KR20170072223A - Liquid crystal alignment treatment agent, liquid crystal alignment film, and liquid crystal display element - Google Patents

Abstract

A liquid crystal alignment treatment agent comprising the following components (A), (B) and (C). Component (A): Heteropoly acid. Component (B): Polymer. (C): a compound having a nitrogen-containing aromatic heterocyclic ring in its molecule.

Description

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

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

BACKGROUND ART A liquid crystal display device is widely used as a display device for realizing a thin and lightweight display device. A liquid crystal alignment film is usually used in this liquid crystal display element to determine the alignment state of the liquid crystal.

In view of the reduction in contrast of the liquid crystal display element and the reduction of the afterimage phenomenon accompanying the high definition of the liquid crystal display element, a liquid crystal alignment film used therefor is required to have a high voltage maintaining ratio. To these, a compound containing one carboxylic acid group in the molecule, a compound containing one carboxylic acid anhydride group in the molecule, and a compound containing one tertiary amino group in the molecule, in addition to polyamic acid and imidized polymer thereof (See, for example, Patent Document 1) is known as a liquid crystal alignment treatment agent containing a very small amount of a compound selected from the group consisting of

In addition, with the high definition of liquid crystal display elements, there is a demand for suppressing the display defects accompanying the contrast of liquid crystal display elements or long-term use. As for these, there has been proposed a liquid crystal alignment film using a liquid crystal alignment treatment agent to which an alkoxysilane compound is added as a technique for enhancing the liquid crystal alignability of the liquid crystal alignment film using polyimide and preventing display defects from occurring in the periphery of the liquid crystal display screen (See, for example, Patent Document 2 or Patent Document 3).

Japanese Patent Application Laid-Open No. 8-76128 Japanese Patent Application Laid-Open No. 61-171762 Japanese Patent Application Laid-Open No. 11-119226

2. Description of the Related Art With the recent enhancement of the performance of liquid crystal display devices, liquid crystal display devices have been used for applications such as large-screen and high-definition liquid crystal televisions and vehicle applications, for example, car navigation systems and meter panels. In such applications, a backlight having a large heating value may be used in order to obtain high brightness. For this reason, the liquid crystal alignment film is required to have high reliability from another viewpoint, that is, high stability against light from the backlight. In particular, if the voltage holding ratio, which is one of the electric characteristics of the liquid crystal display element, is lowered by the light irradiation from the backlight, an exposure failure (also referred to as line exposure), which is one of the display defects of the liquid crystal display element, A liquid crystal display element with high reliability can not be obtained. Therefore, in addition to good initial characteristics, it is required that the liquid crystal alignment film is hard to lower the voltage holding ratio even after exposure to light for a long time, for example.

In mobile applications such as smart phones and cellular phones, the use environment has become more severe than in the past. In other words, it may be used under high temperature and high humidity under the environment of room temperature and low humidity up to now. In such use under high-temperature and high-humidity conditions, there is a problem that water tends to be mixed between the sealant of the liquid crystal display element and the liquid crystal alignment film, and display irregularity is likely to occur near the frame of the liquid crystal display element. Therefore, even under high temperature and high humidity conditions, it is required that such display failure does not occur.

Therefore, an object of the present invention is to provide a liquid crystal alignment film having the above characteristics. That is, an object of the present invention is to provide a liquid crystal alignment film capable of suppressing a decrease in voltage holding ratio even after exposure to light for a long time. In addition, it is an object of the present invention to provide a liquid crystal alignment film in which display unevenness does not occur in the vicinity of a frame of a liquid crystal display element even under high temperature and high humidity conditions.

In addition, it is also an object of the present invention to provide 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 used for the liquid crystal alignment treatment agent.

As a result of intensive studies, the inventors of the present invention have found that a liquid crystal alignment treating agent comprising two kinds of compounds having a specific structure and a polymer is very effective for achieving the above object, and accomplished the present invention.

That is, the present invention has the following points.

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

Component (A): Heteropoly acid.

Component (B): Polymer.

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

(2) The liquid crystal alignment treatment agent according to (1), wherein the heteropoly acid is at least one selected from the group consisting of molybdic acid, silicomolybdic acid, tungstic acid, tungstic acid and tungstomolybdic acid.

(3) The method according to any one of (1) to (3), wherein the polymer is at least one selected from the group consisting of acrylic polymer, methacrylic polymer, novolac resin, polyhydroxystyrene, polyimide precursor, polyimide, polyamide, polyester, 1) or the liquid crystal alignment treatment agent according to (2) above.

(4) The liquid crystal alignment treatment agent according to the above (3), wherein the polymer is a polyimide precursor obtained by the reaction of a diamine component and a tetracarboxylic acid component or a polyimide imidized with the polyimide precursor.

(5) The liquid crystal alignment treating agent according to (4), wherein the diamine component comprises a diamine compound having a lateral chain structure represented by the following formula [2-1] or formula [2-2].

[Chemical Formula 1]

(Wherein Y ¹ is a single bond, - (CH ₂ ) _a - (a is an integer of 1 to 15), -O-, -CH ₂ O-, -CONH-, -NHCO-, -CON (CH ₃ ) , -N (CH ₃₎ CO-, shows a coupler of at least one member selected from the group consisting of -COO- and -OCO- Y ² represents a single bond or _{-. (CH 2) b -} (b is 1 to 15 Y ³ represents a single bond, - (CH ₂ ) _c - (c is an integer of 1 to 15), -O-, -CH ₂ O-, -COO- and -OCO- Y ⁴ represents at least one divalent cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring and a heterocyclic ring, or a divalent organic group having a carbon number of 17 to 51 having a steroid skeleton And any hydrogen atom on the cyclic group may be substituted with an alkyl group having 1 to 3 carbon atoms, an alkoxyl group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluoro-containing alkoxyl group having 1 to 3 carbon atoms, Became Y ⁵ represents at least one cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring and a heterocyclic ring, and any hydrogen atom on these cyclic groups may be substituted with an alkyl group having 1 to 3 carbon atoms, an alkyl group having 1 to 3 carbon atoms , A fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxyl group having 1 to 3 carbon atoms, or a fluorine atom, n represents an integer of 0 to 4. Y ⁶ represents an alkyl group having 1 to 18 carbon atoms, At least one member selected from the group consisting of an alkenyl group having 2 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxyl group having 1 to 18 carbon atoms, and a fluorinated alkoxyl group having 1 to 18 carbon atoms.

(2)

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

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

(3)

(Y represents a structure represented by the above formula [2-1] or formula [2-2], and n1 represents an integer of 1 to 4.)

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

[Chemical Formula 4]

(Z represents at least one structure selected from the group consisting of the structures represented by the following formulas [3a] to [3k]).

[Chemical Formula 5]

(Z ¹ to Z ⁴ each independently represent at least one member 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 method according to any one of (8) to (9) above, wherein the compound of the component (C) is an amine compound having a primary amino group in the molecule and having a nitrogen-containing aromatic heterocyclic ring and the primary amino group being bonded to an aliphatic hydrocarbon group or a non-aromatic cyclic hydrocarbon group Is the liquid crystal alignment treatment agent according to any one of (1) to (7).

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

[Chemical Formula 6]

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

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

(7)

(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 the sum 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 treating agent according to (10) above, wherein S ³ , S ⁴ and S ⁵ in the amine compound represented by the formula [4a-2] each represent a combination selected from the groups or rings described below.

Wherein S ³ is a linear 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 cycloheptane ring, a cyclooctane ring, A cycloheptadecane ring, a cycloheptadecane ring, a cyclooctadecane ring, a cyclododecane ring, a cyclododecane ring, a cyclotetradecane ring, a cyclotetradecane ring, a cyclopentadecane ring, a cyclohexadecane ring, a cycloheptadecane ring, A ring selected from the group consisting of a ring, a cyclic acid ring, a tricycloicoic acid ring, a tricyclodecanoic acid ring, a bicycloheptane ring, a decahydronaphthalene ring, a norbornene ring and an adamantane ring;

S ⁴ represents a single bond, -O-, -NH-, -S-, -SO ₂ -, a hydrocarbon group of 1 to 19 carbon atoms, -CO-O-, -O-CO-, -CO- _{-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-, a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, A cycloheptadecane ring, a cycloheptadecane ring, a cycloheptadecane ring, a cycloheptadecane ring, a cyclohexadecane ring, a cyclohexadecane ring, a cycloheptane ring, a cycloheptane ring, a cycloheptane ring, a cycloheptane ring, , A cyclooctadecane ring, a cyclononadecane ring, a cyclooic acid ring, a tricycloicoic acid ring, a tricyclodecanoic acid ring, a bicycloheptane ring, a decahydronaphthalene ring, a norbornene ring, an adamantane ring, a benzene ring , A naphthalene ring, a tetrahydronaphthalene ring, azulene A thiazole ring, a pyrazole ring, a pyridine ring, a pyrimidine ring, a quinoline ring, a pyrazine ring, an imidazole ring, an imidazole ring, an imidazole ring, a thiazole ring, A carbazole ring, a pyridine ring, a thiadiazole ring, a pyridazine ring, a triazine ring, a pyrazolidine ring, a triazole ring, a pyrazine ring, a benzimidazole ring, a benzoimidazole ring, a quinoxaline ring, An oxadiazole ring, an oxidine ring, a piperazine ring, a piperidine ring, a dioxane ring, an oxadiazole ring, an oxadiazole ring, an oxadiazole ring, an oxidine ring, an oxazole ring, a piperazine ring, A ring and a morpholine ring;

S ⁵ is selected from the group consisting of pyrrole ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, pyridine ring, pyrimidine ring, quinoline ring, pyrazoline ring, A pyrimidine ring, a pyrimidine ring, a phenanthroline ring, a phenanthroline ring, an indole ring, a quinoxaline ring, a pyrimidine ring, a pyrazoline ring, a pyrazoline ring, a triazine ring, a pyrazolidine ring, a triazole ring, A benzothiazole ring, a phenothiazine ring, an oxadiazole ring, and an acridine ring.

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

(13) The liquid crystal aligning material as described in any one of (1) to (10) above, wherein the liquid crystal alignment treating agent is at least one selected from the group consisting of 1] to [12] above.

(14) The liquid crystal aligning material as described in any one of (1) to (11) above, wherein the liquid crystal alignment treatment agent is a liquid crystal alignment agent selected from the group consisting of 1-hexanol, cyclohexanol, 1,2-ethanediol, The liquid crystal alignment treating agent according to any one of (1) to (13) above, which contains at least one solvent selected from the group consisting of solvents represented by the following formulas [D1] to [D3]

[Chemical Formula 8]

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

(15) The liquid crystal alignment treating agent according to any one of (1) to (10), wherein the liquid crystal alignment treating agent is selected from the group consisting of a crosslinkable compound selected from the group consisting of an epoxy group, an isocyanate group, an oxetane group and a cyclocarbonate group, a hydroxyl group, a hydroxyalkyl group and an alkoxyalkyl group having 1 to 3 carbon atoms The liquid crystal alignment treating agent according to any one of (1) to (14) above, which contains a crosslinkable compound having a polymerizable unsaturated bond group or a crosslinkable compound having a polymerizable unsaturated bonding group.

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

(17) A liquid crystal alignment film obtained by applying the liquid crystal alignment treatment agent according to any one of (1) to (15) by an ink jet method.

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

(19) A liquid crystal composition comprising a liquid crystal layer between a pair of substrates provided with electrodes, and comprising a polymerizable compound polymerized by at least one of active energy rays and heat between the pair of substrates is arranged (16) or (17), wherein the liquid crystal alignment film is used for a liquid crystal display device manufactured through a process of polymerizing the polymerizable compound while applying a voltage between the electrodes.

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

(21) A liquid crystal alignment film comprising a liquid crystal layer between a pair of substrates provided with electrodes, wherein a liquid crystal alignment film containing a polymerizable group capable of polymerizing by at least one of active energy rays and heat is disposed between the pair of substrates, The liquid crystal alignment film according to (16) or (17) above, which is used for a liquid crystal display device manufactured through a process of polymerizing the polymerizable group while applying a voltage between the electrodes.

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

The liquid crystal alignment treatment agent containing two specific compounds and polymers of the present invention can obtain a liquid crystal alignment film capable of suppressing a decrease in voltage holding ratio even after exposure to light for a long time. In addition, even under high-temperature and high-humidity conditions, the liquid crystal alignment film is free from display unevenness near the frame of the liquid crystal display element.

The mechanism by which the liquid crystal display element having the above-described excellent characteristics can be obtained for some reason by the present invention is not necessarily obvious, but is estimated as follows.

The present invention is 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 further, a liquid crystal display device having the liquid crystal alignment film .

Component (A): Heteropoly acid (also referred to as a specific compound).

Component (B): Polymer.

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

As the effects of the specific compound, the following can be considered. As a factor of lowering the voltage holding ratio, a large amount of ionic impurity components may exist in the liquid crystal. On the other hand, when the liquid crystal display element is exposed to light irradiation for a long time to decompose the liquid crystal, it is considered that the specific compound adsorbs the ionic impurity component generated at that time, thereby suppressing a decrease in the voltage holding ratio. It is also believed that a compound having a nitrogen-containing aromatic heterocyclic ring in the molecule can enhance the above effect by a nitrogen-containing aromatic heterocyclic ring contained in the structure.

