4-aminophenoxy) diphenylfluorene, 2,2 '-Bis [4- (4-amino (Phenoxy) phenyl] propane, 2,2'-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 2,2'-bis (4-aminophenyl) hexafluoro Propane, 2,2'-bis (3-aminophenyl) hexafluoropropane, 2,2'-bis (3-amino-4-methylphenyl) hexafluoropropane, 2,2'-bis ( 4-aminophenyl) propane, 2,2'-bis (3-aminophenyl) propane, 2,2'-bis (3-amino-4-methylphenyl) propane, 1,3- Bis (4-aminophenoxy) propane, 1,3-bis (3-aminophenoxy) propane, 1,4-bis (4-aminophenoxy) butane, 1,4-bis (3-Aminophenoxy) butane, 1,5-bis (4-aminophenoxy) pentane, 1,5-bis (3-aminophenoxy) pentane, 1,6- Bis (4-aminophenoxy) hexane, 1,6-bis (3-aminophenoxy) hexane, 1,7-bis (4-aminophenoxy) heptane, 1,7 -Bis (3-aminophenoxy) heptane, 1,8-bis (4-aminophenoxy) octane, 1,8-bis (3-aminophenoxy) octane, 1, 9-bis (4-aminophenoxy) nonane, 1,9-bis (3-aminophenoxy) nonane, 1,10-bis (4-aminophenoxy) decane, 1 , 10-bis (3-aminophenoxy) decane, 1,11-bis (4-aminophenoxy) undecane, 1,11-bis (3-aminophenoxy) undec Alkane, 1,12-bis (4-aminophenoxy) Dioxane, 1,12-bis (3-aminophenoxy) dodecane, bis (4-aminocyclohexyl) methane, bis (4-amino-3-methylcyclohexyl) methane, 1, 3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8 -Diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, 1,12-diaminododecane, and the like.

In addition, for other diamine compounds, for example, a diamine compound represented by the following formula [D1] to [DA15] may be used.

(p represents an integer from 1 to 10).

(L ¹ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. N represents an integer of 1 to 5).

A diamine compound represented by the following formula [DA16] may be used.

(A ¹ represents -O-, -NH-, -N (CH ₃ )-, -CONH-, -NHCO-, -CH ₂ O-, -OCO-, -CON (CH ₃ )-and -N ( At least one selected from the group consisting of CH ₃ ) CO-. A ² represents a group selected from the group consisting of a single bond, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, a non-aromatic cyclic hydrocarbon group, and an aromatic hydrocarbon group. At least 1. A ³ represents a single bond, -O-, -NH-, -N (CH ₃ )-, -CONH-, -NHCO-, -COO-, -OCO-, -CON (CH ₃ )- , -N (CH ₃ ) CO- and -O (CH ₂ ) _m- (m is an integer of 1 to 5), at least one selected from the group. A ⁴ represents a nitrogen-containing aromatic heterocyclic ring. P1 represents 1 ~ 4 integer).

Other diamine compounds can be used singly or in combination with specific polyfluorene-imide-based polymers in solvents, liquid crystal alignment when used as a liquid crystal alignment film, or electrical characteristics of liquid crystal display elements. Mixed use.

In preparing the tetracarboxylic acid component of the specific polyfluorene-imide-based polymer, it is preferable to use a tetracarboxylic dianhydride (also referred to as a specific tetracarboxylic acid component) represented by the following formula [3].

In the formula [3], Z represents at least one structure selected from the group consisting of the structures shown in the formulas [3a] to [3k].

Z in the formula [3], from the viewpoints of ease of synthesis or ease of polymerization reactivity at the time of manufacturing a polymer, is based on the formulas [3a], [3c], [3d], and [3e] The structure shown by the formula [3f], [3g] or [3k] is preferred. Preferred is a structure represented by formula [3a], formula [3e], formula [3f], formula [3g], or formula [3k]. Particularly preferred is a structure represented by formula [3e], formula [3f], formula [3g], or formula [3k].

The proportion of the specific tetracarboxylic acid component is preferably more than 1 mole% relative to the all-tetracarboxylic acid component. More preferably, it is 5 mol% or more. Particularly preferred is 10 mol% or more. The best one can suppress the decrease in voltage holding rate caused by prolonged exposure to light, and examples include 10 to 90 mol%.

In the case of using a tetracarboxylic acid component having the structure represented by the formula [3e], [3f], [3g], or [3k], when the amount of the tetracarboxylic acid component is 20 mol% or more of the total tetracarboxylic acid component , You can get the desired effect. It is preferably at least 30 mol%. The tetracarboxylic acid component may be a tetracarboxylic acid component having a structure represented by the formula [3e], [3f], [3g], or [3k].

The tetracarboxylic acid component in the present invention can be used in a range that does not impair the effect of the present invention. Ingredients.

Specifically, for example, pyromellitic acid, 2,3,6,7-naphthalenetetracarboxylic acid, 1,2,5,6-naphthalenetetracarboxylic acid, 1,4,5,8-naphthalenetetracarboxylic acid, 2,3,6,7-anthracene tetracarboxylic acid, 1,2,5,6-anthracene tetracarboxylic acid, 3,3 ', 4,4'-biphenyltetracarboxylic acid, 2,3,3', 4 '-Biphenyltetracarboxylic acid, bis (3,4-dicarboxyphenyl) ether, 3,3', 4,4'-benzophenone tetracarboxylic acid, bis (3,4-dicarboxyphenyl)碸, bis (3,4-dicarboxyphenyl) methane, 2,2-bis (3,4-dicarboxyphenyl) propane, 1,1,1,3,3,3-hexafluoro-2,2 -Bis (3,4-dicarboxyphenyl) propane, bis (3,4-dicarboxyphenyl) dimethylsilane, bis (3,4-dicarboxyphenyl) diphenylsilane, 2,3, 4,5-pyridine tetracarboxylic acid, 2,6-bis (3,4-dicarboxyphenyl) pyridine, 3,3 ', 4,4'-diphenylphosphonium tetracarboxylic acid, 3,4,9, 10-fluorene tetracarboxylic acid or 1,3-diphenyl-1,2,3,4-cyclobutanetetracarboxylic acid and the like.

Specific tetracarboxylic acid components and other tetracarboxylic acid components can be compatible with the solubility of certain polyimide polymers in solvents, liquid crystal alignment when used as a liquid crystal alignment film, or electrical characteristics of liquid crystal display elements. One kind or two or more kinds are mixed and used.

The method for producing a specific polyfluorene-based polymer is not particularly limited. It is usually prepared for reacting a diamine component with a tetracarboxylic acid component. In general, two or more types of tetracarboxylic acid components selected from the group consisting of tetracarboxylic dianhydrides and derivatives of tetracarboxylic acids and two or more types of diamine compounds are used. A method for preparing a polyamic acid by reacting an amine component. Specifically, for example, a method in which polycarboxylic acid is prepared by polycondensing a tetracarboxylic dianhydride and a primary or secondary diamine compound, and a tetracarboxylic acid and a primary or secondary diamine can be used. Dehydration polycondensation A method for preparing a polyphosphonic acid by combining the reactions, or a method for preparing a polyphosphonic acid by reacting a tetracarboxylic acid dihalide with a primary or secondary diamine compound.

In the method for preparing a polyalkylamino alkyl ester, a method of polycondensing a tetracarboxylic acid obtained by esterifying a carboxylic acid dialkyl with a primary or secondary diamine compound can be used to make the carboxylic dialkyl ester A method for reacting a tetracarboxylic dihalide obtained with the reaction with a primary or secondary diamine compound, or a method for converting a carboxyl group of a polyamic acid into an ester.

In the method for producing polyimide, for example, a method in which the aforementioned polyamidic acid or polyamidoalkyl ester is ring-closed to form polyimide can be used.

The reaction between the diamine component and the tetracarboxylic acid component is usually carried out in a diamine component and a tetracarboxylic acid component in an organic solvent. The organic solvent used at this time is not particularly limited as long as it can dissolve the produced polyimide precursor. The following are specific examples of the organic solvent used in the reaction, but are not limited to these examples.

For example, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, γ-butyrolactone, N, N-dimethylformamide, N, N-dimethylacetamidine Amines, dimethylsulfinium or 1,3-dimethyl-tetrahydroimidazolone. In order to improve the solubility of the polyfluorene imide precursor in a solvent, methyl ethyl ketone, cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone, or the following formula can be used. [D-1] to a solvent represented by the formula [D-3].

(D ¹ represents an alkyl group having 1 to 3 carbon atoms. D ² represents an alkyl group having 1 to 3 carbon atoms. D ³ represents an alkyl group having 1 to 4 carbon atoms).

These can be used alone or in combination. Moreover, even if it is a solvent which cannot dissolve a polyfluorene imide precursor, as long as it does not precipitate a polyfluorene imide precursor, you may mix and use it with the said solvent. In addition, the water in the organic solvent is used to hinder the polymerization reaction and even cause the generated polyimide precursor to be hydrolyzed. Therefore, the organic solvent is preferably one that is dehydrated and dried.

When the diamine component and the tetracarboxylic acid component are reacted in an organic solvent, for example, a solution obtained by dispersing or dissolving the diamine component in an organic solvent may be added, and the tetracarboxylic acid component may be added to the stirring or dispersed. Or a method of adding to an organic solvent by dissolution, a method of dissolving a tetracarboxylic acid component in an organic solvent, or a method of adding a diamine component to a dissolved solution, or a method of adding a diamine component and a tetracarboxylic acid component alternately Etc., any of these methods can be used. In addition, in the case where the diamine component and the tetracarboxylic acid component are respectively reacted by using a plurality of types, they may be reacted in a state of being mixed first, the reactions may be sequentially performed separately, or the respective reactions may be obtained. It is also possible to use a low molecular weight body as a polymer by performing a mixed reaction. The polymerization temperature at this time can be selected at any temperature from -20 ° C to 150 ° C, and is preferably in the range of -5 ° C to 100 ° C. In addition, although the reaction can be carried out at any concentration, if the concentration is too low, it will be difficult to obtain a polymer with a high molecular weight. When the concentration is too high, Because the viscosity of the reaction solution is too high, uniform stirring is not easy. 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 an organic solvent is added at a high concentration at the beginning of the polymerization reaction.

In the polymerization reaction of the polyimide precursor, the ratio of the total mole number of the diamine component to the total mole number of the tetracarboxylic acid component is preferably 0.8 to 1.2. It is the same as the usual polymerization reaction. 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 by subjecting the aforementioned polyimide precursor to ring closure. The ring closure ratio (also known as amidation ratio) of the amido acid group is not necessarily 100%, and it can be combined with Use or purpose to make arbitrary adjustments. Among them, the specific polyfluorene imide polymer in the present invention is preferably a polyfluorene imine in which a polyfluorine imide precursor is fluorinated. At this time, the imidization rate of fluorene is preferably 40 to 90%. The better is 50 ~ 90%.

The method of polyimide precursor imidization can be exemplified by heating the polyimide precursor solution with hot imidization, or adding a catalyst to the polyimide precursor solution. Method of imidization. The temperature at which the polyimide precursor is thermally imidized in the solution is 100 ° C. to 400 ° C., preferably 120 ° C. to 250 ° C., and preferably the water generated by the imidization reaction is continuously discharged. The reaction is preferably performed in an out-of-system process.

Polyimide precursor catalyst imidization is to add alkaline catalyst and acid anhydride to the solution of polyimide precursor, and carry out at -20 ~ 250 ℃, preferably 0 ~ 180 ℃ Performed by stirring. The amount of alkaline catalyst is 0.5 to 30 mol times of the amino acid group, preferably 2 to 20 mol. Times, the amount of acid anhydride is 1 to 50 mole times of the amino acid group, preferably 3 to 30 mole times. Examples of the basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine, and trioctylamine. Among them, pyridine is preferred because it can maintain an appropriate basicity during the reaction. Examples of the acid anhydride include acetic anhydride, trimellitic anhydride, pyromellitic anhydride, and the like. Among them, acetic anhydride is more preferably used after the reaction is completed. The rate of catalyst imidization can be controlled by adjusting the amount of catalyst, reaction temperature and reaction time.

