TW201634589A - Liquid crystal alignment treatment agent, liquid crystal alignment film, and liquid crystal display element - Google Patents

Abstract

Disclosed is a liquid crystal alignment treatment agent comprising the following components (A), (B), and (C), wherein the component (A) is a heteropoly acid, the component (B) is a polymer, and the component (C) is a compound that includes a nitrogen-containing aromatic heterocycle in the molecule thereof.

Description

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

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

The liquid crystal display element is a display device which can realize a thin type and a light weight, and is currently widely used. In general, in the liquid crystal display device, a liquid crystal alignment film is often used in order to determine the alignment state of the liquid crystal.

With the high definition of the liquid crystal display element, the viewpoint of suppressing the decrease in contrast of the liquid crystal display element or reducing the afterimage phenomenon, and even in the liquid crystal alignment film used therein, a high voltage holding ratio is sought. In this regard, it is known to use a compound containing a very small amount of a compound containing a carboxylic acid group in a molecule other than polyacrylic acid or a ruthenium imidized polymer thereof, and a compound having a carboxylic acid anhydride group in the molecule. And a liquid crystal alignment treatment agent of a compound selected from a compound having one tertiary amino group in the molecule (for example, refer to Patent Document 1).

Further, with the high definition of the liquid crystal display element, it has been sought to suppress the decrease in the contrast of the liquid crystal display element or the long-term use. Problems such as poor display. In order to improve the liquid crystal alignment property and reduce the problem of poor display in the peripheral portion of the liquid crystal display screen, it has been proposed to use an alkoxydecane compound in the liquid crystal alignment film using polyimine. A proposal of a liquid crystal alignment film of a liquid crystal alignment agent (for example, refer to Patent Document 2 or Patent Document 3).

[Previous Technical Literature] [Patent Literature]

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

[Patent Document 2] JP-A-61-171762

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

With the recent increase in the performance of liquid crystal display elements, liquid crystal display elements are often used in large-screen and high-definition liquid crystal televisions, or in automotive applications such as car navigation systems or odometer plates. In these applications, for the purpose of obtaining high brightness, etc., there is a case where a backlight having a large amount of heat is required to be used. Therefore, in the liquid crystal alignment film, from the other viewpoints, high reliability is sought, that is, there is a requirement for high stability of light generated by the backlight. In particular, when the voltage holding ratio, which is one of the electrical characteristics of the liquid crystal display element, is lowered by the light generated by the backlight, the residual image of the liquid crystal display element is likely to be defective. A poor (also known as linear afterimage) phenomenon, and a liquid crystal display element having high reliability cannot be obtained. Therefore, in the liquid crystal alignment film, in addition to the initial characteristics, it is necessary to improve the voltage holding ratio, for example, after exposure to light for a long period of time.

Moreover, in portable applications such as smart phones and mobile phones, the use environment becomes more severe when compared with the past. That is, in addition to the room temperature and low humidity environment so far, there are cases where it is used under high temperature and high humidity. In the use of these high-temperature and high-humidity conditions, since water is easily mixed between the liquid crystal display element sealing agent and the liquid crystal alignment film, there is a problem that display spots and the like are likely to occur in the vicinity of the fore edge of the liquid crystal display element. Therefore, there is a need for a situation in which such display defects do not occur even under high temperature and high humidity conditions.

Accordingly, the present invention has an object of providing 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 which can suppress a decrease in voltage holding ratio after exposure to light for a long period of time. Further, even under conditions of high temperature and high humidity, the liquid crystal alignment film which displays spots is not generated in the vicinity of the forefront of the liquid crystal display element.

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

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

That is, the present invention is the one having the following requirements.

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

(A) Ingredients: heteropoly acid.

(B) Ingredients: Polymer.

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

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

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

(4) The liquid crystal alignment treatment agent according to the above (3), wherein the polymer is a polyimine precursor obtained by reacting a diamine component with a tetracarboxylic acid component or the polyimine precursor Polyimine obtained by imidization of hydrazine.

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

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

[Chemical 2]-Y ⁷ -Y ⁸ [2-2]

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

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

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

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

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

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

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

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

[Chemical 6] H ₂ NS ¹ -S ² [4a-1]

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

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

[Chemical 7] H ₂ NS ³ -S ⁴ -S ⁵ [4a-2]

(S ³ represents an aliphatic hydrocarbon group or a non-aromatic cyclic hydrocarbon group having 1 to 10 carbon atoms. S ⁴ represents a single bond, -O-, -NH-, -S-, -SO ₂ - and a carbon number of 1 to 19 At least one selected from the group consisting of two organic groups, the total of the carbon atoms of S ³ and S ⁴ is from 1 to 20. S ⁵ represents a nitrogen-containing heterocyclic ring.

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

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, Cycloheptane ring, cyclooctane ring, cyclodecane ring, cyclodecane ring, cycloundecyl ring, cyclododecane ring, cyclotridecane ring, cyclotetradecane ring, cyclopentadecane ring, ring Hexadecane ring, cycloheptadecane ring, cyclooctadecane ring, cyclodecadecane ring, icosene ring, eicosene ring, tricyclododecane (docosane) a selected one selected from the group consisting of a ring, a bicycloheptane ring, a decahydronaphthalene ring, a norbornene ring, and an adamantane ring; and S ⁴ is a single bond, -O-, -NH-, -S -, -SO ₂ -, a hydrocarbon group having 1 to 19 carbon atoms, -CO-O-, -O-CO-, -CO-NH-, -NH-CO-, -CO-, -CF ₂ -, -C (CF ₃ ) ₂ -, -CH(OH)-, -C(CH ₃ ) ₂ -, -Si(CH ₃ ) ₂ -, -O-Si(CH ₃ ) ₂ -, -Si(CH ₃ ) ₂ -O-, -O-Si(CH ₃ ) ₂ -O-, cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, ring anthracene ring, Cyclodecane ring, cycloundecane ring, cyclododecane ring, cyclotridecane ring, cyclotetradecane ring, cyclopentadecane , cyclohexadecane ring, cycloheptadecane ring, cyclooctadecane ring, cyclodecadecane ring, icosene ring, eicosene ring, tricyclododecane (docosane) ring, bicycloheptane ring, decahydronaphthalene ring, norbornene ring, adamantane ring, benzene ring, naphthalene ring, tetrahydronaphthalene ring, anthracene ring, anthracene ring, anthracene ring, anthracene ring, phenanthrene ring , anthracene ring, pyrrole ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, pyridine ring, pyrimidine ring, quinoline ring, pyrazoline ring, isoquinoline ring, indazole ring, anthracene ring, thiadipine Oxazole ring Ring, three Ring, pyrazolidine ring, triazole ring, pyridyl Ring, benzimidazole ring, benzoimidazole ring, cinnoline ring, phenanthroline ring, anthracene ring, quinoxaline ring, benzothiazole ring, brown Thio (phenothiazine) ring, oxazole ring, acridine ring, oxazole ring, piperazine ring, piperidine ring, dioxane ring and morpholine (morpholine) ring selected by the group; S ⁵ is By pyrrole ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, pyridine ring, pyrimidine ring, quinoline ring, pyrazoline ring, isoquinoline ring, indazole ring, anthracene ring, thiadiazole ring ,despair Ring, pyrazoline ring, three Ring, pyrazolidine ring, triazole ring, pyridyl Ring, benzimidazole ring, benzimidazole ring, octyl ring, phenanthroline ring, anthracene ring, quinoxaline ring, benzothiazole ring, phenothiazine (phenothiazine) one selected from the group consisting of a ring, an oxazole ring, and an acridine ring.

(12) The liquid crystal alignment treatment agent according to any one of the above (1), wherein the solvent containing the component (B) and the component (C) is mixed under heating.

The liquid crystal alignment treatment agent according to any one of the above-mentioned (1), wherein the liquid crystal alignment treatment agent contains N-methyl-2-pyrrolidone and N-B. A solvent selected from the group consisting of phenyl-2-pyrrolidone and γ-butyrolactone.

The liquid crystal alignment treatment agent according to any one of the above-mentioned (1), wherein the liquid crystal alignment treatment agent contains 1-hexanol, cyclohexanol, 1,2-B. Alkanediol, 1,2-propanediol, propylene glycol monobutyl ether, ethylene glycol monobutyl ether, dipropylene glycol dimethyl ether, and a group of solvents represented by the following formula [D1]~[D3] are selected At least one solvent.

(D ¹ represents an alkyl group having 1 to 3 carbon atoms of .D ² represents an alkyl group having a carbon number of 1 to 3, II.D ³ represents an alkyl group having 1 to 4 carbon atoms of).

The liquid crystal alignment treatment agent according to any one of the above-mentioned (1), wherein the liquid crystal alignment treatment agent is contained a crosslinkable compound selected from the group consisting of an epoxy group, an isocyanate group, an oxypropylene group and a cyclic carbonate group, and a hydroxyl group, a hydroxyalkyl group and an alkoxyalkyl group having 1 to 3 carbon atoms; A cross-linking compound selected from the group, or a cross-linking compound having a polymerizable unsaturated bond group.

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

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

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

(19) The liquid crystal alignment film according to the above (16) or (17), wherein the liquid crystal alignment layer is provided between the pair of substrates, and the active energy ray is disposed between the pair of substrates. A liquid crystal display device obtained by a step of polymerizing the polymerizable compound by applying a voltage between the electrodes by a liquid crystal composition of a polymerizable compound polymerized by at least one of heat.

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

(21) The liquid crystal alignment film according to the above (16) or (17), wherein the liquid crystal alignment layer is provided between the pair of substrates, and the active energy ray is disposed between the pair of substrates. a polymerizable group of liquid crystal alignment films polymerized by at least one of heat, and passed through the front A liquid crystal display element obtained by applying a voltage between electrodes and polymerizing the polymerizable group.

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

In the liquid crystal alignment treatment agent containing two specific compounds and polymers of the present invention, a liquid crystal alignment film which can suppress a decrease in voltage holding ratio even after exposure to light for a long period of time can be obtained. Further, even under conditions of high temperature and high humidity, a liquid crystal alignment film which displays spots is not generated in the vicinity of the fore edge of the liquid crystal display element.

In the present invention, the mechanism of action for obtaining a liquid crystal display element having the above-described excellent characteristics is not completely understood, but it is presumed to be as follows.

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

(A) Ingredients: Heteropolyacids (also known as specific compounds).

(B) Ingredients: Polymer.

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

The effect of a specific compound is as follows. One of the main causes of the decrease in the voltage holding ratio is that most of the ionic impurities are present in the liquid crystal. For this, it is speculated that the liquid crystal display element is exposed to a long time. In the case where the liquid crystal is decomposed by light irradiation, the ionic impurity component generated at this time is adsorbed by the specific compound, and the decrease in the voltage holding ratio can be suppressed. Further, a compound having a nitrogen-containing aromatic heterocyclic ring in the molecule is estimated to further enhance the above effects based on the nitrogen-containing aromatic heterocyclic ring contained in the structure.

Further, in the polymer, a polyimine precursor obtained by reacting a diamine component with a tetracarboxylic acid component or a polyimine obtained by hydrazine imidation of the polyimine precursor is used. In the diamine component, a diamine compound having a structure represented by the above formula [2-1] or formula [2-2] is used, and it is used in a vertical VA (Vertical Alignment) mode, PSA (Polymer Sustained Alignment). In the case of the liquid crystal display element of the mode and the SC-PVA mode, in particular, since the structure shown in the formula [2-1] is a rigid structure, the liquid crystal display element having the liquid crystal alignment film having the structure is used, and the light such as ultraviolet rays is stabilized. It can suppress the decrease of the voltage holding ratio and the generation of ionic impurities.

In addition, the liquid crystal display element having the liquid crystal alignment film obtained by the liquid crystal alignment treatment agent of the present invention has excellent reliability and can be applied to a liquid crystal television having a large screen and high definition. In particular, when a liquid crystal display element is produced, it is useful for a liquid crystal display element using a PSA mode or an SC-PVA mode that emits high-energy ultraviolet rays.

[Formation of the Invention] <specific compound>

The specific compound in the present invention is a heteropolyacid.