It is also possible to use a polyimide precursor obtained by the reaction of a diamine component and a tetracarboxylic acid component or a polyimide obtained by imidizing the polyimide precursor to the polymer and to the diamine component at that time, When a diamine compound having a structure represented by the formula [2-2] is used in a liquid crystal display device of a vertical alignment (VA) mode, a polymer sustained alignment (PSA) mode and an SC-PVA mode, Since the structure represented by the formula [2-1] exhibits a rigid structure, the liquid crystal display element using the liquid crystal alignment film having this structure is stable against light such as ultraviolet rays, and generates ionic impurities Can be suppressed.

Thus, the liquid crystal display device comprising the liquid crystal alignment film obtained from the liquid crystal alignment treatment agent of the present invention has excellent reliability, and can be suitably used for a liquid crystal television of a large screen and high precision. Particularly, when a liquid crystal display device is manufactured, it is useful for a liquid crystal display device using a PSA mode or an SC-PVA mode for irradiating high-energy ultraviolet rays.

<Specific compound>

The specific compound in the present invention is heteropoly acid.

Heteropoly acid is typically exemplified by a Keggin type represented by the following formula [1-1] or a Dawson type chemical structure represented by the formula [1-2] in which a hetero atom is located at the center of the molecule (V), molybdenum (Mo), and tungsten (W), and a polyacid formed by condensation of an oxygen atom of a different element. Examples of the oxyacids of such different kinds of elements include oxygen (Si), phosphorus (P) and arsenic (As).

[Chemical Formula 9]

Specific examples of the heteropoly acid compound include phosphoromolybdic acid, silicomolybdic acid, tungstic acid, tungstic acid, or tungstomolybdic acid, and it is preferable to use them in the present invention. These may be used alone or in combination of two or more. Further, the heteropoly acid compound in the present invention is available as a commercial product, and may be synthesized by a known method.

Heteropoly acid can be obtained by quantitative analysis such as elemental analysis or the like insofar as the number of elements is large or small from the structure represented by the general formula and is either commercially available or synthesized appropriately according to known synthesis methods, And can be used in the invention.

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

[Chemical formula 10]

These may be those which have a high or low number of P (phosphorus), O (oxygen), W (tungsten) or Mo (molybdenum) in these formulas, those obtained as a commercial product thereof, Can be used in the present invention as long as they are appropriately synthesized according to the synthesis method. In this case, the mass of the heteropoly acid specified in the present invention is not a mass of pure tungstic acid (synthetic tungstic acid content) in a synthetic material or a commercial product, but a form available as a commercially available product and a product which can be isolated by a known synthetic method , Hydration water, other impurities, and the like.

<Polymer>

The polymer in the present invention may be at least one kind selected from the group consisting of acrylic polymer, methacrylic polymer, novolak resin, polyhydroxystyrene, polyimide precursor, polyimide, polyamide, polyester, cellulose and polysiloxane It is preferably a polymer. More preferred are polyimide precursors, polyimides or polysiloxanes. Particularly preferred are polyimide precursors or polyimides (collectively, referred to as specific polyimide-based polymers).

&Lt; Specific polyimide polymer &

When a specific polyimide-based polymer is used for the polymer of the present invention, it is preferable that they are a polyimide precursor or polyimide obtained by reacting a diamine component and a tetracarboxylic acid component.

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

(11)

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

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

The specific polyimide polymer is preferably a polyimide polymer represented by the following formula [D] because it is relatively easily obtained by using a tetracarboxylic acid dianhydride represented by the following formula [B] and a diamine represented by the following formula [C] And a polyimide obtained by imidizing the polyamic acid is preferable. Among them, in the present invention, from the viewpoint of physical and chemical stability of the liquid crystal alignment film, it is preferable that the polyimide is imidized with a polyimide precursor.

[Chemical Formula 12]

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

[Chemical Formula 13]

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

In addition, the polymers of the usual synthesis techniques, equation [D] obtained in the above-mentioned formula [A] represented by A ¹ and A carbon number of alkyl group of 1-8 of Figure ^2, and the equation [A] represented by A ³ and A ⁴ An alkyl group having 1 to 5 carbon atoms or an acetyl group may be introduced.

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

Among them, when the liquid crystal alignment treatment agent of the present invention is used in a liquid crystal display device of a VA mode, a PSA mode or an SC-PVA mode, the following formula [2-1] or [2-2] It is preferable to use a diamine compound having a side chain structure (also referred to as a specific side chain structure) represented by the following formula

[Chemical Formula 14]

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

Y ¹ represents a single bond, - (CH ₂ ) _a - (a is an integer of 1 to 15), -O-, -CH ₂ O-, or -COO-, in terms of the availability of raw materials or ease of synthesis. . More preferred is a single bond, - (CH ₂ ) _a - (a is an integer of 1 to 10), -O-, -CH ₂ O- or -COO-.

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

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

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

Y ⁵ is preferably a benzene ring or a cyclohexane ring.

Y ⁶ is preferably an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 10 carbon atoms, an alkoxyl group having 1 to 18 carbon atoms, or a fluorinated alkoxyl group having 1 to 10 carbon atoms. More preferably an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, or an alkoxyl group having 1 to 12 carbon atoms. Particularly preferably an alkyl group having 1 to 9 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, or an alkoxyl group having 1 to 9 carbon atoms.

n is preferably from 0 to 3, more preferably from 0 to 2, from the viewpoint of availability of the raw material and ease of synthesis.

Preferred combinations of Y ¹ , Y ² , Y ³ , Y ⁴ , Y ⁵ , Y ⁶ and n are given in Tables 6 to 47 of pages 13 to 34 of WO2011 / 132751 (2-1) to (2-629). In each table of the International Publication, Y ¹ to Y ⁶ in the present invention are represented as Y ¹ to Y ⁶ , and Y ¹ to Y ⁶ are read in the same manner as Y ¹ to Y ⁶ . In (2-605) to (2-629) listed in the tables of International Publication, the organic group having a steroid skeleton and having a carbon number of 17 to 51 in the present invention is an organic group having a steroid skeleton and having a carbon number of 12 to 25 Organic group, but the organic group having 12 to 25 carbon atoms having a steroid skeleton is referred to as an organic group having a steroid skeleton and having 17 to 51 carbon atoms.

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

[Chemical Formula 15]

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

Y ⁷ is preferably a single bond, -O-, -CH ₂ O-, -CONH-, -CON (CH ₃ ) - or -COO-. 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, it is preferable to use the structure represented by the formula [2-1] in that the specific side chain structure can obtain a high and stable liquid crystal vertical alignment property.

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

[Chemical Formula 16]

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

The detailed contents and preferable combinations of Y ¹ , Y ² , Y ³ , Y ⁴ , Y ⁵ , Y ⁶ and n in the formula [2-1] are the same as in the formula [2-1] 2-2], the detailed contents and preferable combination of Y ⁷ and Y ⁸ are as shown in the above formula [2-2].

n1 is preferably 1 in view of ease of synthesis.

Specific examples of the side chain type diamine compound having a specific side chain structure represented by the formula [2-1] include specifically the diamine compounds represented by the following formulas [2a-1] to [2a-31] .

[Chemical Formula 17]

(R ¹ are _{each, -O-, -OCH 2 -, -CH} 2 O-, -COOCH 2 -. And shows the coupler of at least one member selected from the group consisting of -CH ^₂ OCO- R ₂ are each, A linear or branched alkyl group having 1 to 18 carbon atoms, a linear or branched alkoxyl group having 1 to 18 carbon atoms, a linear or branched alkyl group having 1 to 18 carbon atoms, or a linear chain having 1 to 18 carbon atoms Or branched fluorine-containing alkoxyl group.

[Chemical Formula 18]

(R ³ is a group consisting of -COO-, -OCO-, -CONH-, -NHCO-, -COOCH ₂ -, -CH ₂ OCO-, -CH ₂ O-, -OCH ₂ - and -CH ₂ - R ⁴ represents a linear or branched alkyl group having 1 to 18 carbon atoms, a linear or branched alkoxyl group having 1 to 18 carbon atoms, a straight-chain or branched alkoxyl group having 1 to 18 carbon atoms, A branched or branched fluorine-containing alkyl group, or a linear or branched fluorine-containing alkoxyl group having 1 to 18 carbon atoms.)

[Chemical Formula 19]

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

[Chemical Formula 20]

(R ⁷ each represents a linear or branched alkyl group having a carbon number of 3-12, the cis 1,4-cyclohexylene-a reason trans, trans isomers).

[Chemical Formula 21]

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

[Chemical Formula 22]

(A ₄ represents a linear or branched alkyl group having 3 to 18 carbon atoms which may be substituted with a fluorine atom, A ₃ represents a 1,4-cyclohexylene group or a 1,4-phenylene group, A ₂ represents oxygen * indicates the atom or -COO- (provided that combined hand tagged "*" are combined and a _3). a ₁ is a bond hand attached to an oxygen atom or -COO- * (However, the "*" (CH ₂ ) &lt; / RTI &gt; a ₂ ). A ₁ represents an integer of 0 or 1; and a ₂ represents an integer of 2 to 10. and a ₃ represents an integer of 0 or 1.)

(23)

&Lt; EMI ID =

(25)

(26)

(27)

Among the above-mentioned formulas [2a-1] to [2a-31], preferable diamine compounds are the compounds represented by formulas [2a-1] to [2a-6], formulas [2a- 2a-22] to formula [2a-31].

Specific examples of the side chain type diamine compound having a specific side chain structure represented by the above formula [2-2] include a diamine compound represented by the following formulas [2a-32] to [2a-35] .

(28)

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

The use ratio of the specific diamine compound (2) is preferably 10 to 70 mol% with respect to the total diamine component, particularly when it is used in a VA mode, PSA mode or SC-PVA mode liquid crystal display device. , More preferably 20 to 70 mol%, and particularly preferably 20 to 60 mol%.

The specific side chain type diamine compound may be used alone or in combination of two or more kinds depending on the solubility of the specific polyimide type polymer in a solvent, the liquid crystal alignment property when used as a liquid crystal alignment film, Can be mixed and used.

In addition, the specific side chain type diamine compound is suitably used in accordance with the display mode of the liquid crystal display element, that is, TN (Twisted Nematic) mode, IPS (In-plane Switching) mode, VA mode, PSA mode and SC- You can choose to use it.

As the diamine component for producing a specific polyimide polymer, the following diamine compounds (also referred to as other diamine compounds) may be used.

Specific examples include 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- , 5-diaminobenzoic acid, 4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'- Phenyl, 3,3'-dihydroxy-4,4'-diaminobiphenyl, 3,3'-dicarboxy-4,4'-diaminobiphenyl, 3,3'-difluoro- 4'-diaminobiphenyl, 3'-diaminobiphenyl, 3,3'-diaminobiphenyl, 2,2'-diaminobiphenyl, Diaminobiphenyl, 2,3'-diaminobiphenyl, 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 2 , 2'-diaminodiphenylmethane, 2,3'-diaminodiphenylmethane, 4,4'-diaminodiphenyl Diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 2,2'-diaminodiphenyl ether, 2,3'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, Bis (4-aminophenyl) silane, dimethyl-bis (3-aminophenyl) silane, Phenyl) silane, 4,4'-thiodianiline, 3,3'-thiodianiline, 4,4'-diaminodiphenylamine, 3,3'-diaminodiphenylamine, 3,4'- Aminodiphenylamine, 2,2'-diaminodiphenylamine, 2,3'-diaminodiphenylamine, N-methyl (4,4'-diaminodiphenyl) amine, N-methyl Diaminodiphenyl) amine, N-methyl (3,4'-diaminodiphenyl) amine, N-methyl (2,2'- Diaminodiphenyl) amine, 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 3,4'-diaminobenzophenone, 1,4-diaminonaphthalene, 2,2'- Diaminobenzophenone, 2,3'-diaminobenzophenone, 1,5-di Diaminodiphenylsulfone, 1,6-diaminonaphthalene, 1,6-diaminonaphthalene, 1,7-diaminonaphthalene, 1,8-diaminonaphthalene, 2,5-diaminonaphthalene, Bis (4-aminophenyl) propane, 1, 2-bis (4-aminophenyl) (3-aminophenyl) propane, 1,4-bis (4-aminophenyl) butane, 1,4-bis ) Benzene, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis Benzene, 1,4-bis (4-aminobenzyl) benzene, 1,3-bis (4-aminophenoxy) benzene, ] Dianiline, 4,4 '- [1,3-phenylenebis (methylene)] dianiline, 3,4' - [1,4- 1,3-phenylenebis (methylene)] dianiline, 3,3 '- [l, 3-phenylenebis Phenylenebis [(3-aminophenyl) methanone], 1,3-phenylenebis [(4-aminophenyl) methanone] Phenanthrene], 1,4-phenylenebis (4-aminophenyl) methanone], 1,3-phenylenebis [ (4-aminobenzoate), 1,3-phenylenebis (3-aminobenzoate), bis (4-aminophenyl) terephthalate Bis (3-aminophenyl) isophthalate, N, N '- (1,4-phenylene) bis (4-aminophenyl) isophthalate, bis Amide), N, N '- (1,3-phenylene) bis (4-aminobenzamide) Aminophenyl) terephthalamide, N, N'-bis (3-aminophenyl) terephthalamide, N, N'- , N'-bis (4-aminophenyl) iso Bis (4-aminophenoxy) diphenyl sulfone, 2, 3-aminophenyl) isophthalamide, N, Bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 2,2'-bis (4 (Aminophenyl) hexafluoropropane, 2,2'-bis (3-aminophenyl) hexafluoropropane, 2,2'- Bis (3-aminophenyl) propane, and 2,2'-bis (3-aminophenyl) Bis (3-aminophenoxy) butane, 1, 5-bis (3-aminophenoxy) Bis (4-aminophenoxy) pentane, 1,6-bis (4-aminophenoxy) pentane, 1,6-bis ) Hexane, 1,7-bis (4-aminophenoxy) heptane, 1,7-bis Heptane, 1,8-bis (4-aminophenoxy) octane, 1,8-bis (3-aminophenoxy) Bis (3-aminophenoxy) decane, 1,11-bis (4-aminophenoxy) decane, 1,10- Undecane, 1,11-bis (3-aminophenoxy) undecane, 1,12-bis (4-aminophenoxy) dodecane, 1,12- 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 or 1,12- Diaminododecane, and the like.