When the polyfluorene imide precursor or polyfluorene imide is recovered from the polyfluorene imide precursor or polyimide reaction solution, the reaction solution may be put into a solvent to cause precipitation. Examples of the solvent used for the precipitation include methanol, ethanol, isopropanol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, toluene, benzene, and water. The polymer that is precipitated after being put into the solvent can be dried under normal pressure or reduced pressure under normal pressure or reduced pressure after being recovered by filtration. In addition, when the polymer after precipitation recovery is repeated 2 to 10 times to re-dissolve and recover the polymer in an organic solvent, the impurities in the polymer can be reduced. The solvents used at this time, for example, alcohols, ketones, or hydrocarbons, when using more than three types of solvents selected from these, it is preferable to improve the purification efficiency by one layer.

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

As mentioned above, the specific polyfluorene imide polymer in the present invention can suppress the decrease of the voltage holding rate after being exposed to light for a long period of time. Polyimide is preferred. The hydrazone imidization ratio at this time is preferably in the above range.

<(C) component‧Specific amine compound>

The component (C) in the present invention is a compound having a nitrogen-containing aromatic heterocyclic ring in the molecule, wherein the molecule has a primary amine group and a nitrogen-containing aromatic heterocyclic ring, and the aforementioned primary amine group is a bond An amine compound (also referred to as a specific amine compound) derived from an aliphatic hydrocarbon group or a non-aromatic cyclic hydrocarbon group is preferred.

Since this specific amine compound contains only one amine group in the molecule, it can prevent the precipitation of polymers or cause gelation when preparing liquid crystal alignment treatment agents or during storage of liquid crystal alignment treatment agents. possibility.

The amine group contained in the specific amine compound must be bonded to a divalent aliphatic hydrocarbon group or a non-aromatic cyclic hydrocarbon group without aromatic hydrocarbons from the viewpoint of easily forming a salt with the polymer or easily performing a bonding reaction. Knot.

Specific examples of the aliphatic hydrocarbon group include a linear alkylene group, an alkylene group having a branched structure, and a divalent hydrocarbon group having an unsaturated bond. The carbon number of the aliphatic hydrocarbon group is preferably 1 to 20. Particularly preferred is a carbon number of 1 to 15, and the best is a carbon number of 1 to 10.

Specific examples of the non-aromatic cyclic hydrocarbon group include a ring Propane ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, cyclononane ring, cyclodecane ring, cycloundecane ring, cyclododecane ring, ring Tridecane ring, cyclotetradecane ring, cyclopentadecane ring, cyclohexadecane ring, cycloheptadecane ring, cyclooctadecane ring, cyclononadecane ring, icosene ring, A tricyclic eicosene ring, a docosane ring, a dicycloheptane ring, a decalin ring, a norbornene ring or an adamantane ring, and the like. A non-aromatic cyclic hydrocarbon group having a ring of 3 to 20 carbon atoms is preferred. Particularly preferred is a ring formed from 3 to 15 carbons, and the most preferred is a ring formed from 3 to 10 carbons.

The nitrogen-containing aromatic heterocyclic ring contained in the specific amine compound is a nitrogen-containing aromatic heterocyclic ring having a structure represented by the following formula [4-a], [4-b], or [4-c].

(M represents a linear or branched alkyl group having 1 to 5 carbon atoms).

Specific examples of the nitrogen-containing aromatic heterocyclic ring include a pyrrole ring, an imidazole ring, an oxazole ring, a thiazole ring, a pyrazole ring, a pyridine ring, a pyrimidine ring, a quinoline ring, a pyrazoline ring, and an isoquinoline ring. Carbazole ring, purine ring, thiadiazole ring, Ring, pyrazoline ring, tris Ring, pyrazidine ring, triazole ring, pyr Ring, benzimidazole ring, benzimidazole ring, octyline ring, phenanthroline ring, indole ring, quinoxaline ring, benzothiazole ring, phenothialine (phenothiazine) ring, oxazole ring or acridine ring and the like. In addition, the carbon atoms of these nitrogen-containing aromatic heterocyclic rings may have a substituent containing a hetero atom.

A preferred specific amine compound is, for example, a compound represented by the following formula [4a-1].

[Chem. 39] H ₂ NS ¹ -S ² [4a-1]

S ¹ represents a divalent organic group having an aliphatic hydrocarbon group or a non-aromatic cyclic hydrocarbon group. Among them, an aliphatic hydrocarbon group having 1 to 20 carbon atoms or a non-aromatic cyclic hydrocarbon group having 3 to 20 carbon atoms is preferable. Preferred are aliphatic hydrocarbon groups having 1 to 15 carbon atoms, cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, cyclononane ring, cyclodecane Ring, cycloundecane ring, cyclododecane ring, cyclotridecane ring, cyclotetradecane ring, norbornene ring or adamantane ring. Particularly preferred is a linear or branched alkyl group having 1 to 10 carbon atoms.

S ² represents a nitrogen-containing aromatic heterocyclic ring, and has the same structure as described above, and contains the structure represented by the formula [4-a], [4-b], or [4-c].

Specific examples thereof include the structures listed above. Among these, pyrrole ring, imidazole ring, pyrazole ring, pyridine ring, pyrimidine ring, Ring, three Ring, triazole ring, pyridine Ring, benzimidazole ring, benzimidazole ring, quinoxaline ring, azepine ring, diazepine ring, 1,5-naphthyridine ring, brown Ring or 呔 The ring is better.

In addition, from the viewpoints that the nitrogen-containing aromatic heterocyclic ring and the carboxyl group in the polymer are likely to form a salt or to generate an electrostatic interaction with hydrogen bonding, S ¹ in the aforementioned formula [4a-1] is not included in S ² It is preferable that adjacent substituents of the formula [4-a], [4-b] or [4-c] are bonded together.

In the preferred combination of S ¹ and S ² in formula [4a-1], S ¹ is an aliphatic hydrocarbon group having 1 to 20 carbon atoms or a non-aromatic cyclic hydrocarbon group having 3 to 20 carbon atoms, and S ² is pyrrole Ring, imidazole ring, pyrazole ring, pyridine ring, pyrimidine ring, Ring, three Ring, triazole ring, pyridine Ring, benzimidazole ring, benzimidazole ring, quinoxaline ring, azepine ring, diazepine ring, 1,5-diazepine ring, brown Ring or 呔 ring.

A preferable specific amine compound is, for example, an amine compound represented by the following formula [4a-2].

[Chem. 40] H ₂ NS ³ -S ⁴ -S ⁵ [4a-2]

In the formula [4a-2], S ³ , S ^4, and S ⁵ are as defined above, and among them, the following contents are preferable.

S ³ , linear or branched alkyl group having 1 to 10 carbon atoms, unsaturated alkyl group having 1 to 10 carbon atoms, cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, cycloheptane Ring, cyclooctane ring, cyclononane ring, cyclodecane ring, cycloundecane ring, cyclododecane ring, cyclotridecane ring, cyclotetradecane ring, cyclopentadecanyl ring, cyclohexadecane Ring, cycloheptadecane ring, cyclooctadecane ring, cyclononadecane ring, cycloicosene ring, eicosene ring, docosane ring, A bicycloheptane ring, decalin ring, norbornene ring or adamantane ring is preferred. Preferred is a linear or branched alkylene group having 1 to 10 carbon atoms.

S ⁴ with a single bond, -O-, -NH-, -S-, -SO _2- , a hydrocarbon group having 1 to 19 carbon atoms, -CO-O-, -O-CO-, -CO-NH-, -NH-CO-, -CO-, -CF _2- , -C (CF ₃ ) _2- , -CH (OH)-, -C (CH ₃ ) _2- , -Si (CH ₃ ) ₂ -,- O-Si (CH ₃ ) _2- , -Si (CH ₃ ) ₂ -O-, -O-Si (CH ₃ ) ₂ -O-, cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclohexane Alkane ring, cycloheptane ring, cyclooctane ring, cyclononane ring, cyclodecane ring, cycloundecane ring, cyclododecane ring, cyclotridecane ring, cyclotetradecane ring, cyclopentadecane ring Ring, cyclohexadecane ring, cycloheptadecane ring, cyclooctadecane ring, cyclononadecane ring, cycloicosene ring, icocosene ring, eicosene ring, tricyclic twenty-two ring Docosane ring, dicycloheptane ring, decahydronaphthalene ring, norbornene ring, adamantane ring, benzene ring, naphthalene ring, tetrahydronaphthalene ring, fluorene ring, indene ring, fluorene ring, anthracene ring, phenanthrene Ring, pyrene ring, pyrrole ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, pyridine ring, pyrimidine ring, quinoline ring, pyrazoline ring, isoquinoline ring, carbazole ring, purine ring, thiazole Diazole ring, da Ring, three Ring, pyrazidine ring, triazole ring, pyr Ring, benzimidazole ring, benzimidazole ring, octyline ring, phenanthroline ring, indole ring, quinoxaline ring, benzothiazole ring, phenothialine A phenothiazine ring, an oxazole ring, an acridine ring, an oxazole ring, a piperazine ring, a piperidine ring, a dioxane ring, or a morpholin ring is preferred.

S ⁵ as pyrrole ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, pyridine ring, pyrimidine ring, quinoline ring, pyrazoline ring, isoquinoline ring, carbazole ring, purine ring, thiadi Azole ring, da Ring, pyrazoline ring, tris Ring, pyrazidine ring, triazole ring, pyr Ring, benzimidazole ring, benzimidazole ring, octyline ring, phenanthroline ring, indole ring, quinoxaline ring, benzothiazole ring, phenothialine (phenothiazine) ring, oxazole ring or acridine ring is preferred.

In addition, in view of the electrostatic interaction between the nitrogen-containing aromatic heterocyclic ring and the carboxyl group in the polymer, which is likely to form a salt or a hydrogen bond, S ⁴ in the formula [4a-2] is not included in S ⁵ It is preferable that the adjacent carbon atoms of the formula [4-a], [4-b] or [4-c] are bonded together.

Specific examples of the specific amine compound in the present invention include amine compounds represented by the following formulas [M1] to [M156].

Among them, the formulas [M10], [M11], [M14], [M16], [M17], [M19], [M20], [M35], [M36], and [M40], formula [M49], formula [M50], formula [M52], formula [M60], formula [62], formula [M68], formula [M69], formula [M76], formula [M77], formula [M82], formula [M100], formula [M101], formula [M108], formula [M109], formula [M118], formula [M120], formula [M121], formula [M128], formula [M135], formula [M136], [M140], or [M143] is preferred. The better ones are formula [M16], formula [M17], formula [M35], formula [M36], formula [M40], formula [M49], [M50], [M52], [M60], [62], [M68], [M69], [M100], [M101], [M108], [M109], [M118], [M120], [M121], [M128], [M135], [M136], or [M140].

These specific amine compounds can be used in combination of one or two or more in combination with characteristics such as the solubility of the specific amine compound in a solvent, the liquid crystal alignment when used as a liquid crystal alignment film, or the electrical characteristics of a liquid crystal display element.

<Liquid crystal alignment treatment agent>

The liquid crystal alignment treatment agent of the present invention is a coating solution for forming a liquid crystal alignment film (also referred to as a resin film), a specific compound, a polymer, and a coating solution for forming a liquid crystal alignment film containing a specific amine compound and a solvent.