The heteropoly acid, which is represented by the chemical structure of the Dawson type represented by the Keggin type or the formula [1-2] represented by the following formula [1-1], has a structure in which a hetero atom is located at the center of the molecule, and An isopoly acid of an oxo acid such as vanadium (V), molybdenum (Mo) or tungsten (W), and a polyacid obtained by condensing an oxyacid of a different element. Examples of the oxyacids of the different elements include argon (Si), phosphorus (P), and arsenic (As) oxyacids.

Specific examples of the heteropoly acid compound include, for example, phosphomolybdic acid, decyl molybdate, phosphotungstic acid, lanthanum tungstic acid or phosphotungstic acid. In the present invention, those using these components are preferred. Moreover, these may be used alone or in combination of two or more types. Further, the heteropoly acid compound in the present invention can be obtained as a commercially available product, or can be synthesized by a known method.

In the quantitative analysis such as elemental analysis, the number of elements known from the structure represented by the general formula may be obtained by commercially available articles, or may be appropriately synthesized by a known synthesis method. Both can be used in the present invention.

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

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

In the quantitative analysis, whether the number of P (phosphorus), O (oxygen), or W (tungsten) or Mo (molybdenum) in the formula is more or less, it is commercially available. The article method acquirer, or a person who is appropriately synthesized by a known synthesis method, can be used in the present invention. In this case, the mass of the heteropoly acid specified in the present invention means not only the quality of the pure phosphotungstic acid in the composition or the commercial product (the content of the phosphotungstic acid) but also the form obtained by the commercially available article. It is also possible to know the full mass in the state of the synthetic method, including the state of hydrated water or other impurities.

<polymer>

The polymer of the present invention is an acrylic polymer, a methacrylic polymer, a novolak resin, a polyhydroxystyrene, a polyimine precursor, a polyimine, a polyamide, a polyester, a cellulose, and a poly Preferably, at least one polymer selected from the group consisting of siloxanes is preferred. Preferred are polyamidiene precursors, polyimine or polyoxyalkylene. Particularly preferred are polyamidene precursors or polyimines (also collectively referred to as specific polyimine polymers).

<Specific Polyimine Polymer>

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

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

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

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

The specific polyimine-based polymer is obtained by using a tetracarboxylic dianhydride represented by the following formula [B] and a diamine represented by the following formula [C] as a raw material, and can be obtained in a simple manner. Preferably, the polyaminic acid consisting of the structural formula of the repeating unit represented by the following formula [D] or the polyimine obtained by imidating the polyamic acid with hydrazine is preferred. Among them, in the present invention, from the viewpoint of the physical and chemical stability of the liquid crystal alignment film, it is preferred that the polyimine precursor is ruthenium imidized.

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

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

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

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

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

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

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

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

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

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

Y ⁶ , an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 18 carbon atoms or a carbon number of 1 to 10 A fluoroalkoxy group is preferred. More preferably, it is an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 18 carbon atoms or an alkoxy group having 1 to 12 carbon atoms. Particularly preferred are an alkyl group having 1 to 9 carbon atoms, an alkenyl group having 2 to 12 carbon atoms or an alkoxy group having 1 to 9 carbon atoms.

n, from the viewpoint of availability of raw materials or easy synthesis, preferably from 0 to 3, preferably from 0 to 2.

A preferred combination of Y ¹ , Y ² , Y ³ , Y ⁴ , Y ⁵ , Y ⁶ and n is, for example, Table 6 of pages 13 to 34 of International Publication WO2011/132751 (2011.10.27). (2-1) to (2-629) disclosed in Table 47 are the same combinations. Further, in the tables of the International Publications, Y ¹ to Y ⁶ in the present invention are denoted as Y1 to Y6, and therefore Y1 to Y6 are read as Y ¹ to Y ⁶ . Further, in (2-605) to (2-629) disclosed in the tables of the International Publications, the organic group having a carbon number of 17 to 51 having a cholesterol skeleton in the present invention is a carbon number which is indicated as having a cholesterol skeleton. The organic base of 12 to 25, therefore, has an organic group having a carbon number of 12 to 25 in the cholesterol skeleton, and should be interpreted as an organic group having a carbon number of 17 to 51 of a cholesterol skeleton.

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

[化15]-Y ⁷ -Y ⁸ [2-2]

In the formula [2-2], Y ⁷ and Y ⁸ are as defined above, and those of the following are preferred.

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

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

In the present invention, the viewpoint of obtaining the vertical alignment of the liquid crystal having high stability with respect to the specific side chain structure is preferable, and the structure represented by the formula [2-1] is preferable.

The diamine compound having a specific side chain structure is preferably a diamine compound (also referred to as a specific side chain type diamine compound) represented by the following formula [2a].

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

Further, the details and preferred combinations of Y ¹ , Y ² , Y ³ , Y ⁴ , Y ⁵ , Y ⁶ and n in the formula [2-1], as shown in the above formula [2-1] The details and preferred combinations of Y ⁷ and Y ^{8 in} the formula [2-2] include the contents of the above formula [2-2].

N1, it is easy to synthesize the viewpoint, and 1 is better.

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

(R ¹ represents at least one bonding group selected from the group consisting of -O-, -OCH ₂ -, -CH ₂ O-, -COOCH ₂ -, and -CH ₂ OCO-, respectively. R ² represents a linear or branched alkyl group having 1 to 18 carbon atoms, a linear or branched alkoxy group having 1 to 18 carbon atoms, a linear or branched fluorine-containing alkyl group having 1 to 18 carbon atoms, or carbon A linear or branched fluorine-containing alkoxy group of 1 to 18).

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

(R ⁵ represents -COO-, -OCO-, -CONH-, -NHCO-, -COOCH ₂ -, -CH ₂ OCO-, -CH ₂ O-, -OCH ₂ -, -CH ₂ -, - At least one bonding group selected from the group consisting of O- and -NH-. R ⁶ represents a fluorine group, a cyano group, a trifluoromethyl group, a nitro group, an azo group, a methyl group, an ethyl group, respectively. At least one selected from the group consisting of an ethoxy group and a hydroxy group.

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

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

(A ₄ represents a linear or branched alkyl group having 3 to 18 carbon atoms which may be substituted by a fluorine atom. A ₃ represents a 1,4-cyclohexylene group or a 1,4-phenylene group. A ₂ represents an oxygen atom. or -COO - * (wherein, with "*" key of bonding with A ₃ is a bond) .A ₁ represents an oxygen atom or -COO - * (wherein, with "*" key of bonding with the ( CH ₂ )a ₂ ) Bonding). Further, a ₁ represents an integer of 0 or 1. a ₂ represents an integer from 2 to 10. a ₃ represents an integer of 0 or 1.)

In the above formulas [2a-1] to [2a-31], preferred diamine compounds are of the formula [2a-1] to the formula [2a-6], the formula [2a-9] to the formula [2a-13] or the formula. [2a-22]~Form [2a-31].

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

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

The ratio of use of the specific diamine compound (2), particularly in the case of a liquid crystal display device of the VA mode, the PSA mode or the SC-PVA mode, is preferably 10 to 70 mol% based on the entire diamine component. Preferably, it is 20 to 70 mol%, and particularly preferably 20 to 60 mol%.

In addition, the specific side chain type diamine compound can be blended with a solubility of a specific polyimine-based polymer in a solvent, a liquid crystal alignment property as a liquid crystal alignment film, or an electrical property of a liquid crystal display element, etc. It is used in combination of two or more kinds.

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

As the diamine component of the specific polyimine-based polymer, for example, the following diamine compound (also referred to as another diamine compound) can be used.

Specifically, for example, 2,4-dimethyl-m-phenylenediamine, 2,6-diaminotoluene, m-phenylenediamine, p-phenylenediamine, 2,4 -diaminophenol, 3,5-diaminophenol, 3,5-diaminobenzyl alcohol, 2,4-diaminobenzyl alcohol, 4,6-diaminoresorcinol, 2,4 -diamine benzoic acid, 2,5-diamino benzoic acid or 3,5-diamino benzoic acid, 4,4'-diamine linkage Benzene, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 3,3'-dihydroxy -4,4'-diaminobiphenyl, 3,3'-dicarboxy-4,4'-diaminobiphenyl, 3,3'-difluoro-4,4'-biphenyl, 3,3 '-Trifluoromethyl-4,4'-diaminobiphenyl, 3,4'-diaminobiphenyl, 3,3'-diaminobiphenyl, 2,2'-diaminobiphenyl , 2,3'-diaminobiphenyl, 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane , 2,2'-diaminodiphenylmethane, 2,3'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether , 3,4'-diaminodiphenyl ether, 2,2'-diaminodiphenyl ether, 2,3'-diaminodiphenyl ether, 4,4'-sulfonyldiphenylamine, 3, 3'-sulfonyldiphenylamine, bis(4-aminophenyl)decane, bis(3-aminophenyl)decane, dimethyl-bis(4-aminophenyl)decane, dimethyl- Bis(3-aminophenyl)decane, 4,4'-thiodiphenylamine, 3,3'-thiodiphenylamine, 4,4'-diaminodiphenylamine, 3,3'-diaminodiphenylamine , 3,4'-diaminodiphenylamine, 2,2'-diaminodiphenyl Amine, 2,3'-diaminodiphenylamine, N-methyl(4,4'-diaminodiphenyl)amine, N-methyl(3,3'-diaminodiphenyl)amine , N-methyl (3,4'-diaminodiphenyl)amine, N-methyl (2,2'-diaminodiphenyl)amine, N-methyl (2,3'-di Aminodiphenyl)amine, 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 3,4'-diaminobenzophenone, 1,4 -diaminonaphthalene, 2,2'-diaminobenzophenone, 2,3'-diaminobenzophenone, 1,5-diaminonaphthalene, 1,6-diaminonaphthalene, 1,7-Diaminonaphthalene, 1,8-diaminonaphthalene, 2,5-diaminonaphthalene, 2,6-diaminonaphthalene, 2,7-diaminonaphthalene, 2,8-di Amino naphthalene, 1,2-bis(4-aminophenyl)ethane, 1,2-bis(3-aminophenyl)ethane, 1,3-bis(4-aminophenyl)propane , 1,3-bis(3-aminophenyl)propane, 1,4-bis(4-aminophenyl)butane, 1,4-double (3-aminophenyl)butane, bis(3,5-diethyl-4-aminophenyl)methane, 1,4-bis(4-aminophenoxy)benzene, 1,3- Bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenyl)benzene, 1,3-bis(4-aminophenyl)benzene, 1,4-bis(4- Aminobenzyl)benzene, 1,3-bis(4-aminophenoxy)benzene, 4,4'-[1,4-phenylenebis(methyl)diphenylamine, 4,4' - [1,3-phenylene bis(methyl))diphenylamine, 3,4'-[1,4-phenylenebis(methyl)diphenylamine, 3,4'-[1, 3-phenylphenylbis(methyl)diphenylamine, 3,3'-[1,4-phenylenebis(methyl)diphenylamine, 3,3'-[1,3-phenylene Bis(methyl)diphenylamine, 1,4-phenylphenylbis[(4-aminophenyl)methanone, 1,4-phenylphenylbis[(3-aminophenyl)methyl Ketone], 1,3-phenylene bis[(4-aminophenyl)methanone], 1,3-phenylene bis[(3-aminophenyl)methanone], 1,4-stretch Phenyl bis(4-aminobenzoate), 1,4-phenylene bis(3-aminobenzoate), 1,3-phenylene bis(4-aminobenzoate) ), 1,3-phenylene bis(3-aminobenzoate), bis(4-aminophenyl)terephthalate, bis(3-aminophenyl)terephthalic acid Acid ester, double (4- Aminophenyl)isophthalate, bis(3-aminophenyl)isophthalate, N,N'-(1,4-phenylene)bis(4-aminobenzoic acid) Indoleamine, N,N'-(1,3-phenylene)bis(4-aminobenzamide), N,N'-(1,4-phenylene)bis(3-amino Benzalamine, N,N'-(1,3-phenylene)bis(3-aminobenzamide), N,N'-bis(4-aminophenyl)terephthalene Amine, N,N'-bis(3-aminophenyl)terephthalamide, N,N'-bis(4-aminophenyl)isophthalamide, N,N'-bis (3 -aminophenyl)isophthalamide, 9,10-bis(4-aminophenyl)anthracene, 4,4'-bis(4-aminophenoxy)diphenylanthracene, 2,2 '-bis[4-(4-amino group) Phenoxy)phenyl]propane, 2,2'-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2,2'-bis(4-aminophenyl)hexafluoro Propane, 2,2'-bis(3-aminophenyl)hexafluoropropane, 2,2'-bis(3-amino-4-methylphenyl)hexafluoropropane, 2,2'-bis ( 4-aminophenyl)propane, 2,2'-bis(3-aminophenyl)propane, 2,2'-bis(3-amino-4-methylphenyl)propane, 1,3- Bis(4-aminophenoxy)propane, 1,3-bis(3-aminophenoxy)propane, 1,4-bis(4-aminophenoxy)butane, 1,4-double (3-Aminophenoxy)butane, 1,5-bis(4-aminophenoxy)pentane, 1,5-bis(3-aminophenoxy)pentane, 1,6- Bis(4-aminophenoxy)hexane, 1,6-bis(3-aminophenoxy)hexane, 1,7-bis(4-aminophenoxy)heptane, 1,7 - bis(3-aminophenoxy)heptane, 1,8-bis(4-aminophenoxy)octane, 1,8-bis(3-aminophenoxy)octane, 1, 9-bis(4-aminophenoxy)decane, 1,9-bis(3-aminophenoxy)decane, 1,10-bis(4-aminophenoxy)decane, 1 , 10-bis(3-aminophenoxy)decane, 1,11-bis(4-aminophenoxy)undecane, 1,11-bis(3-aminophenoxy) eleven Alkane, 1,12-bis(4-aminophenoxy) Dioxane, 1,12-bis(3-aminophenoxy)dodecane, bis(4-aminocyclohexyl)methane, bis(4-amino-3-methylcyclohexyl)methane, 1, 3-Diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8 - diaminooctane, 1,9-diaminodecane, 1,10-diaminodecane, 1,11-diaminoundecane or 1,12-diaminododecane.