As the other diamine compounds, diamine compounds represented by the following formulas [D1] to [DA15] may be used.

[Chemical Formula 29]

(30)

(31)

(p represents an integer of 1 to 10).

(32)

(33)

(L ¹ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and n represents an integer of 1 to 5)

(34)

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

(35)

(A ¹ is -O-, -NH-, -N (CH ₃ ) -, -CONH-, -NHCO-, -CH ₂ O-, -OCO-, -CON (CH ₃ ) ₃ ) CO-, and A ² represents at least one member 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 A ³ is 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), A ⁴ represents a nitrogen-containing aromatic heterocyclic ring, p 1 represents Represents an integer of 1 to 4.)

The other diamine compound may be used alone or in combination of two or more thereof depending on the solubility of the specific polyimide 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 device .

The tetracarboxylic acid dianhydride (also referred to as a specific tetracarboxylic acid component) represented by the following formula [3] is preferably used as the tetracarboxylic acid component for producing the specific polyimide-based polymer.

(36)

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

The Z in the formula [3] can be represented by the formula [3a], the formula [3c], the formula [3d], the formula [3e] and the formula [3f] , The formula [3g] or the formula [3k] is preferable. More preferred is a structure represented by formula [3a], formula [3e], formula [3f], formula [3g] or formula [3k]. Particularly preferred is a structure represented by the formula [3e], the formula [3f], the formula [3g] or the formula [3k].

The use ratio of the specific tetracarboxylic acid component is preferably 1 mol% or more with respect to the total tetracarboxylic acid component. More preferred is 5 mol% or more. Particularly preferred is 10 mol% or more, and most preferably 10 to 90 mol% from the viewpoint of suppressing a decrease in voltage holding ratio after exposure to long-time light irradiation.

When the tetracarboxylic acid component having the structure represented by the formula [3e], the formula [3f], the formula [3g] or the formula [3k] is used, the amount of the tetracarboxylic acid component is preferably 20 mol% Or more, a desired effect can be obtained. Preferably, it is at least 30 mol%. The tetracarboxylic acid component may be all the tetracarboxylic acid component having the structure represented by the formula [3e], the formula [3f], the formula [3g] or the formula [3k].

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

Specific examples thereof include pyromellitic acid, 2,3,6,7-naphthalenetetracarboxylic acid, 1,2,5,6-naphthalenetetracarboxylic acid, 1,4,5,8-naphthalenetetracar 2, 5, 6-anthracenetetracarboxylic acid, 3,3 ', 4,4'-biphenyltetracarboxylic acid, 2, (3,4-dicarboxyphenyl) ether, 3,3 ', 4,4'-benzophenonetetracarboxylic acid, bis (3,4- Bis (3,4-dicarboxyphenyl) sulfone, bis (3,4-dicarboxyphenyl) methane, 2,2- Bis (3,4-dicarboxyphenyl) propane, bis (3,4-dicarboxyphenyl) dimethylsilane, bis (3,4-dicarboxyphenyl) pyridine, 3,3 ', 4,4'-diphenylsulfone tetracarboxylic acid, 3,4,9,10-phe Lyrenetetracarboxylic acid or 1,3-diphenyl-1,2,3,4-cyclo And the like shot tetracarboxylic acid.

The specific tetracarboxylic acid component and other tetracarboxylic acid component are preferably selected from the group consisting of 1 to 1, 1 to 2, and 1 to 3, depending on the solubility of the specific polyimide polymer in a solvent, the liquid crystal alignment property when used as a liquid crystal alignment film, Or a mixture of two or more species.

The method for producing the specific polyimide polymer is not particularly limited. It is usually obtained by reacting a diamine component and a tetracarboxylic acid component. In general, a tetracarboxylic acid dianhydride and a derivative of the tetracarboxylic acid are reacted with at least one tetracarboxylic acid component and one or more diamine compounds comprising a diamine compound, And a method of obtaining a polyamic acid. Specifically, there are a method of polycondensing a tetracarboxylic acid dianhydride and a primary or secondary diamine compound to obtain a polyamic acid, a method of dehydrating polycondensation reaction of a tetracarboxylic acid and a primary or secondary diamine compound, A method of obtaining an acid or a method of reacting a tetracarboxylic acid dihalide with a primary or secondary diamine compound to obtain a polyamic acid is used.

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

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

The reaction of the diamine component and the tetracarboxylic acid component is usually carried out in an organic solvent with the diamine component and the tetracarboxylic acid component. The organic solvent to be used at this time is not particularly limited as long as it dissolves the resulting polyimide precursor. Specific examples of the organic solvent used in the reaction are shown below, but the present invention is not limited to these examples.

Examples of the solvent include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, gamma -butyrolactone, N, N-dimethylformamide, N, N-dimethylacetamide, 1,3-dimethyl-imidazolidinone, and the like. When the solvent solubility of the polyimide precursor is high, it is preferable to use methyl ethyl ketone, cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone or the following formula [D- D-3] can be used.

(37)

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

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

When the diamine component and the tetracarboxylic acid component are reacted in an organic solvent, the solution in which the diamine component is dispersed or dissolved in an organic solvent is stirred, and the tetracarboxylic acid component is directly added or dispersed or dissolved in an organic solvent A method in which a diamine component is added to a solution in which a tetracarboxylic acid component is dispersed or dissolved in an organic solvent, a method in which a diamine component and a tetracarboxylic acid component are alternately added, and the like. May be used. When a plurality of the diamine component and the tetracarboxylic acid component are used in the reaction, they may be reacted in a preliminarily mixed state, or they may be reacted individually in a sequential manner, or the low molecular weight compounds reacted individually may be mixed and reacted, . The polymerization temperature at that time may be any temperature between -20 DEG C and 150 DEG C, preferably between -5 DEG C and 100 DEG C. The reaction can be carried out at an arbitrary concentration. However, if the concentration is too low, it becomes difficult to obtain a polymer having a high molecular weight. If the concentration is too high, the viscosity of the reaction liquid becomes too high, and uniform stirring becomes difficult. Therefore, the content is preferably 1 to 50% by mass, and more preferably 5 to 30% by mass. The initial stage of the polymerization reaction may be carried out at a high concentration, and then an organic solvent may be added.

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

The polyimide is a polyimide obtained by ring closure of the polyimide precursor. The closed rate (also referred to as imidization rate) of the amidic acid group does not necessarily have to be 100% and can be arbitrarily adjusted depending on the purpose and purpose. Among them, the specific polyimide-based polymer in the present invention is preferably a polyimide obtained by imidizing a polyimide precursor. The imidization rate at that time is preferably 40 to 90%. More preferred is 50 to 90%.

Methods for imidizing the polyimide precursor include thermal imidization in which the solution of the polyimide precursor is heated as it is, or catalyst imidation in which the catalyst is added to the solution of the polyimide precursor. The temperature at which the polyimide precursor is thermally imidized in a solution is 100 ° C to 400 ° C, preferably 120 ° C to 250 ° C, and it is preferable to carry out the removal while removing water generated by the imidization reaction out of the system.

The catalyst imidation of the polyimide precursor can be carried out by adding a basic catalyst and an acid anhydride to the polyimide precursor solution and stirring at -20 to 250 ° C, preferably 0 to 180 ° C. The amount of the basic catalyst is 0.5 to 30 moles, preferably 2 to 20 moles, of the amide group, and the amount of the acid anhydride is 1 to 50 moles, preferably 3 to 30 moles, of the amide group. Examples of the basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine, trioctylamine, and the like. Among them, pyridine is preferable since it has a suitable basicity for promoting the reaction. Examples of the acid anhydride include acetic anhydride, trimellitic anhydride, and pyromellitic anhydride. Above all, use of acetic anhydride is preferable since purification after completion of the reaction becomes easy. The imidization rate by the catalyst imidization can be controlled by controlling the amount of catalyst, the reaction temperature and the reaction time.

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

The molecular weight of the polyimide polymer is preferably from 5,000 to 1,000,000, as measured by GPC (Gel Permeation Chromatography), in consideration of the strength of the liquid crystal alignment film obtained therefrom, the workability at the time of forming the liquid crystal alignment film, desirable. Among these, 10,000 to 150,000 are preferable.

As described above, the specific polyimide polymer in the present invention is a polyimide obtained by subjecting the above-described polyimide precursor to a catalyst imidation, in that the reduction of the voltage holding ratio can be suppressed even after exposure to light for a long time desirable. The imidization rate at that time is preferably in the above-described range.

<Component (C) Specific amine compound>

The component (C) in the present invention is a compound having a nitrogen-containing aromatic heterocyclic ring in the molecule. Among them, one having a primary amino group and a nitrogen-containing aromatic heterocyclic ring in the molecule, Or an amine compound (also referred to as a specific amine compound) bonded to a hydrocarbon group or a non-aromatic cyclic hydrocarbon group.

Since this specific amine compound has only one amino group contained in the molecule, it is possible to avoid the possibility that problems such as precipitation and gelation of the polymer occur during preparation of the liquid crystal alignment treatment agent and preservation of the liquid crystal alignment treatment agent.

The amino group contained in the specific amine compound needs to be bonded to a divalent aliphatic hydrocarbon group or a nonaromatic cyclic hydrocarbon group that does not contain an aromatic hydrocarbon in the molecule from the viewpoint of ease of salt formation or coupling reaction with the polymer .

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. More preferably, the aliphatic hydrocarbon group has 1 to 20 carbon atoms. Particularly preferred are those having 1 to 15 carbon atoms, and most preferably 1 to 10 carbon atoms.

Specific examples of the non-aromatic cyclic hydrocarbon group include a cyclopropane ring, a cyclopentane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a cyclooctane ring, a cyclononane ring, a cyclodecane ring, a cyclooctane ring, A cyclohexadecane ring, a cycloheptadecane ring, a cyclooctadecane ring, a cyclononadecane ring, a cyclooctadecane ring, a tricyclohexane ring, a cycloheptadecane ring, a cycloheptadecane ring, a cycloheptadecane ring, a cycloheptadecane ring, A tricyclodecanoic acid ring, a bicycloheptane ring, a decahydronaphthalene ring, a norbornene ring or an adamantane ring. More preferred is a cyclic non-aromatic cyclic hydrocarbon group having 3 to 20 carbon atoms. Particularly preferred is a ring having 3 to 15 carbon atoms, and most preferably a ring having 3 to 10 carbon atoms.

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

(38)

(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, an isoquinoline ring, A pyrimidine ring, a pyrazoline ring, a pyrimidine ring, a pyrimidine ring, a pyrimidine ring, a pyrimidine ring, a pyrimidine ring, a pyrimidine ring, a pyrimidine ring, An indole ring, a quinoxaline ring, a benzothiazole ring, a phenothiazine ring, an oxadiazole ring, an acridine ring and the like. The carbon atom of these nitrogen-containing aromatic heterocyclic rings may have a substituent including a hetero atom.

The specific amine compound more preferable is a compound represented by the following formula [4a-1].

[Chemical Formula 39]

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. More 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, A cyclododecane ring, a cyclotetradecane ring, a cyclotetradecane ring, a norbornene ring, or an 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 contains the structure represented by the formula [4-a], the formula [4-b] or the formula [4-c]

Specific examples thereof include the structures described above. Of these, preferred are pyrrole ring, imidazole ring, pyrazole ring, pyridine ring, pyrimidine ring, pyridazine ring, triazine ring, triazole ring, pyrazine ring, benzimidazole ring, benzoimidazole ring, quinoxaline ring, An azepine ring, a diazepine ring, a naphthyridine ring, a phenazine ring, or a phthalazine ring are preferable.

The expression contained in from the point of view of ease of electrostatic interaction, such as a nitrogen-containing aromatic heterocyclic ring and the polymer forming a salt of the carboxyl group or the hydrogen bonds in the formula [4a-1] is in the S ^1, S ² [4- a], the formula [4-b], or the formula [4-c].

Expression combination of preferred S ¹ and S ² in the [4a-1] is, S ¹ a, the number of carbon atoms and from 1 to 20 aliphatic hydrocarbon group or a carbon number of 3 to 20 non-aromatic cyclic hydrocarbon group, S ² a pyrrole ring , Imidazole ring, pyrazole ring, pyridine ring, pyrimidine ring, pyridazine ring, triazine ring, triazole ring, pyrazine ring, benzimidazole ring, benzimidazole ring, quinoxaline ring, A naphthylidene ring, a phenazine ring, or a phthalazine ring.

A more specific specific amine compound is an amine compound represented by the following formula [4a-2].

(40)

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

S ³ represents a linear 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 cycloheptane ring, a cyclooctane ring, A cycloheptadecane ring, a cycloheptadecane ring, a cyclooctadecane ring, a cyclooctadecane ring, a cyclododecane ring, a cyclotetradecane ring, a cyclotetradecane ring, a cyclopentadecane ring, a cyclohexadecane ring, a cycloheptadecane ring, A tricyclodecanoic acid ring, a tricyclodecanoic acid ring, a bicycloheptane ring, a decahydronaphthalene ring, a norbornene ring or an adamantane ring are preferable. More preferred is a linear or branched alkylene group having 1 to 10 carbon atoms.