The proportion of the specific compound in the liquid crystal alignment treatment agent is preferably as described below. That is, it is preferably 1 to 30 parts by mass based on 100 parts by mass of the entire polymer. It is preferably 1 to 20 parts by mass, and particularly preferably 3 to 15 parts by mass.

The specific compound may be directly added to a solution containing a polymer and a solvent, or may be added to a solution diluted with an appropriate solvent.

The proportion of the specific amine compound in the liquid crystal alignment treatment agent is preferably as described below. That is, it is preferably 1 to 40 parts by mass based on 100 parts by mass of the entire polymer. The best is 1 part by mass ~ 30 parts by mass, particularly preferably 1 to 20 parts by mass.

The specific amine compound may be directly added to a solution containing a polymer and a solvent, but it is preferably added to a solution adjusted to a concentration of 0.1 to 10% by mass using an appropriate solvent. The solvent at this time is, for example, a solvent capable of dissolving the aforementioned specific polyfluorene-based polymer.

After adding the specific amine compound, it is preferable to heat the solution containing the specific amine compound and the polymer. In particular, it is more preferable to use a specific polyfluorene-imide polymer for the polymer. Specifically, for example, when heating, a specific polyfluorene-based polymer can be bonded or interacted to increase the ratio of the specific amine compound. When used as a liquid crystal alignment film, the hardening of the present invention can be further improved. . At this time, the temperature in the heating case is preferably 10 to 100 ° C, and more preferably 20 to 80 ° C.

Among the polymer components in the liquid crystal alignment treatment agent, a specific polyimide-based polymer is preferably used, but it may also be used in combination with other polymers. At this time, the content of other polymers is preferably 0.5 to 15 parts by mass based on 100 parts by mass of the specific polyimide-based polymer. It is preferably 1 to 10 parts by mass. Examples of other polymers include acrylic polymers, methacrylic polymers, novolac resins, polyhydroxystyrene, polyamides, polyesters, celluloses, and polysiloxanes.

The solvent in the liquid crystal alignment treatment agent is from the viewpoint that a uniform liquid crystal alignment film can be formed by coating, and the solvent content in the liquid crystal alignment treatment agent is preferably 70 to 99.9% by mass. The content can be appropriately changed according to the film thickness of the liquid crystal alignment film for the purpose.

The solvent used for the liquid crystal alignment treatment agent is not particularly limited as long as it is a solvent that can dissolve the polymer (also referred to as a good solvent). In the following, specific examples of good solvents when using a specific polyfluorene-imide-based polymer will be listed, but the invention is not limited to these examples.

For example, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, dimethylimine Rhenium, γ-butyrolactone, 1,3-dimethyl-tetrahydroimidazolidone, methyl ethyl ketone, cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone, and the like.

Among them, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone or γ-butyrolactone is more preferably used.

In addition, when it is desired to improve the solubility of a specific polyimide-based polymer in a solvent, it is preferable to use a solvent represented by the aforementioned formula [D-1] to [D-3].

The use ratio of the good solvent in the liquid crystal alignment treatment agent is preferably 10 to 100% by mass of the entire solvent contained in the liquid crystal alignment treatment agent. It is preferably 20 to 90% by mass, and particularly preferably 30 to 80% by mass.

Among the liquid crystal alignment treatment agents, a solvent (also referred to as a lean solvent) that can improve the coating property or surface smoothness of the liquid crystal alignment film when the liquid crystal alignment treatment agent is applied, as long as the effect of the present invention is not impaired. The following are specific examples of the lean solvent, but are not limited to these examples.

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-methyl ring Hexanol, 3-methylcyclohexanol, 1,2-ethanediol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol Alkanediol, 1,4-butanediol, 2,3-butanediol, 1,5-pentanediol, 2-methyl-2,4-pentanediol, 2-ethyl- 1,3-hexanediol, dipropyl ether, dibutyl ether, dihexyl ether, dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, 1,2-butane Oxyethane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ether, diethylene glycol dibutyl ether, 2-pentanone, 3-pentanone, 2-hexanone , 2-heptanone, 4-heptanone, 3-ethoxybutyl acetate, 1-methylpentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate , Ethylene glycol monoacetate, ethylene glycol diacetate, propylene carbonate, ethylene carbonate, 2- (methoxymethoxy) ethanol, ethylene glycol monobutyl ether, ethylene glycol monoisopentyl Ether, ethylene glycol monohexyl ether, 2- (hexyloxy) ethanol, furfuryl alcohol, diethylene glycol, propylene glycol, propylene glycol Butyl ether, 1- (butoxyethoxy) propanol, propylene glycol monomethyl ether acetate, dipropylene glycol, 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 mono Diethyl ether acetate, diethylene glycol monobutyl ether acetate, 2- (2-ethoxyethoxy) ethyl acetate, diethylene glycol acetate, triethylene glycol, triethylene glycol Alcohol monomethyl ether, triethylene glycol monoethyl ether, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether, methyl pyruvate, ethyl pyruvate, 3 -Methyl methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-methoxypropionate Methyl, 3-ethoxypropionic acid, 3-methoxypropionic acid, 3-methoxypropionic acid propyl, 3-methoxypropionic acid butyl, methyl lactate, ethyl lactate, n-propyl lactate Esters, n-butyl lactate, isoamyl lactate, or solvents represented by the aforementioned formulas [D-1] to [D-3].

Among them, 1-hexanol, cyclohexanol, 1,2-ethanediol, 1,2-propanediol, propylene glycol monobutyl ether, ethylene glycol monobutyl ether, dipropylene glycol dimethyl ether, or It is preferable to use the solvents represented by the aforementioned formulas [D-1] to [D-3].

The use ratio of these lean solvents is preferably 1 to 70% by mass of the entire solvent contained in the liquid crystal alignment treatment agent. It is preferably 1 to 60% by mass, and particularly preferably 5 to 60% by mass.

In the liquid crystal alignment treatment agent of the present invention, a crosslinkable compound selected from the group consisting of an epoxy group, an isocyanate group, an propylene oxide group, and a cyclic carbonate group is introduced, a hydroxyl group, a hydroxyalkyl group, and a carbon number of 1 are introduced. A cross-linking compound selected from a group of ~ 3 alkoxyalkyl groups, or a cross-linking compound having a polymerizable unsaturated bond group (also collectively referred to as a specific cross-linking compound) is preferred. In this case, the compound must have two or more of these groups.

Crosslinkable compounds having an epoxy group or an isocyanate group, for example, bisphenol acetone glycidyl ether, phenol-phenol novolac epoxy resin, cresol-novolac epoxy resin, triglycidyl isotricyanate, Glycidylamino diphenyl, tetraglycidyl-m-xylylenediamine, tetraglycidyl-1,3-bis (aminoethyl) cyclohexane, tetraphenylglycidyl ether ethane, triphenyl Glycidyl ether ethane, bisphenol hexafluoroacetone diglycidyl Ether, 1,3-bis (1- (2,3-glycidoxy) -1-trifluoromethyl-2,2,2-trifluoromethyl) benzene, 4,4-bis (2, 3-glycidoxy) octafluorobiphenyl, triglycidyl-p-aminophenol, tetraglycidyl xylene diamine, 2- (4- (2,3-glycidoxy) phenyl ) -2- (4- (1,1-bis (4- (2,3-glycidoxy) phenyl) ethyl) phenyl) propane or 1,3-bis (4- (1- ( 4- (2,3-glycidoxy) phenyl) -1- (4- (1- (4- (2,3-glycidoxy) phenyl) -1-methylethyl) Phenyl) ethyl) phenoxy) -2-propanol and the like.

The cross-linkable compound having a propylene oxide group is a cross-linkable compound having at least two propylene oxide groups represented by the following formula [4A].

Specific examples include crosslinkable compounds represented by formulas [4a] to [4k] disclosed in pages 58 to 59 of International Publication WO2011 / 132751 (published 2011.10.27).

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

Specifically, for example, International Publication The cross-linking compounds represented by the formulas [5-1] to [5-42] disclosed in pages 76 to 82 of WO2012 / 014898 (published 2012.2.2) are disclosed.

A crosslinkable compound having at least one kind of group selected from the group consisting of a hydroxyl group and an alkoxy group, for example, an amine-based resin having a hydroxyl group or an alkoxy group, for example, a melamine resin, a urea resin, or fluorene Resin, acetylene urea-formaldehyde resin, succinimidylamine-formaldehyde resin or ethylene urea-formaldehyde resin. Specific examples thereof include melamine derivatives in which a hydrogen atom of an amine group is replaced by a methylol group or an alkoxymethyl group, or a benzofluorene. Derivatives, or acetylene urea. The melamine derivative or benzofluorene Derivatives can exist as dimers or trimers. Of these, each three The ring is preferably one having 3 to 6 hydroxymethyl or alkoxymethyl groups on average.

These melamine derivatives or benzofluorene Derivatives, for example, every three MX-750 with 3.7 methoxymethyl groups on average MW-30 (above, manufactured by Sanwa Chemical Co., Ltd.) or CYMEL ^® 300, 301, 303, 350, 370, 771, 325, 327, 703, 712 and other methoxy groups substituted by an average of 5.8 methoxymethyl rings Methylated melamine, CYMEL ^® 235, 236, 238, 212, 253, 254 and other methoxymethylated butoxymethylated melamine, CYMEL ^® 506, 508 and other butoxymethylated melamine, CYMEL ^® 1141 and other carboxyl-containing methoxymethylated isobutoxymethylated melamine, CYMEL ^® 1123 and other methoxymethylated ethoxymethylated benzofluorene Methoxymethylated butoxymethylated benzopyrene, CYMEL ^® 1123-10 , CYMEL ^® 1128, etc. , CYMEL ^® 1125-80 and other carboxyl-containing methoxymethylated ethoxymethylated benzopyrene (Above, manufactured by Mitsui Cyanoamide Corporation) and the like. Examples of acetylene ureas include butoxymethylated acetylene ureas such as CYMEL ^® 1170, hydroxymethylated acetylene ureas such as CYMEL ^® 1172, and methoxymethylolated acetylene ureas such as POWDERLIMK 1174.

Benzene with a hydroxyl or alkoxy group, or a phenolic compound, for example, 1,3,5-gins (methoxymethyl) benzene, 1, 2,4-gins (isopropoxymethyl) benzene, 1 4,4-bis (sec-butoxymethyl) benzene or 2,6-dihydroxymethyl-p-tert-butylphenol. More specifically, the cross-linkable compounds represented by the formulas [6-1] to [6-48], as disclosed in pages 62 to 66 of International Publication WO2011 / 132751 (published on 2011.10.27), can be listed. Wait.

A crosslinkable compound having a polymerizable unsaturated bond, for example, three trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylic acid in the molecule Crosslinkable compounds of polymerizable unsaturated groups such as esters, tris (meth) acryloxyethoxytrimethylolpropane or glycerol polyglycidyl ether poly (meth) acrylate; ethylene glycol di ( (Meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate , Polypropylene glycol di (meth) acrylate, butanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, ethylene oxide bisphenol A type di (meth) acrylate, Propylene oxide bisphenol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, glycerol di (meth) acrylate, pentaerythritol di (meth) acrylate, Glycol Di Glycidyl ether di (meth) acrylate, diethylene glycol diglycidyl ether di (meth) acrylate, diglycidyl phthalate di (meth) acrylate, or neopentyl glycol tert-valerate A crosslinkable compound having two polymerizable unsaturated groups in the molecule such as di (meth) acrylate and the like.

The content of the specific crosslinkable compound in the liquid crystal alignment treatment agent is preferably 1 to 50 parts by mass relative to 100 parts by mass of the entire polymer component. When it is preferable to obtain the effect that can be achieved by performing a crosslinking reaction, it is 1 to 30 parts by mass, particularly preferably 1 to 10 parts by mass.