Further, as the other diamine compound, for example, a diamine compound represented by the following formula [D1] to formula [DA15] can also be used.

(p represents an integer from 1 to 10).

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

Further, a diamine compound represented by the following formula [DA16] can also be used.

(A ¹ represents -O-, -NH-, -N(CH ₃ )-, -CONH-, -NHCO-, -CH ₂ O-, -OCO-, -CON(CH ₃ )-, and -N ( CH ₃ ) at least one selected from the group consisting of CO-. A ² represents a group selected from the group consisting of a single bond, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, a non-aromatic cyclic hydrocarbon group, and an aromatic hydrocarbon group. At least one. A ³ represents a single bond, -O-, -NH-, -N(CH ₃ )-, -CONH-, -NHCO-, -COO-, -OCO-, -CON(CH ₃ )- At least one selected from the group consisting of -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. p1 represents 1 An integer of ~4).

The other diamine compound may be one or more selected from the group consisting of a solubility of a specific polyimine-based polymer in a solvent, a liquid crystal alignment property as a liquid crystal alignment film, or an electrical property of a liquid crystal display device. Mixed use.

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

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

Z in the formula [3], in terms of easiness of synthesis or easiness of polymerization reactivity at the time of producing a polymer, etc., by the formula [3a], the formula [3c], the formula [3d], and the formula [3e] The structure represented by the formula [3f], the formula [3g] or the formula [3k] is preferred. Preferred is a structure represented by the formula [3a], the formula [3e], the formula [3f], the formula [3g] or the formula [3k]. Particularly preferred is a structure represented by the formula [3e], the formula [3f], the formula [3g] or the formula [3k].

The proportion of the specific tetracarboxylic acid component to be used is preferably 1 mol% or more based on the total tetracarboxylic acid component. Preferably, it is 5 mol% or more. It is particularly preferably 10 mol% or more, and the best one is to suppress the decrease in the voltage holding ratio caused by prolonged exposure to light irradiation, and examples thereof include 10 to 90 mol%.

Moreover, when the tetracarboxylic acid component of the structure represented by the above formula [3e], formula [3f], formula [3g] or formula [3k] is used, when the amount used is 20 mol% or more of the entire tetracarboxylic acid component, , you can get the desired effect. It is preferably 30 mol% or more. Further, all of the tetracarboxylic acid component may be a tetracarboxylic acid component having a structure represented by the formula [3e], the formula [3f], the formula [3g] or the formula [3k].

In the tetracarboxylic acid component of the present invention, other tetracarboxylic acids other than the specific tetracarboxylic acid component can be used without impairing the effects of the present invention. Ingredients.

Specifically, for example, pyromellitic acid, 2,3,6,7-naphthalenetetracarboxylic acid, 1,2,5,6-naphthalenetetracarboxylic acid, 1,4,5,8-naphthalenetetracarboxylic acid, 2,3,6,7-decanetetracarboxylic acid, 1,2,5,6-nonanedicarboxylic acid, 3,3',4,4'-biphenyltetracarboxylic acid, 2,3,3',4 '-Biphenyltetracarboxylic acid, bis(3,4-dicarboxyphenyl)ether, 3,3',4,4'-benzophenonetetracarboxylic acid, bis(3,4-dicarboxyphenyl) Bismuth, bis(3,4-dicarboxyphenyl)methane, 2,2-bis(3,4-dicarboxyphenyl)propane, 1,1,1,3,3,3-hexafluoro-2,2 - bis(3,4-dicarboxyphenyl)propane, bis(3,4-dicarboxyphenyl)dimethyl decane, bis(3,4-dicarboxyphenyl)diphenyl decane, 2,3, 4,5-pyridinetetracarboxylic acid, 2,6-bis(3,4-dicarboxyphenyl)pyridine, 3,3',4,4'-diphenylphosphonium tetracarboxylic acid, 3,4,9, 10-decanetetracarboxylic acid or 1,3-diphenyl-1,2,3,4-cyclobutanetetracarboxylic acid or the like.

The specific tetracarboxylic acid component and the other tetracarboxylic acid component may be blended with a solvent of a specific polyamidimide polymer, a liquid crystal alignment property as a liquid crystal alignment film, or an electrical property of a liquid crystal display element, etc. One type or two or more types are used in combination.

The method of producing a specific polyimine-based polymer is not particularly limited. It is usually prepared by reacting a diamine component with a tetracarboxylic acid component. In general, at least one tetracarboxylic acid component selected from the group consisting of a tetracarboxylic dianhydride and a derivative of a tetracarboxylic acid thereof, and a dicarboxylic acid component formed from one or more diamine compounds A method in which an amine component is reacted to obtain a polyamic acid. Specifically, for example, a method in which a tetracarboxylic dianhydride and a primary or secondary diamine compound are polycondensed to obtain a poly-proline can be used, and a tetracarboxylic acid and a primary or secondary diamine can be used. Compound dehydration condensation A method of producing a poly-proline by a reaction, or a method of producing a poly-proline by reacting a tetracarboxylic acid dihalide with a primary or secondary diamine compound.

In the method for producing a polyalkyl amide, a method of polycondensing a tetracarboxylic acid obtained by esterifying a carboxylic acid dialkyl with a primary or secondary diamine compound, and a carboxylic acid dialkyl ester can be used. A method of reacting a tetracarboxylic acid dihalide with a primary or secondary diamine compound, or a method of converting a carboxyl group of a polylysine to an ester.

In the method for producing a polyimine, for example, a method in which the polyamic acid or polyalkyl amide is ring-closed to form a polyimine can be used.

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

For example, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, γ-butyrolactone, N,N-dimethylformamide, N,N-dimethylacetamidine An amine, dimethyl hydrazine or 1,3-dimethyl-tetrahydroimidazolidone or the like. Further, in order to increase the solubility of the polyimide precursor in the solvent, methyl ethyl ketone, cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone or the following formula may be used. [D-1]~ a solvent represented by the formula [D-3].

(D ¹ represents an alkyl group having 1 to 3 carbon atoms of .D ² represents an alkyl group having a carbon number of 1 to 3, II.D ³ represents an alkyl group having 1 to 4 carbon atoms of).

These may be used singly or in combination. Further, even in the case where the solvent of the polyimide intermediate precursor is not dissolved, it may be used in combination with the above solvent as long as it does not precipitate in the range of the polyimide precursor. Further, the moisture in the organic solvent is a factor which hinders the polymerization reaction, and even causes the hydrolysis of the produced polyimide precursor, so that the organic solvent is preferably dried by dehydration.

When the diamine component and the tetracarboxylic acid component are reacted in an organic solvent, for example, a solution obtained by dispersing or dissolving a diamine component in an organic solvent may be mentioned, and a tetracarboxylic acid component may be added during stirring or dispersed. Or a method of dissolving in an organic solvent, a method of dissolving a tetracarboxylic acid component in an organic solvent, or a method of adding a diamine component to a dissolved solution, and a method of mutually adding a diamine component and a tetracarboxylic acid component Etc., any of these methods can be used. Further, the diamine component and the tetracarboxylic acid component are each reacted using a plurality of kinds, and the reaction may be carried out in a state of being mixed first, or may be carried out in sequence, or may be obtained by each reaction. It is also possible to carry out a mixed reaction of a low molecular weight body as a polymer. The polymerization temperature at this time can be selected at any temperature from -20 ° C to 150 ° C, preferably from -5 ° C to 100 ° C. Further, although the reaction can be carried out at any concentration, when the concentration is too low, it is difficult to obtain a polymer having a high molecular weight, and when the concentration is too high, It is not easy to perform uniform stirring because the viscosity of the reaction liquid is too high. Therefore, it is preferably from 1 to 50% by mass, more preferably from 5 to 30% by mass. It can also be used at a high concentration in the initial stage of the polymerization reaction, followed by addition of an organic solvent.

In the polymerization reaction of the polyimine precursor, the ratio of the total number of moles of the diamine component to the total number of moles of the tetracarboxylic acid component is preferably 0.8 to 1.2. It is the same as the usual polymerization reaction, and the closer the molar ratio is to 1.0, the larger the molecular weight of the produced polyimide intermediate precursor.

The polyimine is a polyimine obtained by subjecting the polyimine precursor to a ring closure, and the ring closure ratio (also referred to as the ruthenium imidation ratio) of the valine group is not necessarily 100%, and it can be matched. Use or purpose for any adjustment. Among them, the specific polyimine-based polymer in the present invention is preferably a polyimine which is obtained by hydrazing a polyimide precursor. At this time, the imidization ratio of ruthenium is preferably 40 to 90%. Preferably, it is 50 to 90%.

The method for imidating the polyimine precursor ruthenium may, for example, be a hydrazine imidization of heating the polyimine precursor solution or adding a catalyst to the polyimide precursor solution. The method of imidization of the medium. The temperature at which the polyimide precursor is thermally imidized in the solution is from 100 ° C to 400 ° C, preferably from 120 ° C to 250 ° C, and preferably the water formed by the hydrazine imidization reaction is continuously discharged. It is preferred to carry out the process outside the reaction system.

The ruthenium imide of the polyimide precursor is added to the solution of the polyimide precursor by adding a basic catalyst and an acid anhydride at -20 to 250 ° C, preferably 0 to 180 ° C. It is carried out by stirring. The amount of alkaline catalyst is 0.5 to 30 moles, preferably 2 to 20 moles, of the amidate group. The amount of the acid anhydride is 1 to 50 moles, preferably 3 to 30 moles, of the valerine group. Examples of the basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine or trioctylamine. Among them, pyridine is preferred because it maintains an appropriate basicity during the reaction. Examples of the acid anhydride include acetic anhydride, trimellitic anhydride, and pyromellitic anhydride. Among them, it is preferred to use acetic anhydride to carry out purification after completion of the reaction. The imidization rate of the imidization of the catalyst can be controlled by adjusting the amount of the catalyst, the reaction temperature and the reaction time.