S ⁴ represents a single bond, -O-, -NH-, -S-, -SO ₂ -, a hydrocarbon group having 1 to 19 carbon atoms, -CO-O-, -O-CO-, -CO- _{-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-, a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, A cycloheptadecane ring, a cycloheptadecane ring, a cycloheptadecane ring, a cycloheptadecane ring, a cyclohexadecane ring, a cyclohexadecane ring, a cycloheptane ring, a cycloheptane ring, a cycloheptane ring, a cycloheptane ring, , A cyclooctadecane ring, a cyclononadecane ring, a cyclooic acid ring, a tricycloicoic acid ring, a tricyclodecanoic acid ring, a bicycloheptane ring, a decahydronaphthalene ring, a norbornene ring, an adamantane ring, a benzene ring , A naphthalene ring, a tetrahydronaphthalene ring, an azul ring A thiazole ring, a pyrazole ring, a pyridine ring, a pyrimidine ring, a quinoline ring, a pyrazine ring, an imidazole ring, an imidazole ring, an imidazole ring, a thiazole ring, A carbazole ring, a pyridine ring, a thiadiazole ring, a pyridazine ring, a triazine ring, a pyrazolidine ring, a triazole ring, a pyrazine ring, a benzimidazole ring, a benzoimidazole ring, a quinoxaline ring, An oxadiazole ring, an oxidine ring, a piperazine ring, a piperidine ring, a dioxane ring, an oxadiazole ring, an oxadiazole ring, an oxadiazole ring, an oxidine ring, an oxazole ring, a piperazine ring, A ring or morpholine ring is preferred.

S ⁵ represents 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, an isoquinoline ring, a carbazole ring, a purine ring, A pyrimidine ring, a pyrimidine ring, a phenanthroline ring, a phenanthroline ring, an indole ring, a quinoxaline ring, a pyrimidine ring, a pyrazoline ring, a pyrazoline ring, a triazine ring, a pyrazolidine ring, a triazole ring, A benzothiazole ring, a phenothiazine ring, an oxadiazole ring, or an acridine ring are preferable.

Further, in view of ease of electrostatic interaction, such as a nitrogen-containing aromatic heterocyclic ring and the polymer forming a salt of the carboxyl group or a hydrogen bond in formula [4a-2] in S ^4, the formula contained in the S ⁵ [4a ], The formula [4-b], or the formula [4-c].

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

(41)

(42)

(43)

(44)

[Chemical Formula 45]

(46)

(47)

(48)

(49)

(50)

(51)

(52)

(53)

(54)

(55)

(56)

(57)

Among them, the formula [M10], the formula [M11], the formula [M14], the formula [M16], the formula [M17], the formula [M19], the formula [M20] M60], [M50], [M50], [M60], and [M60] M100], the expression [M121], the expression [M128], the expression [M135], the expression [M100], the expression [ M136], the formula [M140] or the formula [M143] is preferable. More preferred are the compounds represented by the formula [M16], the formula [M17], the formula [M35], the formula [M36], the formula [M40], the formula [M49], the formula [M50] M128], [M108], [M108], [M118], [M120], and [M121], and the expressions [ [M128], the formula [M135], the formula [M136], or the formula [M140].

These specific amine compounds can be used singly or in combination of two or more kinds, depending on the solubility of a specific amine compound in a solvent, the liquid crystal alignability when used as a liquid crystal alignment layer, or the electrical characteristics of a liquid crystal display element.

&Lt; 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), and is a coating solution for forming a liquid crystal alignment film containing a specific compound, a polymer, a specific amine compound and a solvent.

The use ratio of the specific compound in the liquid crystal alignment treatment agent is preferably as follows. That is, it is preferably 1 part by mass to 30 parts by mass with respect to 100 parts by mass of all the polymers. More preferably 1 part by mass to 20 parts by mass, and particularly preferably 3 parts by mass to 15 parts by mass.

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

The use ratio of the specific amine compound in the liquid crystal alignment treatment agent is preferably as follows. That is, it is preferably 1 part by mass to 40 parts by mass with respect to 100 parts by mass of all the polymers. More preferably 1 part by mass to 30 parts by mass, and particularly preferably 1 part by mass 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 preferable to add the solution after adjusting the concentration to 0.1 to 10% by mass with a suitable solvent. As the solvent at this time, a solvent in which the specific polyimide polymer described above is dissolved may, for example, be mentioned.

It is also preferable to heat the solution containing the specific amine compound and the polymer after adding the specific amine compound. In particular, it is more preferable to use a specific polyimide polymer for the polymer. Specifically, by heating, the proportion of the specific amine compound bonded or interacted with the specific polyimide polymer increases, and when the liquid crystal alignment film is used, the curing of the present invention can be further enhanced. At that time, the temperature for heating is preferably 10 to 100 占 폚, more preferably 20 to 80 占 폚.

As the polymer component in the liquid crystal alignment treatment agent, it is preferable to use a specific polyimide-based polymer, but other polymers may be mixed. At that time, the content of the other polymer is preferably 0.5 part by mass to 15 parts by mass with respect to 100 parts by mass of the specific polyimide polymer. More preferably 1 part by mass to 10 parts by mass. Examples of the other polymer include the above-mentioned acrylic polymer, methacrylic polymer, novolac resin, polyhydroxystyrene, polyamide, polyester, cellulose or polysiloxane.

The solvent in the liquid crystal alignment treatment agent preferably has a content of the solvent in the liquid crystal alignment treatment agent of 70 to 99.9 mass% from the viewpoint of forming a uniform liquid crystal alignment film by coating. This content can be appropriately changed depending on the film thickness of the intended liquid crystal alignment film.

The solvent used in the liquid crystal alignment treatment agent is not particularly limited as long as it is a solvent (also referred to as a good solvent) that dissolves the polymer. Specific examples of the positive solvent in the case of using a specific polyimide polymer are given below, but the present invention is not limited to these examples.

Examples of the solvent include N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N- 1,3-dimethyl-imidazolidinone, methyl ethyl ketone, cyclohexanone, cyclopentanone, or 4-hydroxy-4-methyl-2-pentanone.

Among them, it is preferable to use N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone or? -Butyrolactone.

When the solubility of the specific polyimide polymer in the solvent is high, it is preferable to use the solvent represented by the formula [D-1] to [D-3].

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

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

Butanol, isobutyl alcohol, tert-butyl alcohol, 1-pentanol, 2-pentanol, 3-pentanol, 2-methyl-1-butanol, Butanol, neopentyl alcohol, 1-hexanol, 2-methyl-1-pentanol, 2-methyl- Butanol, 1-heptanol, 2-heptanol, 3-heptanol, 1-octanol, 2-octanol, 2-ethyl-1-hexanol, cyclohexanol, 1-methylcyclohexanol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,3-propanediol, Butanediol, 1,5-pentanediol, 2-methyl-2,4-pentanediol, 2-ethyl-1,3-hexanediol, dipropyl ether, dibutyl ether, dihexyl ether, dioxane, Ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, 1,2-butoxyethane, diethylene glycol dimethyl ether, Ethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dibutyl ether, 2-pentanone, 3-pentanone, 2-hexanone, 2-heptanone, 4- (2-ethylhexyl) acetate, ethylene glycol monoacetate, ethylene glycol diacetate, propylene carbonate, ethylene carbonate, 2- (methoxymethoxy) ethanol, ethylene glycol monobutyl Propylene glycol monobutyl ether, ethylene glycol monohexyl ether, ethylene glycol monohexyl ether, 2- (hexyloxy) ethanol, furfuryl alcohol, diethylene glycol, propylene glycol, propylene glycol monobutyl ether, 1- , Propylene glycol monomethyl ether acetate, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol dimethyl Ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monoacetate, ethylene glycol diacetate, diethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, Glycol monobutyl ether acetate, 2- (2-ethoxyethoxy) ethyl acetate, diethylene glycol acetate, triethylene glycol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, methyl lactate, ethyl lactate, methyl acetate , Ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether acetate, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, methylethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-methoxypropionic acid, 3-methoxy D-1] to [D-1] to [D-1] to [D- 1] to [D- 3], and the like.

Among them, 1-hexanol, cyclohexanol, 1,2-ethanediol, 1,2-propanediol, propylene glycol monobutyl ether, ethylene glycol monobutyl ether, dipropylene glycol dimethyl ether, ] To [D-3] is preferably used.

The use ratio of these poor solvents is preferably 1 to 70 mass% of the total solvent contained in the liquid crystal alignment treatment agent. More preferably, it is 1 to 60% by mass, particularly preferably 5 to 60% by mass.

The liquid crystal alignment treating agent of the present invention is preferably selected from the group consisting of a crosslinking compound selected from the group consisting of an epoxy group, an isocyanate group, an oxetane group and a cyclocarbonate group, a hydroxyl group, a hydroxyalkyl group and an alkoxyalkyl group having 1 to 3 carbon atoms It is preferable to introduce a crosslinkable compound or a crosslinkable compound having a polymerizable unsaturated bonding group (collectively referred to as a specific crosslinkable compound). At this time, these groups need to have two or more of the compounds.

Examples of the crosslinkable compound having an epoxy group or an isocyanate group include bisphenol acetone glycidyl ether, phenol novolac epoxy resin, cresol novolak epoxy resin, triglycidyl isocyanurate, tetraglycidyl amino diphenylene Tetraglycidyl-1,3-bis (aminoethyl) cyclohexane, tetraphenyl glycidyl ether ethane, triphenyl glycidyl ether ethane, bisphenol hexafluoroacetate Diglycidyl ether, 1,3-bis (1- (2,3-epoxypropoxy) -1-trifluoromethyl-2,2,2-trifluoromethyl) benzene, 4,4-bis 2- (4- (2,3-epoxypropoxy) phenyl) -2- (4-methylpentanoyloxyphenyl) octafluorobiphenyl, triglycidyl-p-aminophenol, tetraglycidyl methadienyldiamine, 2- (4- (1, 4- (2,3-epoxypropoxy) phenyl) ethyl) phenyl) propane or 1,3- Oxy) phenyl) -1- (4- (1- (4- (2,3-epoxypropoxy) phenyl) -1-methylethyl) phenyl) ethyl) phenoxy) -2-propanol.

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

(58)

Specific examples thereof include crosslinkable compounds represented by the formulas [4a] to [4k] shown on pages 58 to 59 of International Publication No. WO2011 / 132751 (published on October 22, 2011).

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

[Chemical Formula 59]

Specific examples thereof include crosslinkable compounds represented by the formulas [5-1] to [5-42] listed on pages 76 to 82 of International Publication WO2012 / 014898 (published on February 22, 2012).

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

Examples of such melamine derivatives or benzoguanamine derivatives include, for example, MX-750 in which methoxymethyl groups are substituted in an average of 3.7 methoxymethyl groups per one triazine ring on the market, methoxymethyl groups per one triazine ring on average are substituted by 5.8 MW-30 (manufactured by Sanwa Chemical Co., Ltd.) or methoxymethylated melamine such as Cymel 300, 301, 303, 350, 370, 771, 325, 327, 703, 712, Cymel 235, 212, 253 and 254, methoxymethylated isobutoxymethylated melamine containing carboxyl groups such as Cymel 1141, methoxymethylated methoxy methylated melamines such as Cymel 1123, Ethoxymethylated benzoguanamine, methoxymethylated butoxymethylated benzoguanamine such as Cymel 1123-10, butoxymethylated benzoguanamine such as Cymel 1128, carboxyl-containing methoxymethylated ethoxy, such as Cymel 1125-80, Methylation Load block Ana min can be given (or more, between the mid-Mitsui Ana Company). Examples of glycoluril include butoxymethylated glycoluril such as Cymel 1170, methylol glycoluryl such as Cymel 1172, and methoxymethylolglycoluril such as Powderlink 1174, and the like.

Examples of the benzene or phenolic compound having a hydroxyl group or alkoxyl group include 1,3,5-tris (methoxymethyl) benzene, 1,2,4-tris (isopropoxymethyl) benzene, 1,4-bis (sec-butoxymethyl) benzene, 2,6-dihydroxymethyl-p-tert-butylphenol and the like. More specifically, the crosslinkable compounds represented by the formulas [6-1] to [6-48], which are listed on pages 62 to 66 of WO2011 / 132751 (published on October 22, 2011), can be mentioned.

Examples of the crosslinkable compound having a polymerizable unsaturated bond include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, tri ) Acryloyloxyethoxy trimethylol propane or glycerin polyglycidyl ether poly (meth) acrylate, a crosslinkable compound having three polymerizable unsaturated groups in its molecule, ethylene glycol di (meth) acrylate, diethylene glycol Acrylate, diethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (Meth) acrylate, neopentyl glycol di (meth) acrylate, ethylene oxide bisphenol A type di (meth) acrylate, propylene oxide (Meth) acrylates such as bisphenol type di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, glycerin di (meth) acrylate, pentaerythritol di (meth) acrylate, ethylene glycol diglycidyl ether di (Meth) acrylate such as diethylene glycol diglycidyl ether di (meth) acrylate, diethylene glycol diglycidyl ether di (meth) acrylate, phthalic acid diglycidyl ester di (meth) acrylate or hydroxypivalic acid neopentyl glycol di And a crosslinking compound having two groups in the molecule.