Among the liquid crystal alignment treatment agents, a compound that can improve the uniformity of the thickness of the liquid crystal alignment film or the surface smoothness when the liquid crystal alignment treatment agent is applied within a range that does not impair the effects of the present invention. In addition, a compound or the like that can improve the adhesion between the liquid crystal alignment film and the substrate may be used.

Examples of the compound that improves the uniformity or surface smoothness of the liquid crystal alignment film include fluorine-based surfactants, polysiloxane-based surfactants, and non-ionic surfactants. Specific examples include, for example, F-TOP EF301, EF303, and EF352 (above, manufactured by Dow Chemical Co., Ltd.), Meflon F171, F173, R-30 (above, manufactured by Dainippon Paint Co., Ltd.), and FLUORAD FC430, FC431 (above, manufactured by Sumitomo 3M), AsahiGuard AG710, Seflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (above, manufactured by Asahi Glass Co., Ltd.), etc. The use ratio of these surfactants is preferably 0.01 to 2 parts by mass relative to 100 parts by mass of all polymer components contained in the liquid crystal alignment treatment agent. It is preferably 0.01 to 1 part by mass.

Compound for improving adhesion between liquid crystal alignment film and substrate Specific examples include a functional silane-containing compound or an epoxy group-containing compound. For example, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-ureidopropane Trimethoxysilane, 3-ureidopropyltriethoxysilane, N-ethoxycarbonyl-3-aminopropyltrimethoxysilane, N-ethoxycarbonyl-3-aminopropyltrisilane Ethoxysilane, N-triethoxysilylpropyltriethyltriamine, N-trimethoxysilylpropyltriethyltriamine, 10-trimethoxysilane-1,4,7-triaza Decane, 10-triethoxysilane-1,4,7-triazadecane, 9-trimethoxysilane-3,6-diazanonyl acetate, 9-triethoxysilane -3,6-diazanonyl acetate, N-benzyl-3-aminopropyltrimethoxysilane, N-benzyl-3-aminopropyltriethoxysilane, N-benzene 3-Aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N-bis (oxyethylene) -3-aminopropyltrimethoxysilane, N-bis (oxyethylene) -3-aminopropyltriethyl Oxysilane, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol diglycidyl ether, 2,2-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-diglycidylaminomethyl) cyclohexane Or N, N, N ', N',-tetraglycidyl-4,4'-diaminodiphenylmethane and the like.

It can be used in proportion with the compounds adhered to these substrates. For 100 parts by mass of all polymer components contained in the liquid crystal alignment treatment agent, it is preferably 0.1 to 30 parts by mass. It is preferably 1 to 20 parts by mass. If it is less than 0.1 parts by mass, the effect of improving adhesion will not be achieved. If it exceeds 30 parts by mass, the storage stability of the liquid crystal alignment treatment agent may deteriorate.

To the liquid crystal alignment treatment agent, in addition to the compounds other than those described above, a dielectric body or a conductive substance may be added for the purpose of changing the electrical properties such as the dielectric constant and conductivity of the liquid crystal alignment film within a range that does not impair the effects of the present invention.

<Liquid crystal alignment film and liquid crystal display element>

The liquid crystal alignment treatment agent of the present invention can be used as a liquid crystal alignment film user after being coated and sintered on a substrate and then subjected to alignment treatment such as rubbing treatment or light irradiation. In addition, in the case of a liquid crystal display element used in the VA mode, it can also be used as a liquid crystal alignment film without alignment treatment. The substrate used at this time is not particularly limited as long as it is a substrate with high transparency. In addition to a glass substrate, a plastic substrate such as an acrylic substrate or a polycarbonate substrate can also be used. From the viewpoint of simplifying the manufacturing process, it is preferable to use a substrate formed with an ITO (IndiumTinOxide) electrode or the like used as a liquid crystal driver. Moreover, in a reflective liquid crystal display element, if it is only a single-sided substrate, an opaque substrate such as a silicon wafer may be used, and in this case, an electrode that reflects light may also be used.

The application method of the liquid crystal alignment treatment agent is not particularly limited. Generally speaking, it is generally used for screen printing, lithographic printing, relief printing, etc. Flexo printing or inkjet method. Other coating methods include, for example, a dipping method, a roll coating method, a slit coating method, a spin coater method, or a spray method, and these methods can be used according to the purpose.

After the liquid crystal alignment treatment agent is coated on the substrate, the solvent used for the liquid crystal alignment treatment agent is mixed with a heating means such as a hot plate, a thermal cycle type oven, or an IR (infrared) type oven, and the temperature is preferably 30 to 300 ° C. The solvent is evaporated at a temperature of 30 ~ 250 ° C, and it is used as a liquid crystal alignment film. If the thickness of the sintered liquid crystal alignment film is too thick, it is disadvantageous from the viewpoint of power consumption of the liquid crystal display element. If it is too thin, the reliability of the liquid crystal display element may be reduced. Therefore, it is preferably 5 to 300 nm. It is preferably 10 to 100 nm. Like the liquid crystal display elements used in the TN mode or IPS mode, when the liquid crystal is tilted or horizontally aligned, the sintered liquid crystal alignment film can be subjected to rubbing or polarized ultraviolet irradiation.

According to the liquid crystal display element of the present invention, as described above, after the liquid crystal alignment treatment agent of the present invention is used to prepare a substrate with a liquid crystal alignment film, a liquid crystal cell can be produced by a known method as a liquid crystal display element.

A method for manufacturing a liquid crystal cell, for example, preparing a pair of substrates having a liquid crystal alignment film, and spreading a spacer on the liquid crystal alignment film of a single-sided substrate so that the liquid crystal alignment film surface faces inward, and bonding the substrate on the other side Then, a method of injecting liquid crystal under reduced pressure for sealing, or a method of attaching and sealing a substrate after the liquid crystal is dropped onto a liquid crystal alignment film surface with a spacer (also referred to as ODF: One Drop Filling method) is exemplified.

The liquid crystal alignment treatment agent of the present invention is also suitable for use with a liquid crystal layer between a pair of substrates having electrodes, and between the pair of substrates. A liquid crystal composition containing a polymerizable compound polymerized by at least one of active energy ray and heat is arranged, and the polymerizable compound is made by applying at least one of a voltage between electrodes, an irradiation of active energy ray, and heating. A liquid crystal display element obtained by the polymerization step. Among them, it is preferable to use ultraviolet rays as the active energy rays. The wavelength of the ultraviolet rays is 300 to 400 nm, preferably 310 to 360 nm. In the case of polymerization by heating, the heating temperature is 40 to 120 ° C, preferably 60 to 80 ° C. Moreover, you may perform ultraviolet rays and heat processing simultaneously.

The above-mentioned liquid crystal display device is a device that controls the pretilt angle of liquid crystal molecules by using the PSA mode. In the PSA mode, a small amount of a photopolymerizable compound, such as a photopolymerizable monomer, is mixed into a liquid crystal material. After the liquid crystal cell is combined, a specific voltage is applied to the liquid crystal layer, and the photopolymerizable compound is irradiated with ultraviolet rays or the like. The pretilt angle of the liquid crystal molecules is controlled by the generated polymer. Because the alignment state of the liquid crystal molecules when the polymer is generated, there will also be memory after the voltage is removed, so the pretilt angle of the liquid crystal molecules can be adjusted by means of an electric field formed on the liquid crystal layer. In addition, in the PSA mode, since rubbing treatment is unnecessary, it is also suitable for forming a liquid crystal layer of a vertical alignment type in which it is difficult to control the pretilt angle through the rubbing treatment. That is, in the liquid crystal display element of the present invention, after a substrate with a liquid crystal alignment film is prepared from a liquid crystal alignment treatment agent through the method described above, a liquid crystal cell is prepared, and at least one of ultraviolet radiation and heating is used to make a polymerizable compound. Polymerization, and can control the alignment of liquid crystal molecules.

An example of a method for manufacturing a liquid crystal cell in the PSA mode is given below. That is, a liquid crystal is produced according to the above-mentioned production method. Unit cell. In this liquid crystal, a polymerizable compound polymerized by heat or ultraviolet irradiation is mixed. The polymerizable compound is, for example, a compound having one or more polymerizable unsaturated groups such as an acrylate group or a methacrylate group in the molecule. At this time, the polymerizable compound is preferably 0.01 to 10 parts by mass, and more preferably 0.1 to 5 parts by mass, with respect to 100 parts by mass of the liquid crystal component. When the polymerizable compound is less than 0.01 parts by mass, the polymerizable compound does not polymerize and the alignment of the liquid crystal cannot be controlled. When it exceeds 10 parts by mass, there are too many unreacted polymerizable compounds, which may reduce the residual image of the liquid crystal display element. characteristic. After the liquid crystal cell is fabricated, an AC or DC voltage is applied to the liquid crystal cell, and the polymerizable compound is polymerized by irradiating heat or ultraviolet rays. In this way, the alignment of the liquid crystal molecules can be controlled.

In addition, the liquid crystal alignment treatment agent of the present invention includes a liquid crystal layer between a pair of substrates having electrodes, and a polymerizable group containing at least one of active energy rays and heat polymerized between the pair of substrates. The liquid crystal alignment film is a liquid crystal display element prepared by applying a voltage between the electrodes, that is, the SC-PVA mode can also be used. Among them, it is preferable to use ultraviolet rays as the active energy rays. The wavelength of the ultraviolet rays is 300 to 400 nm, preferably 310 to 360 nm. In the case of polymerization by heating, the heating temperature is 40 to 120 ° C, preferably 60 to 80 ° C. Moreover, you may perform ultraviolet rays and heat processing simultaneously.

When a liquid crystal alignment film containing a polymerizable group polymerized via at least one of active energy rays and heat is to be prepared, for example, a method for adding a polymerizable group-containing compound to a liquid crystal alignment treatment agent, or using a polymerizable group Method of polymer composition based on the base.

When an example of producing a liquid crystal cell in the SC-PVA mode is listed, for example, the following is shown. That is, a liquid crystal cell is manufactured according to the above-mentioned manufacturing method. Subsequently, by applying an AC or DC voltage to the liquid crystal cell, the orientation of the liquid crystal molecules can be controlled by irradiating heat or ultraviolet rays.

As described above, the present invention provides a liquid crystal alignment treatment agent of the present invention, which can suppress a decrease in voltage holding rate even after being exposed to light for a long time. In addition, even under high temperature and high humidity conditions, The liquid crystal display film does not generate a display spot near the front edge of the liquid crystal display element. Therefore, the liquid crystal display element obtained by using the liquid crystal alignment treatment agent of the present invention has excellent reliability, and is suitable for use in large-scale liquid crystal televisions, small and medium-sized car navigation systems, and smart phones. In particular, the liquid crystal alignment treatment agent of the present invention is useful for a liquid crystal alignment film using a liquid crystal display element of a VA mode, a PSA mode, and a SC-PVA mode.

[Example]

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

(Specific compound)

S1: Phosphotungstic acid (manufactured by Japan New Metals Corporation)

S2: Phosphomolybdic acid (12 molybdo (IV) phosphate and water) (manufactured by Kanto Chemical Co., Ltd.)