In the case where the produced polyimine precursor or polyimine is recovered from the reaction solution of the polyimine precursor or the polyimine, the reaction solution may be added to a solvent to precipitate. Examples of the solvent used for the precipitation include methanol, ethanol, isopropanol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, toluene, benzene or water. The precipitated polymer is introduced into the solvent, and after filtration and filtration, it can be dried under normal pressure or under reduced pressure at normal temperature or under heating. Further, when the polymer recovered by precipitation is repeatedly re-dissolved in an organic solvent for 2 to 10 times, the impurities in the polymer can be lowered. In the solvent to be used at this time, for example, an alcohol, a ketone or a hydrocarbon, etc., when three or more kinds of solvents selected from the above are used, it is preferable to further improve the purification efficiency by one layer.

The molecular weight of the polyimine-based polymer is a weight average molecular weight measured by a GPC (Gel Permeation Chromatography) method in consideration of the strength of the obtained liquid crystal alignment film, workability at the time of formation of a liquid crystal alignment film, and coating property. 5,000~1,000,000 is preferred. among them, It is preferably 10,000 to 150,000.

As described above, the specific polyamidimide-based polymer of the present invention can suppress the decrease in voltage holding ratio after exposure to light for a long period of time, and the imidization of the above-mentioned polyimide precursor by ruthenium oxime Polyimine is preferred. The imidization ratio at this time is preferably in the above range.

<(C) ingredient ‧ specific amine compound>

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

Since the specific amine compound has only one amine group contained in the molecule, it is possible to avoid precipitation of the polymer or gelation during storage of the liquid crystal alignment agent or in the storage of the liquid crystal alignment agent. possibility.

The amine group contained in a specific amine compound has a tendency to form a salt with a polymer or is easy to undergo a bonding reaction, and must be a divalent aliphatic hydrocarbon group or a non-aromatic cyclic hydrocarbon group bond containing no aromatic hydrocarbon in the molecule. Knot.

Specific examples of the aliphatic hydrocarbon group include a linear alkyl group, an alkyl group having a branched structure, or a divalent hydrocarbon group having an unsaturated bond. Preferably, the aliphatic hydrocarbon group has a carbon number of from 1 to 20. Particularly preferred is a carbon number of 1 to 15, and the best one is a carbon number of 1 to 10.

Specific examples of the non-aromatic cyclic hydrocarbon group include, for example, a ring Propane ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, cyclodecane ring, cyclodecane ring, cycloundecyl ring, cyclododecane ring, ring a tridecane ring, a cyclotetradecane ring, a cyclopentadecane ring, a cyclohexadecane ring, a cycloheptadecane ring, a cyclooctadecane ring, a cyclopentadecane ring, an icosene ring, An eicosene ring, a docosane ring, a bicycloheptane ring, a decahydronaphthalene ring, a norbornene ring or an adamantane ring. Preferred are non-aromatic cyclic hydrocarbon groups of a ring formed by carbon number 3 to 20. Particularly preferred is a ring formed by a carbon number of 3 to 15, and the most preferred one is a ring formed of 3 to 10 carbon atoms.

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

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

Specific examples of the nitrogen-containing aromatic heterocyclic ring include a pyrrole ring, an imidazole ring, an oxazole ring, a thiazole ring, a pyrazole ring, a pyridine ring, a pyrimidine ring, a quinoline ring, a pyrazoline ring, and an isoquinoline ring. , carbazole ring, anthracene ring, thiadiazole ring, hydrazine Ring, pyrazoline ring, three Ring, pyrazolidine ring, triazole ring, pyridyl Ring, benzimidazole ring, benzimidazole ring, octyl ring, phenanthroline ring, anthracene ring, quinoxaline ring, benzothiazole ring, phenothiazine (phenothiazine) ring, oxazole ring or acridine ring. Further, the carbon atom of the nitrogen-containing aromatic heterocyclic ring may have a substituent containing a hetero atom.

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

H ₂ NS ¹ -S ² [4a-1]

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

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

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

Further, in view of the fact that the nitrogen-containing aromatic heterocyclic ring and the carboxyl group in the polymer are likely to form a salt or an electrostatic interaction which is liable to cause hydrogen bonding, S ¹ in the above formula [4a-1] is not contained in the S ² It is preferred that the substituents of the formula [4-a], the formula [4-b] or the formula [4-c] are bonded to each other.

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

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

H ₄ NS ³ -S ⁴ -S ⁵ [4a-2]

In the formula [4a-2], S ³ , S ⁴ and S ⁵ are as defined above, and those of the following are preferred.

S ³ , 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, and a cycloheptane Ring, cyclooctane ring, cyclopethane ring, cyclodecane ring, cycloundecyl ring, cyclododecane ring, cyclotridecane ring, cyclotetradecane ring, cyclopentadecane ring, cyclohexadecane Ring, cycloheptadecane ring, cyclooctadecyl ring, cyclodecadecane ring, icosene ring, eicosene ring, trioxodocosane ring, A bicycloheptane ring, a decahydronaphthalene ring, a norbornene ring or an adamantane ring is preferred. Preferred are straight-chain or branched alkyl groups having a carbon number of 1 to 10.

S ⁴ , a single bond, -O-, -NH-, -S-, -SO ₂ -, a hydrocarbon group having 1 to 19 carbon atoms, -CO-O-, -O-CO-, -CO-NH-, -NH-CO-, -CO-, -CF ₂ -, -C(CF ₃ ) ₂ -, -CH(OH)-, -C(CH ₃ ) ₂ -, -Si(CH ₃ ) ₂ -, - O-Si(CH ₃ ) ₂ -, -Si(CH ₃ ) ₂ -O-, -O-Si(CH ₃ ) ₂ -O-, cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclohexane Alkane ring, cycloheptane ring, cyclooctane ring, cyclodecane ring, cyclodecane ring, cycloundecyl ring, cyclododecane ring, cyclotridecane ring, cyclotetradecane ring, cyclopentadecane Ring, cyclohexadecane ring, cycloheptadecane ring, cyclooctadecane ring, cyclopentadecane ring, icosene ring, eicosene ring, tricyclic twenty-two Docosane ring, bicycloheptane ring, decahydronaphthalene ring, norbornene ring, adamantane ring, benzene ring, naphthalene ring, tetrahydronaphthalene ring, anthracene ring, anthracene ring, anthracene ring, anthracene ring, phenanthrene Ring, anthracene ring, pyrrole ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, pyridine ring, pyrimidine ring, quinoline ring, pyrazoline ring, isoquinoline ring, indazole ring, anthracene ring, thiophene Diazole ring, hydrazine Ring, three Ring, pyrazolidine ring, triazole ring, pyridyl Ring, benzimidazole ring, benzimidazole ring, octyl ring, phenanthroline ring, anthracene ring, quinoxaline ring, benzothiazole ring, phenothiazine The (phenothiazine) ring, the oxazole ring, the acridine ring, the oxazole ring, the piperazine ring, the piperidine ring, the dioxane ring or the florin ring is preferred.

S ⁵ , pyrrole ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, pyridine ring, pyrimidine ring, quinoline ring, pyrazoline ring, isoquinoline ring, indazole ring, anthracene ring, thiadipine Oxazole ring Ring, pyrazoline ring, three Ring, pyrazolidine ring, triazole ring, pyridyl Ring, benzimidazole ring, benzimidazole ring, octyl ring, phenanthroline ring, anthracene ring, quinoxaline ring, benzothiazole ring, phenothiazine (phenothiazine) ring, oxazole ring or acridine ring is preferred.

Further, in view of the electrostatic interaction between the nitrogen-containing aromatic heterocyclic ring and the carboxyl group in the polymer, or the formation of a hydrogen bond, the S ⁴ in the formula [4a-2] is not included in the S ⁵ It is preferred that the carbon atom of the formula [4-a], the formula [4-b] or the formula [4-c] is bonded.

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

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

The specific amine compound may be used in combination of one or two or more kinds of the properties of the specific amine compound in the solvent, the liquid crystal alignment property as a liquid crystal alignment film, or the electrical properties of the liquid crystal display element.

<Liquid alignment treatment agent>

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

The ratio of use of the specific compound in the liquid crystal alignment agent is preferably as described below. That is, it is preferably 1 part by mass to 30 parts by mass based on 100 parts by mass of the total polymer. It is preferably from 1 part by mass to 20 parts by mass, particularly preferably from 3 parts by mass to 15 parts by mass.

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

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

The specific amine compound may be directly added to the solution containing the polymer and the solvent, but it is preferably added to a solution adjusted to a concentration of 0.1 to 10% by mass using a suitable solvent. The solvent at this time is, for example, a solvent which can dissolve the specific polyimine-based polymer described above.

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

Among the polymer components in the liquid crystal alignment agent, a specific polyimine-based polymer is preferably used, but it may be used in combination with other polymers. In this case, the content of the polymer other than the other is preferably 0.5 parts by mass to 15 parts by mass based on 100 parts by mass of the specific polyamidene-based polymer. It is preferably 1 part by mass to 10 parts by mass. Other polymers other than the above may, for example, be the above-mentioned acrylic polymer, methacrylic polymer, novolak resin, polyhydroxystyrene, polyamine, polyester, cellulose or polyoxyalkylene.

The solvent in the liquid crystal alignment treatment agent can form a uniform liquid crystal alignment film by coating, and the solvent content in the liquid crystal alignment treatment agent is preferably from 70 to 99.9% by mass. This content can be appropriately changed in accordance with the film thickness of the intended liquid crystal alignment film.

The solvent used for the liquid crystal alignment treatment agent is not particularly limited as long as it can dissolve the solvent of the polymer (also referred to as a good solvent). Specific examples of the good solvent when a specific polyimine-based polymer is used will be described below, but are not limited to these examples.

For example, N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, dimethyl Anthracene, γ-butyrolactone, 1,3-dimethyl-tetrahydroimidazolidone, methyl ethyl ketone, cyclohexanone, cyclopentanone or 4-hydroxy-4-methyl-2-pentanone.

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

Further, in order to increase the solubility of the specific polyimine-based polymer in a solvent, it is preferred to use a solvent represented by the above formula [D-1] to formula [D-3].

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

In the liquid crystal alignment treatment agent, a solvent (also referred to as a poor solvent) for improving the coating property or surface smoothness of the liquid crystal alignment film when the liquid crystal alignment treatment agent is applied can be used without impairing the effects of the present invention. The following are specific examples of the poor solvent, but are not limited to the examples.

For example, ethanol, isopropanol, 1-butanol, 2-butanol, isobutanol, tert-butanol, 1-pentanol, 2-pentanol, 3-pentanol, 2-methyl-1-butene Alcohol, isoamyl alcohol, tert-pentanol, 3-methyl-2-butanol, neopentyl alcohol, 1-hexanol, 2-methyl-1-pentanol, 2-methyl-2-pentanol, 2-ethyl-1-butanol, 1- Heptanol, 2-heptanol, 3-heptanol, 1-octanol, 2-octanol, 2-ethyl-1-hexanol, cyclohexanol, 1-methylcyclohexanol, 2-methyl ring Hexanol, 3-methylcyclohexanol, 1,2-ethanediol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butyl Alkanediol, 1,4-butanediol, 2,3-butanediol, 1,5-pentanediol, 2-methyl-2,4-pentanediol, 2-ethyl- 1,3-hexanediol, dipropyl ether, dibutyl ether, dihexyl ether, dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, 1,2-butyl Oxyethane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ether, diethylene glycol dibutyl ether, 2-pentanone, 3-pentanone, 2-hexanone , 2-heptanone, 4-heptanone, 3-ethoxybutyl acetate, 1-methylpentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate , ethylene glycol monoacetate, ethylene glycol diacetate, propylene carbonate, ethylene carbonate, 2-(methoxymethoxy)ethanol, ethylene glycol monobutyl ether, ethylene glycol monoisobutyl Ether, ethylene glycol monohexyl ether, 2-(hexyloxy)ethanol, decyl alcohol, diethylene glycol, propylene glycol, propylene glycol Butyl ether, 1-(butoxyethoxy)propanol, propylene glycol monomethyl ether acetate, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol dimethyl ether, tripropylene glycol monomethyl ether, Ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monoacetate, ethylene glycol diacetate, diethylene glycol single Ethyl acetate, diethylene glycol monobutyl ether acetate, 2-(2-ethoxyethoxy)ethyl acetate, diethylene glycol acetate, triethylene glycol, triethylene glycol Alcohol monomethyl ether, triethylene glycol monoethyl ether, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether, pyruvate methyl, pyruvate ethyl, 3 -Methoxypropionic acid methyl, 3-ethoxypropionic acid methylethyl, 3-methoxypropionic acid , 3-ethoxypropionic acid, 3-methoxypropionic acid, 3-methoxypropionic acid propyl, 3-methoxypropionic acid butyl, methyl lactate, ethyl lactate, lactate n-propyl An ester, n-butyl lactate, isoamyl lactate or a solvent represented by the above formula [D-1] to formula [D-3].