The content of the specific crosslinkable compound in the liquid crystal alignment treatment agent is preferably 1 to 50 parts by mass with respect to 100 parts by mass of all the polymer components. More preferably, it is 1 to 30 parts by mass, particularly preferably 1 to 10 parts by mass, in order to proceed the crosslinking reaction to exhibit the desired effect.

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

Examples of the compound that improves the uniformity of the film thickness of the liquid crystal alignment film and the surface smoothness include a fluorine-based surfactant, a silicon-based surfactant, and a nonionic-based surfactant. Specifically, for example, EF301, EF303 and EF352 (manufactured by TOKEM PRODUCTS CO., LTD.), Megafac F171, F173 and R-30 (manufactured by Dainippon Ink and Chemicals Inc.), FLORAD FC430 and FC431 (Manufactured by Asahi Glass Co., Ltd.), Asahi Guard AG710, Surfron S-382, SC101, SC102, SC103, SC104, SC105 and SC106 (manufactured by Asahi Glass Co., Ltd.). The use ratio of these surfactants is preferably 0.01 to 2 parts by mass based on 100 parts by mass of all the polymer components contained in the liquid crystal alignment treatment agent. More preferred is 0.01 to 1 part by mass.

Specific examples of the compound that improves the adhesion between the liquid crystal alignment film and the substrate include a functional silane-containing compound and an epoxy group-containing compound. For example, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N- (2-aminoethyl) -3 3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, N-ethoxy (2-aminoethyl) Aminopropyltriethoxysilane, N-trimethoxysilylpropyltriethoxysilane, N-trimethoxysilylpropyltriethoxysilane, N-trimethoxysilylpropyltriethoxysilane, N-trimethoxysilylpropyltriethoxysilane, Amine, 10-trimethoxysilyl-1,4,7-triazadecane, 10-triethoxysilyl-1,4,7-triazadecane, 9-trimethoxysilyl-3,6-diazanonyl Acetate, 9-triethoxysilyl-3,6-diazanonyl acetate, N-benzyl-3-aminopropyltrimethoxysilane, N-benzyl-3-aminopropyltriethoxysilane, N- Bis (oxyethylene) -3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N- Aminopropyltriethoxysilane, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neo Pentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5,6 Tetraglycidyl-2,4-hexanediol, N, N, N ', N', -tetraglycidyl-m-xylylenediamine, 1,3-bis (N, N-diglycidylamino Methyl) cyclohexane or N, N, N ', N', -tetraglycidyl-4,4'-diaminodiphenylmethane and the like.

The ratio of the compound to be adhered to the substrate is preferably 0.1 to 30 parts by mass with respect to 100 parts by mass of all the polymer components contained in the liquid crystal alignment treatment agent. More preferred is 1 to 20 parts by mass. If the amount is less than 0.1 part by mass, the effect of improving the adhesion can not be expected. If the amount is more than 30 parts by mass, the storage stability of the liquid crystal alignment treatment agent may be deteriorated.

The liquid crystal alignment treatment agent may contain a dielectric substance or a conductive substance for the purpose of changing electric characteristics such as the dielectric constant and conductivity of the liquid crystal alignment film as long as the effect of the present invention is not impaired, in addition to the above-mentioned compounds.

<Liquid Crystal Alignment Film / Liquid Crystal Display Device>

The liquid crystal alignment treatment agent of the present invention can be used as a liquid crystal alignment film after being applied and baked on a substrate and subjected to an orientation treatment by rubbing treatment, light irradiation, or the like. In the case of a liquid crystal display element for a VA mode or the like, it can be used as a liquid crystal alignment film without alignment treatment. The substrate to be used at this time is not particularly limited as long as it is a substrate having high transparency. A plastic substrate such as an acrylic substrate or a polycarbonate substrate can be used in addition to a glass substrate. From the viewpoint of simplifying the process, it is preferable to use a substrate on which an ITO (Indium Tin Oxide) electrode for liquid crystal driving is formed. In a reflective liquid crystal display device, an opaque substrate such as a silicon wafer can be used as long as it is a substrate on only one side. In this case, a material that reflects light such as aluminum can also be used as the electrode in this case.

The method of applying the liquid crystal alignment treatment agent is not particularly limited, but industrially, a method of screen printing, offset printing, flexographic printing, or inkjet printing is generally used. Other coating methods include a dipping method, a roll coater method, a slit coater method, a spinner method, and a spraying method, and they may be used depending on the purpose.

After the liquid crystal alignment treatment agent is applied onto the substrate, it is heated to 30 to 300 占 폚, preferably 30 to 300 占 폚, depending on the solvent used for the liquid crystal alignment treatment agent by a heating means such as a hot plate, a heat- The liquid crystal alignment layer can be formed by evaporating the solvent at a temperature of 30 to 250 ° C. When the thickness of the liquid crystal alignment layer after firing is too large, the power consumption of the liquid crystal display element is disadvantageously deteriorated. When the thickness is too thin, the reliability of the liquid crystal display element may deteriorate. Therefore, the thickness is preferably 5 to 300 nm Is 10 to 100 nm. When a liquid crystal is tilted or horizontally aligned as in a TN mode or IPS mode liquid crystal display device, the fired liquid crystal alignment film is treated by rubbing, polarized ultraviolet irradiation, or the like.

In the liquid crystal display element of the present invention, a substrate on which a liquid crystal alignment film is formed from the liquid crystal alignment treatment agent of the present invention is formed by the above-mentioned technique, and then a liquid crystal cell is produced by a known method to form a liquid crystal display element.

As a manufacturing method of the liquid crystal cell, for example, a pair of substrates on which a liquid crystal alignment film is formed is prepared, spacers are dispersed on the liquid crystal alignment film of the substrate of the single chamber, and the liquid crystal alignment film surface is inward, A liquid crystal is dropped onto the surface of the liquid crystal alignment film on which the spacer is dispersed, and then the substrate is bonded and sealed (ODF: One Drop Filling Quot; method &quot;).

The liquid crystal alignment treatment agent of the present invention is a liquid crystal alignment treatment agent which has a liquid crystal layer between a pair of substrates provided with electrodes and includes a polymerizable compound polymerized by at least one of active energy rays and heat between a pair of substrates The present invention is preferably used for a liquid crystal display device produced by a process of arranging a composition and polymerizing a polymerizable compound by at least one of irradiation of an active energy ray and heating while applying a voltage between electrodes. Here, as the active energy ray, ultraviolet rays are suitable. The ultraviolet ray has a wavelength of 300 to 400 nm, preferably 310 to 360 nm. In the case of polymerization by heating, the heating temperature is 40 to 120 占 폚, preferably 60 to 80 占 폚. In addition, ultraviolet rays and heating may be simultaneously performed.

The liquid crystal display element described above controls the pretilt of the liquid crystal molecules by the PSA mode method. In the PSA mode, a small amount of a photopolymerizable compound, for example, a photopolymerizable monomer, is incorporated into a liquid crystal material, and after a liquid crystal cell is assembled, a predetermined voltage is applied to the liquid crystal layer, And controls the pretilt of the liquid crystal molecules by the produced polymer. Since the alignment state of the liquid crystal molecules when the polymer is produced is stored even after the voltage is removed, the pretilt of the liquid crystal molecules can be adjusted by controlling the electric field or the like formed on the liquid crystal layer. In addition, in the PSA mode, since the rubbing process is not required, it is suitable for forming a vertical alignment type liquid crystal layer which is difficult to control the pre-tilt by the rubbing process. That is, the liquid crystal display element of the present invention can be obtained by obtaining a substrate on which a liquid crystal alignment film is formed from a liquid crystal alignment treatment agent by the above-mentioned technique, preparing a liquid crystal cell, and polymerizing the polymerizable compound by at least one of irradiation with ultraviolet rays and heating The orientation of the liquid crystal molecules can be controlled.

An example of the production of the liquid crystal cell of the PSA mode is as follows, for example. That is, the liquid crystal cell is fabricated by the manufacturing method described above. The liquid crystal at that time is mixed with a polymerizable compound which is polymerized by irradiation with heat or ultraviolet rays. Examples of the polymerizable compound include a compound having at least one polymerizable unsaturated group such as an acrylate group or a methacrylate group in the molecule. At that time, the polymerizable compound is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, per 100 parts by mass of the liquid crystal component. When the amount of the polymerizable compound is less than 0.01 part by mass, the polymerizable compound is not polymerized and the alignment of the liquid crystal can not be controlled. When the amount is larger than 10 parts by mass, unreacted polymerizable compound increases, . After the liquid crystal cell is manufactured, the polymerizable compound is polymerized by applying heat or ultraviolet rays while applying alternating current or direct current voltage to the liquid crystal cell. Thus, the orientation of the liquid crystal molecules can be controlled.

The liquid crystal alignment treatment agent of the present invention comprises a liquid crystal layer between a pair of substrates provided with electrodes and includes a polymerizable group polymerized by at least one of active energy rays and heat between the pair of substrates Or a SC-PVA mode, which is manufactured through a process of arranging a liquid crystal alignment film to which a voltage is applied between electrodes. Here, as the active energy ray, ultraviolet rays are suitable. The ultraviolet ray has a wavelength of 300 to 400 nm, and more preferably 310 to 360 nm. In the case of polymerization by heating, the heating temperature is from 40 to 120 캜, more preferably from 60 to 80 캜. In addition, ultraviolet rays and heating may be simultaneously performed.

In order to obtain a liquid crystal alignment film containing a polymerizable group polymerized by at least one of an active energy ray and heat, a method of adding a compound containing the polymerizable group to a liquid crystal alignment treatment agent, a method of using a polymer component containing a polymerizable group Method.

An example of manufacturing a liquid crystal cell in the SC-PVA mode is as follows, for example. That is, the liquid crystal cell is fabricated by the manufacturing method described above. Thereafter, alignment of liquid crystal molecules can be controlled by applying heat or ultraviolet rays while applying alternating current or direct current voltage to the liquid crystal cell.

By using the liquid crystal alignment treatment agent of the present invention as described above, it is possible to suppress the decrease of the voltage holding ratio even after exposure to light for a long period of time, and furthermore, display irregularity occurs near the frame of the liquid crystal display element even under high temperature and high humidity conditions Can be provided. Therefore, the liquid crystal display device manufactured using the liquid crystal alignment treatment agent of the present invention has excellent reliability and can be suitably used for a large-size liquid crystal television, a small-sized car navigation system, a smart phone, and the like. In particular, the liquid crystal alignment treatment agent of the present invention is useful for a liquid crystal alignment film of a liquid crystal display element using a VA mode, a PSA mode and an SC-PVA mode.

Example

Hereinafter, the present invention will be described more specifically by way of examples, but the present invention is not limited thereto.

Abbreviations used in Synthesis Examples, Examples and Comparative Examples are as follows.

(Specific compound)

S1: tungstic acid (manufactured by Nippon Shin Co., Ltd.)

S2: phosphomolybdic acid (12 mol ribodo (IV) phosphoric acid n hydrate) (Kanto Chemical)

(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}

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

A5: 1,3-Diamino-4-octadecyloxybenzene

(60)

(Other diamine compound)

B1: p-phenylenediamine

B2: m-phenylenediamine

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

B4: 4,4'-diaminodiphenylamine

B5: 3,5-diaminobenzoic acid

(61)

(Specific tetracarboxylic acid dianhydride)

C1: 1,2,3,4-Cyclobutane tetracarboxylic acid dianhydride

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

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

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

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

(62)

(Crosslinkable compound)

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

(63)

(menstruum)

NMP: N-methyl-2-pyrrolidone

NEP: N-ethyl-2-pyrrolidone

? -BL:? -butyrolactone

BCS: ethylene glycol monobutyl ether

PB: Propylene glycol monobutyl ether

DME: dipropylene glycol dimethyl ether

(Specific amine compound)

L1: 3-Picolylamine

L2: N- (3-aminopropyl) -imidazole

&Lt; EMI ID =

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

(KD-803, KD-805, manufactured by Shodex) at room temperature gel permeation chromatography (GPC-101, manufactured by Showa Denko K.K.).

Column temperature: 50 ° C

Eluent: N, N'- dimethylformamide (as an additive, lithium bromide-hydrate (LiBr · H ₂ O) is 30 m㏖ / ℓ (L), phosphoric acid anhydrous crystal (o- phosphoric acid) is 30 m㏖ / ℓ , Tetrahydrofuran (THF) of 10 ml / l)

Flow rate: 1.0 ml / min

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

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

(DMSO-d6, 0.05 mass% TMS (tetramethylsilane)) mixture was placed in an NMR (nuclear magnetic resonance) sample tube (NMR sampling tube standard, phi 5 Product) (0.53 ml) was added, and completely dissolved by ultrasonic wave. This solution was subjected to proton NMR measurement at 500 MHz using an NMR measuring instrument (JNW-ECA500, manufactured by Nippon Dental Electronics Co., Ltd.). A proton originating from a structure which is not changed before and after imidization is defined as a reference proton, and the peak accumulation value of the proton and the proton peak accumulation value derived from the NH group of the amide acid appearing in the vicinity of 9.5 ppm to 10.0 ppm Value was obtained by the following equation.

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

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

&Quot; Synthesis of polyimide polymer &quot;

&Lt; Synthesis Example 1 &

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

NMP was added to the obtained polyamic acid solution (30.0 g) to dilute to 6 mass%, acetic anhydride (3.90 g) and pyridine (2.40 g) were added as imidation catalysts and reacted at 70 ° C for 4 hours . The reaction solution was poured into methanol (460 ml), and the resulting precipitate was separated by filtration. The precipitate was washed with methanol, and dried at 100 ° C under reduced pressure to obtain a polyimide powder (1). The polyimide had an imidization ratio of 84%, a number average molecular weight of 19,300 and a weight average molecular weight of 52,300.