(Specific side chain type diamine compound)

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

A2: 1,3-diamino-5- [4- (trans-4-n-heptylcyclohexyl) phenoxymethyl] benzene

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

A4: a diamine compound represented by the following formula [B4]

A5: 1,3-diamino-4-octadecyloxybenzene

(Other diamine compounds)

B1: p-phenylenediamine

B2: m-phenylene diamine

B3: a diamine compound represented by the following formula [B3]

B4: 4,4'-diaminodiphenylamine

B5: 3,5-diaminobenzoic acid

(Specific tetracarboxylic dianhydride)

C1: 1,2,3,4-cyclobutane tetracarboxylic dianhydride

C2: Bicyclo [3,3,0] octane-2,4,6,8-tetracarboxylic dianhydride

C3: tetracarboxylic dianhydride represented by the following formula [C3]

C4: tetracarboxylic dianhydride represented by the following formula [C4]

C5: tetracarboxylic dianhydride represented by the following formula [C5]

(Crosslinkable compound)

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

(Solvent)

NMP: N-methyl-2-pyrrolidone

NEP: N-ethyl-2-pyrrolidone

γ-BL: γ-butyrolactone

BCS: ethylene glycol monobutyl ether

PB: propylene glycol monobutyl ether

DME: Dipropylene glycol dimethyl ether

(Specific amine compound)

L1: picolyl amine

L2: N- (3-aminopropyl) -imidazole

"Molecular weight measurement of polyimide polymers"

The measurement was performed in the following manner using a normal-temperature gel permeation chromatography (GPC) device (GPC-101, manufactured by Showa Denko Corporation) and a column (KD-803, KD-805, manufactured by Shodex).

Column temperature: 50 ℃

Eluent: N, N'-dimethylformamide (additive: lithium bromide-water compound (LiBr‧H ₂ O): 30mmol / L (liter); phosphoric acid‧anhydrous crystal (o-phosphoric acid): 30mmol / L L, tetrahydrofuran (THF) is 10ml / L)

Flow rate: 1.0ml / min

Standard samples for the production of calibration lines: TSK standard polyethylene oxide (molecular weight; approximately 900,000, 150,000, 100,000, and 30,000) (manufactured by Tosoh Corporation) and polyethylene glycol (molecular weight: approximately 12,000, 4,000, and 1,000) (polymerization By Bio-Experimental Corporation).

"Determination of the fluorene imidization rate of polyfluorene polymers"

20 mg of polyfluorene imide powder was placed in an NMR (nuclear magnetic resonance) sample tube (NMR standard sampling tube, Φ5 (manufactured by Kusano Science Co., Ltd.)), and added Dihydromethylene sulfene (DMSO-d6, 0.05% by mass TMS (tetramethylsilane) mixed product) (0.53 ml) was applied and completely dissolved by ultrasound. The proton NMR of this solution at 500 MHz was measured using an NMR measuring machine (JNW-ECA500, manufactured by Japan Electronic Data Corporation). The hydrazone imidization rate is determined by using protons generated from structures that have not changed before and after hydrazone imidization as the reference protons. It is calculated using the peak value of the protons, and the uranium compounds appearing around 9.5 ppm to 10.0 ppm. The integrated value of the proton peak generated by the NH group of the acid is obtained by the following formula.

醯 Imidization rate (%) = (1-α‧x / y) × 100

(where x is the cumulative peak value of protons generated by the NH group of sulfamic acid, y is the cumulative peak value of reference protons, and α is polyamidic acid (fluorene imidization rate is 0%). One NH matrix proton of amino acid, the proportion of its reference protons).

"Synthesis of Polyimide Polymers" <Synthesis example 1>

C4 (5.51g, 18.4mmol), A5 (0.78g, 2.07mmol) and B1 (2.01g, 18.6mmol) were mixed in NMP (17.4g), and after reacting at 40 ° C for 6 hours, C1 (0.40) was added g, 2.04 mmol) and NMP (8.70 g), and reacted at 40 ° C. for 6 hours to obtain a polyamic acid solution having a resin solid content concentration of 25% by mass.

NMP was added to the obtained polyamic acid solution (30.0 g) to dilute to 6 mass%, and then acetic anhydride (3.90 g) and pyridine (2.40 g) were added as the phosphonium imidization catalyst, and reacted at 70 ° C for 4 hours. hour. This reaction solution was poured into methanol (460 ml), and the obtained precipitate was filtered off. This precipitate was washed with methanol and dried under reduced pressure at 100 ° C to obtain a polyfluorene imine powder (1). The polyimide has a fluorene imidization rate of 84%, a number average molecular weight of 19,300, and a weight average molecular weight of 52,300.

<Synthesis example 2>

C2 (6.55g, 26.2mmol), A3 (4.92g, 11.4mmol), B1 (2.46g, 22.7mmol) and B3 (0.77g, 3.79mmol) were mixed in NEP (33.8g) and reacted at 80 ° C After 5 hours, C1 (2.20 g, 11.2 mmol) and NEP (16.9 g) were added, and a reaction was performed at 40 ° C. for 6 hours to obtain a polyamic acid solution (2) having a resin solid content concentration of 25% by mass. The number average molecular weight of this polyamic acid was 19,500, and the weight average molecular weight was 65,800.

<Synthesis example 3>

To the polyamidic acid solution (2) (30.0 g) obtained in Synthesis Example 2, NEP was added to dilute to 6 mass%, and then acetic anhydride (4.50 g) and pyridine (3.30 g) were added as the phosphonium imidization catalyst. , And reacted at 80 ° C for 4 hours. This reaction solution was poured into methanol (460 ml), and the obtained precipitate was filtered off. This precipitate was washed with methanol and dried under reduced pressure at 100 ° C to obtain a polyfluorene imine powder (3). The polyimide has a fluorinated imidization rate 81%, the number average molecular weight is 17,500, and the weight average molecular weight is 45,300.

<Synthesis example 4>

C2 (3.32 g, 13.3 mmol), A2 (2.65 g, 6.72 mmol), B1 (0.54 g, 4.99 mmol) and B4 (1.00 g, 5.02 mmol) were mixed in NEP (16.3 g), and reacted at 80 ° C After 5 hours, C1 (0.65 g, 3.31 mmol) and NEP (8.16 g) were added, and a reaction was performed at 40 ° C. for 6 hours to obtain a polyamic acid solution having a resin solid content concentration of 25% by mass.

To the obtained polyamidic acid solution (30.0 g), NEP was added to dilute to 6 mass%, and then acetic anhydride (4.50 g) and pyridine (3.30 g) were added as the phosphonium imidization catalyst, and reacted at 80 ° C for 3 hours. hour. This reaction solution was poured into methanol (460 ml), and the obtained precipitate was filtered off. This precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimide powder (4). This polyfluorene imine has an imidization ratio of 70%, a number average molecular weight of 18,300, and a weight average molecular weight of 46,000.

<Synthesis example 5>

C2 (2.30 g, 9.19 mmol), A1 (2.83 g, 7.44 mmol) and B2 (1.21 g, 11.2 mmol) were mixed in NMP (16.3 g), and after reacting at 80 ° C for 5 hours, C1 (1.80 g , 9.18 mmol) and NMP (8.13 g), after reacting at 40 ° C. for 6 hours, a polyamic acid solution having a resin solid content concentration of 25% by mass was obtained.

To the obtained polyamic acid solution (30.0 g), NMP was added After diluting to 6% by mass, acetic anhydride (3.80 g) and pyridine (2.40 g) were added as a sulfonium imidization catalyst, and reacted at 60 ° C for 2 hours. This reaction solution was poured into methanol (460 ml), and the obtained precipitate was filtered off. This precipitate was washed with methanol and dried under reduced pressure at 100 ° C to obtain a polyfluorene imine powder (5). The polyimide has a fluorene imidation rate of 55%, a number average molecular weight of 17,500, and a weight average molecular weight of 45,100.

<Synthesis example 6>

C2 (2.30 g, 9.19 mmol), A5 (2.80 g, 7.43 mmol) and B2 (1.21 g, 11.2 mmol) were mixed in NMP (16.2 g), and after reacting at 80 ° C for 5 hours, C1 (1.80 g , 9.18 mmol) and NMP (8.10 g), after reacting at 40 ° C. for 6 hours, a polyamic acid solution having a resin solid content concentration of 25% by mass was obtained.

NMP was added to the obtained polyamidic acid solution (30.0g) to dilute to 6% by mass, and then acetic anhydride (3.80g) and pyridine (2.40g) were added as the imidization catalyst, and reacted at 60 ° C. 2 hour. This reaction solution was poured into methanol (460 ml), and the obtained precipitate was filtered off. This precipitate was washed with methanol and dried under reduced pressure at 100 ° C to obtain a polyfluorene imine powder (6). The polyimide has a fluorene imidation ratio of 55%, a number average molecular weight of 16,800, and a weight average molecular weight of 43,900.

<Synthesis example 7>

C2 (2.68 g, 10.7 mmol), A4 (2.23 g, 4.53 mmol), B2 (0.78 g, 7.21 mmol), and B3 (1.29 g, 6.35 mmol) in NMP (16.8g), after reacting at 80 ° C for 5 hours, C1 (1.40g, 7.14mmol) and NMP (8.37g) were added, and after reacting at 40 ° C for 6 hours, the solid content concentration of the resin was 25 mass % Polyamine solution.

NMP was added to the obtained polyamidic acid solution (30.0g) to dilute to 6% by mass, and then acetic anhydride (3.80g) and pyridine (2.40g) were added as the imidization catalyst, and reacted at 60 ° C. 2 hour. This reaction solution was poured into methanol (460 ml), and the obtained precipitate was filtered off. This precipitate was washed with methanol and dried under reduced pressure at 100 ° C to obtain a polyfluorene imine powder (7). The polyimide has a fluorene imidation rate of 52%, a number average molecular weight of 14,800, and a weight average molecular weight of 38,300.

<Synthesis example 8>

C3 (4.10 g, 18.3 mmol), A2 (2.92 g, 7.40 mmol), B1 (0.60 g, 5.55 mmol) and B5 (0.85 g, 5.59 mmol) were mixed in NMP (25.4 g) and reacted at 40 ° C After 8 hours, a polyamic acid solution having a resin solid content concentration of 25% by mass was obtained.

After adding NMP to the obtained polyamidic acid solution (30.0g) and diluting to 6% by mass, acetic anhydride (4.50g) and pyridine (3.30g) as the phosphonium imidization catalyst were added, and reacted at 80 ° C for 3 hour. This reaction solution was poured into methanol (460 ml), and the obtained precipitate was filtered off. This precipitate was washed with methanol and dried under reduced pressure at 100 ° C to obtain a polyfluorene imine powder (8). The polyimide has a hydrazone imidation ratio of 75%, a number average molecular weight of 18,200, and a weight average molecular weight of 46,300.

<Synthesis example 9>

C4 (3.57 g, 11.9 mmol), A3 (2.23 g, 5.15 mmol), B2 (0.93 g, 8.60 mmol) and B4 (0.69 g, 3.46 mmol) were mixed in NMP (16.6 g) and reacted at 80 ° C After 5 hours, C1 (1.00 g, 5.10 mmol) and NMP (8.27 g) were added, and a reaction was performed at 40 ° C. for 6 hours to obtain a polyamic acid solution having a resin solid content concentration of 25% by mass.

After adding NEP to the obtained polyamidic acid solution (30.0g) and diluting to 6% by mass, acetic anhydride (4.50g) and pyridine (3.30g) as the phosphonium imidization catalyst were added, and reacted at 80 ° C for 4 hours. hour. This reaction solution was poured into methanol (460 ml), and the obtained precipitate was filtered off. This precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimide powder (9). This polyfluorene imine has an imidization ratio of 85%, a number average molecular weight of 15,500, and a weight average molecular weight of 40,100.

<Synthesis example 10>

C2 (1.42 g, 5.68 mmol), A2 (3.01 g, 7.63 mmol) and B1 (1.24 g, 11.5 mmol) were mixed in NMP (16.9 g), and after reacting at 80 ° C for 5 hours, C5 (2.80 g) was added , 13.2 mmol) and NMP (8.47 g), after reacting at 40 ° C. for 6 hours, a polyamic acid solution having a resin solid content concentration of 25% by mass was obtained.