Wherein, 1-hexanol, cyclohexanol, 1,2-ethanediol, 1,2-propanediol, propylene glycol monobutyl ether, ethylene glycol monobutyl ether, dipropylene glycol dimethyl ether or It is preferred to use a solvent represented by the above formula [D-1] to formula [D-3].

The use ratio of the poor solvent is preferably from 1 to 70% by mass based on the total amount of the solvent contained in the liquid crystal alignment agent. It is preferably from 1 to 60% by mass, particularly preferably from 5 to 60% by mass.

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

a crosslinkable compound having an epoxy group or an isocyanate group, for example, bisphenol acetone glycidyl ether, phenol novolak epoxy resin, cresol novolac epoxy resin, triglycidyl isocyanurate, four Glycidylamine diphenyl, tetraglycidyl-m-xylylenediamine, tetraglycidyl-1,3-bis(aminoethyl)cyclohexane, tetraphenylglycidyl ether, triphenyl Glycidyl ether ethane, bisphenol hexafluoroacetone diglycidyl Ether, 1,3-bis(1-(2,3-epoxypropoxy)-1-trifluoromethyl-2,2,2-trifluoromethyl)benzene, 4,4-bis (2, 3-glycidoxy)octafluorobiphenyl, triglycidyl-p-aminophenol, tetraglycidyl metaxylenediamine, 2-(4-(2,3-epoxypropoxy)phenyl )-2-(4-(1,1-bis(4-(2,3-epoxypropoxy)phenyl)ethyl)phenyl)propane or 1,3-bis(4-(1-() 4-(2,3-epoxypropoxy)phenyl)-1-(4-(1-(4-(2,3-epoxypropoxy)phenyl)-1-methylethyl) Phenyl)ethyl)phenoxy)-2-propanol and the like.

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

Specifically, a crosslinkable compound represented by the formula [4a] to the formula [4k] disclosed in pages 58 to 59 of International Publication WO2011/132751 (2011.10.27) can be mentioned.

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

Specifically, for example, an international public bulletin A cross-linking compound represented by the formula [5-1] to the formula [5-42] disclosed in pages 76 to 82 of WO2012/014898 (published in 2012.2.2).

a crosslinkable compound having at least one selected from the group consisting of a hydroxyl group and an alkoxy group, for example, an amine-based resin having a hydroxyl group or an alkoxy group, for example, a melamine resin, a urea resin, or a hydrazine Resin, acetylene urea-formaldehyde resin, amber decyl amide-formaldehyde resin or ethylene urea-formaldehyde resin. Specifically, for example, a melamine derivative or a benzofluorene in which a hydrogen atom of an amine group is substituted with a methylol group or an alkoxymethyl group or both may be used. Derivatives, or acetylene urea, and the like. The melamine derivative or benzopyrene The derivative may exist as a dimer or a trimer. Each of these three The ring is preferably one having an average of 3 or more and 6 or less methylol groups or alkoxymethyl groups.

These melamine derivatives or benzopyrene Derivatives, for example, each of the three commercially available products MX-750, each of which is replaced by 3.7 methoxymethyl groups MW-30 (above, manufactured by Sanwa Chemical Co., Ltd.) or CYMEL ^® 300, 301, 303, 350, 370, 771, 325, 327, 703, 712, etc., substituted by 5.8 methoxymethyl groups. Methylated melamine, CYMEL ^® 235, 236, 238, 212, 253, 254 and other methoxymethylated butoxymethylated melamine, CYMEL ^® 506, 508 and other butoxymethylated melamine, CYMEL ^® 1141, etc. the carboxyl group-containing methoxymethylated isobutoxymethyl melamine, CYMEL ^® 1123, etc. methoxymethylated ethoxymethylated benzo quack , CYMEL ^® 1123-10 and other methoxymethylated butoxymethylated benzopyrene , CYMEL ^® 1128 and other butoxymethylated benzopyrene Carboxy-containing methoxymethylated ethoxymethylated benzopyrene such as CYMEL ^® 1125-80 (above, Mitsui Cyanamide Co., Ltd.), etc. Further, acetylene urea of example, CYMEL ^® 1170, etc. butoxymethyl acetylene urea, CYMEL ^® 1172 methylolated acetylene urea, etc., etc., POWDERLIMK 1174 etc. methoxy methylolated acetylene urea.

Benzene having a hydroxyl group or an alkoxy group, or a phenolic compound, for example, 1,3,5-glycol (methoxymethyl)benzene, 1,2,4-para(isopropoxymethyl)benzene, 1 , 4-bis(sec-butoxymethyl)benzene or 2,6-dihydroxymethyl-p-tert-butylphenol. More specifically, a crosslinkable compound represented by the formula [6-1] to the formula [6-48] disclosed in pages 62 to 66 of International Publication WO2011/132751 (2011.10.27) is mentioned. Wait.

a crosslinkable compound having a polymerizable unsaturated bond, for example, having three trimethylolpropane tri(meth)acrylates, pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylic acid in the molecule a crosslinkable compound of a polymerizable unsaturated group such as an ester, tris(meth)acryloyloxyethoxy trimethylolpropane or glycerol polyglycidyl ether poly(meth)acrylate; ethylene glycol II ( Methyl) acrylate, diethylene glycol di(meth) acrylate, tetraethylene glycol di(meth) acrylate, polyethylene glycol di(meth) acrylate, propylene glycol di(meth) acrylate , polypropylene glycol di(meth)acrylate, butanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, ethylene oxide bisphenol A type di(meth)acrylate, Propylene oxide bisphenol type di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, glycerol di(meth)acrylate, pentaerythritol di(meth)acrylate, Ethylene glycol Glycidyl ether di(meth)acrylate, diethylene glycol diglycidyl ether di(meth)acrylate, diglycidyl diacetate di(meth)acrylate or hydroxy-t-valeric acid neopentyl glycol A crosslinkable compound having two polymerizable unsaturated groups in a molecule such as di(meth)acrylate.

The content of the specific crosslinkable compound in the liquid crystal alignment agent is preferably from 1 to 50 parts by mass based on 100 parts by mass of the total polymer component. It is preferably 1 to 30 parts by mass, particularly preferably 1 to 10 parts by mass, in order to obtain the intended effect of the crosslinking reaction.

In the liquid crystal alignment treatment agent, when the liquid crystal alignment treatment agent is applied, a compound which can improve the film thickness uniformity or surface smoothness of the liquid crystal alignment film can be used without departing from the effects of the present invention. Further, a compound or the like which can improve the adhesion between the liquid crystal alignment film and the substrate can be used.

Examples of the compound which improves the film thickness uniformity or the surface smoothness of the liquid crystal alignment film include a fluorine-based surfactant, a polyfluorene-based surfactant, and a nonionic surfactant. Specifically, for example, F-TOP EF301, EF303, EF352 (above, manufactured by Dow Chemical Manufacturing Co., Ltd.), Megfried F171, F173, R-30 (above, manufactured by Dainippon Paint Co., Ltd.), FLUORAD FC430, FC431 (above, Sumitomo 3M), AsahiGuard AG710, Shaflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (above, manufactured by Asahi Glass Co., Ltd.). The proportion of the surfactant to be used 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 agent. It is preferably 0.01 to 1 part by mass.

a compound which improves the adhesion of a liquid crystal alignment film to a substrate Specific examples thereof include a compound containing a functional decane or a compound containing an epoxy group. For example, 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 2-aminopropyltrimethoxydecane, 2-aminopropyltriethoxydecane, N- (2-Aminoethyl)-3-aminopropyltrimethoxydecane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxydecane, 3-ureidopropyl Trimethoxy decane, 3-ureidopropyl triethoxy decane, N-ethoxycarbonyl-3-aminopropyltrimethoxy decane, N-ethoxycarbonyl-3-aminopropyl three Ethoxy decane, N-triethoxydecanepropyltriethyltriamine, N-trimethoxydecanepropyltriethyltriamine, 10-trimethoxydecane-1,4,7-triaza Decane, 10-triethoxydecane-1,4,7-triazadecane, 9-trimethoxydecane-3,6-diazadecyl acetate, 9-triethoxydecane -3,6-diazaindolyl acetate, N-benzyl-3-aminopropyltrimethoxydecane, N-benzyl-3-aminopropyltriethoxydecane, N-benzene 3-aminopropyltrimethoxydecane, N-phenyl-3-aminopropyltriethoxydecane, N-bis(oxyvinyl)-3-aminopropyltrimethoxydecane, N-bis(oxyvinyl)-3-aminopropyltriethyl Oxydecane, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5,6-tetraglycidyl-2, 4-hexanediol, N,N,N',N',-tetraglycidyl-m-xylylenediamine, 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane Or N, N, N', N', - tetraglycidyl-4,4'-diaminodiphenylmethane, and the like.

The ratio of the compounds that can be adhered to the substrates, It is preferably 0.1 to 30 parts by mass based on 100 parts by mass of all the polymer components contained in the liquid crystal alignment agent. It is preferably 1 to 20 parts by mass. When it is less than 0.1 part by mass, the effect of improving the adhesion is not obtained, and when it exceeds 30 parts by mass, the storage stability of the liquid crystal alignment agent may be deteriorated.

In the liquid crystal alignment treatment agent, a dielectric or a conductive material for the purpose of changing the electrical properties such as the dielectric constant or the electrical conductivity of the liquid crystal alignment film may be added to the liquid crystal alignment treatment agent in addition to the above-described effects.

<Liquid alignment film ‧ Liquid crystal display element>

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

The coating method of the liquid crystal alignment treatment agent is not particularly limited, and industrially, generally, screen printing, lithography, and convex printing are used. The method is performed by a method such as Flexo printing or inkjet method. Other coating methods include, for example, a dipping method, a roll coating method, a slit coating method, a spin coater method, or a spray method, and these methods can be used for the purpose.

After the liquid crystal alignment treatment agent is applied onto the substrate, the solvent used in the liquid crystal alignment treatment agent is blended at a temperature of 30 to 300 ° C, preferably via a heating means such as a hot plate, a heat cycle type oven, or an IR (infrared) type oven. The solvent is evaporated at a temperature of 30 to 250 ° C to serve as a liquid crystal alignment film. When the thickness of the liquid crystal alignment film after sintering is too thick, it is disadvantageous in that the liquid crystal display element consumes electric power. If it is too thin, the reliability of the liquid crystal display element is lowered. Therefore, it is preferably 5 to 300 nm. Good for 10~100nm. In the case of a liquid crystal display element for a TN mode or an IPS mode, when the liquid crystal is tilted or horizontally aligned, the liquid crystal alignment film after sintering may be subjected to rubbing or polarized ultraviolet light irradiation or the like.

In the liquid crystal display device of the present invention, after the substrate to which the liquid crystal alignment film is applied can be obtained by the liquid crystal alignment treatment agent of the present invention, a liquid crystal cell can be produced by a known method as a liquid crystal display element.

In the method of producing a liquid crystal cell, for example, a pair of substrates on which a liquid crystal alignment film is formed is prepared, and a spacer is spread on a liquid crystal alignment film of a single-sided substrate, and the liquid crystal alignment film surface faces inward, and the substrate on the other side is bonded Then, the liquid crystal is injected under reduced pressure for sealing, or the liquid crystal is dropped into the liquid crystal alignment film surface on which the spacer is dispersed, and then the substrate is bonded and sealed (also referred to as ODF: One Drop Filling method).

The liquid crystal alignment treatment agent of the present invention is also suitably used for having a liquid crystal layer between one of the electrodes and between the pair of substrates. A liquid crystal composition containing a polymerizable compound polymerized by at least one of an active energy ray and a heat, and a polymerizable compound is applied to at least one of irradiation and heating of the active energy ray via a voltage applied between the electrodes A liquid crystal display element produced by the polymerization step. Among them, the active energy ray is preferably ultraviolet light. The wavelength of the ultraviolet light is 300 to 400 nm, preferably 310 to 360 nm. In the case of polymerization by heating, the heating temperature is 40 to 120 ° C, preferably 60 to 80 ° C. Further, ultraviolet rays and heat treatment can be simultaneously performed.