&Lt; Synthesis Example 2 &

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

&Lt; Synthesis Example 3 &

To the polyamic acid solution (2) (30.0 g) obtained in Synthesis Example 2, NEP was added and diluted to 6 mass%, acetic anhydride (4.50 g) and pyridine (3.30 g) were added as an imidation catalyst, The reaction was carried out at 80 ° C for 4 hours. This reaction solution was poured into methanol (460 ml), and the resulting precipitate was separated by filtration. The precipitate was washed with methanol, and dried at 100 ° C under reduced pressure to obtain a polyimide powder (3). The imidization ratio of the polyimide was 81%, the number average molecular weight was 17,500, and the weight average molecular weight was 45,300.

&Lt; Synthesis Example 4 &

(2.32 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) After the reaction, C1 (0.65 g, 3.31 mmol) and NEP (8.16 g) were added and reacted at 40 DEG C for 6 hours to obtain a polyamic acid solution having a resin solid content concentration of 25 mass%.

NEP was added to the obtained polyamic acid solution (30.0 g) to dilute to 6 mass%, acetic anhydride (4.50 g) and pyridine (3.30 g) were added as imidation catalysts and reacted at 80 ° C for 3 hours . The reaction solution was poured into methanol (460 ml), and the resulting precipitate was separated by filtration. The precipitate was washed with methanol and dried under reduced pressure at 100 ° C to obtain a polyimide powder (4). The polyimide had an imidization rate of 70%, a number average molecular weight of 18,300 and a weight average molecular weight of 46,000.

&Lt; Synthesis Example 5 &

C2 (2.30 g, 9.19 mmol), Al (2.83 g, 7.44 mmol) and B2 (1.21 g, 11.2 mmol) were mixed in NMP (16.3 g) 9.18 mmol) and NMP (8.13 g) were added and reacted at 40 占 폚 for 6 hours to obtain a polyamic acid solution having a resin solid content concentration of 25 mass%.

NMP was added to the obtained polyamic acid solution (30.0 g) to dilute to 6 mass%, acetic anhydride (3.80 g) and pyridine (2.40 g) were added as imidation catalysts and the mixture was reacted at 60 ° C for 2 hours . The reaction solution was poured into methanol (460 ml), and the resulting precipitate was separated by filtration. The precipitate was washed with methanol and dried under reduced pressure at 100 ° C to obtain a polyimide powder (5). The imidization ratio of the polyimide was 55%, and the number average molecular weight was 17,500 and the weight average molecular weight was 45,100.

&Lt; 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) 9.18 mmol) and NMP (8.10 g) were added and reacted at 40 占 폚 for 6 hours to obtain a polyamic acid solution having a resin solid content concentration of 25 mass%.

NMP was added to the obtained polyamic acid solution (30.0 g) to dilute to 6 mass%, acetic anhydride (3.80 g) and pyridine (2.40 g) were added as imidation catalysts and the mixture was reacted at 60 ° C for 2 hours . The reaction solution was poured into methanol (460 ml), and the resulting precipitate was separated by filtration. The precipitate was washed with methanol, and dried at 100 ° C under reduced pressure to obtain a polyimide powder (6). The imidization ratio of the polyimide was 55%, and the number average molecular weight was 16,800 and the weight average molecular weight was 43,900.

&Lt; Synthesis Example 7 &

(1.28 g, 6.35 mmol) and B2 (0.78 g, 7.25 mmol) were mixed in NMP (16.8 g) and heated to 80 &lt; 0 &gt; C for 5 hours After the reaction, C1 (1.40 g, 7.14 mmol) and NMP (8.37 g) were added and reacted at 40 DEG C for 6 hours to obtain a polyamic acid solution having a resin solid content concentration of 25 mass%.

NMP was added to the obtained polyamic acid solution (30.0 g) to dilute to 6 mass%, acetic anhydride (3.80 g) and pyridine (2.40 g) were added as imidation catalysts and the mixture was reacted at 60 ° C for 2 hours . The reaction solution was poured into methanol (460 ml), and the resulting precipitate was separated by filtration. The precipitate was washed with methanol, and dried at 100 ° C under reduced pressure to obtain a polyimide powder (7). The imidization ratio of the polyimide was 52%, the number average molecular weight was 14,800, and the weight average molecular weight was 38,300.

&Lt; Synthesis Example 8 &

(0.90 g, 5.59 mmol) and B5 (0.85 g, 5.59 mmol) were mixed in NMP (25.4 g), and the mixture was stirred at 40 ° C for 8 hours To obtain a polyamic acid solution having a resin solid content concentration of 25 mass%.

NMP was added to the resultant polyamic acid solution (30.0 g) to dilute it to 6 mass%, acetic anhydride (4.50 g) and pyridine (3.30 g) were added as an imidation catalyst and reacted at 80 ° C for 3 hours . The reaction solution was poured into methanol (460 ml), and the resulting precipitate was separated by filtration. The precipitate was washed with methanol and dried under reduced pressure at 100 ° C to obtain a polyimide powder (8). The imidization ratio of the polyimide was 75%, the number average molecular weight was 18,200, and the weight average molecular weight was 46,300.

&Lt; Synthesis Example 9 &

(0.69 g, 3.46 mmol) and B4 (0.69 g, 3.46 mmol) were mixed in NMP (16.6 g) and treated at 80 &lt; 0 &gt; C for 5 h After the reaction, C1 (1.00 g, 5.10 mmol) and NMP (8.27 g) were added and reacted at 40 DEG C for 6 hours to obtain a polyamic acid solution having a resin solid content concentration of 25 mass%.

NEP was added to the obtained polyamic acid solution (30.0 g) to dilute to 6 mass%, acetic anhydride (4.50 g) and pyridine (3.30 g) were added as an imidation catalyst and the reaction was carried out at 80 ° C for 4 hours . The reaction solution was poured into methanol (460 ml), and the resulting precipitate was separated by filtration. The precipitate was washed with methanol and dried under reduced pressure at 100 ° C to obtain a polyimide powder (9). The imidization ratio of the polyimide was 85%, the number average molecular weight was 15,500, and the weight average molecular weight was 40,100.

&Lt; Synthesis Example 10 &

The reaction was carried out at 80 ° C for 5 hours and then C5 (2.80 g, 5.63 mmol) was added to the reaction mixture, 13.2 mmol) and NMP (8.47 g) were added and reacted at 40 占 폚 for 6 hours to obtain a polyamic acid solution having a resin solid content concentration of 25 mass%.

NEP was added to the obtained polyamic acid solution (30.0 g) to dilute to 6 mass%, acetic anhydride (4.50 g) and pyridine (3.30 g) were added as imidation catalysts and reacted at 80 ° C for 3.5 hours . The reaction solution was poured into methanol (460 ml), and the resulting precipitate was separated by filtration. The precipitate was washed with methanol and dried under reduced pressure at 100 占 폚 to obtain a polyimide powder (10). The polyimide had an imidization ratio of 78%, a number average molecular weight of 16,600 and a weight average molecular weight of 43,400.

Table 1 shows the polyimide polymer obtained in Synthesis Example.

* 1: Polyamide acid.

&Quot; Production of liquid crystal alignment treatment agent &quot;

In the following Examples and Comparative Examples, production examples of liquid crystal alignment treatment agents are described. This liquid crystal alignment treatment agent is also used for manufacturing and evaluating a liquid crystal display element. Tables 2 to 4 show the respective liquid crystal alignment treatment agents obtained in Examples and Comparative Examples.

Evaluation of inkjet application property of liquid crystal alignment treatment agent &quot;

Using the liquid crystal alignment treatment agents obtained in the later-described Examples 4 and 7, evaluation of the ink-jet application performance was carried out. Specifically, an ITO (indium tin oxide) electrode in which these liquid crystal alignment treatment agents are subjected to pressure filtration with a membrane filter having a pore diameter of 1 m and cleaned with pure water and IPA (isopropyl alcohol) The ITO surface of the formed substrate (100 mm in length × 100 mm in width and 0.7 mm in thickness) was coated with a coating area of 70 × 70 mm, a nozzle pitch of 0.423 mm, a scan pitch of 0.5 mm and a coating speed of 40 mm / . At that time, HIS-200 (manufactured by Hitachi Plant Technologies Co., Ltd.) was used for the ink jet applicator. The time from application to temporary drying was 60 seconds, and the temporary drying was performed on a hot plate at 70 DEG C for 5 minutes.

Evaluation of coating properties was carried out by visually observing the coated film surface of the substrate on which the liquid crystal alignment film obtained above was formed. Specifically, the surface of the coated film was visually observed under a sodium lamp to confirm the presence of pinholes. As a result, all of the liquid crystal alignment films obtained in any of the Examples showed no pinholes on the coated film surface, and a liquid crystal alignment film excellent in film film property was obtained.

Evaluation of display non-uniformity characteristics in the vicinity of frame of liquid crystal cell (normal cell)

The liquid crystal alignment treatment agent obtained in the later-described Examples and Comparative Examples was pressure-filtered with a membrane filter having a pore diameter of 1 占 퐉 and cleaned with pure water and IPA to obtain a substrate (40 mm long × 30 mm wide, ), And subjected to a heat treatment on a hot plate at 100 占 폚 for 5 minutes and a heat cycle type clean oven at 230 占 폚 for 30 minutes to obtain an ITO substrate on which a liquid crystal alignment film with a thickness of 100 nm was formed. The substrates of the liquid crystal alignment treatment agents of Examples 4 and 7 were produced under the same conditions as those of the above-mentioned &quot; Evaluation of inkjet application property of liquid crystal alignment treatment agent &quot; (substrate: ITO (40 mm long x 30 mm wide and 0.7 mm thick) on which the electrodes were formed was used. Thereafter, heat treatment was performed at 230 DEG C for 30 minutes in a thermocycling type clean oven to obtain a liquid crystal alignment film having a thickness of 100 nm Thereby forming an ITO substrate.

Next, the coated surface of the substrate was subjected to a rubbing treatment using a rayon cloth with a rubbing apparatus having a roll diameter of 120 mm at a roll rotation speed of 1000 rpm, a roll advancing speed of 50 mm / sec, and a pressing amount of 0.1 mm.

Thereafter, two substrates after the rubbing treatment were prepared, and the coating film was interposed between the spacers of 6 占 퐉 with the coated film side inward, and bonded together with a sealant to prepare empty cells. The liquid crystal was injected into the empty cell by a vacuum injection method and the injection port was sealed to obtain a liquid crystal cell. Further, in Example 1 and Comparative Examples 1 to 3, MLC-3018U (manufactured by Merck Japan) was used for the liquid crystal, and MLC-6608 (Merck &amp; Japan) was used.

Using the obtained liquid crystal cell, the display non-uniformity characteristics in the vicinity of the frame of the liquid crystal cell were evaluated. Specifically, the polarizing plate and the backlight were used to evaluate the liquid crystal alignability in the vicinity of the sealant by visual observation. As a result, all of the liquid crystal cells obtained in Examples and Comparative Examples exhibited uniform liquid crystal alignability.

Thereafter, the liquid crystal cell was stored in a high-temperature and high-humidity bath having a temperature of 80 캜 and a humidity of 90% for 96 hours, and the liquid crystal orientation property near the sealing agent was evaluated under the same conditions as above. The evaluation showed that, after storage in a high-temperature and high-humidity bath, no disturbance of liquid crystal orientation was observed near the sealant, the evaluation was superior to the evaluation (good display in Tables 5 to 7). Tables 5 to 7 show the results of the display non-uniformity characteristics in the vicinity of the frame of the liquid crystal cell after being stored in the high-temperature and high-humidity bath.

Evaluation of voltage holding ratio (normal cell)

The voltage holding ratio was evaluated using a liquid crystal cell manufactured under the same conditions as those described above under &quot; evaluation of display non-uniformity characteristics in the vicinity of the frame of the liquid crystal cell (normal cell) &quot;. Specifically, a voltage of 1 V is applied to a liquid crystal cell obtained by the above method at a temperature of 80 캜 for 60 하고, a voltage after 50 ㎳ is measured, and a voltage holding ratio (also referred to as VHR) ). The measurement was carried out by using a voltage sustaining ratio measuring device (VHR-1) (manufactured by Toyotec Corporation) under the conditions of a voltage of ± 1 V, a pulse width of 60 μs, a flame period: 50 ㎳.

Ultraviolet rays of 50 J / cm 2 in terms of 365 nm in terms of 365 nm were irradiated to the liquid crystal cell in which the voltage holding ratio was measured immediately after the liquid crystal cell was prepared, using a table type UV curing apparatus (HCT3B28HEX-1 And the voltage holding ratio was measured under the same conditions as described above.

In this evaluation, the value of the voltage holding ratio immediately after the fabrication of the liquid crystal cell was high, and the value (after the ultraviolet irradiation) of the value after the ultraviolet irradiation The smaller the better, the better the evaluation. In Tables 5 to 7, values of each VHR are shown.

&Lt; Example 1 &gt;

NMP (7.83 g) and? -BL (23.5 g) were added to the polyimide powder (1) (2.50 g) obtained in Synthesis Example 1 and dissolved by stirring at 70 占 폚 for 24 hours. To this solution, a 10% by mass NMP solution of L1 (1.25 g) and BCS (7.83 g) were added and the mixture was stirred at 50 占 폚 for 15 hours. Thereafter, S1 (0.25 g) was added and stirred at 25 占 폚 for 6 hours to obtain a liquid crystal alignment treatment agent (1). No abnormality such as turbidity or precipitation was observed in this liquid crystal alignment treatment agent, and it was confirmed that the solution was a homogeneous solution.