To the obtained polyfluorenic acid solution (30.0 g), NEP was added to dilute to 6% by mass, and then acetic anhydride was added as a phosphonium imidization catalyst. (4.50 g) and pyridine (3.30 g), and reacted at 80 ° C for 3.5 hours. This reaction solution was poured into methanol (460 ml), and the obtained precipitate was filtered off. This precipitate was washed with methanol and dried under reduced pressure at 100 ° C to obtain a polyfluorene imine powder (10). The polyimide has a hydrazone imidation rate of 78%, a number average molecular weight of 16,600, and a weight average molecular weight of 43,400.

Table 1 shows polyimide-based polymers obtained in the synthesis examples.

* 1: Polyamic acid.

"Manufacturing of liquid crystal alignment treatment agent"

In Examples and Comparative Examples described later, examples of manufacturing liquid crystal alignment treatment agents are described. In addition, the liquid crystal alignment treatment agent is also used in the production and evaluation of liquid crystal display elements. The liquid crystal alignment treatment agents obtained in Examples and Comparative Examples are shown in Tables 2 to 4.

"Evaluation of Inkjet Coating Property of Liquid Crystal Alignment Treatment Agent"

The liquid crystal alignment treatment agents obtained in Examples 4 and 7 described later were used to evaluate the inkjet coating properties. Specifically, for example, these liquid crystal alignment treatment agents are subjected to pressure filtration using a membrane filter having a pore size of 1 μm, and ITO (indium tin oxide) is washed with pure water and IPA (isopropanol). ) On the ITO surface of the electrode substrate (100mm vertical × 100mm horizontal, 0.7mm thickness), the coating area is 70 × 70mm, the nozzle pitch is 0.423mm, the scanning pitch is 0.5mm, and the coating speed is 40mm / sec. Coating. At this time, the inkjet coater used HIS-200 (made by Hitachi Equipment Technology Co., Ltd.). The time from application to pre-drying was 60 seconds, and pre-drying was performed on a hot plate under conditions of 70 ° C. and 5 minutes.

The applicability was evaluated by visually observing the coating film surface of the substrate provided with the liquid crystal alignment film obtained as described above. Specifically, for example, the surface of a coating film is visually observed under a sodium lamp, and the presence or absence of a sand hole is confirmed. As a result, it was confirmed that the liquid crystal alignment film obtained in any of the examples had no sand holes on the surface of the coating film, and a liquid crystal alignment film having excellent coating film properties could be obtained.

`` Evaluation of the display spot characteristics near the front edge of the liquid crystal cell (general cell) ''

The liquid crystal alignment treatment agents obtained in the examples and comparative examples described later were filtered under pressure using a membrane filter with a pore size of 1 μm, and were spin-coated on a substrate with ITO electrodes (40 mm in height × 30 mm in width) washed with pure water and IPA. , Thickness 0.7mm), heat-treated at 230 ° C for 30 minutes in a heating cycle cleaning oven at 100 ° C for 5 minutes on a hot plate to obtain a 100nm ITO substrate with a liquid crystal alignment film . In addition, the liquid crystal alignment treatment agents of Examples 4 and 7 were prepared under the same conditions as the above "Evaluation of the inkjet coating property of the liquid crystal alignment treatment agent" (the substrates were the same as those described above using pure water and IPA). The cleaned substrate with ITO electrodes (40 mm in height × 30 mm in width, 0.7 mm in thickness) was then washed in a thermal cycle cleaning oven at 230 ° C for 30 minutes to form a 100 nm film. ITO substrate for liquid crystal alignment film.

Next, the coated surface of this substrate was rubbed with a friction device with a roller diameter of 120 mm, a nylon cloth, and a roller rotation speed of 1000 rpm, a roller speed of 50 mm / sec, and an extrusion amount of 0.1 mm. deal with.

Subsequently, two pieces of the substrate after the rubbing treatment were prepared, and a 6 μm spacer was sandwiched with the coating film surface as the inner side, and the surrounding cells were adhered with a sealant to obtain an empty cell. Liquid crystal is injected into the empty cell using a reduced pressure injection method, and the injection port is sealed to obtain a liquid crystal cell. Moreover, Example 1 In Comparative Examples 1 to 3, MLC-3018U (manufactured by Mock Japan Co., Ltd.) was used as the liquid crystal, and other examples and comparative examples were used as the liquid crystal. MLC-6608 (Mock Japan) was used as the liquid crystal.

Using the obtained liquid crystal cell, evaluation of display spot characteristics near the front edge of the liquid crystal cell was performed. Specifically, for example, the polarizing plate and the backlight are used to evaluate the liquid crystal alignment near the sealant by visual observation. As a result, all the liquid crystal cells obtained in Examples and Comparative Examples showed uniform liquid crystal alignment.

Subsequently, the liquid crystal cell was stored in a high-temperature and high-humidity tank at a temperature of 80 ° C and a humidity of 90% for 96 hours, and the alignment of the liquid crystal near the sealant was evaluated under the same conditions as above. The evaluation method is that when the liquid crystal alignment disorder is not found near the sealant after storage in a high-temperature and high-humidity tank, the evaluation is excellent (good expressions in Tables 5 to 7). Tables 5 to 7 show the results of the speckle characteristics near the frontal edge of the liquid crystal cell after being stored in a high-temperature and high-humidity tank.

`` Assessment of Voltage Holding Rate (General Cell) ''

The liquid crystal cell produced under the same conditions as the above "Evaluation of the display spot characteristics near the front edge of the liquid crystal cell (general cell)" under the same conditions was used to evaluate the voltage holding ratio. Specifically, for example, at a temperature of 80 ° C., a voltage of 60 μs at a voltage of 1 V is applied to the liquid crystal cell obtained by the above method, the voltage after 50 ms is measured, and the result of calculating to what extent the voltage can be saved is used as the voltage retention rate (Also known as VHR). The measurement was performed using a voltage holding ratio measuring device (VHR-1) (manufactured by Toyo Technology Co., Ltd.). Voltage: ± 1V, Pulse Width: 60μs, Flame Period: 50ms.

In addition, using a desk-type UV curing device (HCT3B28HEX-1) (manufactured by CENLITE), the liquid crystal cell after the voltage retention was measured immediately after the liquid crystal cell was manufactured was irradiated with 50 J / cm ² converted into 365 nm. Under ultraviolet light, the voltage holding ratio was measured under the same conditions as above.

In this evaluation, the value of the voltage retention rate after the production of the liquid crystal cell is higher. In addition, the value of the voltage retention rate after the production of the liquid crystal cell (also referred to as the initial stage) is the value after the ultraviolet irradiation (also referred to as the initial stage). When the reduction in UV irradiation is reduced, it is excellent in this evaluation. Tables 5 to 7 show the values of each VHR.

<Example 1>

To the polyfluorene imine powder (1) (2.50 g) obtained in Synthesis Example 1, NMP (7.83 g) and γ-BL (23.5 g) were added, and the mixture was stirred at 70 ° C for 24 hours to be dissolved. A 10 mass% NMP solution (1.25 g) and BCS (7.83 g) of L1 were added to this solution, and stirred at 50 ° C for 15 hours. Subsequently, S1 (0.25 g) was added, and it stirred at 25 degreeC for 6 hours, and obtained the liquid-crystal aligning agent (1). In this liquid crystal alignment treatment agent, no abnormal phenomenon such as turbidity or precipitation was found, and it was confirmed that this was a uniform solution.

<Example 2>

The solid content of the resin obtained by the synthesis method of Synthesis Example 2 was 25 mass A 10% by mass NEP solution (0.75g) of NEP (16.0g), PB (15.7g), and L1 was added to the polyamic acid solution (2) (10.0g) in an amount of 100%, and stirred at 50 ° C for 15 hours. Subsequently, S1 (0.125 g) was stirred at 25 ° C. for 6 hours to obtain a liquid crystal alignment treatment agent (2). In this liquid crystal alignment treatment agent, no abnormal phenomenon such as turbidity or precipitation was found, and it was confirmed that this was a uniform solution.

<Example 3>

To the polyfluorene imine powder (3) (2.50 g) obtained in Synthesis Example 3, NEP (23.5 g) was added, and the mixture was stirred at 70 ° C for 24 hours to be dissolved. A 10% by mass NEP solution (1.25 g), BCS (3.92 g), and PB (11.8 g) of L1 were added to this solution, and stirred at 50 ° C for 15 hours. Subsequently, S1 (0.25 g) was stirred at 25 ° C. for 6 hours to obtain a liquid crystal alignment treatment agent (3). In this liquid crystal alignment treatment agent, no abnormal phenomenon such as turbidity or precipitation was found, and it was confirmed that this was a uniform solution.

<Example 4>

To the polyfluorene imine powder (3) (1.50 g) obtained in Synthesis Example 3, NEP (16.5 g) and γ-BL (4.14 g) were added, and the mixture was stirred at 70 ° C for 24 hours to be dissolved. A 10% by mass NEP solution (0.75 g), PB (16.5 g), and DME (4.14 g) of L1 were added to this solution, and stirred at 50 ° C for 15 hours. Subsequently, S1 (0.15 g) was stirred at 25 ° C. for 6 hours to obtain a liquid crystal alignment treatment agent (4). In this liquid crystal alignment treatment agent, no abnormal phenomenon such as turbidity or precipitation was found, and it was confirmed that this was a uniform solution.

<Example 5>

To the polyfluorene imine powder (4) (2.50 g) obtained in Synthesis Example 4, NEP (23.5 g) was added, and the mixture was stirred at 70 ° C for 24 hours to be dissolved. A 10 mass% NEP solution (1.75 g) and PB (15.7 g) of L1 were added to this solution, and stirred at 50 ° C for 15 hours. Subsequently, S1 (0.175 g) was stirred at 25 ° C. for 6 hours to obtain a liquid crystal alignment treatment agent (5). In this liquid crystal alignment treatment agent, no abnormal phenomenon such as turbidity or precipitation was found, and it was confirmed that this was a uniform solution.

<Example 6>

To the polyfluorene imine powder (4) (2.50 g) obtained in Synthesis Example 4, NEP (23.5 g) was added, and the mixture was stirred at 70 ° C for 24 hours to be dissolved. A 10% by mass NEP solution (1.25 g) and PB (15.7 g) of L1 were added to this solution, and stirred at 50 ° C for 15 hours. Subsequently, S1 (0.175 g) was stirred at 25 ° C. for 6 hours to obtain a liquid crystal alignment treatment agent (6). In this liquid crystal alignment treatment agent, no abnormal phenomenon such as turbidity or precipitation was found, and it was confirmed that this was a uniform solution.

<Example 7>

NEP (18.6 g) was added to the polyfluorene imine powder (4) (1.50 g) obtained in Synthesis Example 4, and the mixture was stirred at 70 ° C. for 24 hours to be dissolved. A 10% by mass NEP solution (1.05 g) and PB (22.8 g) of L1 were added to this solution, and stirred at 50 ° C for 15 hours. Subsequently, S1 (0.105g), in After stirring at 25 ° C for 6 hours, a liquid crystal alignment treatment agent (7) was obtained. In this liquid crystal alignment treatment agent, no abnormal phenomenon such as turbidity or precipitation was found, and it was confirmed that this was a uniform solution.

<Example 8>

NMP (19.6 g) was added to the polyfluorene imide powder (5) (2.50 g) obtained in Synthesis Example 5, and the mixture was stirred at 70 ° C. for 24 hours to be dissolved. A 10% by mass NMP solution (0.75 g), BCS (3.92 g), and PB (15.7 g) of L1 were added to this solution, and stirred at 50 ° C for 15 hours. Subsequently, S2 (0.175 g) was stirred at 25 ° C for 6 hours to obtain a liquid crystal alignment treatment agent (8). In this liquid crystal alignment treatment agent, no abnormal phenomenon such as turbidity or precipitation was found, and it was confirmed that this was a uniform solution.