The liquid crystal display element described above is a method of controlling the pretilt angle of liquid crystal molecules by using a PSA mode. In the PSA mode, a small amount of a photopolymerizable compound, for example, a photopolymerizable monomer, is added to the liquid crystal material, and after a liquid crystal cell is combined, a specific voltage is applied to the liquid crystal layer, and the photopolymerizable compound is irradiated with ultraviolet rays or the like. The pretilt angle of the liquid crystal molecules is controlled by the generated polymer. Since the alignment state of the liquid crystal molecules during the formation of the polymer is also present after the voltage is removed, the pretilt angle of the liquid crystal molecules can be adjusted by the electric field formed in the liquid crystal layer or the like. Further, in the PSA mode, since the rubbing treatment is unnecessary, it is also suitable for forming a vertical alignment type liquid crystal layer which is not easily controlled by the rubbing treatment. In other words, in the liquid crystal display device of the present invention, the liquid crystal alignment film is obtained from the liquid crystal alignment film by the liquid crystal alignment treatment agent, and then the liquid crystal cell is produced, and at least one of ultraviolet irradiation and heating is used to polymerize the compound. Polymerization, which can control the alignment of liquid crystal molecules.

When one of the liquid crystal cell production methods of the PSA mode is exemplified, for example, the following contents are shown. That is, the liquid crystal is produced according to the above manufacturing method. Unit cell. In the liquid crystal at this time, a polymerizable compound which is polymerized by irradiation with heat or ultraviolet rays is mixed. The polymerizable compound is, for example, a compound having one or more polymerizable unsaturated groups such as an acrylate group or a methacrylate group in the molecule. In this case, 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 parts by mass, the polymerizable compound does not cause polymerization, and the alignment of the liquid crystal cannot be controlled. When the amount is more than 10 parts by mass, the amount of the unreacted polymerizable compound is too large, and the residual image of the liquid crystal display element is lowered. characteristic. After the liquid crystal cell is produced, a voltage of alternating current or direct current is applied to the liquid crystal cell, and the polymerizable compound is polymerized by irradiation with heat or ultraviolet rays. In this way, the alignment of the liquid crystal molecules can be controlled.

In addition, the liquid crystal alignment treatment agent of the present invention includes a liquid crystal layer between one of the electrodes, and a polymerizable group containing at least one of an active energy ray and heat between the pair of substrates. The liquid crystal alignment element is obtained by a step of applying a voltage between the electrodes, that is, the SC-PVA mode can also be used. Among them, the active energy ray is preferably ultraviolet light. The wavelength of the ultraviolet light is 300 to 400 nm, preferably 310 to 360 nm. In the case of polymerization by heating, the heating temperature is 40 to 120 ° C, preferably 60 to 80 ° C. Further, ultraviolet rays and heat treatment can be simultaneously performed.

When a liquid crystal alignment film containing a polymerizable group polymerized by at least one of an active energy ray and a heat is produced, for example, a method of adding a polymerizable group-containing compound to a liquid crystal alignment treatment agent, or a polymerizable property may be used. The method of polymerizing the base, and the like.

When one of the liquid crystal cells in which the SC-PVA mode is produced is exemplified, for example, the following contents are shown. That is, a liquid crystal cell is produced in accordance with the above production method. Subsequently, the alignment of the liquid crystal molecules can be controlled by applying heat or ultraviolet light to a voltage of alternating current or direct current applied to the liquid crystal cell.

As described above, the present invention provides a liquid crystal alignment treatment agent of the present invention, which can suppress a decrease in voltage retention rate even after exposure to light for a long period of time, and further, even under conditions of high temperature and high humidity, A liquid crystal alignment film is not formed in the vicinity of the fore edge of the liquid crystal display element. Therefore, the liquid crystal display element produced by using the liquid crystal alignment treatment agent of the present invention has excellent reliability and is suitable for use in a large-sized liquid crystal television, a small and medium-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 using a liquid crystal display element of a VA mode, a PSA mode, and an SC-PVA mode.

[Examples]

The present invention will be more specifically described by the following examples, but is not limited thereto. The abbreviations used in the synthesis examples, examples, and comparative examples are as follows.

(specific compound)

S1: phosphotungstic acid (manufactured by Nippon Shinshin Co., Ltd.)

S2: phosphomolybdic acid (12 molybdo (IV) phosphate n water) (made by Kanto Chemical Co., Ltd.)

(specific side chain type diamine compound)

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

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

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

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

A5: 1,3-diamino-4-octadecyloxybenzene

(other diamine compounds)

B1: p-phenylenediamine

B2: m-phenylene diamine

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

B4: 4,4'-diaminodiphenylamine

B5: 3,5-diamino benzoic acid

(specific tetracarboxylic dianhydride)

C1:1,2,3,4-cyclobutanetetracarboxylic dianhydride

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

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

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

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

(crosslinkable compound)

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

(solvent)

NMP: N-methyl-2-pyrrolidone

NEP: N-ethyl-2-pyrrolidone

γ-BL: γ-butyrolactone

BCS: ethylene glycol monobutyl ether

PB: propylene glycol monobutyl ether

DME: Dipropylene glycol dimethyl ether

(specific amine compound)

L1: 3-picolylamine

L2: N-(3-aminopropyl)-imidazole

"Measurement of molecular weight of polyamidene-based polymers"

The measurement was carried out in the following manner using a room temperature gel permeation chromatography (GPC) apparatus (GPC-101, manufactured by Showa Denko Co., Ltd.) and a column (KD-803, KD-805, manufactured by Shodex Co., Ltd.).

Column temperature: 50 ° C

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

Flow rate: 1.0ml/min

Standard sample for the production of calibration lines: TSK standard polyethylene oxide (molecular weight; about 900,000, 150,000, 100,000 and 30,000) (manufactured by Tosoh Corporation) and polyethylene glycol (molecular weight: about 12,000, 4,000 and 1,000) (polymerization) Laboratory company).

"Determination of the imidization ratio of polyamidene-based polymers"

20 mg of polyimine powder was placed in an NMR (nuclear magnetic resonance) sample tube (NMR standard sampling tube, Φ5 (manufactured by Kusano Scientific Co., Ltd.)), and added Dihydro dimethyl hydrazine (DMSO-d6, 0.05% by mass TMS (tetramethyl decane) mixture) (0.53 ml) was applied, and ultrasonic waves were applied to completely dissolve it. The proton NMR of this solution at 500 MHz was measured using an NMR measuring machine (JNW-ECA500, manufactured by JEOL Ltd.). The imidization ratio of ruthenium is determined by using a proton generated by a structure which is not changed before and after imidization as a reference proton, which is a peak integrated value using the proton, and a guanamine which appears in the vicinity of 9.5 ppm to 10.0 ppm. The peak value of the proton peak generated by the acid NH group is obtained by the following formula.

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

(x is the proton peak value calculated from the NH group of the proline, y is the peak integrated value of the reference proton, and α is the poly-proline (the imineization rate is 0%), relative to 醯One NH substrate of aminic acid, the ratio of the number of reference protons).

"Synthesis of Polyimine Polymers" <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), and reacted at 40 ° C for 6 hours, then added C1 (0.40). g, 2.04 mmol) and NMP (8.70 g) were reacted at 40 ° C for 6 hours to obtain a polyamic acid solution having a resin solid concentration of 25% by mass.

After the NMP was diluted to 6 mass% in the obtained polyamic acid solution (30.0 g), acetic anhydride (3.90 g) and pyridine (2.40 g) as a ruthenium catalyst were added, and the reaction was carried out at 70 ° C. hour. The reaction solution was poured into methanol (460 ml), and the obtained precipitate was filtered. This precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (1). The polyimine had an oxime imidization ratio of 84%, a number average molecular weight of 19,300, and a weight average molecular weight of 52,300.

<Synthesis Example 2>

C2 (6.55 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) and reacted at 80 ° C After 5 hours, C1 (2.20 g, 11.2 mmol) and NEP (16.9 g) were added, and the reaction was carried out at 40 ° C for 6 hours to obtain a polyamic acid solution (2) having a resin solid concentration of 25% by mass. The polyamic acid had a number average molecular weight of 19,500 and a weight average molecular weight of 65,800.

<Synthesis Example 3>

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

<Synthesis Example 4>

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

After the NEPP was diluted to 6 mass% in the obtained polyamic acid solution (30.0 g), acetic anhydride (4.50 g) and pyridine (3.30 g) as a ruthenium catalyst were added, and the reaction was carried out at 80 ° C. hour. The reaction solution was poured into methanol (460 ml), and the obtained precipitate was filtered. This precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (4). The polyimine had a hydrazine imidation ratio of 70%, a number average molecular weight of 18,300, and a weight average molecular weight of 46,000.

<Synthesis Example 5>

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

Add NMP to the obtained polyaminic acid solution (30.0 g) After diluting to 6% by mass, acetic anhydride (3.80 g) and pyridine (2.40 g) as a ruthenium catalyst were added, and the mixture was reacted at 60 ° C for 2 hours. The reaction solution was poured into methanol (460 ml), and the obtained precipitate was filtered. This precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (5). The polyimine had a hydrazine imidation ratio of 55%, a number average molecular weight of 17,500, and a weight average molecular weight of 45,100.

<Synthesis Example 6>

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

After the NMP was diluted to 6 mass% in the obtained polyamidic acid solution (30.0 g), acetic anhydride (3.80 g) and pyridine (2.40 g) as a ruthenium amide catalyst were added, and the reaction was carried out at 60 ° C. hour. The reaction solution was poured into methanol (460 ml), and the obtained precipitate was filtered. This precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (6). The polyimine had a hydrazine imidation ratio of 55%, a number average molecular weight of 16,800, and a weight average molecular weight of 43,900.

<Synthesis Example 7>

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

After the NMP was diluted to 6 mass% in the obtained polyamidic acid solution (30.0 g), acetic anhydride (3.80 g) and pyridine (2.40 g) as a ruthenium amide catalyst were added, and the reaction was carried out at 60 ° C. hour. The reaction solution was poured into methanol (460 ml), and the obtained precipitate was filtered. This precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (7). The polyimine had a ruthenium iodide ratio of 52%, a number average molecular weight of 14,800, and a weight average molecular weight of 38,300.

<Synthesis Example 8>

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

After the NMP was diluted to 6 mass% in the obtained polyamic acid solution (30.0 g), acetic anhydride (4.50 g) and pyridine (3.30 g) as a ruthenium amide catalyst were added, and the reaction was carried out at 80 ° C. hour. The reaction solution was poured into methanol (460 ml), and the obtained precipitate was filtered. This precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (8). The polyimine had a hydrazine imidation ratio of 75%, a number average molecular weight of 18,200, and a weight average molecular weight of 46,300.

<Synthesis Example 9>

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

After the NEPP was diluted to 6% by mass in the obtained polyamic acid solution (30.0 g), acetic anhydride (4.50 g) and pyridine (3.30 g) as a ruthenium catalyst were added, and the reaction was carried out at 80 ° C. hour. The reaction solution was poured into methanol (460 ml), and the obtained precipitate was filtered. This precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (9). The polyimine had an oxime imidization ratio of 85%, a number average molecular weight of 15,500, and a weight average molecular weight of 40,100.

<Synthesis Example 10>

C2 (1.42 g, 5.68 mmol), A2 (3.01 g, 7.63 mmol) and B1 (1.24 g, 11.5 mmol) were mixed in NMP (16.9 g), and reacted at 80 ° C for 5 hours, then C5 (2.80 g) was added. 1,3.2 mmol) and NMP (8.47 g) were reacted at 40 ° C for 6 hours to obtain a polyamic acid solution having a resin solid concentration of 25% by mass.