&Lt; Example 2 &gt;

NEP (16.0 g), PB (15.7 g) and NEP solution of 10 mass% of L1 (0.75 g) were added to polyamic acid solution (2) (10.0 g) having a resin solid content concentration of 25 mass% g), and the mixture was stirred at 50 占 폚 for 15 hours. Thereafter, S1 (0.125 g) was added and stirred at 25 占 폚 for 6 hours to obtain a liquid crystal orientation treating agent (2). No abnormality such as turbidity or precipitation was observed in this liquid crystal alignment treatment agent, and it was confirmed that the solution was a homogeneous solution.

&Lt; Example 3 &gt;

NEP (23.5 g) was added to the polyimide powder (3) (2.50 g) obtained in Synthesis Example 3 and dissolved by stirring at 70 占 폚 for 24 hours. To this solution was added a NEP solution (1.25 g) of L1% by mass, BCS (3.92 g) and PB (11.8 g), and the mixture was stirred at 50 占 폚 for 15 hours. Thereafter, S1 (0.25 g) was added and stirred at 25 占 폚 for 6 hours to obtain a liquid crystal alignment treating agent (3). No abnormality such as turbidity or precipitation was observed in this liquid crystal alignment treatment agent, and it was confirmed that the solution was a homogeneous solution.

<Example 4>

NEP (16.5 g) and? -BL (4.14 g) were added to the polyimide powder (3) (1.50 g) obtained in Synthesis Example 3 and dissolved by stirring at 70 占 폚 for 24 hours. To this solution was added NEP solution (0.75 g) of 10% by mass of L1, PB (16.5 g) and DME (4.14 g), and the mixture was stirred at 50 占 폚 for 15 hours. Thereafter, S1 (0.15 g) was added and stirred at 25 占 폚 for 6 hours to obtain liquid crystal alignment treatment agent (4). No abnormality such as turbidity or precipitation was observed in this liquid crystal alignment treatment agent, and it was confirmed that the solution was a homogeneous solution.

&Lt; Example 5 &gt;

NEP (23.5 g) was added to the polyimide powder (4) (2.50 g) obtained in Synthesis Example 4 and dissolved by stirring at 70 占 폚 for 24 hours. To this solution, a 10% by mass NEP solution of L1 (1.75 g) and PB (15.7 g) were added and the mixture was stirred at 50 占 폚 for 15 hours. Then, S1 (0.175 g) was added and stirred at 25 占 폚 for 6 hours to obtain liquid crystal alignment treatment agent (5). No abnormality such as turbidity or precipitation was observed in this liquid crystal alignment treatment agent, and it was confirmed that the solution was a homogeneous solution.

&Lt; Example 6 &gt;

NEP (23.5 g) was added to the polyimide powder (4) (2.50 g) obtained in Synthesis Example 4 and dissolved by stirring at 70 占 폚 for 24 hours. To this solution, a 10% by mass NEP solution of L1 (1.25 g) and PB (15.7 g) were added and the mixture was stirred at 50 占 폚 for 15 hours. Then, S1 (0.175 g) was added and stirred at 25 占 폚 for 6 hours to obtain a liquid crystal alignment treatment agent (6). No abnormality such as turbidity or precipitation was observed in this liquid crystal alignment treatment agent, and it was confirmed that the solution was a homogeneous solution.

&Lt; Example 7 &gt;

NEP (18.6 g) was added to the polyimide powder (4) (1.50 g) obtained in Synthesis Example 4 and dissolved by stirring at 70 占 폚 for 24 hours. To this solution was added a 10% by mass NEP solution (1.05 g) of L1 and 22.8 g of PB, and the mixture was stirred at 50 占 폚 for 15 hours. Thereafter, S1 (0.105 g) was added and stirred at 25 占 폚 for 6 hours to obtain a liquid crystal alignment treatment agent (7). No abnormality such as turbidity or precipitation was observed in this liquid crystal alignment treatment agent, and it was confirmed that the solution was a homogeneous solution.

&Lt; Example 8 &gt;

NMP (19.6 g) was added to the polyimide powder (5) (2.50 g) obtained in Synthesis Example 5 and dissolved by stirring at 70 占 폚 for 24 hours. To this solution was added an NMP solution (0.75 g) of 10% by mass of L1, 3.92 g of BCS and 15.7 g of PB, and the mixture was stirred at 50 占 폚 for 15 hours. Thereafter, S2 (0.175 g) was added and stirred at 25 캜 for 6 hours to obtain a liquid crystal alignment treatment agent (8). No abnormality such as turbidity or precipitation was observed in this liquid crystal alignment treatment agent, and it was confirmed that the solution was a homogeneous solution.

With respect to the evaluation of the display non-uniformity characteristic (normal cell) in the vicinity of the frame of the liquid crystal cell, when the test was carried out in the high temperature and high humidity chamber at a temperature of 80 DEG C and a humidity of 90% for 168 hours (The other conditions are the same as the above conditions). As a result, no disturbance of liquid crystal alignability was observed in the vicinity of the sealant among the liquid crystal cells.

&Lt; Example 9 &gt;

NMP (19.6 g) was added to the polyimide powder (6) (2.50 g) obtained in Synthesis Example 5 and dissolved by stirring at 70 占 폚 for 24 hours. To this solution was added an NMP solution (0.75 g) of 10% by mass of L1, 3.92 g of BCS and 15.7 g of PB, and the mixture was stirred at 50 占 폚 for 15 hours. Thereafter, S2 (0.175 g) was added and stirred at 25 캜 for 6 hours to obtain a liquid crystal alignment treatment agent (9). No abnormality such as turbidity or precipitation was observed in this liquid crystal alignment treatment agent, and it was confirmed that the solution was a homogeneous solution.

With respect to the evaluation of the display non-uniformity characteristic (normal cell) in the vicinity of the frame of the liquid crystal cell, when the test was carried out in the high temperature and high humidity chamber at a temperature of 80 DEG C and a humidity of 90% for 168 hours (The other conditions are the same as the above conditions). As a result, disturbance of the liquid crystal alignment property was observed in the vicinity of the sealant among the liquid crystal cells.

&Lt; Example 10 &gt;

NEP (23.5 g) was added to the polyimide powder (7) (2.50 g) obtained in Synthesis Example 7 and dissolved by stirring at 70 占 폚 for 24 hours. To this solution was added a NEP solution (1.75 g) of 10% by mass of L2, BSC (3.92 g) and PB (11.8 g), and the mixture was stirred at 50 占 폚 for 15 hours. Thereafter, S1 (0.30 g) was added and stirred at 25 占 폚 for 6 hours to obtain a liquid crystal alignment treating agent (10). No abnormality such as turbidity or precipitation was observed in this liquid crystal alignment treatment agent, and it was confirmed that the solution was a homogeneous solution.

&Lt; Example 11 &gt;

NEP (27.4 g) was added to the polyimide powder (8) (2.50 g) obtained in Synthetic Example 8 and dissolved by stirring at 70 占 폚 for 24 hours. To this solution, a 10% by mass NEP solution of L1 (1.75 g) and PB (11.8 g) were added and the mixture was stirred at 50 占 폚 for 15 hours. Thereafter, S2 (0.125 g) was added and stirred at 25 占 폚 for 6 hours to obtain a liquid crystal alignment treating agent (11). No abnormality such as turbidity or precipitation was observed in this liquid crystal alignment treatment agent, and it was confirmed that the solution was a homogeneous solution.

&Lt; Example 12 &gt;

NMP (19.6 g) was added to the polyimide powder (9) (2.50 g) obtained in Synthesis Example 9 and dissolved by stirring at 70 占 폚 for 24 hours. To this solution was added an NMP solution (2.50 g) of 10% by mass of L1, BCS (7.83 g) and PB (11.8 g), and the mixture was stirred at 50 占 폚 for 15 hours. Thereafter, S1 (0.25 g) was added and stirred at 25 占 폚 for 6 hours to obtain a liquid crystal alignment treatment agent (12). No abnormality such as turbidity or precipitation was observed in this liquid crystal alignment treatment agent, and it was confirmed that the solution was a homogeneous solution.

&Lt; Example 13 &gt;

NEP (23.5 g) was added to the polyimide powder (10) (2.50 g) obtained in Synthesis Example 10 and dissolved by stirring at 70 占 폚 for 24 hours. To this solution, 10% by mass of NEP solution of L1 (3.00 g), BCS (7.83 g) and PB (7.83 g) were added and the mixture was stirred at 50 占 폚 for 15 hours. Thereafter, S2 (0.175 g) was added and stirred at 25 占 폚 for 6 hours to obtain a liquid crystal alignment treatment agent (13). No abnormality such as turbidity or precipitation was observed in this liquid crystal alignment treatment agent, and it was confirmed that the solution was a homogeneous solution.

&Lt; Example 14 &gt;

NEP (23.5 g) was added to the polyimide powder (11) (2.50 g) obtained in Synthesis Example 11 and dissolved by stirring at 70 占 폚 for 24 hours. To this solution was added a 10% by mass NEP solution (1.25 g) of L2, BCS (7.83 g) and PB (7.83 g), and the mixture was stirred at 50 占 폚 for 15 hours. Thereafter, S2 (0.175 g) was added and stirred at 25 캜 for 6 hours to obtain a liquid crystal alignment treatment agent 14. No abnormality such as turbidity or precipitation was observed in this liquid crystal alignment treatment agent, and it was confirmed that the solution was a homogeneous solution.

&Lt; Comparative Example 1 &

NMP (7.83 g) and? -BL (23.5 g) were added to the polyimide powder (1) (2.50 g) obtained in Synthesis Example 1 and dissolved by stirring at 70 占 폚 for 24 hours. To this solution, BCS (7.83 g) was added and stirred at 25 占 폚 for 6 hours to obtain a liquid crystal alignment treatment agent (15). No abnormality such as turbidity or precipitation was observed in this liquid crystal alignment treatment agent, and it was confirmed that the solution was a homogeneous solution.

&Lt; Comparative Example 2 &

NMP (7.83 g) and? -BL (23.5 g) were added to the polyimide powder (1) (2.50 g) obtained in Synthesis Example 1 and dissolved by stirring at 70 占 폚 for 24 hours. To this solution, S1 (0.25 g) and BCS (7.83 g) were added and stirred at 25 占 폚 for 6 hours to obtain a liquid crystal alignment treatment agent 16. No abnormality such as turbidity or precipitation was observed in this liquid crystal alignment treatment agent, and it was confirmed that the solution was a homogeneous solution.

&Lt; Comparative Example 3 &

NMP (7.83 g) and? -BL (23.5 g) were added to the polyimide powder (1) (2.50 g) obtained in Synthesis Example 1 and dissolved by stirring at 70 占 폚 for 24 hours. To this solution, a 10 mass% NMP solution of L1 (1.25 g) and BCS (7.83 g) were added and stirred at 50 占 폚 for 15 hours to obtain a liquid crystal alignment treatment agent 17. No abnormality such as turbidity or precipitation was observed in this liquid crystal alignment treatment agent, and it was confirmed that the solution was a homogeneous solution.

&Lt; Comparative Example 4 &

NEP (23.5 g) was added to the polyimide powder (3) (2.50 g) obtained in Synthesis Example 3 and dissolved by stirring at 70 占 폚 for 24 hours. To this solution, BCS (3.92 g) and PB (11.8 g) were added and stirred at 25 占 폚 for 6 hours to obtain a liquid crystal alignment treatment agent (18). No abnormality such as turbidity or precipitation was observed in this liquid crystal alignment treatment agent, and it was confirmed that the solution was a homogeneous solution.

&Lt; Comparative Example 5 &

NEP (23.5 g) was added to the polyimide powder (3) (2.50 g) obtained in Synthesis Example 3 and dissolved by stirring at 70 占 폚 for 24 hours. To this solution, S1 (0.25 g), BCS (3.92 g) and PB (11.8 g) were added and stirred at 25 占 폚 for 6 hours to obtain a liquid crystal alignment treatment agent (19). No abnormality such as turbidity or precipitation was observed in this liquid crystal alignment treatment agent, and it was confirmed that the solution was a homogeneous solution.

&Lt; Comparative Example 6 &gt;

NEP (23.5 g) was added to the polyimide powder (3) (2.50 g) obtained in Synthesis Example 3 and dissolved by stirring at 70 占 폚 for 24 hours. To this solution was added a NEP solution (1.25 g) of L1% by mass, BCS (3.92 g) and PB (11.8 g) and the mixture was stirred at 50 占 폚 for 15 hours to obtain a liquid crystal alignment treating agent 20. No abnormality such as turbidity or precipitation was observed in this liquid crystal alignment treatment agent, and it was confirmed that the solution was a homogeneous solution.

* 1: Represents the amount (parts by mass) of the specific compound introduced into 100 parts by mass of the polyimide polymer.

* 2: The amount (parts by mass) of the specific amine compound introduced into 100 parts by mass of the polyimide-based polymer.

* 3: Represents the proportion of the polyimide polymer in the liquid crystal alignment treatment agent.

* 1: Disturbance of liquid crystal alignability was observed in the vicinity of the sealant among the liquid crystal cells.