In addition, regarding the "evaluation of the display spot characteristics near the frontal edge of the liquid crystal cell (general cell)", in addition to the aforementioned standard test, an emphasis test is also performed as follows, and stored in a high temperature and high humidity tank at a temperature of 80 ° C and a humidity of 90% Evaluation is performed after 168 hours (the other conditions are the same as the aforementioned conditions). As a result, in the liquid crystal cell, it was confirmed that the liquid crystal alignment around the sealant did not appear disordered.

<Example 9>

NMP (19.6 g) was added to the polyfluorene imine powder (6) (2.50 g) obtained in Synthesis Example 5, and the mixture was stirred at 70 ° C. for 24 hours to be dissolved. A 10% by mass NMP solution (0.75 g), BCS (3.92 g), and PB (15.7 g) of L1 were added to this solution, and stirred at 50 ° C for 15 hours. Subsequently, S2 (0.175 g) was stirred at 25 ° C. for 6 hours to obtain a liquid crystal alignment treatment agent (9). In this liquid crystal alignment treatment agent, no abnormal phenomenon such as turbidity or precipitation was found, and it was confirmed that this was a uniform solution.

In addition, regarding the "evaluation of the display spot characteristics near the frontal edge of the liquid crystal cell (general cell)", in addition to the aforementioned standard test, an emphasis test is also performed as follows, and stored in a high temperature and high humidity tank at a temperature of 80 ° C and a humidity of 90% Evaluation is performed after 168 hours (the other conditions are the same as the aforementioned conditions). As a result, it was confirmed that in the liquid crystal cell, the liquid crystal alignment around the sealant was not disturbed.

<Example 10>

To the polyfluorene imine powder (7) (2.50 g) obtained in Synthesis Example 7, NEP (23.5 g) was added, and the mixture was stirred at 70 ° C for 24 hours to be dissolved. A 10% by mass NEP solution (1.75 g) of L2, BCS (3.92 g), and PB (11.8 g) were added to this solution, and stirred at 50 ° C for 15 hours. Subsequently, S1 (0.30 g) was stirred at 25 ° C. for 6 hours to obtain a liquid crystal alignment treatment agent (10). In this liquid crystal alignment treatment agent, no abnormal phenomenon such as turbidity or precipitation was found, and it was confirmed that this was a uniform solution.

<Example 11>

NEP (27.4 g) was added to the polyfluorene imide powder (8) (2.50 g) obtained in Synthesis Example 8, and the mixture was stirred at 70 ° C. for 24 hours to be dissolved. A 10 mass% NEP solution (1.75 g) and PB (11.8 g) of L1 were added to this solution, and stirred at 50 ° C. for 15 hours. Subsequently, S2 (0.125g), It stirred at 25 degreeC for 6 hours, and obtained the liquid-crystal aligning agent (11). In this liquid crystal alignment treatment agent, no abnormal phenomenon such as turbidity or precipitation was found, and it was confirmed that this was a uniform solution.

<Example 12>

NMP (19.6 g) was added to the polyfluorene imine powder (9) (2.50 g) obtained in Synthesis Example 9, and the mixture was stirred at 70 ° C. for 24 hours to be dissolved. A 10% by mass NMP solution (2.50 g), BCS (7.83 g), and PB (11.8 g) of L1 were added to this solution, and stirred at 50 ° C for 15 hours. Subsequently, S1 (0.25 g) was stirred at 25 ° C. for 6 hours to obtain a liquid crystal alignment treatment agent (12). In this liquid crystal alignment treatment agent, no abnormal phenomenon such as turbidity or precipitation was found, and it was confirmed that this was a uniform solution.

<Example 13>

NEP (23.5 g) was added to the polyfluorene imine powder (10) (2.50 g) obtained in Synthesis Example 10, and the mixture was stirred at 70 ° C. for 24 hours to be dissolved. A 10% by mass NEP solution (3.00 g), BCS (7.83 g), and PB (7.83 g) of L1 were added to this solution, and stirred at 50 ° C for 15 hours. Subsequently, S2 (0.175 g) was stirred at 25 ° C. for 6 hours to obtain a liquid crystal alignment treatment agent (13). In this liquid crystal alignment treatment agent, no abnormal phenomenon such as turbidity or precipitation was found, and it was confirmed that this was a uniform solution.

<Example 14>

Polyimide powder (11) (2.50 g) obtained in Synthesis Example 11 Then, NEP (23.5 g) was added, and it stirred at 70 degreeC for 24 hours, and was made to melt | dissolve. A 10% by mass NEP solution (1.25 g), BCS (7.83 g), and PB (7.83 g) of L2 were added to this solution, and stirred at 50 ° C for 15 hours. Subsequently, S2 (0.175 g) was stirred at 25 ° C for 6 hours to obtain a liquid crystal alignment treatment agent (14). In this liquid crystal alignment treatment agent, no abnormal phenomenon such as turbidity or precipitation was found, and it was confirmed that this was a uniform solution.

<Comparative example 1>

To the polyfluorene imine powder (1) (2.50 g) obtained in Synthesis Example 1, NMP (7.83 g) and γ-BL (23.5 g) were added, and the mixture was stirred at 70 ° C for 24 hours to be dissolved. BCS (7.83 g) was added to this solution and stirred at 25 ° C for 6 hours to obtain a liquid crystal alignment treatment agent (15). In this liquid crystal alignment treatment agent, no abnormal phenomenon such as turbidity or precipitation was found, and it was confirmed that this was a uniform solution.

<Comparative example 2>

To the polyfluorene imine powder (1) (2.50 g) obtained in Synthesis Example 1, NMP (7.83 g) and γ-BL (23.5 g) were added, and the mixture was stirred at 70 ° C for 24 hours to be dissolved. S1 (0.25 g) and BCS (7.83 g) were added to this solution, and stirred at 25 ° C. for 6 hours to obtain a liquid crystal alignment treatment agent (16). In this liquid crystal alignment treatment agent, no abnormal phenomenon such as turbidity or precipitation was found, and it was confirmed that this was a uniform solution.

<Comparative example 3>

To the polyfluorene imine powder (1) (2.50 g) obtained in Synthesis Example 1, NMP (7.83 g) and γ-BL (23.5 g) were added, and the mixture was stirred at 70 ° C for 24 hours to be dissolved. A 10% by mass NMP solution (1.25 g) and BCS (7.83 g) of L1 were added to this solution, and stirred at 50 ° C for 15 hours to obtain a liquid crystal alignment treatment agent (17). In this liquid crystal alignment treatment agent, no abnormal phenomenon such as turbidity or precipitation was found, and it was confirmed that this was a uniform solution.

<Comparative Example 4>

To the polyfluorene imine powder (3) (2.50 g) obtained in Synthesis Example 3, NEP (23.5 g) was added, and the mixture was stirred at 70 ° C for 24 hours to be dissolved. BCS (3.92g) and PB (11.8g) were added to this solution, and stirred at 25 ° C for 6 hours to obtain a liquid crystal alignment treatment agent (18). In this liquid crystal alignment treatment agent, no abnormal phenomenon such as turbidity or precipitation was found, and it was confirmed that this was a uniform solution.

<Comparative example 5>

To the polyfluorene imine powder (3) (2.50 g) obtained in Synthesis Example 3, NEP (23.5 g) was added, and the mixture was stirred at 70 ° C for 24 hours to be dissolved. S1 (0.25 g), BCS (3.92 g), and PB (11.8 g) were added to this solution, and stirred at 25 ° C. for 6 hours to obtain a liquid crystal alignment treatment agent (19). In this liquid crystal alignment treatment agent, no abnormal phenomenon such as turbidity or precipitation was found, and it was confirmed that this was a uniform solution.

<Comparative Example 6>

To the polyfluorene imine powder (3) (2.50 g) obtained in Synthesis Example 3, NEP (23.5 g) was added, and the mixture was stirred at 70 ° C for 24 hours to be dissolved. A 10% by mass NEP solution (1.25 g), BCS (3.92 g), and PB (11.8 g) of L1 were added to this solution, and stirred at 50 ° C for 15 hours to obtain a liquid crystal alignment treatment agent (20). In this liquid crystal alignment treatment agent, no abnormal phenomenon such as turbidity or precipitation was found, and it was confirmed that this was a uniform solution.

* 1: The amount of introduction of the specific compound (parts by mass) relative to 100 parts by mass of the polyimide-based polymer.

* 2: The introduction amount (parts by mass) of the specific amine compound relative to 100 parts by mass of the polyfluorene-imide-based polymer.

＊ 3: It shows the proportion of polyimide-based polymers in the liquid crystal alignment treatment agent.

* 1: In the liquid crystal cell, the disorder of the alignment of the liquid crystal near the sealant was not observed.

＊ 2: In the liquid crystal cell, the disorder of the liquid crystal alignment in a region from the sealant to a width of 0.3 cm is not found (the width of the disorder of the liquid crystal alignment is wider than that observed in * 1).

＊ 3: In the liquid crystal cell, the disorder of the liquid crystal alignment in the area from the sealant to a width of 0.6 cm is not found (the width of the disorder of the liquid crystal alignment is wider than that observed in * 2).

From the above results, it is known that when the liquid crystal alignment treatment agent of the example of the present invention is compared with the liquid crystal alignment treatment agent of the comparative example, it was confirmed that even when the liquid crystal cell is irradiated with ultraviolet rays, it can suppress the decrease in the voltage holding ratio. Moreover, even when the liquid crystal cell was stored in a high-temperature and high-humidity tank for a long time, the liquid crystal alignment disorder was not observed near the sealant. That is, the liquid crystal alignment treatment agent of the present invention is a method capable of suppressing a decrease in voltage holding ratio even after being exposed to light for a long period of time, and also suppressing the vicinity of the front edge of the liquid crystal display element under conditions of high temperature and high humidity. The liquid crystal alignment film of the occurrence of display spots.

Specifically, examples of the liquid crystal alignment treatment agent using the specific compound, the specific amine compound and the specific polyimide-based polymer in the present invention, and the liquid crystal alignment treatment without using the specific compound and the specific amine compound can be listed. In the comparative example of the agent, it was found that the liquid crystal alignment treatment agent of the comparative example was more deteriorated in the above characteristics. More specifically, examples include a comparison between Example 1 and Comparative Example 1, and a comparison between Example 3 and Comparative Example 4.

Moreover, the comparative example which did not use any liquid crystal aligning agent of a specific compound or a specific amine compound, and compared with an Example, it turned out that the said characteristic is worsened. More specifically, examples include a comparison between Example 1 and Comparative Example 2 or Comparative Example 3, and a comparison between Example 3 and Comparative Example 5 or Comparative Example 6.

In addition, among the specific side chain structures in the present invention, a liquid crystal alignment treatment agent having a specific side chain type diamine compound having a specific side chain structure of the aforementioned formula [2-1], and using a liquid crystal alignment treatment agent having the aforementioned formula [2-2] When comparing liquid crystal alignment treatment agents for diamine compounds with a specific side chain structure, in an emphasis test, it was confirmed that even when the liquid crystal cell is stored in a high-temperature and high-humidity tank for a long time, no liquid crystal alignment is found near the sealant. Sexual disorders. More specifically, for example, in a comparison in which the same conditions in the test are emphasized, a comparison between Example 8 and Example 9 is mentioned.

[Industrial availability]

The liquid crystal alignment treatment agent of the present invention can provide a method capable of suppressing the decrease in voltage holding rate even after being exposed to light irradiation for a long time. It is low, and the sealant and the liquid crystal alignment film have a high degree of adhesiveness. Under high temperature and high humidity conditions, the liquid crystal alignment film that can suppress the occurrence of display spots near the front edge of the liquid crystal display element can be suppressed. In addition, a liquid crystal display element having the liquid crystal alignment film and a liquid crystal alignment treatment agent capable of providing the liquid crystal alignment film are also provided.