After the NEPP was diluted to 6% by mass in the obtained polyamic acid solution (30.0 g), acetic anhydride was added as a ruthenium amide catalyst. (4.50 g) and pyridine (3.30 g) were reacted at 80 ° C for 3.5 hours. The reaction solution was poured into methanol (460 ml), and the obtained precipitate was filtered. This precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (10). The polyimine had a hydrazine imidation ratio of 78%, a number average molecular weight of 16,600, and a weight average molecular weight of 43,400.

The polyimine-based polymer obtained in the synthesis example is shown in Table 1.

* 1: Polyglycine.

"Manufacture of liquid crystal alignment agent"

In the examples and comparative examples described later, the production examples of the liquid crystal alignment treatment agent are described. Further, the liquid crystal alignment treatment agent is also used for production and evaluation of a liquid crystal display element. The liquid crystal alignment treatment agents obtained in the examples and the comparative examples are shown in Tables 2 to 4.

"Evaluation of inkjet coating properties of liquid crystal alignment agents"

The evaluation of inkjet coating properties was carried out by using the liquid crystal alignment treatment agents obtained in Examples 4 and 7 described later. Specifically, for example, these liquid crystal alignment treatment agents are subjected to pressure filtration using a membrane filter having a pore size of 1 μm, and ITO (indium tin oxide) is added for washing with pure water and IPA (isopropyl alcohol). The ITO surface of the electrode substrate (length 100 mm × width 100 mm, thickness 0.7 mm) has a coating area of 70×70 mm, a nozzle pitch of 0.423 mm, a scanning pitch of 0.5 mm, and a coating speed of 40 mm/sec. Coating is carried out. At this time, the inkjet coater used HIS-200 (manufactured by Hitachi Apparatus Co., Ltd.). Further, the time until the pre-drying was applied was 60 seconds, and the pre-drying was carried out on a hot plate at 70 ° C for 5 minutes.

The coating property was evaluated by visually observing the coating film surface of the substrate to which the liquid crystal alignment film obtained above was applied. Specifically, for example, the surface of the coating film is visually observed under a sodium lamp to confirm the presence or absence of sand holes. As a result, it was confirmed that the liquid crystal alignment film obtained in any of the examples showed no sand holes on the surface of the coating film, and a liquid crystal alignment film having excellent coating film properties was obtained.

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

The liquid crystal alignment treatment agent obtained in the examples and the comparative examples described later was pressure-filtered using a membrane filter having a pore size of 1 μm, and spin-coated on a substrate to which an ITO electrode was washed with pure water and IPA (longitudinal 40 mm × horizontal 30 mm). The ITO surface of the thickness of 0.7 mm) was heat-treated at 230 ° C for 30 minutes on a hot plate at 100 ° C for 5 minutes in a heat cycle type clean oven to obtain an ITO substrate having a liquid crystal alignment film with a film thickness of 100 nm. . In addition, in the liquid crystal alignment treatment agents of the fourth embodiment and the seventh embodiment, the substrate was produced under the same conditions as the "evaluation of the inkjet coating property of the liquid crystal alignment treatment agent" (the substrate was made of the same pure water and IPA as described above). The substrate to be cleaned with an ITO electrode (40 mm in length × 30 mm in width, and 0.7 mm in thickness) was then subjected to heat treatment at 230 ° C for 30 minutes in a heat cycle type cleaning oven to form a film thickness of 100 nm. ITO substrate of liquid crystal alignment film.

Next, the coating film surface of the substrate was rubbed using a rubbing device having a drum diameter of 120 mm, and rubbing was performed under the conditions of a drum rotation number of 1000 rpm, a drum speed of 50 mm/sec, and a pressing amount of 0.1 mm. deal with.

Subsequently, two sheets of the rubbed substrate were prepared, and the film surface was formed on the inner side, and a combination of spacers of 6 μm was sandwiched, and a sealant was adhered to the periphery to prepare an empty cell. Liquid crystal is injected into the empty cell by a vacuum injection method, and the injection port is sealed to obtain a liquid crystal cell. Also, embodiment 1 In Comparative Example 1 to Comparative Example 3, MLC-3018U (manufactured by Mok ‧ Japan Co., Ltd.) was used for the liquid crystal, and other examples and comparative examples were used, and MLC-6608 (manufactured by Mok ‧ Japan) was used for the liquid crystal.

The obtained liquid crystal cell was used to evaluate the display spot characteristics near the front edge of the liquid crystal cell. Specifically, for example, a liquid crystal alignment property in the vicinity of the sealant can be evaluated by visual observation using a polarizing plate and a backlight. As a result, all of the liquid crystal cells obtained in the examples and the comparative examples exhibited uniform liquid crystal alignment.

Subsequently, the liquid crystal cell was stored in a high-temperature and high-humidity bath at a temperature of 80 ° C and a humidity of 90% for 96 hours, and the liquid crystal alignment property in the vicinity of the sealant was evaluated under the same conditions as above. In the evaluation method, when liquid crystal alignment is not observed in the vicinity of the sealant after storage in a high-temperature and high-humidity bath, it is excellent in this evaluation (good in Tables 5 to 7). Tables 5 to 7 show the results of the display spot characteristics in the vicinity of the front edge of the liquid crystal cell after storage in a high-temperature and high-humidity bath.

"Evaluation of Voltage Retention Rate (General Cell)"

The evaluation of the voltage holding ratio was carried out using the liquid crystal cell prepared under the same conditions as the "Evaluation of the display spot characteristics in the vicinity of the front edge of the liquid crystal cell" (general cell). Specifically, for example, a voltage of 1 V is applied to the liquid crystal cell obtained by the above method at a temperature of 80 ° C for 60 μs, and the voltage after 50 ms is measured, and the voltage can be stored as a result of the voltage retention rate. (also known as VHR). Further, it was measured using a voltage holding ratio measuring device (VHR-1) (manufactured by Toyo Corporation), Voltage: ±1V, Pulse Width: 60μs, Flame Period: 50ms.

In addition, a liquid crystal cell in which the voltage holding ratio was measured immediately after the production of the liquid crystal cell was measured by a desktop type UV curing device (HCT3B28HEX-1) (manufactured by CENLITE Co., Ltd.), and the conversion was 50 J/cm ² in terms of 365 nm. Ultraviolet rays were measured under the same conditions as above for the voltage holding ratio.

In this evaluation, the value of the voltage holding ratio after the liquid crystal cell is produced is higher, and the value of the voltage holding ratio after the liquid crystal cell is produced (also referred to as the initial stage), the value after the ultraviolet irradiation (also referred to as When the decrease in the ultraviolet ray is reduced, it is excellent in this evaluation. Tables 5 to 7 show the values of the respective VHRs.

<Example 1>

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

<Example 2>

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

<Example 3>

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

<Example 4>

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

<Example 5>

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

<Example 6>

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

<Example 7>

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

<Example 8>

NMP (19.6 g) was added to the polyimine powder (5) (2.50 g) obtained in Synthesis Example 5, and the mixture was stirred at 70 ° C for 24 hours to be dissolved. 10% by mass of N1 solution (0.75 g), BCS (3.92 g) and PB (15.7 g) of L1 were added to the solution, and the mixture was stirred at 50 ° C for 15 hours. Subsequently, S2 (0.175 g) was stirred at 25 ° C for 6 hours to obtain a liquid crystal alignment treatment agent (8). In the liquid crystal alignment treatment agent, no abnormal phenomenon such as turbidity or precipitation was observed, and it was confirmed that it was a homogeneous solution.

In addition, the "Evaluation of the characteristics of the display spot near the front edge of the liquid crystal cell (general cell)" is also carried out in addition to the above-mentioned standard test. The test is carried out in a high-temperature and high-humidity bath at a temperature of 80 ° C and a humidity of 90%. The evaluation was carried out after 168 hours (other conditions are the same as those described above). As a result, it was confirmed that the liquid crystal alignment property in the vicinity of the sealant did not cause a disorder in the liquid crystal cell.

<Example 9>

NMP (19.6 g) was added to the polyimine powder (6) (2.50 g) obtained in Synthesis Example 5, and the mixture was stirred at 70 ° C for 24 hours to be dissolved. 10% by mass of N1 solution (0.75 g), BCS (3.92 g) and PB (15.7 g) of L1 were added to the solution, and the mixture was stirred at 50 ° C for 15 hours. Subsequently, S2 (0.175 g) was stirred at 25 ° C for 6 hours to obtain a liquid crystal alignment treatment agent (9). In the liquid crystal alignment treatment agent, no abnormal phenomenon such as turbidity or precipitation was observed, and it was confirmed that it was a homogeneous solution.

In addition, the "Evaluation of the characteristics of the display spot near the front edge of the liquid crystal cell (general cell)" is also carried out in addition to the above-mentioned standard test. The test is carried out in a high-temperature and high-humidity bath at a temperature of 80 ° C and a humidity of 90%. The evaluation was carried out after 168 hours (other conditions are the same as those described above). As a result, it was confirmed that no disorder was observed in the liquid crystal alignment of the liquid crystal cell in the vicinity of the sealant.

<Example 10>

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

<Example 11>

To the polyimine powder (8) (2.50 g) obtained in Synthesis Example 8, NEP (27.4 g) was added, and the mixture was stirred at 70 ° C for 24 hours to dissolve. A 10 mass% NEP solution (1.75 g) of L1 and PB (11.8 g) were added to the solution, and the mixture was stirred at 50 ° C for 15 hours. Subsequently, S2 (0.125g), The mixture was stirred at 25 ° C for 6 hours to obtain a liquid crystal alignment treatment agent (11). In the liquid crystal alignment treatment agent, no abnormal phenomenon such as turbidity or precipitation was observed, and it was confirmed that it was a homogeneous solution.

<Example 12>

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

<Example 13>

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

<Example 14>

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

<Comparative Example 1>

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

<Comparative Example 2>

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

<Comparative Example 3>

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

<Comparative Example 4>

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

<Comparative Example 5>

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

<Comparative Example 6>

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

*1: The amount (parts by mass) of the specific compound to be added to 100 parts by mass of the polyimine-based polymer.

*2: The amount (parts by mass) of the specific amine compound to be added to 100 parts by mass of the polyimine-based polymer.

*3: indicates the proportion of the polyimine-based polymer in the liquid crystal alignment agent.

* 1: In the liquid crystal cell, no disorder was observed in the liquid crystal alignment near the sealant.

*2: In the liquid crystal cell, no liquid crystal alignment in the region from the sealant to a width of 0.3 cm was found to be disordered (the width of the liquid crystal alignment disorder observed in *1 was wider).

*3: In the liquid crystal cell, no liquid crystal alignment in the region from the sealant to the width of 0.6 cm was found to be disordered (the width of the liquid crystal alignment disorder observed in *2 was wider).

As a result of the above, when the liquid crystal alignment treatment agent of the example of the present invention is compared with the liquid crystal alignment treatment agent of the comparative example, it is confirmed that the liquid crystal cell can be prevented from lowering the voltage holding ratio even when the liquid crystal cell is irradiated with ultraviolet rays. Further, even when the liquid crystal cell was stored in a high-temperature, high-humidity bath for a long period of time, no liquid crystal alignment disorder occurred in the vicinity of the sealant. In other words, the liquid crystal alignment treatment agent of the present invention can suppress the decrease in the voltage holding ratio even after exposure to light for a long period of time, and can suppress the vicinity of the front edge of the liquid crystal display element under the conditions of high temperature and high humidity. A liquid crystal alignment film that exhibits the occurrence of plaques.

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

Further, a comparative example of a liquid crystal alignment treatment agent which is not used for any of a specific compound or a specific amine compound was found to be more deteriorated in the above characteristics as compared with the examples. More specifically, a comparison between Example 1 and Comparative Example 2 or Comparative Example 3, and a comparison between Example 3 and Comparative Example 5 or Comparative Example 6 can be mentioned.

Further, among the specific side chain structures in the present invention, a liquid crystal alignment treatment agent having a specific side chain type diamine compound having a specific side chain structure of the above formula [2-1] is used, and the above formula [2-2] is used. In comparison with the liquid crystal alignment treatment agent of the diamine compound having a specific side chain structure, it was confirmed in the stress test that the liquid crystal cell did not find liquid crystal alignment in the vicinity of the sealant even when stored in a high-temperature, high-humidity bath for a long period of time. The phenomenon of sexual disorder. More specifically, the comparison between Example 8 and Example 9 can be cited, for example, in the comparison of the same conditions in the test.