* 2: Disordering of liquid crystal alignability was observed from the liquid crystal cell up to the width of 0.3 cm from the sealant. (* 1 shows a wider view of disorder of liquid crystal orientation).

* 3: Disordering of the liquid crystal alignability was observed from the liquid crystal cell to the area of the width from the sealant to 0.6 cm (* 2 is more widespread than that of the liquid crystal alignment).

As can be seen from the above results, the liquid crystal alignment treatment agent of the example of the present invention can suppress the decrease of the voltage holding ratio even when the liquid crystal cell is irradiated with ultraviolet rays, as compared with the liquid crystal alignment treatment agent of the comparative example. In addition, even when the liquid crystal cell was stored in a high-temperature and high-humidity bath for a long time, no disturbance of liquid crystal orientation was observed near the sealant. That is, the liquid crystal alignment treatment agent of the present invention is capable of suppressing a decrease in the voltage holding ratio even after exposure to light for a long time and suppressing occurrence of display unevenness near the frame of the liquid crystal display element under high temperature and high humidity conditions. And becomes an alignment film.

Specifically, in the comparative examples of the liquid crystal alignment treatment agent using the specific compound, the specific amine compound and the specific polyimide polymer in the present invention, and the liquid crystal alignment treatment agent not using the specific compound and the specific amine compound, The liquid crystal alignment treatment agent of the comparative example was inferior in the above characteristics. More specifically, the comparison between Example 1 and Comparative Example 1 and the comparison between Example 3 and Comparative Example 4 are made.

It was also found that the comparative example of the liquid crystal alignment treatment agent which was used only for either one of the specific compound or the specific amine compound had inferior properties as compared with the examples. More specifically, the comparison between Example 1 and Comparative Example 2 or Comparative Example 3 and the comparison between Example 3 and Comparative Example 5 or Comparative Example 6 are made.

In addition, in the specific side chain structure of the present invention, the liquid crystal alignment treatment agent using the specific side chain type diamine compound having the specific side chain structure of the formula [2-1] Compared with the liquid crystal alignment treatment agent using a diamine compound having a chain structure, even when the liquid crystal cell was stored in a high temperature and high humidity chamber for a long time in the accelerated test, no disturbance of liquid crystal alignability was observed near the sealant. More specifically, it is a comparison between Example 8 and Example 9 in the comparison under the same conditions in the emphasis test.

Industrial availability

INDUSTRIAL APPLICABILITY The liquid crystal alignment treatment agent of the present invention can suppress deterioration of the voltage holding ratio even after exposure to light for a long period of time and enhance adhesiveness between the sealant and the liquid crystal alignment film and to provide a display near the frame of the liquid crystal display element It is possible to provide a liquid crystal alignment film capable of suppressing occurrence of unevenness. In addition, it is possible to provide a liquid crystal display element having the above liquid crystal alignment film, and a liquid crystal alignment treatment agent capable of providing the above liquid crystal alignment film.

Therefore, the liquid crystal display element having the liquid crystal alignment film obtained from the liquid crystal alignment treatment agent of the present invention has excellent reliability and can be suitably used for a large-sized, high-definition liquid crystal television or the like. The TN element, the STN element, the TFT liquid crystal element, And is useful for an alignment type liquid crystal display element.

Further, the liquid crystal alignment film obtained from the liquid crystal alignment treatment agent of the present invention is also useful for a liquid crystal display element which needs to irradiate ultraviolet rays when a liquid crystal display element is manufactured. That is, a liquid crystal composition comprising a liquid crystal layer between a pair of substrates provided with electrodes, and 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 manufactured through a process of polymerizing the polymerizable compound while applying a voltage between the electrodes, and further, a liquid crystal layer is provided between a pair of substrates provided with electrodes, A liquid crystal alignment film comprising a polymerizable group polymerizing at least one of an active energy ray and a heat is disposed on a substrate and a polymerizable group is polymerized while a voltage is applied between the electrodes.

Claims (22)

A liquid crystal alignment treatment agent comprising the following components (A), (B) and (C).
Component (A): Heteropoly acid.
Component (B): Polymer.
(C): a compound having a nitrogen-containing aromatic heterocyclic ring in its molecule. The method according to claim 1,
Wherein the heteropoly acid is at least one selected from the group consisting of molybdic acid, silicomolybdic acid, tungstic acid, tungstic acid, and tungstomolybdic acid. 3. The method according to claim 1 or 2,
Wherein the polymer is at least one selected from the group consisting of acrylic polymer, methacrylic polymer, novolac resin, polyhydroxystyrene, polyimide precursor, polyimide, polyamide, polyester, cellulose and polysiloxane. The method of claim 3,
Wherein the polymer is a polyimide precursor obtained by reacting a diamine component and a tetracarboxylic acid component, or a polyimide precursor obtained by imidizing the polyimide precursor. 5. The method of claim 4,
Wherein the diamine component comprises a diamine compound having a side chain structure represented by the following formula [2-1] or [2-2].
[Chemical Formula 1]

(Wherein Y ¹ is a single bond, - (CH ₂ ) _a - (a is an integer of 1 to 15), -O-, -CH ₂ O-, -CONH-, -NHCO-, -CON (CH ₃ ) , -N (CH ₃₎ CO-, shows a coupler of at least one member selected from the group consisting of -COO- and -OCO- Y ² represents a single bond or _{-. (CH 2) b -} (b is 1 to 15 Y ³ represents a single bond, - (CH ₂ ) _c - (c is an integer of 1 to 15), -O-, -CH ₂ O-, -COO- and -OCO- Y ⁴ represents at least one divalent cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring and a heterocyclic ring, or a divalent organic group having a carbon number of 17 to 51 having a steroid skeleton And any hydrogen atom on the cyclic group may be substituted with an alkyl group having 1 to 3 carbon atoms, an alkoxyl group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluoro-containing alkoxyl group having 1 to 3 carbon atoms, Became Y ⁵ represents at least one cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring and a heterocyclic ring, and any hydrogen atom on these cyclic groups may be substituted with an alkyl group having 1 to 3 carbon atoms, an alkyl group having 1 to 3 carbon atoms , A fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxyl group having 1 to 3 carbon atoms, or a fluorine atom, n represents an integer of 0 to 4. Y ⁶ represents an alkyl group having 1 to 18 carbon atoms, At least one member selected from the group consisting of an alkenyl group having 2 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxyl group having 1 to 18 carbon atoms, and a fluorinated alkoxyl group having 1 to 18 carbon atoms.
(2)

(Y ⁷ represents a single bond, -O-, -CH ₂ O-, -CONH-, -NHCO-, -CON (CH ₃ ) -, -N (CH ₃ ) CO-, -COO- and -OCO- And Y ⁸ represents an alkyl group having 8 to 18 carbon atoms or a fluorine-containing alkyl group having 6 to 18 carbon atoms. 6. The method of claim 5,
Wherein the diamine compound is represented by the following formula [2a].
(3)

(Y represents a structure represented by the above formula [2-1] or formula [2-2], and n1 represents an integer of 1 to 4.) 7. The method according to any one of claims 4 to 6,
Wherein the tetracarboxylic acid component comprises a tetracarboxylic acid dianhydride represented by the following formula [3].
[Chemical Formula 4]

(Z represents at least one structure selected from the group consisting of the structures represented by the following formulas [3a] to [3k]).
[Chemical Formula 5]

(Z ¹ to Z ⁴ each independently represent at least one member 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 method according to any one of claims 1 to 7,
Wherein the compound of the component (C) is an amine compound having one primary amino group and one nitrogen-containing aromatic heterocyclic ring in the molecule and the primary amino group is bonded to an aliphatic hydrocarbon group or a non-aromatic cyclic hydrocarbon group, Treatment agent. 9. The method of claim 8,
Wherein the amine compound is represented by the following formula [4a-1].
[Chemical Formula 6]

(S ¹ represents a divalent organic group having an aliphatic hydrocarbon group or a non-aromatic cyclic hydrocarbon group, and S ² represents a nitrogen-containing heterocyclic ring.) 9. The method of claim 8,
Wherein the amine compound is represented by the following formula [4a-2].
(7)

(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 the sum of the carbon atoms of S ³ and S ⁴ is 1 to 20. S ⁵ represents a nitrogen-containing heterocyclic ring. 11. The method of claim 10,
And S ³ , S ⁴ and S ⁵ in the amine compound represented by the formula [4a-2] each represent a combination selected from the groups or rings described below.
Wherein S ³ is a linear 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 cycloheptane ring, a cyclooctane ring, A cycloheptadecane ring, a cycloheptadecane ring, a cyclooctadecane ring, a cyclododecane ring, a cyclododecane ring, a cyclotetradecane ring, a cyclotetradecane ring, a cyclopentadecane ring, a cyclohexadecane ring, a cycloheptadecane ring, A ring selected from the group consisting of a ring, a cyclic acid ring, a tricycloicoic acid ring, a tricyclodecanoic acid ring, a bicycloheptane ring, a decahydronaphthalene ring, a norbornene ring and an adamantane ring;
S ⁴ represents a single bond, -O-, -NH-, -S-, -SO ₂ -, a hydrocarbon group of 1 to 19 carbon atoms, -CO-O-, -O-CO-, -CO- _{-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-, a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, A cycloheptadecane ring, a cycloheptadecane ring, a cycloheptadecane ring, a cycloheptadecane ring, a cyclohexadecane ring, a cyclohexadecane ring, a cycloheptane ring, a cycloheptane ring, a cycloheptane ring, a cycloheptane ring, , A cyclooctadecane ring, a cyclononadecane ring, a cyclooic acid ring, a tricycloicoic acid ring, a tricyclodecanoic acid ring, a bicycloheptane ring, a decahydronaphthalene ring, a norbornene ring, an adamantane ring, a benzene ring , A naphthalene ring, a tetrahydronaphthalene ring, azulene A thiazole ring, a pyrazole ring, a pyridine ring, a pyrimidine ring, a quinoline ring, a pyrazine ring, an imidazole ring, an imidazole ring, an imidazole ring, a thiazole ring, A carbazole ring, a pyridine ring, a thiadiazole ring, a pyridazine ring, a triazine ring, a pyrazolidine ring, a triazole ring, a pyrazine ring, a benzimidazole ring, a benzoimidazole ring, a quinoxaline ring, An oxadiazole ring, an oxidine ring, a piperazine ring, a piperidine ring, a dioxane ring, an oxadiazole ring, an oxadiazole ring, an oxadiazole ring, an oxidine ring, an oxazole ring, a piperazine ring, A ring and a morpholine ring;
S ⁵ is selected from the group consisting of pyrrole ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, pyridine ring, pyrimidine ring, quinoline ring, pyrazoline ring, A pyrimidine ring, a pyrimidine ring, a phenanthroline ring, a phenanthroline ring, an indole ring, a quinoxaline ring, a pyrimidine ring, a pyrazoline ring, a pyrazoline ring, a triazine ring, a pyrazolidine ring, a triazole ring, A benzothiazole ring, a phenothiazine ring, an oxadiazole ring, and an acridine ring. 12. The method according to any one of claims 1 to 11,
A liquid crystal alignment treatment agent obtained by mixing a solvent containing the component (B) and the component (C) under heating. 13. The method according to any one of claims 1 to 12,
Wherein the liquid crystal alignment treatment agent contains at least one solvent selected from the group consisting of N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone and? -Butyrolactone. 14. The method according to any one of claims 1 to 13,
Wherein the liquid crystal alignment treating agent is at least one compound selected from the group consisting of 1-hexanol, cyclohexanol, 1,2-ethanediol, 1,2-propanediol, propylene glycol monobutyl ether, ethylene glycol monobutyl ether, dipropylene glycol dimethyl ether, And at least one solvent selected from the group consisting of solvents represented by the formulas [D1] to [D3].
[Chemical Formula 8]

(D ¹ represents an alkyl group having 1 to 3 carbon atoms, D ² represents an alkyl group having 1 to 3 carbon atoms, and D ³ represents an alkyl group having 1 to 4 carbon atoms.) 15. The method according to any one of claims 1 to 14,
Wherein the liquid crystal alignment treating agent is a crosslinkable compound selected from the group consisting of an epoxy group, an isocyanate group, an oxetane group and a cyclocarbonate group, a crosslinkable compound selected from the group consisting of a hydroxyl group, A compound, or a crosslinkable compound having a polymerizable unsaturated bonding group. A liquid crystal alignment film obtained from the liquid crystal alignment treatment agent according to any one of claims 1 to 15. A liquid crystal alignment film obtained by applying the liquid crystal alignment treatment agent according to any one of claims 1 to 15 by an ink jet method. A liquid crystal display element having the liquid crystal alignment film according to claim 16 or 17. 18. The method according to claim 16 or 17,
A liquid crystal composition comprising a liquid crystal layer between a pair of substrates provided with electrodes and comprising a polymerizable compound polymerized by at least one of active energy rays and heat is disposed between the pair of substrates, Wherein the polymerizable compound is used in a liquid crystal display device manufactured through a process of polymerizing the polymerizable compound while applying a voltage between the polymerizable compound and the polymerizable compound. A liquid crystal display element having the liquid crystal alignment film according to claim 19. 18. The method according to claim 16 or 17,
A liquid crystal alignment film comprising a liquid crystal layer between a pair of substrates provided with electrodes and including a polymerizable group polymerized by at least one of active energy rays and heat is disposed between the pair of substrates, Wherein the liquid crystal alignment film is used for a liquid crystal display device manufactured through a process of polymerizing the polymerizable group while applying a voltage. A liquid crystal display element having the liquid crystal alignment film according to claim 21.