In summary, a liquid crystal display element having a liquid crystal alignment film obtained by the liquid crystal alignment treatment agent of the present invention has excellent reliability, and is suitable for large-screen and high-definition liquid crystal televisions. For TN elements, STN, etc. Elements, TFT liquid crystal elements, and particularly vertical alignment type liquid crystal display elements are useful.

In addition, the liquid crystal alignment film obtained by the liquid crystal alignment treatment agent of the present invention is also useful for a liquid crystal display element that must be irradiated with ultraviolet rays when a liquid crystal display element is manufactured. That is, a liquid crystal layer having a liquid crystal layer between a pair of substrates including one electrode, and a liquid crystal composition containing a polymerizable compound polymerized by at least one of active energy rays and heat is disposed between the pair of substrates. A liquid crystal display element produced by applying a voltage to polymerize the polymerizable compound, and if a liquid crystal layer is provided between a pair of substrates having electrodes, a via A liquid crystal alignment film of a polymerizable group liquid crystal alignment film polymerized by at least one of energy rays and heat, and a step of applying a voltage between the electrodes to polymerize the polymerizable group is particularly useful.

Claims (19)

A liquid crystal alignment treatment agent, which contains the following components (A), (B), and (C); (A): Phosphomolybdic acid, silomolybdic acid, phosphotungstic acid, silotungstic acid, and tungsten tungsten At least one heteropoly acid selected from the group formed by molybdic acid; (B) Ingredients: acrylic polymer, methacrylic polymer, novolac resin, polyhydroxystyrene, polyimide precursor, polyimide At least one polymer selected from the group consisting of fluorenimine, polyamidoamine, polyester, cellulose, and polysiloxane; (C) component: a primary amine group and a nitrogen-containing aromatic group in the molecule Heterocyclic, and the aforementioned primary amine group is a compound of an amine compound obtained by bonding to an aliphatic hydrocarbon group or a non-aromatic cyclic hydrocarbon group. The liquid crystal alignment treatment agent according to claim 1, wherein the polymer is a polyimide precursor obtained by reacting a diamine component and a tetracarboxylic acid component, or the polyimide precursor is subjected to fluoridation. And obtained polyimide. The liquid crystal alignment treatment agent according to claim 2, wherein the diamine component is a diamine compound having a side chain structure represented by the following formula [2-1] or formula [2-2]; (Y ¹ represents a single bond,-(CH ₂ ) _a- (a is an integer from 1 to 15), -O-, -CH ₂ O-, -CONH-, -NHCO-, -CON (CH ₃ )- , -N (CH ₃ ) CO-, -COO-, and -OCO- selected from at least one type of bond group; Y ² represents a single bond or-(CH ₂ ) _b- (b is 1 ~ An integer of 15); Y ³ represents a group formed by a single bond,-(CH ₂ ) _c- (c is an integer of 1 to 15), -O-, -CH ₂ O-, -COO-, and -OCO- At least one selected; Y ⁴ represents a divalent cyclic group of at least one selected from the group consisting of a benzene ring, a cyclohexane ring, and a heterocyclic ring, or a carbon number of 17 to 51 having a cholesterol skeleton Divalent organic groups, any of the hydrogen atoms on the aforementioned cyclic group can be substituted by an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, carbon Substituted by a fluorine-containing alkoxy group or a fluorine atom having a number of 1 to 3; Y ⁵ represents at least one kind of cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring and a heterocyclic ring, and these cyclic groups Any of the above hydrogen atoms can be substituted by an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, and a fluorine-containing alkoxy group having 1 to 3 carbon atoms. or substituted with fluorine atoms; n represents an integer of 0 to 4; Y ⁶ represents alkoxy of 1 to 18 carbon atoms of Selected from the group consisting of alkenyl with 2 to 18 carbons, fluorinated alkyl with 1 to 18 carbons, alkoxy with 1 to 18 carbons and fluorinated alkoxy with 1 to 18 carbons 1 type) [Chemical 2] -Y ⁷ -Y ⁸ [2-2] (Y ⁷ represents a single bond, -O-, -CH ₂ O-, -CONH-, -NHCO-, -CON (CH ₃ ) -, -N (CH ₃ ) CO-, -COO-, and -OCO- selected from at least one type of bonding group; Y ⁸ is an alkyl group having 8 to 18 carbon atoms or 6 to 6 carbon atoms 18 fluoroalkyl group). The liquid crystal alignment treatment agent according to claim 3, wherein the diamine compound is represented by the following formula [2a]; (Y represents the structure represented by the aforementioned formula [2-1] or [2-2]; n1 represents an integer of 1 to 4). The liquid crystal alignment treatment agent according to claim 2, wherein the aforementioned tetracarboxylic acid component is one containing a tetracarboxylic dianhydride represented by the following formula [3]; (Z represents at least one structure selected from the group consisting of the structures represented by the following formulas [3a] to [3k]) (Z ¹ to Z ⁴ each independently represent at least one selected from the group consisting of a hydrogen atom, a methyl group, a chlorine atom, and a benzene ring; Z ⁵ and Z ⁶ each independently represent a hydrogen atom or a methyl group). The liquid crystal alignment treatment agent according to claim 1, wherein the amine compound is represented by the following formula [4a-1]; [ Chem . 6] H ₂ NS ¹ -S ² [4a-1] (S ¹ represents a fat Divalent organic group of a monovalent hydrogen group or a non-aromatic cyclic hydrocarbon group; S ² represents a nitrogen-containing heterocyclic ring). The liquid crystal alignment treatment agent according to claim 1, wherein the amine compound is represented by the following formula [4a-2]; [ Chem . 7] H ₂ NS ³ -S ⁴ -S ⁵ [4a-2] (S ³ Represents an aliphatic hydrocarbon group or a non-aromatic cyclic hydrocarbon group having a carbon number of 1 to 10; S ⁴ represents a bivalence consisting of a single bond, -O-, -NH-, -S-, -SO _2- , and a carbon number of 1 to 19 At least one selected from the group consisting of organic groups, the total of carbon atoms in S ³ and S ⁴ is 1 to 20; S ⁵ represents a nitrogen-containing heterocyclic ring). The liquid crystal alignment treatment agent according to claim 7, wherein S ³ , S ^4, and S ⁵ in the amine compound represented by the aforementioned formula [4a-2] are each formed by a combination selected by a base or a ring described below. S ³ is a straight or branched alkyl group having 1 to 10 carbon atoms, an unsaturated alkyl group having 1 to 10 carbon atoms, a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a ring Heptane ring, cyclooctane ring, cyclononane ring, cyclodecane ring, cycloundecane ring, cyclododecane ring, cyclotridecane ring, cyclotetradecane ring, cyclopentadecane ring, ring ten Hexane ring, cycloheptadecane ring, cyclooctadecane ring, cyclononadecane ring, cycloicocosane ring, tricycloicocosane ring, tricyclic behenane ring, dicycloheptane ring, ten One selected from the group consisting of a hydronaphthalene ring, a norbornene ring and an adamantane ring; S ⁴ is a single bond, -O-, -NH-, -S-, -SO _2- , carbon number 1 ~ 19 hydrocarbon group, -CO-O-, -O-CO-, -CO-NH-, -NH-CO-, -CO-, -CF _2- , -C (CF ₃ ) _2- , -CH ( OH)-, -C (CH ₃ ) _2- , -Si (CH ₃ ) _2- , -O-Si (CH ₃ ) _2- , -Si (CH ₃ ) ₂ -O-, -O-Si (CH ₃ ) ₂ -O-, cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, ring Heptane ring, cyclooctane ring, cyclononane ring, cyclodecane ring, cycloundecane ring, cyclododecane ring, cyclotridecane ring, cyclotetradecane ring, cyclopentadecane ring, ring ten Hexane ring, cycloheptadecane ring, cyclooctadecane ring, cyclononadecane ring, cycloicocosane ring, tricycloicocosane ring, tricyclic behenane ring, dicycloheptane ring, ten Hydronaphthalene ring, norbornene ring, adamantane ring, benzene ring, naphthalene ring, tetrahydronaphthalene ring, fluorene ring, indene ring, fluorene ring, anthracene ring, phenanthrene ring, fluorene ring, pyrrole ring, imidazole ring, oxazole Ring, thiazole ring, pyrazole ring, pyridine ring, pyrimidine ring, quinoline ring, pyrazoline ring, isoquinoline ring, carbazole ring, purine ring, thiadiazole ring, Ring, three Ring, pyrazidine ring, triazole ring, pyr Ring, benzimidazole ring, benzimidazole ring, octyline ring, phenoline ring, indole ring, quinoxaline ring, benzothiazole ring, phenothialine Ring, oxazole ring, acridine ring, oxazole ring, piperazine ring, piperidine ring, dioxane ring and morpholin ring; S ⁵ is selected from the group consisting of pyrrole ring and imidazole Ring, oxazole ring, thiazole ring, pyrazole ring, pyridine ring, pyrimidine ring, quinoline ring, pyrazoline ring, isoquinoline ring, carbazole ring, purine ring, thiadiazole ring, Ring, pyrazoline ring, tris Ring, pyrazidine ring, triazole ring, pyr Ring, benzimidazole ring, benzoimidazole ring, octyline ring, morpholine ring, indole ring, quinoxaline ring, benzothiazole ring, phenothiazine One selected from the group consisting of ring, oxazole ring and acridine ring. The liquid crystal alignment treatment agent according to any one of claim 1 to claim 8, which is obtained by mixing a solvent containing the aforementioned component (B) and component (C) under heating. The liquid crystal alignment treatment agent according to any one of claim 1 to claim 8, wherein the liquid crystal alignment treatment agent contains N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone And at least one selected from the group consisting of γ-butyrolactone. The liquid crystal alignment treatment agent according to any one of claim 1 to claim 8, wherein the liquid crystal alignment treatment agent contains 1-hexanol, cyclohexanol, 1,2-ethanediol, 1,2 -At least one selected from the group consisting of propanediol, propylene glycol monobutyl ether, ethylene glycol monobutyl ether, dipropylene glycol dimethyl ether, and a solvent represented by the following formula [D1] to [D3]; (D ¹ represents an alkyl group having 1 to 3 carbon atoms; D ² represents an alkyl group having 1 to 3 carbon atoms; D ³ represents an alkyl group having 1 to 4 carbon atoms). The liquid crystal alignment treatment agent according to any one of claim 1 to claim 8, wherein the liquid crystal alignment treatment agent contains a group consisting of an epoxy group, an isocyanate group, an propylene oxide group, and a cyclic carbonate group. Selected crosslinkable compounds, selected crosslinkable compounds consisting of hydroxyl, hydroxyalkyl, and alkoxyalkyl groups having 1 to 3 carbon atoms, or crosslinkability with polymerizable unsaturated bond groups Compound. A liquid crystal alignment film, which is obtained by the liquid crystal alignment treatment agent according to any one of claim 1 to claim 8. A liquid crystal alignment film, which is obtained by applying the liquid crystal alignment treatment agent according to any one of claim 1 to claim 8 by an inkjet method. A liquid crystal display element having the liquid crystal alignment film of claim 13. For example, the liquid crystal alignment film of claim 13, which is used for having a liquid crystal layer between a pair of substrates having electrodes, and a polymerizable polymer containing at least one of active energy rays and heat is disposed between the pair of substrates. The liquid crystal composition of the compound is a liquid crystal display element produced by a step of applying a voltage between the electrodes to polymerize the polymerizable compound. A liquid crystal display element comprising the liquid crystal alignment film of claim 16. For example, the liquid crystal alignment film of claim 13, which is used for having a liquid crystal layer between a pair of substrates having electrodes, and a polymerizable polymer containing at least one of active energy rays and heat is disposed between the pair of substrates. Based liquid crystal alignment film, and a liquid crystal display element obtained by applying a voltage between the electrodes to polymerize the polymerizable group. A liquid crystal display element comprising the liquid crystal alignment film of claim 18.