[Industrial use]

The liquid crystal alignment treatment agent of the present invention can provide a reduction in voltage retention rate even after exposure to light for a long period of time. The liquid crystal alignment film which is low in adhesion between the sealant and the liquid crystal alignment film and which suppresses the occurrence of display spots in the vicinity of the front edge of the liquid crystal display element under high temperature and high humidity conditions. Further, 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 are also provided.

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

Further, the liquid crystal alignment film obtained by the liquid crystal alignment treatment agent of the present invention is also useful for liquid crystal display elements which are required to be irradiated with ultraviolet rays when producing a liquid crystal display element. In other words, a liquid crystal layer is provided between one of the electrodes and the substrate, and a liquid crystal composition containing a polymerizable compound polymerized by at least one of an active energy ray and heat is disposed between the pair of substrates, and the electrode is passed through the electrode. A liquid crystal display device obtained by a step of applying a voltage to polymerize the polymerizable compound, and a liquid crystal layer between the pair of substrates is provided for one of the electrodes, and the active layer is disposed between the pair of substrates. A liquid crystal display element obtained by a step of polymerizing the polymerizable group by applying a voltage between the electrodes and a liquid crystal alignment film of a polymerizable polymer which is polymerized at least one of energy lines and heat is particularly useful.

Claims (22)

A liquid crystal alignment treatment agent comprising the following (A) component, (B) component and (C) component; (A) component: heteropoly acid; (B) component: polymer; (C) component: intramolecular A compound having a nitrogen-containing aromatic heterocyclic ring. The liquid crystal alignment treatment agent according to claim 1, wherein the heteropoly acid is at least one selected from the group consisting of phosphomolybdic acid, lanthanum molybdate, phosphotungstic acid, lanthanum tungstic acid, and phosphotungstic acid. The liquid crystal alignment treatment agent according to claim 1, wherein the polymer is an acrylic polymer, a methacrylic polymer, a novolak resin, a polyhydroxystyrene, a polyimine precursor, a polyimine, a polyfluorene. At least one selected from the group consisting of amines, polyesters, celluloses, and polyoxyalkylenes. The liquid crystal alignment treatment agent of claim 3, wherein the polymer is a polyimine precursor obtained by reacting a diamine component with a tetracarboxylic acid component or the polyimide precursor is imidized And get the polyimine. The liquid crystal alignment treatment agent of claim 4, wherein the diamine component is a diamine compound having a side chain structure represented by the following formula [2-1] or formula [2-2]; (Y ¹ represents a single bond, -(CH ₂ ) _a - (a is an integer from 1 to 15), -O-, -CH ₂ O-, -CONH-, -NHCO-, -CON(CH ₃ )- And at least one selected from the group consisting of -N(CH ₃ )CO-, -COO-, and -OCO-; Y ² represents a single bond or -(CH ₂ ) _b - (b is 1~) An integer of 15); Y ³ represents a group consisting of a single bond, -(CH ₂ ) _c - (c is an integer from 1 to 15), -O-, -CH ₂ O-, -COO-, and -OCO- At least one selected; Y ⁴ represents at least one divalent cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring and a heterocyclic ring, or a carbon number of 17 to 51 having a cholesterol skeleton a divalent organic group, an arbitrary hydrogen atom on the above cyclic group, an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, or carbon a fluoroalkoxy group or a fluorine atom substituted with 1 to 3; Y ⁵ represents at least one cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring and a hetero ring, and the cyclic group Any of the above hydrogen atoms may be an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, or a fluorine-containing alkoxy group having 1 to 3 carbon atoms. or substituted with fluorine atoms; n represents an integer of 0 to 4; Y ⁶ represents alkoxy of 1 to 18 carbon atoms of At least one 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 alkoxy group having 1 to 18 carbon atoms, and a fluorine-containing alkoxy group having 1 to 18 carbon atoms. 1 kind) [Chemical 2]-Y ⁷ -Y ⁸ [2-2] (Y ⁷ represents a single bond, -O-, -CH ₂ O-, -CONH-, -NHCO-, -CON(CH ₃ ) At least one selected from the group consisting of -, -N(CH ₃ )CO-, -COO-, and -OCO-; Y ⁸ is an alkyl group having a carbon number of 8 to 18 or a carbon number of 6~ 18 fluoroalkyl groups). The liquid crystal alignment treatment agent according to claim 5, wherein the diamine compound is represented by the following formula [2a]; (Y represents a structure represented by the above formula [2-1] or formula [2-2]; n1 represents an integer of 1 to 4). The liquid crystal alignment treatment agent according to claim 4, wherein the tetracarboxylic acid component is a tetracarboxylic acid dianhydride represented by the following formula [3]; (Z represents a structure of at least one selected from the group consisting of the structures represented by the following formulas [3a] to [3k]) (Z ¹ to Z ⁴ each independently represent at least one selected from the group consisting of a hydrogen atom, a methyl group, a chlorine atom and a benzene ring; and Z ⁵ and Z ⁶ each independently represent a hydrogen atom or a methyl group). The liquid crystal alignment treatment agent of claim 1, wherein the aforementioned (C) The compound of the component has one primary amino group and a nitrogen-containing aromatic heterocyclic ring in the molecule, and the primary amine group is an amine compound obtained by bonding to an aliphatic hydrocarbon group or a non-aromatic cyclic hydrocarbon group. The liquid crystal alignment treatment agent according to claim 8, wherein the amine compound is represented by the following formula [4a-1]; [Chem. 6] H ₂ NS ¹ -S ² [4a-1] (S ¹ represents fat A monovalent organic group of a monovalent hydrogen- or non-aromatic cyclic hydrocarbon group; S ² represents a nitrogen-containing heterocyclic ring). The liquid crystal alignment treatment agent according to claim 8, wherein the amine compound is represented by the following formula [4a-2]; [Chemical 7] H ₂ NS ³ -S ⁴ -S ⁵ [4a-2] (S ³ An aliphatic hydrocarbon group or a non-aromatic cyclic hydrocarbon group having 1 to 10 carbon atoms; and S ⁴ represents a valence of a single bond, -O-, -NH-, -S-, -SO ₂ - and a carbon number of 1 to 19 At least one selected from the group consisting of organic groups, the total of carbon atoms of S ³ and S ⁴ is 1 to 20; and S ⁵ is a nitrogen-containing hetero ring). The liquid crystal alignment treatment agent according to claim 10, wherein the S ³ , S ⁴ and S ⁵ in the amine compound represented by the above formula [4a-2] are each formed by a combination selected from the groups or rings described below. ; 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, or a ring. Heptane ring, cyclooctane ring, cyclodecane ring, cyclodecane ring, cycloundecyl ring, cyclododecane ring, cyclotridecane ring, cyclotetradecane ring, cyclopentadecane ring, ring ten Hexacyclo ring, cycloheptadecane ring, cyclooctadecane ring, cyclodecadecane ring, cyclohexadecane ring, tricyclohexadecane ring, tricyclotetracosane ring, bicycloheptane ring, ten One selected from the group consisting of a hydrogen naphthalene ring, a norbornene ring, and an adamantane ring; S ⁴ is a single bond, -O-, -NH-, -S-, -SO ₂ -, carbon number 1 Hydrocarbyl group of ~19, -CO-O-, -O-CO-, -CO-NH-, -NH-CO-, -CO-, -CF ₂ -, -C(CF ₃ ) ₂ -, -CH ( OH)-, -C(CH ₃ ) ₂ -, -Si(CH ₃ ) ₂ -, -O-Si(CH ₃ ) ₂ -, -Si(CH ₃ ) ₂ -O-, -O-Si(CH _{3) 2} -O-, cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, Heptane ring, cyclooctane ring, cyclodecane ring, cyclodecane ring, cycloundecyl ring, cyclododecane ring, cyclotridecane ring, cyclotetradecane ring, cyclopentadecane ring, ring ten Hexacyclo ring, cycloheptadecane ring, cyclooctadecane ring, cyclodecadecane ring, cyclohexadecane ring, tricyclohexadecane ring, tricyclotetracosane ring, bicycloheptane ring, ten Hydrogen naphthalene ring, norbornene ring, adamantane ring, benzene ring, naphthalene ring, tetrahydronaphthalene ring, anthracene ring, anthracene ring, anthracene ring, anthracene ring, phenanthrene ring, anthracene ring, pyrrole ring, imidazole ring, oxazole Ring, thiazole ring, pyrazole ring, pyridine ring, pyrimidine ring, quinoline ring, pyrazoline ring, isoquinoline ring, indazole ring, anthracene ring, thiadiazole ring, anthracene Ring, three Ring, pyrazolidine ring, triazole ring, pyridyl Ring, benzimidazole ring, benzimidazole ring, octyl ring, phenanthroline ring, anthracene ring, quinoxaline ring, benzothiazole ring, phenothiazine One selected from the group consisting of a ring, an oxazole ring, an acridine ring, an oxazole ring, a piperazine ring, a piperidine ring, a dioxane ring, and a florin ring; S ⁵ is a pyrrole ring, an imidazole Ring, oxazole ring, thiazole ring, pyrazole ring, pyridine ring, pyrimidine ring, quinoline ring, pyrazoline ring, isoquinoline ring, indazole ring, anthracene ring, thiadiazole ring, hydrazine Ring, pyrazoline ring, three Ring, pyrazolidine ring, triazole ring, pyridyl Ring, benzimidazole ring, benzoimidazole ring, octyl ring, phenanthroline ring, anthracene ring, quinoxaline ring, benzothiazole ring, phenothiazine One selected from the group consisting of a ring, an oxazole ring, and an acridine ring. The liquid crystal alignment treatment agent according to any one of claims 1 to 11, which is obtained by mixing a solvent containing the component (B) and the component (C) under heating. The liquid crystal alignment treatment agent according to any one of claims 1 to 11, wherein the liquid crystal alignment treatment agent contains N-methyl-2-pyrrolidone and N-ethyl-2-pyrrolidone And at least one solvent selected from the group consisting of γ-butyrolactone. The liquid crystal alignment treatment agent according to any one of Claims 1 to 11, wherein the liquid crystal alignment treatment agent contains 1-hexanol, cyclohexanol, 1,2-ethanediol, 1, 2 a solvent selected from the group consisting of propane diol, propylene glycol monobutyl ether, ethylene glycol monobutyl ether, dipropylene glycol dimethyl ether, and a solvent represented by the following formula [D1] to formula [D3]; (D ¹ represents an alkyl group having 1 to 3 carbon atoms; D ² represents an alkyl group having 1 to 3 carbon atoms; and D ³ represents an alkyl group having 1 to 4 carbon atoms). The liquid crystal alignment treatment agent according to any one of claims 1 to 11, wherein the liquid crystal alignment treatment agent is contained, and is composed of an epoxy group and an isocyanate. a crosslinkable compound selected from the group consisting of an acid ester group, an oxypropylene group and a cyclic carbonate group, selected from the group consisting of a hydroxyl group, a hydroxyalkyl group and an alkoxyalkyl group having 1 to 3 carbon atoms. A crosslinkable compound or a crosslinkable compound having a polymerizable unsaturated bond group. A liquid crystal alignment film obtained by the liquid crystal alignment treatment agent according to any one of claims 1 to 11. A liquid crystal alignment film obtained by applying an inkjet method to a liquid crystal alignment treatment agent according to any one of claims 1 to 11. A liquid crystal display element characterized by having the liquid crystal alignment film of claim 16. The liquid crystal alignment film according to claim 16, which is provided with a liquid crystal layer between the pair of substrates, and a polymerizable layer containing at least one of the active energy ray and the heat disposed between the pair of substrates A liquid crystal display device obtained by a step of polymerizing the polymerizable compound by applying a voltage between the electrodes. A liquid crystal display element comprising the liquid crystal alignment film of claim 19. The liquid crystal alignment film according to claim 16, which is provided with a liquid crystal layer between the pair of substrates, and a polymerizable layer containing at least one of the active energy ray and the heat disposed between the pair of substrates A liquid crystal display element obtained by a step of polymerizing the polymerizable group by applying a voltage between the electrodes. A liquid crystal display element comprising the liquid crystal alignment film of claim 21.